Corrosion and Degradation OF: Metallic Materials

I F P PUBLICATIONS
b Franqois ROPITAL
Professor, IF P
CORROSION
AND DEGRADATION
OF METALLIC
MATERIALS
Understanding of the phenomena
and applications in petroleum
and process industries
Preface by
Yves CHAUVIN
Nobel Prize in Chemistry 2005
Translated from the French

by Trevor Jones (Lionbridge)
2010
t Editions TECHNIP 2s rue Cinoux, 7501s PARIS, FRANCE

FROM THE SAME PUBLISHER
* Multiphase Production
Pipeline Transport, Pumping and Metering
J. FALCIMAIGNE, S . DECARRE
A Geoscientist’s Guide to Petrophysics

B. ZINSZNER, F.M. PERRIN
Acido-Basic Catalysis (2 vols.)

Application to Refining and Petrochemistry
C. MARCILLY
Petroleum Microbiology (2 vols.)

J.P. VANDECASTEELE
Physico-Chemical Analysis of Industrial Catalysts

A Practical Guide to Characterisation
1. LYNCH
Chemical Reactors
From Design to Operation
P. TRAMBOUZE, J.P. EUZEN
Petrochemical Processes (2 vols.)

Technical and Economic Characteristics
A. CHAUVEL, G. LEFEBVRE
The Technology of Catalytic Oxidations (2 vols.)

P. ARPENTIMIER, F. CAVAMI, F. TRlFlRO
- Marine Oil Spills and Soils Contaminated by Hydrocarbous

C. BOCARD
This book is a translation of “Corrosion et degradation des materiaux metalliques”

0 Editions Technip, 2009
All rights reserved.

No part of this publication may be reproduced or transmitted in any form or by any means, electronic or
mechanical, including photocopy, recording, or any information storage and retrieval system, without the
prior written permission of the publisher.
0Editions Technip, Paris, 2010.

Printed in France
ISBN 978-2-7 108-0944-9
Introduction
Controlling the corrosion of equipment used in industrial processes and especially in the
petroleum industry is a major importance in guaranteeing their continued development
under optimum conditions in terms of reliability and safety. To meet society’s demand for
fuel, the petroleum industry must control all hydrocarbon production, transportation, refin-
ing, and storage processes. The reliability of the equipment used during these steps is highly
critical. The choice of materials, generally metallic, is based on knowledge acquired by spe-
cialists over the past decades and on studies dedicated to satisfying the new objectives of the
petroleum industry and the new petroleum environments. For example, the development of
oil fields storing oil and gas at increasingly high temperatures, with high contents in acid
gases such as C 0 2 and H2S, requires an excellent knowledge of the corrosion resistance of
equipment used for drilling, production and transportation of petroleum effluents. Similarly,
the traditional refining industry must adapt in order to process crude oils that are becoming
increasingly corrosive due to the presence of naphthenic acids and high concentrations of
sulfur containing products in order to convert them into low-sulfur fuels and thereby limit
their impact on the environment during combustion. Manufacture of synthetic fuels from
natural gas, coal or biomass via synthesis gas, for example, requires in-depth knowledge of
the corrosion resistance of the metallic materials used to make the equipment of these new
processes. The refineries must also limit their energy requirements and reduce their external
water demand for the heat exchanger circuits, which means that the flows must be recycled.
As a result, the water composition will contain more corrosive elements and the water cir-
cuits will be more sensitive to corrosion.
The aim of the petroleum industry is to produce large quantities of fuels under economi-
cally viable conditions. By analysing the experience acquired on equipment behaviour and
by creating monitoring and inspection programs, the corrosion costs can be included with
the operating costs. However, any unplanned operating shutdown caused by corrosion gen-
erates high additional costs, whether direct (repair or replacement of damaged equipment) or
indirect (immobilisation of the production tool).
XVI Introduction
The total cost worldwide of all types of corrosion and its prevention is estimated at
between 2% and 4% of the GNP. The petroleum production and refining industries represent
respectively 1% and 2.7% of this total cost [4]. For the United States, this corresponds to a
direct cost of 1.4 billion dollars per year for the upstream petroleum sector and 3.7 billion
dollars per year for the downstream sector [4]. The total cost (direct and indirect impacts) of
corrosion and its prevention can be estimated at about 10 billion dollars per year for the
American petroleum industry and at about 35 billion dollars per year for the worldwide
petroleum industry.
For the petroleum production industry, 43% of the corrosion cost concerns surface pipe-
lines and development costs, 34% casings and 23% the investments related to corrosion. For
surface petroleum production, the cost of corrosion is estimated at 0.2 dollars per barrel of
oil produced and at 0.09 dollars per barrel of water produced [2]: as shown on Figure 0.1, a
large proportion concerns the cost of anticorrosion chemical treatments, then inspection,
monitoring and repair costs.
Monitoring Staff
Figure 0.1
Distribution of corrosion costs (source: corrosioncost.com).
In the refining industry, 46% of the cost concerns maintenance, 38% the reactors and
equipment and 16% the cost due to clogging. The cost of corrosion control is estimated at
0.3 1 dollars per barrel for the complete chain of refining processes. As shown on Figure 0.2,
for a distillation unit, the cost of corrosion control, between 0.0 15 and 0.1 1 dollars per bar-
rel, includes the corrosion coupons, sensors, inhibitors and non destructive testing.
The above figures have been taken from financial reports based on equipment and pro-
cesses operating under standard conditions. They do not include any unscheduled events.
The few major accidents in the petroleum industry caused by corrosion sadly illustrate these
exceptional costs and their impact on the environment and the human safety. In 1984, an
absorption column of a plant for treatment of acid gas by MEA-based chemical solvents
split and was blown more than a kilometre away. The accident left 17 dead and 17 more
injured, and caused more than $100 million worth of damage. Investigators found that the
accident was due to stress corrosion of hard brittle steel where repair welds had been made
Introduction XVII
12
Coupons Probes Inhibitors NDE Total

(non destructive
evaluation)
Figure 0.2
Distribution of corrosion control costs for a distillation unit
(source: corrosioncost.com).
ten years earlier [5]. In 2006, leaks caused by bacterial corrosion stopped oil production
from Alaska for several days, creating tension on the oil market [ l ; 31.
These examples show that corrosion control is a key issue for the technical and financial
performance of the petroleum industry. The various actors in the industry as well as anyone
else interested should therefore be able to obtain basic information on the impacts of envi-
ronments specific to the petroleum industry, the corrosion resistance of metallic equipment
and the main methods of preventing corrosion.
This book therefore aims to provide basic information to non-specialists in corrosion
and/or in the petroleum industry to understand the main phenomena involved in the corro-
sion and degradation of metallic materials in this industry. The information contained in this
document may also be useful for processes in other industries such as chemistry or water
treatment.
The book is composed of 3 main sections which may be consulted independently,
depending on the reader’s requirements and knowledge.
Section 1 describes depending on the chemical environment (and therefore the equip-
ment and/or process) the main phenomena encountered in the petroleum industry and the
solutions implemented to prevent them. Mechanisms leading to corrosion in these specific
environments are described. If necessary, the reader may refer to the specific chapters in
Section 3 provided for reference, to obtain details concerning the corresponding basic corro-
sion mechanisms. Similarly, for the prevention methods, cross-references are given to chap-
ters in Section 2 describing the techniques.
XVIII Introduction
Section 2 tackles the various protection techniques (design, choice of metallic alloys,
application of coatings, use of corrosion inhibitors or bactericide additives, cathodic protec-
tion) and corrosion monitoring techniques used in the petroleum industry.
Section 3 presents the basic information on the main steels and alloys used in the petro-
leum industry (structure, properties), the main corrosion modes and other damage modes
(high temperature ageing) affecting metallic materials.
An index and a glossary are provided at the end of the book to guide the reader.
REFERENCE LIST
(2006) Corrosion apparent cause of Alaskan pipeline leak. Pipeline and Gas Journal 233,4, pp. 2.
Bhaskaran R, Palaniswamy N, Rengaswamy NS, and Jayachandran M (2005) A review of diffe-
ring approaches used to estimate the cost of corrosion (and their relevance in the development of
modem corrosion prevention and control strategies). Anti-Corrosion Methods and Materials 52,
I , pp. 29-4 1.
Griffoulieres C (2007) Environmental accidents. BP agrees to pay almost 300 million. Info
Chimie Magazine 44,483, pp. 15.
Tems R and Al-Zahrani AM (2006) Cost of corrosion in oil production and refining. Saudi
Aramco Journal of Technology, pp. 2-14.
Vercalin CH ( 1 987) Safety guidelinesiExplosion at union oil. Hydrocarbon Processing 66, 1,
pp. 83-84.
Preface
I was honoured by FranCois Ropital’s request to introduce his book which provides an
update of the knowledge on the understanding and prevention of the main phenomena caus-
ing corrosion and degradation of metallic materials in the petroleum and process industries.
As we will see throughout this review of the mechanisms involved, corrosion is a serious
problem encountered at every stage in the production, transport, refining and chemistry of
oil, especially due to the consequences of the resulting unplanned stoppages.
Due to the nature of the role it plays in this domain, IFP is well aware of the problems
related to corrosion in the petroleum industry; this of course explains why companies fre-
quently rely on its expertise.
Nearly twenty years ago now, I liked to visit the “museum” created by the sadly missed
Yves Lefebvre, who at the time was responsible for corrosion problems at IFP. Amongst all
the “horrors” exhibited, the one that impressed me the most was bacterial corrosion which
had made a perfectly cylindrical hole in the bends of steel tubes over 10 mm thick!
I also remember more serious problems, such as mercury corrosion of aluminium
exchangers in a natural gas liquefaction plant in Algeria; it took quite some time to discover
that the corrosion was in fact due to mercury contained in the gas itself.
Personally during my career at IFP, I have never been faced with problems related to cor-
rosion, since the various processes I studied only involved relatively pure olefins under mod-
erate temperature conditions. For instance, after a few preliminary investigations on speci-
mens, the lifetime of the carbon steel used to manufacture the reactor was found to be very
long, not suffering any corrosion: although the reaction medium contained Lewis acids such
as aluminium chloride, the corrosion mechanism was blocked by absence of protons.
This book benefits from several decades of experience acquired by IFP in the field of
corrosion. It undoubtedly represents an effective vector in the transfer of knowledge of the
processes involved in the corrosion of metallic materials and its prevention.
Yves Chauvin
Nobel Prize in Chemistry 2005
Contents
Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . XI
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . XI11
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xv
Chapitre 1
MAIN CORROSION PHENOMENA ENCOUNTERED IN OIL AND GAS
PRODUCTION. REFINING AND PETROCHEMISTRY INDUSTRIES:
CORROSION MECHANISMS AND PREVENTIVE SOLUTIONS
1.1 Presentation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 Carbon dioxide corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.2.1 Equipment concerned by C 0 2 corrosion ..................... 3
1.2.2 Mechanisms and parameters influencing C 0 2 corrosion . . . . . . . . . . . . . . . . 4
1.2.3 Example of C02 corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.2.4 Acidity and C02 corrosion prediction models . . . . . . . . . ......... 8
1.2.5 Prevention of C 0 2 corrosion ......... 8
1.3 Corrosion by water containing H, S . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
1.3.1 Equipment concerned by H2S corrosion . . . . . . . .............. 8
1.3.2 Mechanisms and parameters influencing H2S corrosion . . . . . . . . . . . . . . . . 9
1.3.3 Selection of materials for use in H2S environment . . . . . . . . . . . . . . . . . . . . 13
1.4 Corrosion by mercury and liquid metals . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
1.4.1 Equipment concerned by mercury corrosion . . . . . . . . . . . . . . . . . . . . . . . . 13
1.4.2 Mechanisms involved in mercury embrittlement of aluminium . . . . . . . . . . . 14
1.4.3 Example of mercury corrosion . . . . . . .. 14
1.4.4 Other metallic materials sensitive to liquid metal embrittlement . . . . . . . . . . 15
1.4.5 Prevention of liquid metal embrittlement . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
1.5 Corrosion by the bacteria present in water, soil and crudes . . . 16
1.5.1 Stakes of biocorrosion in the petroleum industry . . . . . . . . . . . . 16
1.5.2 Means used to detect and combat biocorrosion . . . . . . . . . . . . . . . . . . . . . . 17
1.5.2.1 Use of non-corrodable materials . . . . . . . . . . . ......... 17
VI Contents
1.5.2.2 Construction of a non aggressive bacterial environment . . 17

1.5.2.3 Use of bactericides ......... ........ 17
1.5.2.4 Use of cathodic protection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
1.5.2.5 Protective coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
1.5.2.6 Detection of corrosive micro organisms . . . . ..... 19
1.6 Corrosion caused by the chlorides present in water . . . . . . . . . . . . . . . . . . . 20
1.6.1 Equipment concerned by corrosion due to chlorides present in water . . . . . . . . 20
1.6.2 Mechanisms and parameters influencing corrosion by water containing chlorides. 20
1.6.3 Example of corrosion by water containing chlorides ....... 22
1.6.4 Prevention of localised corrosion of stainless steels by water containing chlorides. 22
1.7 Hydrolysis of chlorides into HCl . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
1.7.1 Equipment concerned by hydrolysis of chlorides into HCI . . . . . . . . . . . . . . . 23
1.7.2 Mechanisms and parameters governing corrosion . . . . . . . . . . . . . . 23
1.7.3 Example of corrosion by HC1 formed by hydrolysis of chlorides 25
1.7.4 Prevention of corrosion by HC1 formed by hydrolysis of chlorides . . . . . . . . . 25
1.8 Corrosion by concentrated acids: HCI, H2S04 or HF . . . . 26
1.8.1 Corrosion by concentrated hydrochloric acid . . . . . . . . . . . . . . . . . . . . . . . . . 26
1.8.1.1 Equipment concerned by HCl corrosion . 26
1.8.1.2 Mechanisms and parameters governing H rrosion . . . . . . . . . . 26
1 3.1.3 Example of HCI corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
1.8.1.4 Prevention of HC1 corrosion . . . . . ..... ... 27
1.8.2 Corrosion by concentrated sulfuric acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
1.8.2.1 Equipment concerned by H2S04 corrosion . . . . . . . . . . . . . . . . . . . 28
28
29
......................... 29
1 2.3 Hydrofluoric acid corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
1.8.3.1 Equipment concerned by HF corrosion . . . . . . . . . 30
1.8.3.2 Mechanisms and parameters governing HF corrosio 32
1.8.3.3 Example of HF corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
1.8.3.4 Prevention of HF corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
1.9 Stress corrosion in alkaline and quasi-neutral media . . . . . . . . 34
1.9.1 Caustic stress corrosion . . . . . . . . . . . . ......................... 34
1.9.1.1 Equipment concerned by caustic corrosion . . . . . . . . . . . . . . . . . . . 34
1.9.1.2 Mechanisms and parameters governing caustic corrosion . . . . . . . . 34
1.9.1.3 Example of caustic corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
1.9.1.4 Prevention of caustic soda corrosion . 34
1.9.2 Carbonate stress corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
1.9.2.1 Equipment concerned by carbonate corrosion . . 36
1.9.2.2 Mechanisms and parameters governing carb 36
1.9.2.3 Example of carbonate corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . 37
1.9.2.4 Prevention of carbonate corrosion . ... 37
1.9.3 Stress corrosion in near neutral medium . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
1.9.3.1 Equipment concerned by corrosion in near neutral medium . . . . . . . 38
1.9.3.2 Mechanisms and parameters governing corrosion in near neutral medium 38
1.9.3.3 Example of corrosion in near-neutral medium . .... .. 38
1.9.3.4 Prevention of corrosion in near-neutral medium . . . . . . . . . . . . . . . 38
Contents VII
1.10 Alcohol (methanol and ethanol) corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . 39

1.10.1 Equipment concerned by alcohol corrosion . . . . . . . . . . 39
1.10.2 Mechanisms and parameters governing methanol corrosi 39
1.10.3 Mechanisms and parameters governing ethanol fuel corrosion . . . . . . . . . . . 40
1.10.4 Example of ethanol corrosion .................. 40
1.10.5 Prevention of alcohol corrosion . . . .... 40
1.1 1 Corrosion by acid gas chemical solvents. . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
1.1 1.1 Introduction: principles of acid gas removal by chemical solvents . . . . . . . . . 41
1.1 1.2 Mechanisms and parameters governing corrosion in acid gas treatment plants. . 43
1.1 1.2.1 Acid gas corrosion .... . . . . 43
1.1 1.2.2 Corrosion by amin 44
1.1 1.3 Equipment concerned by corrosion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
1.1 1.3.1 Absorber. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
1.1 1.3.2 Rich amine lines ................. 45
1.1 1.3.3 Richilean amine e ....... 46
1.1 1.3.4 Regenerator and acid gas outlet (condenser, reflux drum). . . . . 46
1.1 1.3.5 Reboiler . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
1.1 1.3.6 Lean amine lines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
1.1 1.4 Examples of corrosion by acid gas solvents. ...... . . 47
1.1 1.5 Prevention of corrosion in acid gas treatment units. . . . 47
1.1 1.5.1 Operating conditions of the units . . . . . . . . . . . . . . . . . . . . . . . . . 49
1.1 1.5.2 Use of corrosion inhibitors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
1.1 1S . 3 Corrosion monitoring .................. 50
1.1 1.5.4 Choice of appropriate metallurgies 50
1.12 Corrosion by crude oil containing naphthenic acids. . . . . . . . . . . . . . . . . . 52
1.12.1 Equipment concerned by naphthenic acid corrosion. . . . . . . . . . . . . . . . . . . 52
1.12.2 Mechanisms and parameters governing naphthenic acid corrosion. . . . . . . . . 52
53
54
54
1.13 Corrosion during the formation of polythionic acids 55
55
56
1.13.3 Example of polythionic acid corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
1.13.4 Prevention of polythionic acid corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
1.14 Decarburisation by high temperature hydrogen attack . . . . . . . . . . . . 58
1.14.1 Equipment concerned by high temperature hydrogen attack . . . . . . . . . . . . . 58
1.14.2 Mechanisms and parameters governing high temperature hydrogen attack . . . 58
1.14.3 Example of high temperature hydrogen attack . . ..... 59
1.14.4 Prevention of high temperature hydrogen attack. . . . . . . . . . . . . . . . . . . . . . 60
1.14.5 Hydrogen-induced disbonding of stainless steel overlays . . . . . . 61
1.14.6 Hydridation of titanium equipment 61
1.15 High temperature oxidation. 62
1.15.1 Equipment concerned by h 62
1.15.2 Mechanisms and parameters governing high temperature oxidation. ....... 62
1.15.3 High temperature oxidation prediction models. . . . . . . . . . . . . 62
VIII Contents
I . 15.4 Example of high temperature oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63

I .15.5 Prevention of high temperature oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
1.16 High temperature sulfidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
1.16.1 Equipment concerned by high temperature sulfidation . . . . . . . . . . . . . . . . . . 65
1. 16.2 Mechanisms and parameters governing high temperature sulfidation . . . . . . . . 65
I . 16.3 High temperature sulfidation prediction models . . . . . . . . . . . . . . . . . . . . . . . 65
I .16.4 Example of high temperature sulfidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
1.16.5 Prevention of high temperature sulfidation . . . . . . . . . . . . . . . . . . . . . 66
1.17 Carburisation, coking, metal dusting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
1.17.1 Coking . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
1.17.1.1 Catalytic and pyrolytic mechanisms . . . . . . . . . . . . . . . . . . . . . . . 68
1.17.1.2 Example of pyrolytic coking . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
1.17.1.3 Prevention of coking . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
1.17.2 Metal dusting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
1 .l7.2.1 Metal dusting mechanisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
1.17.2.2 Example of metal dusting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
1.17.2.3 Prevention of metal dusting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
1.17.3 Carburisation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
1.l7.3.1 Carburisation mechanisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
1.17.3.2 Example of carburisation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
1.17.3.3 Prevention of carburisation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
1.18 Molten salt corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
1.18.1 Equipment concerned by molten salt corrosion . . . . . . . . . . . . . . . . . . . . . . . 73
1.18.2 Mechanisms and parameters governing molten salt corrosion . . . . . . . . . . . . . 73
1.18.3 Example of molten salt corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
1 .18.4 Prevention of molten salt corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
Chapitre 2
PREVENTION OF CORROSION AND DEGRADATION
OF METALLIC MATERIALS USED IN THE PETROLEUM INDUSTRY
2.1 Corrosion prevention by appropriate selection and design of materials
and equipment ............................. ..... 83
2.1.1 Data concerning the corrosion type and propagation rate . . . . . . . . . . . . . . . . 83
2.1.2 Control of operating parameters . . . . . . . ............... 84
2.1.3 Equipment design . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
2.2 Use of coatings, corrosion inhibitors or cathodic protection 87
2.2.1 Protection by coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
2.2.1.1 Principle ....................................... 87
2.2.1.2 Organic coatings an ......................... 88
2.2.1.3 Composite liner . . . 92
2.2.1.4 Inorganic coating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
2.2.1.5 Cladding . . . 94
2.2.1.6 Anticorrosion cements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
2.2.1.7 Surface treatments . . . . . . 95
2.2.2 Cathodic protection of structures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
Contents IX
2.2.2.1 Principle ............................ 96

2.2.2.2 History o ore applications . . . . . . . . . . . . . . . . 96
2.2.2.3 Problems encountered (design, checks of cathodic protection
2.2.3.1 Principle .. ........................ 98
2.2.3.3 Gas phase inhibitors. ......... ......... 103

2.3 Corrosion detection, control and monitoring. . . . . . . . . . . . .
2.3.1 Introduction ..............................
2.3.2.1 Indirect methods ............................... 106

2.3.2.2 Direct methods ................... 116
2.3.3 Detection and inspection ...... 125
2.3.3.1 Non-destructiv
2.3.3.3 Inspection plans and RBI .............................. 137
Chapitre 3
FUNDAMENTALS ON METALLIC ALLOYS AND CORROSION
3.1 Basic information concerning the metallic materials used

in the petroleum sector, their structure and properties . . . . . . . . . . . . . . . 147
3.1.1 Structure of metallic alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 147
3.1.1.1 Crystallographic structures of alloys . . . . . . . . . . . . . . . . . . . . . . 148
3.1.1.2 Alloy equilibrium diagr .............. 152
3.1.1.3 Application to the Fe-C ......... 154
3.1.1.4 Steel heat treatments: time-temperature transformation diagram 155
3.1.1.5 Metallurgical transformations during steel welding operations . . . . 158
3.1.1.6 Influence of the various addition elements on steel properties. . . . . 158
3. I .2 Mechanical behaviour of metallic materials ............. 160
3.1.2.1 Introduction. . . . . . . . . . . . . . . . .
3.1.2.2 Tensile test . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.2.3 Elastic and plastic strain mechanisms in metals. . . . . . . .
3.1.2.4 Damage and failure mechanisms . . . . . . . . . . . . . . . . . . . . . . . . . 167
3.1.2.5 Ductile failure and brittle failure ................ 168
3.1.2.6 Description of mechanical stresses and behaviours . . . . . . . . . . . . 170
3.1.2.7 Types of mechanical test .......................... 174
3.1.3 Alloys used in the petroleum industry ... 187
3.1.3.1 Ferrous metals (iron content > 50%) . . . . . . . . . . . . . . . . . . . . . . 188
of metallic materials ...................... 199
3.2.1.1 Free enthalpy of a corrosion reaction

3.2.1.2 Ellingham diagrams . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20 1
X Contents
3.2.2 Chemical corrosion in liquid phase ................. 202

3.2.3 Electrochemical corrosion in liquid 202
3.2.3.1 Electrochemical reaction 202
3.2.3.2 Faraday's law . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 203
3.2.3.3 Metal - electrolyte interface . . . . . . ..... 203
3.2.3.4 Electrochemical thermodynamic equi m . . . . ............. 203
3.2.3.5 Pourbaix diagrams: potential-pH equilibria . . . . . 206
3.2.3.6 Electrochemical kinetics. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 209
3.2.4 High temperature gas phase corrosion . . . . . . . . . . . . . . 217
3.2.4.1 Main high temperature corrosive gases . . . . . . . . . . . . . . . . . . . . . 217
3.2.4.2 High temperature corrosion mechanisms: oxidation and sulfidation . 218
3.3 The various forms of corrosion ....................... 224
3.3.1 Uniform corrosion ................................... 224
225
226
3.3.2.2 Concentration cell . . . . . . . . . . . . . . . . . . . . . . . . . 226
3.3.3 Pitting corrosion. . . . . 228
3.3.4 Crevice corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 229
230
23 1
3.3.6.1 Stress corrosion mechanisms ............... 232
3.3.6.2 Corrosion fatigue. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 232
3.3.7 Erosion-corrosion . . . . . . . . . . . . . . . . . . . . 233
3.4 Bacterial corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 233
3.4.1 Biofilms and biofouling . . . . . . . . 234
3.4.2 Anaerobic corrosion by sulfidogenic 235
3.4.2.1 Microorganisms. . . . . . . 235
3.4.2.2 Biocorrosion process . . . 235
3.4.3 Corrosion by iron oxidising bacteria. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 236
3.4.4 Corrosion by acidogenic bacteria. . 237
3.5 Other damage modes - Ageing of metallic materials . . . . . . . . . . . . . . . . . . 238
3.5.1 Embrittlement of low alloy steels. . . . . . . . . . . . . . . . . . . . . . . . . . . . 238
3.5.1.1 Temper embrittlement 238
3.5.1.2 Creep embrittlement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 239
3.5.2 475 "C embrittlement of stainless steels . . . . . . . . . . . . . . . . . . . . . . . . . . . . 239
3.5.3 Intergranular sensitisation of stainless steels . . 239
3.5.4 Precipitation of intermetallic phases. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24 1
Annexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 245
Glossary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 251
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 255
1
Main corrosion phenomena encountered
in oil and gas production,
refining and petrochemistry industries:
corrosion mechanisms and preventive solutions
1.I PRESENTATION
This section describes, depending on the chemical environment (and therefore the equip-
ment and/or process), the main corrosion phenomena encountered in the petroleum industry.
It also discusses the main solutions frequently used to prevent this corrosion. The mecha-
nisms governing corrosion in these specific petroleum environments are described. If neces-
sary, the reader may refer to the specific chapters in Section 3 provided for reference, to
obtain further details concerning the corresponding basic mechanisms of the types of corro-
sion mentioned. Similarly, for the prevention methods, cross-references are given to chap-
ters in Section 2 describing the techniques.
Seventeen corrosive environments found throughout the petroleum chain (from the oil
well to refining or to the basic petrochemical compounds) are detailed. Some of these envi-
ronments are specific to one petroleum domain (upstream, acid gas treatment, downstream)
while others may be encountered in several domains. Table 1. I lists these corrosive environ-
ments and the petroleum domains where they are encountered.
To give the reader an overview of the equipments and units concerned throughout the
petroleum chain “from well to fuel” by the various environments listed in Table 1.1, a block
diagram is given on Figure 1.1.
T
Water or gas injection
I
4
Wellhead
3
Tubing
Casing
Tubing
Casing
1.
PackerReseNolr
Prodmiionwells
Gas
water
Packer
Reservoir
l",ectlO" wells
tuu
s
HP stream
4
%
I?.
Other-
I Gas H-
Sulfur
water Water
water
Block diagram showing the locations of corro: ve agents in the petroleum industry.
Chapitre I Muin corrosion phenomena encountered in oil and gas production 3
Table 1.1 Lists of corrosive chemical environments detailed in Section 1

and the petroleum domains where they are encountered.
Corrosive environment Oil and gas Acid gas Refining

Paragraph production treatment petrochemistry
liquid water + C 0 2 1.2 X X X
liquid water + H2S 1.3 X X X
mercury and liquid metals 1.4 X
water + bacteria 1.5 X X
water + chlorides 1 1 . 6 I x I x I X
hydrolysis of chlorides into
1.7 X
HCI
concentrated acids:
HC1, H2S04, HF 1.8 X X
bases: soda and carbonates 1.9 X
alcohols I 1.10 I x I I X
acid gas chemical solvents 1.11 X X
crude with naphthenic acids 1.12 X
polythionic acids I 1.13 I I I X
high temperature hydrogen
decarburisation
I 1.14
I I x
high temperature oxidation 1.15 X
high temperature sulfidation 1.16 X
carburisation, coking, metal
dusting
I 1.17
I II x
molten salts I 1.18 I I X
1.2 CARBON DIOXIDE CORROSION
1.2.1 Equipment concerned by C02 corrosion
Water containing dissolved carbonic acid is corrosive to carbon and low alloy steels.
Since CO, is an acid gas present in all oil fields in greater or smaller quantities, this type
of corrosion concerns all petroleum production equipment where free water containing car-
bonic acid could come into contact with carbon and low alloy steels: well tubing, wellheads,
separators, pipelines, pumps, etc.
Chemical solvent decarbonation units are also concerned, in particular the overhead sys-
tems of regenerators.
For the refining units, the boiler feedwater and condensate systems are sensitive to this
type of corrosion.
4 Chapitre 1 Main corrosion phenomena encountered in oil and gas production
1.2.2 Mechanisms and parameters influencing COz corrosion
Carbon dioxide dissolved in water causes several types of corrosion in carbon and low alloy
steels: uniform corrosion as well as three variants of localised corrosion, viz. pitting, mesa
attack and flow induced localised corrosion [98]. Carbonic acid is formed when carbon
dioxide dissolves in water, producing iron carbonates and bicarbonates on reaction with car-
bon and low alloy steels:
Dissolution of carbon dioxide (codgas - (C02)liquid
Formation of carbonic acid
First dissociation of carbonic acid
Second dissociation of carbonic acid
COz+H20
H&O3
HCOT
-
-
H2CO3
HCOS+H+
C O P + H+
Iron corrosion reaction
Formation of iron bicarbonate
Formation of iron carbonate
H2C03 + Fe
Fe2++ C0:-
-
Fe2++ 2(HCOj)
A
A
Fe2++ C0:- + H2
Fe(HC03)2
FeC03
The corrosion process is an electrochemical one: oxidation of iron and, due to the acidity
of the aqueous electrolyte, reduction of hydrogen (for further information on electrochemi-
cal corrosion, refer to paragraph 3.2.1).
Types of corrosion caused by carbon dioxide:

- Uniform corrosion by attack of the surface, creating a layer of iron carbonate which
helps to protect the metal;
- Pitting: this phenomenon appears under conditions of low flow rate at temperatures
close to the dew point of water;
- Mesa attack: this localised corrosion develops in case of instability of the iron carbon-
ate layer, at low and medium fluid flow rates. For surfaces partially covered with iron
carbonate, it could also be due to galvanic coupling between the ferrite in the steel and
the cementite trapped in the deposit of FeC03 [61];
- Flow induced localised corrosion: this form of corrosion is generally initiated by pit-
ting or mesa attack. Due to the local flow conditions and the stresses resulting from
the growth of the corrosion deposit, the deposit is tom off and an adherent protective
layer of iron carbonate is unable to reform.
Main parameters injluencing carbon dioxide corrosion:

Corrosion of carbon and low alloy steels by carbonic acid dissolved in water is influ-
enced by numerous interdependent chemical, physical and metallurgical factors:
- Water composition (presence of basic or acidic elements, possibly organic acids). The
acidity of the water in which the C02 is dissolved depends on its composition. In
addition, the water composition may govern the oversaturation conditions (especially
in Fe2+ and/or HCOT andor CaC03) which play a central role in the formation and
stability of the iron carbonate layer;
- The presence, type and concentration of the hydrocarbons associated with water and
the hydrodynamic conditions are also determining factors. When there is no free
Chapitre 1 Main corrosion phenomena encountered in oil and gas production 5
water on the steel surface but adsorption of a continuous hydrocarbon film, corrosion
does not occur. High flow rates and local flow conditions may tear off the corrosion
deposits and accelerate corrosion;
- The partial pressure of C 0 2 (or more precisely its fugacity) is a predominant parame-
ter: C02 solubility is in fact directly proportional to the partial pressure. The water
acidity depends on this parameter and numerous models have been developed to cal-
culate the water pH in order to estimate a corrosion rate. When H2S is also present, its
partial pressure must also be taken into account when calculating the water acidity, as
indicated on Figure 1.2;
- Temperature has a considerable effect on the nature and morphology of the corrosion
deposits which form on the surface of low alloy steels. As shown on Figure 1.3, at
temperatures exceeding 70 "C, the low solubility of FeC03 and the high oversatura-
tion of this compound favour the formation of a protective layer of iron carbonate.
Below 70 "C the temperature activates the process of the electrochemical dissolution
of steel;
- The metallurgy of carbon, low alloy or stainless steels: the chemical composition, heat
treatments and the microstructural state all affect C 0 2 corrosion. The chromium
content plays a dominant role, as shown on Figure 1.4: we see that addition of 3% Cr
to the steel reduces its rate of corrosion by a factor of 10, due to the formation of a
more protective metal carbonate. Small quantities of V, Ti, Mo, Si and Cu also help
reduce the rate of corrosion of micro-alloy steels [96; 971. When the steel contains
more than 11% chromium, its surface is protected by a thin layer of oxide which is
highly resistant to carbon dioxide corrosion.
2.5 I I I I
0.01 0.1 1 10 100
P CO, + P HS
, (bar)
Figure 1.2
pH of condensation water under C 0 2 and H2S pressure [ 131.
6 Chapitre I - Main corrosion phenomena encountered in oil and gas production
14
12
a,
c
e
r 6
.-0
In
g 4
0
20 40 60 80 100 120 140

Temperature ("C)
Figure 1.3
Influence of temperature and C02 partial pressure on the rate of corrosion of
carbon steel [99].
0 1 2 3 4 5
Chromium content of the steel ("A Cr)
Figure 1.4
Influence of chromium content of steels on the C 0 2 corrosion rate [96; 971.
Chapitre 1 Main corrosion phenomena encountered in oil and gas production
9 7
1.2.3 Example of CO2 corrosion
Heat exchanger on a refining unit:

The carbon steel exchanger is at the reactor head. It was initially designed to last one year.
It allowed first cooling of the gas leaving the reactor, down to a temperature of 90 "C-100 "C.
The exchanger is double-pipe counter current type, the average temperatures of the fluids
were as follows:
Process side: Tinlet= 230 "C; Toutlet= 110 "C
Cooling water side: Tinlet= 100 "C; Toutlet= 90 "C
The initial thickness of the pipe was 2.1 mm. The pressure on the pipe side was 25 bars
including 2 bars CO, partial pressure. The speed in the pipes was about 2 m/s to 3 m/s at
inlet and the quantity of liquid condensed in the pipes varied from about 200 L/h to 300 L/h.
The exchanger developed a leak after 9 months operation. The photographs on Figure 1.5
show that there is an uniform corrosion of the inside of the pipe. Temperature gradients are
probably responsible for the non-uniform loss of thickness around the circumference of the
pipe. The rate of corrosion observed on this exchanger is about 2.8 mm/year, a value in agree-
ment with the predictions of the various models detailed in the next paragraph 1.2.4. For this
equipment to meet the 1 year lifetime criterion, 3 mm corrosion allowance should have been
specified during its design.
Figure 1.5
Example of CO, corrosion of a carbon steel exchanger pipe.
8 Chapitre I Main corrosion phenomena encountered in oil and gas production
1.2.4 Acidity and COz corrosion prediction models

Numerous models have been developed by the companies and research centres of the upstream
petroleum domain to assess the acidity of the aqueous electrolyte and predict the range of the cor-
rosion expected for carbon steel [30; 63; 991. The input parameters are the water composition,
temperature, partial pressures of C02 (and of H2S if this gas is present), iron and calcium carbon-
ate saturation conditions (if applicable) and for some models the hydrodynamic conditions. The
corrosion rate predictions are based on laboratory estimations and feedback from oil fields. Mod-
els taking into account the physico-chemical and thermodynamic equilibria can be used to obtain
the water acidity [59]. These are vital tools for the specialists, but they must not be considered as
sufficient engineering means on which to base the choice of materials and their protections.
1.2.5 Prevention of C02 corrosion

The main methods used to prevent C02 corrosion are:
- Injection of amine-, amide- and imidazoline-based corrosion inhibitors and, more
recently, biodegradable additives such as polyamino acids, polysuccinates and polyas-
partates. For further information on the use of these inhibitors, the reader can refer to
paragraph 2.2. A corrosion allowance is often recommended to make up for any mal-
function of the inhibition system: it can be estimated using the models mentioned in
the previous paragraph while remaining compatible with the design rules (6 mm cor-
rosion allowance is generally considered as the maximum value not to be exceeded);
- For steam condensers and hot wet acid gas pipelines using glycol to control the for-
mation of hydrates, injection of neutralising agents to raise the pH above 6;
- Use a stainless steel whose composition will be selected not according to the C 0 2 par-
tial pressure but according to the water salinity and temperature: martensitic (AISI
400 series), austenitic (AISI 300 series) or austeno-ferritic (duplex) stainless steels for
well tubing, pipes and pipelines;
- Use of corrosion resistant coatings or cladding:
organic coatings (especially for areas where water accumulates) in pressure vessels only,
cladding made from stainless steel or even nickel alloys for pressure vessels and
pipelines (especially if the water contains large quantities of mineral or organic
acids in addition to dissolved carbonic acid).
1.3 CORROSION BY WATER CONTAINING H2S
1.3.1 Equipment concerned by H2S corrosion

Like C02, hydrogen sulfide is an acid gas easily soluble in water. In aqueous solution, the
corrosivity of H2S with respect to carbon and low alloy steels is very similar to that of C02.
H2S has an addition characteristic however: it strongly promotes the absorption of hydrogen
in steels and leads to problems of hydrogen embrittlement and cracking.
Since H2S is an acid gas present in numerous oil fields, these types of corrosion concern
all production equipment where free water containing hydrogen sulfide could come into
contact with carbon and low alloy steels: well tubing, wellheads, pipes, pressure vessels,
pipelines, pumps, etc.
Acid gas removal units are also concerned, in particular the overhead system of regenerators.
For the refining units, the boiler feedwater and condensate systems are sensitive to these
types of corrosion.
1.3.2 Mechanisms and parameters influencing H2S corrosion
Concerning uniform corrosion of steels, the action of hydrogen sulfide dissolved in water is
very similar to that of C02. H2S is in fact more soluble but less acidic than C02, the result
being that the final pH of the solution is almost the same for a given partial pressure of H2S or
C02. The corrosion reactions are mostly oxidation of the iron and reduction of the proton (for
further information on electrochemical corrosion, refer to paragraph 3.2.1). In the presence of
H2S, the main corrosion product formed is iron sulfide (Mackinawite) which may, under some
conditions, form an adherent protective deposit on the surface of steels. In this case, the corro-
sion rates are significantly lower than those encountered in pure carbonic medium. It is gener-
ally considered that the presence of H2S reduces the severity of uniform corrosion as compared
to pure C02.media. The mechanism of aqueous H2S corrosion can be described as follows:
Dissolution of hydrogen sulfide
First acid dissociation
Second acid dissociation
(H2S)gas
-
(H2S)liquid
HS- A S2-+H+
(H2S)liquid
HS- + H+
Oxidation of iron
Reduction of the proton
Precipitation of iron sulfide
Fe
H++e-
Fe2++ H2S
-
-
Fe2+ + 2 e-
Ho
FeS + 2 H+
Nevertheless, the major risk in the presence of H2S is not uniform corrosion but the vari-
ous forms of cracking due to hydrogen embrittlement. Further to the proton reduction reac-
tion, the atomic hydrogen has two distinct options:
- it can either react with another hydrogen atom to form a molecule of di-hydrogen (H2)
in solution (recombination),
- or penetrate the metal as absorbed hydrogen (absorption).
Both reactions occur on the surface of the metal and involve adsorbed intermediates. In the
presence of H2S, the equilibrium between these two reactions (recombination vs. absorption) is
shifted strongly towards absorption. The precise mechanism has not been clearly established:
some authors [41] consider that the H2S adsorbed on the surface of the steel acts as poison to
hydrogen recombination, favouring the migration reaction; others [57; 581 suggest a mecha-
nism of direct migration of the hydrogen from solution into the metal, via adsorbed H2S. What-
ever the exact mechanism, we must remember that the presence of H2S favours the migration
of atomic hydrogen into the metal, causing specific problems of embrittlement which may lead
to cracking. These failure modes represent the main risk in H2S medium.
The main forms of steel cracking in H2S media, as defined by NACE MRO175/
ISO15156-1 [12] andNACE MR0103 [24] are:
- SSC (SulJde Stress Cracking): “cracking of metal involving corrosion and tensile
stress (residual and/or applied) in the presence of water and H2S”.
This type of failure is mainly encountered in high strength metallic materials, like
tubing, casing, wire line, etc. or in hard weld zones;
- HIC (Hydrogen Induced Cracking): “planar cracking that occurs in carbon and low
alloy steels when atomic hydrogen diffuses into the steel and then combines to form
molecular hydrogen at trap sites”. HIC takes two different forms:
blistering when the mechanical characteristics of the steel are low enough to accept
deformation,
stepwise cracking, “cracking that connects hydrogen induced cracks on adjacent pla-
nes in a steel”.
This failure mode mainly affects rolled steels with low or medium mechanical cha-
racteristics (rolled welded pipes, steel plate for pressure vessels, etc.) that have a high
density of planar inclusions and/or regions of anomalous microstructure produced by
segregation of impurities (especially MnS inclusions) and alloying elements;
- SOHIC (Stress Oriented Hydrogen Induced Cracking): “staggered small cracks
formed approximately perpendicular to the principal stress (residual or applied) result-
ing in a ladder-like crack array linking (sometimes small) pre-existing HIC cracks”;
- SCC (Stress Corrosion Cracking): “cracking of a metal involving anodic processes of
localised corrosion and tensile stress (residual andor applied) in the presence of water
and H2S”. This type of cracking is found mainly in Corrosion Resistant Alloys
(CRAs) in the presence of chlorides.
Figures 1.6 to 1.9 illustrate some of these cracking modes.
The main parameters affecting the severity of the medium with respect to risks of H2S
cracking are the pH, H2S partial pressure, chloride content and temperature.
Figure I.6
HIC blisters at the surface of a low alloy steel.
Chapitre I Main corrosion phenomena encountered in oil and gas production
9 11
Figure 1.7
Cross section showing SWC.
Figure 1.8
~~
SEM image of a fracture surface typical of SSC after uniaxial tensile test in
H2S medium.
Figure 1.9
~~
Elongated blister associated with mid-wall HIC in a portion of pipeline [ 5 5 ] .

The impact of temperature varies depending on the cracking modes considered. SSC and
HIC (and the variants SWC and SOHIC) occur mainly at ambient temperature. The risks of
encountering these cracking modes drop sharply above 60 "C. In contrast, the risks of SCC
type cracking increase with temperature.
The effect ofpH and the effect of HzSpartialpressure are strongly related. Lower values
of pH generally give rise to higher corrosion rates, by increasing the cathodic reaction of
proton reduction. At the same time, the quantity of hydrogen available to penetrate the metal
is also increased. The H2S partial pressure also has a significant impact on the migration of
hydrogen into steel. An increase in the H2S partial pressure accelerates the rate of hydrogen
migration. For SSC, the effect of pH and H2S partial pressure is well known and can be
described by Figure 1.10 [ 131. Four regions of increasing severity with respect to SSC are
identified. Region 0 is considered as non sour service and no special precautions are
required when selecting steels under these service conditions. In contrast, region 3 is quali-
fied as sour service and the steel grades and welding procedures for use under these condi-
tions must have been approved by strict SSC resistance tests.
For HIC, no severity diagram of this type is currently available. As with SSC however,
the risks of HIC type cracking increase with H2S partial pressure and acidity of the medium.
Lastly, the chloride concentration mainly affects Corrosion Resistant Alloys (CRAs). Dam-
age to the passive oxide film by halide ions may form SSC or SCC crack initiation areas.
Metallurgical parameters are also important factors controlling resistance to the various
forms of cracking.
HIC and its derived forms (SWC, SOHIC) mainly affect carbon or low alloy steels with
low or medium mechanical characteristics. Highly oriented microstructures (rolled products)
Figure 1.10
SSC severity diagram according to standard IS015 156-2.
9 13
are unfavourable, as well as the presence of inclusions, which form areas where hydrogen can
be easily trapped. The most unfavourable chemical elements are sulfur and manganese,
which may contribute to the formation of elongated manganese sulfide inclusions. With this
respect a typical limit of 0.003% by weight of sulfur is generally required for flat-rolled prod-
ucts for use in H2S service.
SSC primarily affects high yield strength steels and requires the presence of applied or
residual stress. Welds are weak points and Post Weld Heat Treatment (PWHT) is generally
required. The microstructure also plays a important role. For CRAs, the most sensitive
microstructures are ferritic and martensitic. For austenitic and duplex grades, the main
cracking mode to be considered is SCC.
1.3.3 Selection of materials for use in H2S environment
To limit the risks of cracking, the materials and welding procedures for use in H2S environ-
ment must be chosen according to strict selection procedures. The recent NACE MRO175/
I S 0 15156 series of standard documents summarises the recommendations for selection or
qualification of materials for use in H2S-containing environments in oil and gas production.
The first part [ 121 presents the general principles for selection of cracking-resistant materi-
als; the second part [ 131 concerns cracking resistant carbon and low alloy steel; the third part
[ 141 is dedicated to cracking resistant CRAs and other alloys. Standard testing procedures
are described for the qualification materials to the various forms of cracking. The main qual-
ification tests are based on NACE TMO177-96 [27], NACE TM0284 [I 11 documents and on
EFC 16 [25] and EFC 17 [26] publications. In the field of oil refining, NACE 8x194 [7]
document provides recommendations on the choice of materials for pressure vessels used in
wet H2S refinery service, while NACE MR 0103-05 [24] document focuses more especially
on materials resistant to Sulfide Stress Cracking (SSC).
1.4 CORROSION BY MERCURY AND LIQUID METALS
1.4.1 Equipment concerned by mercury corrosion
Mercury, in elementary state or as organometallic or inorganic compounds, may be present

in small quantities (traces of less than 50 ppb) in some natural gases. Since this metal is a
liquid over a wide temperature range, it may weaken aluminium and its alloys by a mecha-
nism known as liquid metal embrittlement.
In the field of natural gas production, this affects mainly aluminium components used in
cryogenic processes for the liquefaction of natural gas, especially heat exchangers. This type
of corrosion has appeared on several occasions (Algeria, Indonesia, Thailand, USA) due to
incomplete natural gas demercurisation [37].
In refining, although traces of mercury may be present in the crude oil to be processed,
they may condense at the head of the atmospheric distillation column and weaken the
14 Chapitre I Moin corrosion phenomena encountered in oil and gas production
protective cladding of the Alloy 400 head (65 Ni-32 Cu UNS N04400). In addition, if mer-
cury is introduced by contamination due to breakage of a measuring instrument containing
this element, aluminium, copper-zinc (bronze) and nickel-copper alloys (alloys of series
UNS N04XXX) may be damaged [lo].
1.4.2 Mechanisms involved in mercury embrittlement of aluminium
Corrosion results from liquid metal embrittlement, making the aluminium less ductile due to
its contact with liquid mercury.
The first step in the process would be the formation of an AlHg amalgam on the alumin-
2AIHg + 6H20 -
ium surface. In the presence of water, the amalgam undergoes the following reaction:
2AI(OH), + 2 Hg + 3H2
causing localised corrosion by pitting which initiates cracking.
Penetration of liquid mercury in this incipient crack would locally weaken the atomic
bonds and hence nucleation of numerous dislocations which would be responsible for prop-
agation of the crack, as shown on Figure 1.1 1. Cracking propagates according to a mainly
intergranular mode.
Dislocation injection
~ ~-
Large particles
-
Small plastic zone
Figure 1.11
Crack propagation during liquid metal embrittlement [54].
1.4.3 Example of mercury corrosion
The example given [37] concerns a turbo expander system used on an offshore platform for
natural gas liquefaction. The parts corroded are wheels made from aluminium alloy 6061 T6
(UNS A96061). The main operating conditions were:
- temperature: - 90 "C to - 55 "C,
- pressure: between 27 bars and 82 bars.
Figure 1.12 is a macrographic image of the Al 6061 alloy wheel and a detail of the
cracked zone.
Figure 1.12
Liquid mercury embrittlement of a turbine blade on a liquefied natural gas
(LNG) cryogenic exchanger [37].
1.4.4 Other metallic materials sensitive to liquid metal embrittlement
Other liquid metal environments not specific to the petroleum industry may lead to embrit-
tlement of various metallic materials causing, as with the mercury-aluminium pair, a sub-
stantial decrease in alloy ductility and cracks under low mechanical stress.
Steels are sensitive to embrittlement by liquid cadmium (melting point = 320 "C), liquid
zinc (melting point = 420 "C), liquid lead (melting point = 327 "C). The first two elements
are found as additives in some paints that are used to protect steels against atmospheric cor-
rosion. Cracking will quickly appear if these steels, painted or protected by cadmium plating
or galvanising, are used at temperatures where the coatings are in liquid state [54].
1.4.5 Prevention of liquid metal embrittlement
To avoid this type of corrosion, the liquid metal (even traces) must not be allowed to come
into contact with sensitive alloys:
- Avoid the use of aluminium alloys for treatment of natural gases containing mercury;
- Avoid entry of mercury in the refining circuits;
- Remove mercury from the gas by adsorption on beds of activated carbon or on
microporous adsorbants impregnated with elementary sulfur;

- Protect the aluminium alloys with an adherent coating insensitive to cyclic stress
cracking. For example, the polymeric coating reinforced with metal particles Magna-
plate HCR seems to have proved satisfactory for offshore liquefaction plants [37];
- Do not protect steels which will be used at high temperature or which could occasio-
nally be raised to high temperature (fire) with coatings containing zinc, cadmium or
lead (to avoid attack by these metals at high temperature).
1.5 CORROSION BY THE BACTERIA PRESENT IN WATER, SOIL AND CRUDES
1.5.1 Stakes of biocorrosion in the petroleum industry
Biocorrosion, or Microbiologically Influenced Corrosion (MIC), concerns both the upstream

and the downstream sectors of the petroleum industry. Upstream, the corrosion problems are
similar to those which affect mining infrastructures [56]. Some parts of the installations
(especially those made from carbon steel) are more sensitive than others to biocorrosion
[78]. In particular:
- the dead zones and zones that are stagnant or crossed by a continuous flow of less
than 1.5 d s ,
- zones of pH below 10.5,
- portions whose temperature is less than 100 "C,
- zones containing organic matter, which provide the microorganisms with shelter and
nutrients,
- systems and components operating intermittently (decommissioning, maintenance,
shutdowns).
For example, large quantities of seawater are used for installation of offshore platforms,
as well as recovery and storage of oil and gas. Microorganisms responsible for corrosion
may be found in all production systems where seawater is present [36]. The following equip-
ment is concerned:
- the platform legs, filled with water when the platform is lowered into position. Up to
200 000 m3 of seawater may be flooded into the legs as ballast or displaced when the
leg is used to store crude oil. The tanks in the platform jacket may also contain ballast
water or be used to store drinking water and fuel oil,
- the pipelines, where seawater is used for the hydrostatic tests and may remain for sev-
eral months,
- the tanks, where the pressure is maintained by injection of seawater.
The external parts of the buried or submerged installations can be protected by paint or
coating and cathodic protection. The inside surfaces such as the production columns, well
casings, pressurised equipment, pipes and surface pipelines have to cope with a type of cor-
rosion that electrochemists are not used to dealing with: microbial attack [56]. These instal-
lations are routinely protected by biocide treatments considered as good value with respect
to the risks run. Biocorrosion is an abnormal but permanent threat. Hydrogen sulfide, for
example, produced by Sulfate-Reducing Bacteria (SRB) can react with iron to form FeS.
The resulting colloidal precipitate combined with the cellular biomass may plug the filters,
valves and other control equipment. The danger of biocorrosion has been clearly illustrated
in a series of publications by Elf (now Total) after a subsea pipeline in the Congo split twice
in 1989. The cost of replacing each pipeline had been evaluated at 10 to 20 million dollars
[56].The corrosion damage emerged very quickly on both occasions, with an unusually high
pitting rate of about 1 cm per year [60] the second time the pipe leaked. The results of the
laboratory study conducted to determine the causes of the corrosion clearly showed that
9 17
SRBs and Thiosulfate Reducing Bacteria (TRBs) played a key role in the damage. Scientific
literature describes (in less detail) similar cases of biocorrosion, such as that which occurred
on a flowline of an Indian offshore unit after 6 years continuous use. These articles confirm
the key role played by SRBs in the localised corrosion of carbon steel [ 1331.
In the downstream sector, biocorrosion problems are not specific to the hydrocarbon
industry, but are quite similar to those observed in the other industrial sectors. Biocorrosion
problems in the downstream sector can be avoided or solved by implementing standardised
procedures [56].
1.5.2 Means used to detect and combat biocorrosion
As indicated by Videla [ 1521, the literature on prevention and control of biocorrosion sug-
gests employing two old sayings:
- better be safe than sony,
- cleanliness is essential.
The methods applied to stop or delay biocorrosion [ 1 141 can be classified as follows.
1.5.2.1 Use of non-corrodable materials

Biocorrosion prevention measures start with the design of the system or installation. The
component materials must be selected carefully. Corrosion can be avoided when chemically
inert materials, of suitable strength, are available at a price that is competitive compared with
that of carbon steel. For example, small diameter polymer pipes can be used for water distri-
bution. Large diameter cement pipes protect unpressurised systems against attack by SRBs.
1.5.2.2 Construction of a non aggressive bacterial environment

The ideal non aggressive bacterial environment for a pipe consists of chalk and chalk-sand
mixtures.
1.5.2.3 Use of bactericides

Biocorrosion is most frequently observed during start-up and shutdown activities. Hydrostatic
tests conducted on equipment, tanks and pipes generally include emptying and drying proce-
dures. When the water of the hydrostatic tests is reused, biocide treatment is implemented at
the same time to prevent microbial contamination. The biocides have varied molecular struc-
tures (Figure 1.13). Chlorine, chlorine dioxide, bromine and ozone are typical oxidising agents
used industrially (table 1.2). If chlorine is used, its residual content must be controlled to avoid
pitting and crevice corrosion or stress corrosion cracking (see paragraph 1.6) which may result
from excessive treatment. It has been proposed that non oxidising biocides were more efficient
than oxidising bactericides for global control of algae, fungi and bacteria. Their persistence is
higher and their efficiency independent of the pH [ 1531. One example is Kathon@(Rohm and
Hass trademark), composed of isothiazolones, which has a broad spectrum of activity.
Table 1.2 Biocides used in industrialwater supply networks (source: [153]).
I Name I Biocide activity Properties I Concentration

(mg/L)
Chlorine Bacteria; algae 0.1-0.2
Chlorine dioxide Bacteria; algae
I Bromine I Bacteria; algae
Ozone Bacteria; biofilms 0.2-0.5
Methylene-bis-isocyanate Bacteria
I Isothiazolones I Bacteria; algae; biofilms
Quaternary ammonium Bacteria; algae
Glutaraldehyde Bacteria; fungi; algae; biofilms 10-70
CIO,
C'2 Br2 0 3
Chlorine Chlorine dioxyde Bromine Ozone
R
I+
NC--S-CH2-S-CN R-N-R X-
I
R
Methylen bis(thiocyanate) QUAT (quaternary ammonium)
CH,OH
I X-
OHC M CHO
HOH,C-P+-CH,OH
I
CH,OH
Glutaraldehyde THPS
5-C hloro-2-methyl-4-isothiazoline-3-one 2-Methyl-4-isothiazoline-3-one
Figure 1.13
Molecular structures of biocides.
In recent years, the environmental acceptability of biocides has largely been taken into
account by regulations on the use of commercial products. The use of ozone to protect
industrial water supply networks offers various advantages. In particular, ozone does not
produce any residual clogging [46]. Tetrakis Hydroxymethyl Phosphonium Sulfate (THPS)
is another interesting compound. It has a broad spectrum of action, being efficient against
bacteria, fungi and algae [69]. THPS is used in the petroleum industry because of its ability
to dissolve iron sulfide [153]. Its main advantage lies in its low environmental toxicity.
1.5.2.4 Use of cathodic protection

Cathodic protection, frequently used on pipes to protect them against corrosion, could have
an impact on the development of biofilms. Two cathodic protection techniques are often
used. In the first, the metallic structure is electrically protected by galvanic anodes consist-
ing of a metal alloy less noble than the metal to be protected. In the second technique, an
external current is applied to cancel out the corrosion current. These protection methods are
also discussed in paragraph 2.2.2.
To obtain efficient protection against bacterial corrosion, the current practice consists in
reducing the electrochemical potential of the steel to below - 950 mV (measured using a sat-
urated Cu/CuSO4 reference electrode). Locally, cathodic protection increases the pH, gener-
ates OH- ions and precipitates Ca" and Mg" as CaC03 and Mg(OH)2. It is thought that
cathodic protection reduces the adhesion of aerobic biofilms during the first stages of colo-
nisation.
1.5.2.5 Protective coatings

Protective coatings are an extremely useful tool in preventing the problems caused by bio-
corrosion. The coating must be coherent, adherent, non porous, mechanically resistant to the
dangers encountered during delivery, installation and backfill, and chemically resistant to
prolonged contact with all the environments likely to be encountered [ 1131. Antifouling
paints containing toxic metals are frequently used, especially for metallic parts in contact
with seawater. Like biocides, they must comply with applicable environmental regulations.
1.5.2.6 Detection of corrosive micro organisms

Some traditional microbial methods can be used for detection and enumeration of SRBs,
such as microscopic observation after specific colouring. When the microorganisms cannot
be cultivated, immunological or molecular biology techniques can be used [38]. The Rapid-
check I1 SRB detection system, for example, is an immunological test developed by Conoco.
This test is based on an enzyme-linked immunoassay (ELISA) that detects adenosine-5'-
phosphosulfate (APS) reductase, an enzyme of SRBs. Another powerful approach consists
in using nucleic probes. A probe is a DNA segment which is marked so that after a DNA
hybridisation reaction, any base pairing between the probe and the complementary sequence
of a DNA sample can be detected. It has been demonstrated that this technique can effi-
ciently detect SRBs in aerobic biofilms [ 1341.
1.6 CORROSION CAUSED BY THE CHLORIDES PRESENT IN WATER
1.6.1 Equipment concerned by corrosion due to chlorides present in water

The presence in water of dissolved salts, chlorides such as NaC1, MgC1, and CaCI,, may
cause localised corrosion of stainless steels (in particular the AISI 300 series): pitting, crev-
ice corrosion, stress cracking by attack of their passive film.
In the field of drilling and petroleum production, all stainless steel equipment may be
concerned by this type of corrosion when in contact with water loaded with chlorides and
containing dissolved oxygen: formation water, drilling mud brines, seawater, marine atmo-
sphere, water used for hydrostatic testing.
For acid gas treatment units, the reaction zones and the transfer lines for which steel has
been chosen to withstand corrosion by amine-based solvents (see paragraph 1.7) may be
attacked by the chlorides associated with water and acid pH values.
In the field of refining, all stainless steel pipes and reactors likely to convey water loaded
or contaminated with chlorides may be affected: desalting units, water-cool condensers, con-
densers (process side) at the of the crude distillation column head. Also during the hydro-
static tests on stainless steel reactors and pipelines, special attention must be paid to the
composition of the testing water to prevent any attack by chlorides during the test or when
the equipment is being heated during startup of the process.
Corrosion may also develop under the insulation of stainless steel pipelines or equip-
ment: penetration of water containing chlorides at the stainless steel-lagging interface may
cause corrosion and leaks.
1.6.2 Mechanisms and parameters influencing corrosion

by water containing chlorides
The chlorides present in water may be responsible for three types of localised corrosion on
stainless steels (the mechanisms are discussed in greater detail in paragraph 3.2.3):
- Pitting corrosion: very locally, the chloride ions attack the stainless steel passivation
layer. Although the quantity of corroded metal is very small, this type of attack some-
times results in perforation of the parts affected within a very short period of time;
- Crevice corrosion: this type of corrosion is encountered in small confined spaces
containing stagnant electrolyte, such as the gaps between riveted plates or seals. The
attack mechanism is related to local modification of the medium composition, the
presence of chloride ions causing acidification by local formation of hydrochloric
acid;
- Chloride stress corrosion: this type of corrosion is due to the combined action of
mechanical stress (applied or residual) and the aqueous environment containing chlo-
ride ions and an oxidising agent ( 0 2 or H'). The resulting cracks formed in stainless
steels generally follow a transgranular path.
Chapitre I Main corrosion phenomena encountered in oil and gas production 21
The main parameters affecting these types of localised corrosion of stainless steels are as
follows:
- The water chloride ion concentration, acidity and temperature. As shown on Figure 1.8,
which illustrates the resistance to pitting corrosion of various stainless steel grades, an
increase in each of these parameters increases the sensitivity to the three types of loca-
lised corrosion. For highly acid pH values (below l or 2), corrosion of stainless steels is
no longer localised and becomes uniform (full depassivation);
- The hydrodynamic conditions of low flow rates are an aggravating factor since they
favour fixation of chloride ions on the passive layer. In contrast, high speeds are ben-
eficial;
- The presence of oxygen dissolved in the water favours this type of localised corrosion;
- The mechanical stresses responsible for stress corrosion are both applied and residual
(including those produced when shaping the component or during welding operations);
- The metallurgical composition can be used to improve the resistance of stainless steels,
as shown on Figure 1.14. High chromium, molybdenum and nitrogen contents improve
the resistance to pitting and crevice corrosion by strengthening the passivation layer.
For nickel, concentrations between 8% and 12% seem to offer the least corrosion resis-
tance. Although the resistance of austeno-ferritic stainless steels containing little nickel
is greater than that of austenitic grades (AISI 300 series), they are not totally protected.
For high nickel concentrations, alloys containing over 35% are highly resistant and
those containing at least 45% are virtually insensitive [ 101.
I TemDerature : 49 - 66 "C
51 3
2
00 000 45
40
36 +
10 000 t
32
28
C
1000 25 'a,0
500 C
350 m
4-
150
.-In
(0
100 2
50 18 p
._
30 c
s
h
10
Acidity (pH)
Figure 1.14
Influence of water chloride concentration and acidity on sensitivity of various
stainless steel grades to pitting corrosion (50-65 "C temperature range).
1.6.3 Example of corrosion by water containing chlorides
The images shown on Figure 1.15 illustrate the pitting and stress corrosions of an austenitic
steel AISI 304 (UNS S30400) pipeline during a hydrostatic test with a chloride containing
water. The stress corrosion cracking follows a transgranular path.
500 prn
Figure 1.15
Pitting and stress corrosion of a stainless steel AISI 304 after pressure testing
with water at ambient temperature.
1.6.4 Prevention of localised corrosion of stainless steels

by water containing chlorides
The main recommendations to protect stainless steels against localised damage are as follows:
- Choose the metallic material which offers the best resistance for the water salinity,
acidity, oxygen content and temperature conditions according to data and feedback:
depending on the severity of the medium, possible choices include an austenitic stain-
less steel grade containing molybdenum (type AISI 316 - UNS S3 1600), alloys with
high nickel content (35%-45%0),austeno-ferritic or superaustenitic grades (see para-
graph 3.1.2 for additional information on these stainless steels). For equipment
conveying seawater, use of titanium alloys may prove beneficial [ 1061;
- Design the equipment so that there are no confined spaces or areas where chloride
containg water could stagnate;
- Conduct the hydrostatic tests on stainless steel equipment with water of low chloride
content (a value of less than 20 ppm is generally recommended);
- For lagged stainless steel equipment, application of a coating (such as the aluminium-
based thermal spray coatings) on the steel offers a good protection [ 1541.
1.7 HYDROLYSIS OF CHLORIDES INTO HCI
1.7.1 Equipment concerned by hydrolysis of chlorides into HCI

Hydrolysis of chlorides ofmineral or organic origin into hydrochloric acid may occur dur-
ing several oil refining steps:
- Mainly at the head of atmospheric distillation units and in the downstream exchangers;
- Sometimes the condensation equipment downstream from the heads of vacuum distil-
lation columns may be concerned;

- Organic chlorides may be found with the feedstocks of hydrotreatment units or in
recycle hydrogen, leading to the formation of HCl in these units;

- For catalytic reforming units, chlorides from the catalyst may also generate HCl.
The hydrogen chloride so formed is highly corrosive to numerous metallic materials.
1.7.2 Mechanisms and parameters governing corrosion

Chlorides come from various sources [84; 1501:
- Mineral salts present in crude oils which were not eliminated in the desalting unit.
These mineral salts are generally composed of 75% NaCl, 15% MgCl, and 10% CaC12;
- Organic chlorides: when they are present in the crude at entry to the refinery, being
insoluble in water they are not eliminated by the desalting treatment. These organic
chlorides may come from:
solvents associated with the fracturing fluids injected to stimulate wells,
solvents used to dissolve the deposits of wax and tars in the crude transport pipes,
storage tanks and other equipment,
anticorrosion additives used for upstream production water treatments, especially
oil-soluble quaternary amine based additives,
additives present in lubrication oils recycled in the refining effluents,
spent catalysts and petrochemical by-products.
For inorganic salts, the reaction for the formation of HCl by hydrolysis starts from
MgC12 + 2H20 -
130 "C, as shown on Figure 1.16, according to the following reactions:
- 2HC1+ Mg(OH)2 Hydrolysis rate at 250 "C = 80%

CaC12 + 2H2O
NaCl+H20 - 2HC1+ Ca(OH)2
HCI+NaOH
Hydrolysis rate at 300 "C = 5%
Hydrolysis rate at 300 "C = 0.1%
100
80 -
-.-s?
h
(0
60 -
u)
-2,
e 40 -
I
20 -
Temperature ("C)
Figure 1.16
Effect of temperature on the hydrolysis of magnesium and calcium chlorides [75].
In liquid state, and especially at its dew point, the hydrochloric acid formed causes, on all
steels and some nickel alloys, serious uniform corrosion (see Figure 1.17) or localised pitting
corrosion if HCI droplets condense on the metallic wall. The first droplets which condense are in
fact highly acidic and very corrosive to all steels. The corrosion mechanisms are electrochemical
ones, the anodic and cathodic reactions being respectively oxidation of iron and reduction of
hydrogen ions (for hrther information on electrochemical corrosion, refer to paragraph 3.2.1).
900
-2 800
700
2
2
._ 600
.--
'E
v
500
400
E
6
._
u)
300
?0 200
0
100
n
-1 2 3 4 5 6
PH
Figure 1.17
Effect of dilute hydrochloric acid pH on rate of corrosion of carbon steel at
57 "C [82].
The main factors influencing corrosion by aqueous solutions containing hydrochloric acid are:
- HCl concentration and temperature, which accelerate this type of corrosion as long as
the acid remains in liquid form (see Figure 1.17). The HCl concentration depends on
the chloride concentrations in the feedstock;
- The presence of naphthenic acids in the crude may also increase the rate of hydrolysis
of mineral salts [75];

- The presence of oxygen or oxidising agents (ferric and cupric ions) also has an accele-
rating effect.
The following metallic materials are sensitive to this type of corrosion:
- Carbon and low allow steels when the pH is less than 4.5;
- Martensitic (AISI 400 UNS 4XXXX series) et austenitic (AISI 300 UNS 3XXXX
series) stainless steels are not resistant, irrespective of the HCl concentration and the
temperature, due to their sensitivity to pitting corrosion.
1.7.3 Example of corrosion by HCI formed by hydrolysis of chlorides

Plates made from martensitic stainless steel AISI 410 (UNS S41000) in a depropanisation
unit column were totally corroded after two years service. The service conditions were:
T = 200 "C
Pressure = 15 bars
Feedstock = light gasoline contaminated by organic chlorides
As shown on Figure 1.18, uniform corrosion caused almost complete and regular loss of
thickness of the plates.
A neutralising agent (ammonia in this particular unit) was injected to prevent this corrosion.
Figure 1.18
Corrosion of an AISI 410 stainless steel plate by hydrolysis of organic chlorides.
1.7.4 Prevention of corrosion by HCI formed by hydrolysis of chlorides

The main precautions to prevent this type of corrosion in distillation units are:
Limit the chloride content in the refinery effluents to less than 20 ppm [lo], and less
than 1 ppm if possible [84]. Desalination must therefore be as efficient as possible and
9
all external contamination avoided. The residual magnesium and calcium chlorides
can be converted into more stable sodium salts by injecting sodium hydroxide at the
output of the desalinating unit, but this operation must not produce excessive quanti-
ties of salts which could block the preheat trains located downstream;
- Inject mixtures of neutralising and anticorrosion agents such as ammonia and film-
forming amines, keeping the pH between 5.5 and 6.5 [ 1311;
- Use corrosion resistant alloys including the nickel-copper alloys (Monel400) used as
coatings on the heads of vacuum distillation columns and titanium alloys for the
exchanger tubes at column head.
For hydrotreatment and catalytic reforming units, apart from preventing external con-
tamination, the hydrogen used must have low chloride and HCI contents. Installation of
absorbent beds to remove the chlorides is recommended. In the absence of oxidising agents,
steels can be replaced by nickel alloys containing chromium and molybdenum.
1.8 CORROSION BY CONCENTRATED ACIDS: HCI, H2S04 OR HF
1.8.1 Corrosion by concentrated hydrochloric acid
Hydrochloric acid is sometimes used for well acidification during drilling operations. The
corrosion products formed are highly soluble in the liquid phase, resulting in linear corro-
sion rates, constant over time.
In the refinery this acid may be formed at the head of the distillation, fractionation or
stripper column (see paragraph 1.7).
It is corrosive in concentrated liquid state or when dissolved in a liquid aqueous phase. In
gaseous state, it is not corrosive.
1.8.1.1 Equipment concerned by HCI corrosion

For refining, the equipments concerned are mentioned in paragraph 1.7.1.
For oil and gas drilling, the equipment conveying and injecting HCl to fracture the rocks
must be resistant to this type of corrosion.
1.8.1.2 Mechanisms and parameters governing HCI corrosion

The corrosion mechanisms are electrochemical ones, the anodic and cathodic reactions
being respectively oxidation of the metal and reduction of hydrogen ions (for further infor-
mation on electrochemical corrosion, refer to paragraph 3.2.1).
For steels, the overall reaction is: Fe +3 HCI A FeC13 + 3/2H2
The main parameters governing this corrosion are temperature, acid concentration and
the presence of contaminants and oxidising agents.
1.8.1.3 Example of HCI corrosion

Figure 1.19 shows an example of corrosion of the inside of an aluminium bronze alloy valve
conveying concentrated hydrochloric acid [87]:
Figure 1.19
Corrosion of a aluminium bronze alloy valve by concentrated HCI [87].
1.8.1.4 Prevention of HCI corrosion

The materials offering the greatest resistance to concentrated and hot HCI corrosion (see
Figure 1.20) [2 1; 651 are as follows:
~ Monel400 nickel-copper alloys (UNS N04400) for HCl concentrations less than 15%
and in the absence of oxygen,
- Hastelloy nickel alloys of type B (UNS N10001) or C (UNS N10002) in the absence
of oxidising elements such as oxygen, chlorine or ferric iron dissolved in the solution,
- Zirconium or tantalum,
- Vinyl ester based organic coatings,
- Inhibitors may also be used during well acidification.
1.8.2 Corrosion by concentrated sulfuric acid

Concentrated sulfuric acid is used as catalyst for some alkylation processes. In these units, olefins
such as propylene or butylene react with isobutane to form iso-heptanes and iso-octanes.
Sulfuric acid may be formed during the condensation of sulfurous fumes and may also be
present in wastewater treatment units.
It is generally corrosive in concentrated liquid state (under certain conditions it may nev-
ertheless passivate steels) or dissolved in a liquid aqueous phase. In gaseous state, it is not
corrosive.
I
lncoloy 825
Hastelloy G.G3
k 2 % at 25°C)
I
Monel 400 (without air)
Hastelloy B, 82 Hastelloy B. 82
Copper (without air)
Silicon cast iron (*) .to be confirmed (without chlorine)
0 10 20 30 40
HCI concentration (Yo)
Figure 1.20
Graph showing the HCI corrosion resistance of various materials.
1.8.2.1 Equipment concerned by H2SO4 corrosion

For alkylation units, the following equipment is concerned:
- new and worn sulfuric acid storage tanks [6; 181,
- reactor effluent lines,
- reboilers,
- soda wash reactors,
- depropanisation column heads.
Sulfuric acid may be formed in the fumes output from furnaces by reaction of SO2 and
SO3 with steam as follows:
SO2 + 1/2 O2 SO3
SO3 + H 2 0 H2S04 (in gaseous state above 200 "C).
1.8.2.2 Mechanisms and parameters governing H2SO4 corrosion

The corrosion mechanisms are electrochemical ones, the anodic and cathodic reactions
being respectively oxidation of the metal and reduction of hydrogen ions (for further
information on electrochemical corrosion, refer to paragraph 3.2.1). For steels the overall
tion: Fe + H2SO4 -
reaction results in dissolution of the iron and formation of iron sulfate according to the equa-
FeS04 + H2.
Uniform corrosion is observed if the acid covers the entire metallic part, localised corro-
sion if there is condensation of acid droplets.
The main parameters governing corrosion are temperature, acid concentration, the
hydrodynamic flow rate and the presence of contaminants and oxidising agents. Increasing
the temperature up to the boiling point increases the rate of corrosion. For alloys protected
by the formation of a layer of metal sulfate, serious corrosion will occur if this layer is tom
off by high flow rates. The rate of corrosion is increased by the presence of contaminants
such as chlorine and oxidising agents such as 0 2 , Fe3+, Cu2+ in liquid sulfuric acid.
1.8.2.3 Example of H2SO4 corrosion

A carbon steel furnace tube in a boiler suffered uniform corrosion when the unit was stopped
(Figure 1.21). The fiunace was heated by a heavy crude with high sulfhr content. During shut-
down, the SO3 compounds reacted with atmospheric water vapour, thereby forming sulfuric acid.
Neutralisation by injection of ammonia or carbonated water would have prevented this
corrosion.
Figure 1.21
Example of H,SO, corrosion.
1.8.2.4 Prevention of H2SO4 corrosion

In order of increasing corrosion resistance, the materials to be used are [48; 64; 1241:
- Carbon steel: it can be used for H2S04 concentrations of at least 85% and tempera-
tures below 38 "C when the flow rate does not exceed 0.7 m / s and in the absence of
contaminants (C1 < 200 ppm) and oxidising agents (02,Fe3+, Cu2+). In this case, the
carbon steel is protected by a layer of iron sulfate. Figure 1.22 shows carbon steel cor-
rosion rates for various temperatures and sulfuric acid concentrations;
- Stainless steel AISI 3 16 (UNS S3 1600) is used for flow rates less than 1.2 m/s and
concentrations of more than 20% at ambient temperature;
- Alloy 20 (UNS N08020) can be used for weaker acid concentrations and temperatures
below 50 "C. Figure 1.23 shows stainless steel 316 and alloy 20 corrosion rates for
various temperatures and sulfuric acid concentrations;
- Nickel alloys Hastelloy B2 (UNS N01665) and C276 (UNS N10276) exhibit good cor-
rosion resistance for severe temperature conditions. Figure 1.24 shows the corrosion
rates of these two alloys for various temperatures and sulfuric acid concentrations.
215
I -""
170
01
U
120
a
v
90 1 ' 1
1200 G
1 %
E
3 3
c
4-
F? 175 $
% 75 - / 1.3-5 mm/year
E
E
F F
125
50
25
/ / 0.13-0.5 mm/vear 175
'60 65 70 75 80 85 90 95 100 105 110

Concentration of H,SO, (%)
Figure 1.22
Carbon steel corrosion rate in concentrated H2S04 medium.
1.8.3 Hydrofluoric acid corrosion

Hydrofluoric acid is used as catalyst for another alkylation process. In the presence of water, it
reduces the thickness of some alloys but it also promotes penetration of hydrogen into steels,
causing Hydrogen Induced Cracking (HIC), Stress Oriented Hydrogen Induced Cracking
(SOHIC) and Hydrogen Stress Cracking (HSC). Hydrogen embrittlement of steels was discussed
in detail in paragraph 1.3, when H2S in aqueous solution is the hydrogenation promoter.
1.8.3.1 Equipment concerned by HF corrosion

All equipment of HF alkylation units transporting or in contact with hydrofluoric acid
(pipes, HF regenerator) or vapour condensates containing this acid (exchangers, stripping
columns, reboilers) is concerned. Numerous recommendations are provided in documents
API 751 [28] andNace 5A171 [23].
Sulfuric acid concentration (“h) Sulfuric acid concentration (%)
Figure 1.23
Stainless steel 316 and alloy 20 corrosion rates (milli inch per year) in H2S04
medium.
400
350 milli inchlve,

75
a-
E
20 2
E
E
F
loot-
0-5 milli inch/year
150 65
100-
I I I I
0-5mill inch/year
I II I I
, , I I I
10
I I
0 10 20 30 40 50 60 70 80 90 100 0 10 20 30 40 50 60 70 80 90 100
Sulfuric acid concentration (weight O h ) Sulfuric acid concentration (weight %)
Figure 1.24
Nickel alloy B2 and C276 corrosion rates (milli inch per year) in H2S04
medium.
1.8.3.2 Mechanisms and parameters governing HF corrosion

The thinning corrosion mechanisms are electrochemical ones, the anodic and cathodic reac-
tions being respectively oxidation of the metal and reduction of hydrogen ions.
For iron and steels, this attack results in the formation of iron fluoride:
F e + 3 HF A FeF3 +3/2H2
For steels, anhydrous or highly concentrated (> 65%) hydrofluoric acid flowing at rates
of less than 1 m / s is not very aggressive due to the formation of a protective layer of iron flu-
oride when the temperature is below 66 "C.
The main parameters governing this type of corrosion are:
- the water content (HF concentration) which increases corrosion by destabilising the
protective fluoride layer, as illustrated on Figure 1.25,
- the temperature, which also accelerates corrosion,
- the hydrodynamic flow rate which may destroy the protective metal fluoride layer,
- the presence of oxygen may accelerate the corrosion of carbon steel,
- for Alloy 400 (UNS N04400), a nickel-copper alloy, presence of oxygen may cause
the formation of cupric fluoride and stress cracking [23].
1000
1
0 10 20 30 40 50 60 70 80 90 100
Concentration of hydrofluoric acid in water (weight %)
Figure 1.25
Influence of HF water content on carbon steel corrosion rate between 20 "C
and 40 "C [ 6 ] .
8 33
HF is also a steel hydrogenation promoter. The parameters governing hydrogen induced

embrittlement are the same as those discussed in paragraph 1.3:
- steel composition and microstructure,
- steel mechanical characteristics (global or local mechanical characteristics - non
stress relieved zones that favour hydrogen stress corrosion).
1.8.3.3 Example of HF corrosion

Figure 1.26 shows the influence of carbon steel composition on the HF corrosion rate. This
example is a weld between two tubes of a depropaniser feed line in a HF alkylation unit
(T = 71 “C, the feed contained 0.3% HF and 0.001% water). The tube on the right part of the
weld had copper, chromium and nickel contents far higher than those of the left part [85].
Figure 1.26
Example of HF corrosion [MI.
1.8.3.4 Prevention of HF corrosion

Carbon steel is used for anhydrous or highly concentrated (> 65%) hydrofluoric acid flow-
ing at rates of less than 1 m / s when the temperature is less than 66 “C. Since the presence of
some residual elements in the steel such as copper, nickel and chromium would seem to
accelerate this type of corrosion, it is sometimes recommended to limit the contents on these
elements according to the rule % Cu + % Ni + % Cr < 2.2% [23; 28; 68; 135; 1421. In addi-
tion, the carbon steel must be resistant to hydrogen embrittlement (see paragraph 1.3).
For temperatures greater than 66 “C, the nickel-copper alloy “Alloy 400” is used. If oxy-
gen is present in the hydrofluoric acid, this alloy may be sensitive to stress corrosion [23]: it
is sometimes replaced by Alloy C276 to prevent this risk [lo].
For some applications, a PTFE (polytetrafluoroethylene) coating may prove suitable.
1.9 STRESS CORROSION IN ALKALINE AND QUASI-NEUTRAL MEDIA
1.9.1 Caustic stress corrosion
Bases such as NaOt I and sometimes KOH or LiOH are used in numerous refining and gas treat-
ment processes. Even at low concentrations (50-100 ppin), these bases may cause stress corro-
sion damage in carbon steels, low alloy steels and austenitic stainless steel of AISI 300 series.
1.9.1. I Equipment concerned by caustic corrosion

The main cquipment concerned arc located in areas where soda (or potash) is injected to
neutralise acid effluents (HDS regeneration, reforming, isomerisation, etc.), LPG or light
naphtha treatment processes and boilers and steam generators.
1.9.1.2 Mechanisms and parameters governing caustic corrosion

Caustic agents attack steel according to an clcctrochemical process:
anodic reaction:
cathodic reactions possible in the presence of oxygen:
or
Fe A
-
FeZf+2c
-
0; + 2 H 2 0 + 4e-
2H20+2e-~ H2+20H
40H
Although propagation of this type of stress corrosion is mainly intergranular, transgranu-

lar paths have been reported in the literature [9].
The main parameters governing this typc of corrosion are the caustic agent concentra-
tion, the temperature and the applied or residual stresses on the steel.
Figure 1.27 indicates the domains of resistance to caustic corrosion of various materials
[ 1431. For temperatures below 50 " C , carbon steel is not sensitive to stress corrosion, irre-
spective of the soda concentration.
1.9.1.3 Example of caustic corrosion

Figure 1.28 is an exaniple of stress corrosion cracks near a weld that was not stress relieved:
this carbon steel plate is part of a soda wash tank used in a Merox process for sweetening
FCC LPG. Under normal service conditions, the temperature is below 50 "C. Steam was
injected to remove the plugs of solid soda, raising the temperature and generating stress that
induced cracking of the carbon steel.
1.9.1.4 Prevention of caustic soda corrosion

The main prevention methods are given on Figure 1.27:
Use of stress-relieved carbon steel (including areas where the stecl has been welded or
~
bcnt) up to 80 "C- I00 "C depending on the caustic soda concentration. 1 lcat treat-
ments at 620 "C-650 "C are recommended [9];
220
Limit of use for
stainless steel
200 Limit of use for
stainless steel
(304)(318)
180 due to cracking
Nickel 99% C s 0.15%
0 160
v
$
I
140
9 Stainless steel -
g 120 - nickel alloy
E
e 100
nickel alloy or stellite
Carbon steel
40 - Stress relief Melting point curve
unnecessarry
*On
-0 10 20 36 40 50 60 70 80
Soda concentration in o/o weight
Figure 1.27
Graph showing the caustic corrosion resistance of various materials [ 1431.
Figure 1.28
Example of soda corrosion in an LPG Merox unit.
36 Chapitre I - Main corrosion phenomena encountered in oil and gas production
- Use of austenitic stainless steels up to 120 "C-200 "C for low soda concentrations;
- Use of nickel alloys (Monel400 UNS N0440, Inconel UNS N06XXX) for temperatu-
res above 80 "C and high soda concentrations.
1.9.2 Carbonate stress corrosion
1.9.2.1 Equipment concerned by carbonate corrosion

Carbon and low alloy steels may suffer stress corrosion in FCC and coker units (and in the
associated acid water treatment units) where free water containing carbonate-bicarbonate
ions, H2S and ammonia could be present [127]. The equipment (pipes and reactors) affected
includes the fractionating column overhead condensers and accumulators, the wet gas com-
pressor condensers and surge drums, the light cut fractionating columns and the residual
water treatment units associated with this equipment.
Other processes involving a basic liquid phase loaded with carbonates (e.g. potassium
carbonate): gas (e.g. hydrogen) decarbonation units may be concerned. Cases of stress cor-
rosion have been reported for gas treatment units containing more than 2% C 0 2 at tempera-
tures exceeding 90 "C [lo].
1.9.2.2 Mechanisms and parameters governing carbonate corrosion

This type of stress corrosion follows an intergranular path of fine cracks filled with oxides. It
develops in stressed zones; for welds, cracks propagate parallel to the weld in the residual
stress zones but also in the heat affected zones [ 101; 1 15; 120; 1271.
The main parameters governing this type of corrosion are:
- the pH of the residual free water (due to ammonia),
- the water composition (concentration in carbonates, H,S, cyanides),
- the residual stresses,
- the steel abandon potential.
The water composition is governed by the following chemical equilibria:
NH, + H 2 0 +-+ NH4f + OH-
H2S H HS- + H+ t)S2- + 2HS
C 0 2 + H 2 0 H HCOT + H+ H C0:- + 2H+
Carbon and low alloy steels are sensitive to this type of stress corrosion in alkaline
medium for the following free water acidity domains [29; 101; 1271:
- pH Z 7.6 above an H2S concentration of at least 50 ppm,
- 8 5 pH I 9 above a carbonate concentration of at least 400 ppm,

- pH 2 9 above a carbonate concentration of at least 100 ppm.
This corrosion generally occurs at a potential between - 500 mV/ECS and - 650 mV/
ECS. For aqueous solutions containing H2S, the presence of CN- ions limiting the formation
of the iron sulfide layer could affect the abandon potential by bringing it into the domain of
sensitivity to stress corrosion.
1.9.2.3 Example of carbonate corrosion

The example shown on Figure 1.29 concerns a carbon steel acid water storage tank of an
FCC unit [ 191. The cracks were found at the bottom of the tank near a weld bead. Propaga-
tion is intergranular.
Figure 1.29
Example of carbonate stress corrosion [ 191.
1.9.2.4 Prevention of carbonate corrosion

Post weld heat treatment reduces the probability of stress cracking. Temperatures of at least
625 "C are recommended for this heat treatment [143].
Protecting the carbon or low alloy steel with austenitic stainless steel (AISI 300 series),
nickel alloy (alloy 625 UNS N06625) or nickel-copper (alloy 400 N04400) cladding may also
be effective [ 10; 291. A corrosion inhibitor (e.g. metavanadate) is sometimes added [19].
1.9.3 Stress corrosion in near neutral medium
1.9.3.1 Equipment concerned by corrosion in near neutral medium

Most stress corrosion of carbon steel is encountered on the outside of gas and petroleum
pipelines (Canadian [67], Russian and Argentinean pipelines, Jura pipeline). This type of
corrosion is also sometimes associated with disbonding of the external protective coatings.
1.9.3.2 Mechanisms and parameters governing corrosion in near neutral medium

Unlike those generated in more alkaline media, the cracks developing in near-neutral solu-
tion of pH about 6.5 follow a transgranular path and their initiation and propagation mecha-
nism is relatively independent of the temperature between 5 "C and 50 "C. These transgran-
ular cracks are wider due to anodic dissolution of the side edges. Hydrogen penetration
phenomena are associated with the anodic dissolution reactions [ 1211.
1.9.3.3 Example of corrosion in neameutral medium

Cracks in near-neutral medium have been observed in particular on carbon steel pipelines
protected on the outside by polyethylene strips and less frequently by a bitumen coating.
These cracks are attributed to a lack of cathodic protection under disbonded coatings.
Figure 1.30 illustrates a transgranular path observed under disbonded coating.
Figure 1.30
Example of stress corrosion in near-neutral medium [ 12 11.
1.9.3.4 Prevention of corrosion in near-neutral medium

The main factors to limit steel corrosion in near-neutral medium are:
- limitation of the mechanical characteristics of the steels,
- reduction of welding stresses by post weld heat treatment,

Chapitre I 9 Main corrosion phenomena encountered in oil and gas production 39
- selection of microstructures with small ferrito-bainitic grains rather than ferrito-pearl-

itic structures [ 1091,
- protection with a coating (three-layer polyethylene as described in paragraph 2.2. I).
1.10 ALCOHOL (METHANOL AND ETHANOL) CORROSION
Short-chain alcohols such as methanol and ethanol may cause stress corrosion in carbon steels.
Methanol may also generate stress corrosion cracking in titanium and its alloys (in
particular alloy Ti-6A1-4V UNS R56400).
1.10.1 Equipment concerned by alcohol corrosion
Methanol is used in petroleum production as thermodynamic agent to prevent the formation

of gas hydrates. Methanol storage and transport equipment made from carbon steel and tita-
nium alloy is therefore concerned.
Refrigerated methanol-water mixtures are used as solvent for extraction of acid gases
(C02, H2S) in some gas treatment processes. Carbon steel tanks and transport lines are
potentially concerned.
In the chemical and refining industries, methanol is used to manufacture MethylTertButylEther
(MTBE) by reaction with isobutylene. The carbon steel tanks of these units may be affected.
Ethanol is used as a substitution fuel: carbon steel reservoirs, tanks and pipes are more
especially concerned.
1.10.2 Mechanisms and parameters governing methanol corrosion
The main cause of stress cracking in carbon steels is the presence of water and some chemi-
cal compounds (formic acid, chlorides) in methanol [ 15; 40; 77; 93; 951. Cracking generally
follows an intergranular path.
Electrochemical mechanisms are responsible for this corrosion. In the presence of certain
quantities of water, the oxide film which forms naturally in air would not be stable and
decomposes, forming Fe2+ ions (anodic attack) which react with the methanol and water
according to the reactions:
Fe2+ + H,O
Fe2+ + MeOH
-
-FeOH' + Hf
FeOMe' + Hi
The main parameters responsible for stress corrosion of carbon steels by methanol are
W I , V5l:
- Water content: the corrosion conditions are reported in the literature for water contents
below I%, the sensitivity of cracking being strongest in the range 0.05% to 0.5%;
- Formic acid (methanol degradation product) when present up to 300 ppm, accelerates
stress corrosion;
- When present, chloride ions destabilise the initial protective oxide layer;
- Presence of oxygen may increase the risk of stress corrosion by bringing the steel into
a potential range where it is sensitive to stress corrosion. Moreover, the role played by
oxygen in the degradation of alcohols into corrosive agents (formic acid) should not
be ruled out.
For titanium alloys, methanol stress corrosion follows an intergranular path which is
favoured by the presence of halide ions (chloride, bromide, fluoride). A sufficient quantity
of water (between 2% and 20%) would prevent stress corrosion of titanium alloys [22; 137;
1391.
1.I
0.3 Mechanisms and parameters governing ethanol fuel corrosion
The mechanisms involved in stress corrosion of carbon steels in the presence of ethanol fuel
seem to be similar to those mentioned in the previous paragraph: anodic attack of the oxide
layer associated with mainly intergranular stress cracking [ 151. Cracks may develop within
less than a year. Currently, the main parameters governing this type of corrosion are:
- the water content, increasing the water content favours stress corrosion,
- the high ethanol acidity (low pHe determined according to standard ASTM D6324)
would seem to be an aggravating factor,
- the chloride, sulfide and sulfate contents of ethanol fuel would seem to be major para-
meters [ 151.
1.10-4 Example of ethanol corrosion
Figure 1.3 1 is an example of stress corrosion of a carbon steel ethanol fuel tank [93]. Inter-
granular cracking has propagated parallel to the weld bead, a few millimetres from the heat
affected zone.
1. I 0 3 Prevention of alcohol corrosion
The main method used to prevent methanol or ethanol stress corrosion of carbon steels is to
carry out post weld heat treatment on the welds and all zones subjected to shaping stresses
(folding, bending, etc.). The use of metallic (stainless steel) or organic coating, as well as the
addition of inhibitors (e.g. in ethanol fuel) may sometimes prove efficient.
Titanium alloys should never be used with methanol, unless its minimum water content
is known: the minimum water content must be between 2% and 20%, depending on the tita-
nium alloy composition [ 1371. Applying cathodic protection seems effective in preventing
stress corrosion phenomena [22]. Replacing titanium alloys by stainless steels or nickel
alloys is also a possibility.
9 41
Figure 1.31
Example of ethanol fuel stress corrosion of a tank [93].
1.11 CORROSION BY ACID GAS CHEMICAL SOLVENTS
1.11.1 Introduction: principles of acid gas removal by chemical solvents
Throughout the petroleum chain, the treatment steps are nearly always designed to purify the
fluids, separate various components and eliminate undesirable species, in particular the two
acid gases carbon dioxide and hydrogen sulfide. Treatments to remove C02 and H2S from
natural gas are often implemented as soon as the gas leaves the well. At the other end of the
chain, the refinery gases may also need to be stripped of these acid gases. Lastly, these sepa-
ration treatments are becoming increasingly important in the fight against greenhouse gas
emissions and might be used in a near future for the postcombustion capture of C02 in
fumes from industrial processes.
The most widely used process in all these applications uses alkanolamine-based chemi-
cal solvents (MEA, DEA, MDEA, AMP) capable of reacting preferentially with C02 and
H2S. The first paragraph provides a simplified description of this type of treatment unit (Fig-
ure 1.32). The main components and the operating principle are the same in the three broad
domains concerned: treatment of production acid gases, treatment of refinery gases and
postcombustion CO, capture treatment plants.
Next Page

9
Acid gas
OVERHEAD
CONDENSER
Treated gas REFLUX
A h
DRUM
TANK
ABSORBER
REGENERATOR
9w
=ll II II
.B +-
Flashgas
FLASH
- Raw
f HEAT-EXCHANGER
SCRUBBER
COALESCER
Figure 1.32
Simplified diagram of an alkanolamine acid gas removal unit.
The gas to be treated is introduced in the unit at the bottom of the absorber where it
comes into contact with the solvent. The acid gases (C02 and/or H2S) react and are absorbed
by the solvent according to reactions 1.1 to 1.6 below.
The reaction with H2S, which is the same irrespective of the type of amine considered,
consists of direct proton transfer (Equation 1.1).
RiRzR3N + H2S H RlR2R3NH' + HS- (Equation 1.1)
The reaction with C 0 2 is slightly more complex. Two different mechanisms may be
involved. A first reaction may occur, involving the successive formation of carbonic acid
and bicarbonate (Equation 1.2 and Equation 1.3), followed by direct proton transfer identi-
cal to that observed for H2S (Equation 1.4).
C 0 2 + H2O H H2CO3 (Equation 1.2)
H2CO3 H+ + HCOT (Equation 1.3)
H+ + HCO; + R1R2R3N @ RIR2R3NH' + HCO; (Equation 1.4)
This mechanism may occur for all types of amine. The global kinetics is slow, however,
since it is limited by dissociation of carbonic acid into bicarbonate (Equation 1.3).
For the primary and secondary amines, which have hydrogen bond to the nitrogen, a
second mechanism is possible.
C02 + R I R ~ N H
w RlR2N' + HCOO- (Equation 1.5)
R1R2N++ HCOO- + RlR2NH w R1R2NC00- + RlRzNHt (Equation 1.6)
Previous Page
This second reaction mechanism is generally much faster than the C 0 2 hydrolysis reac-
tion (Equations 1.2 to 1.4). For the primary and secondary amines, there is little difference in
the reaction kinetics between C02 and H2S. For the tertiary amines, however, unable to
form a carbamate, the reaction kinetics with H2S is much faster than with C02. This prop-
erty is put to good advantage to give some solvents selectivity between C 0 2 and H2S.
At the liquid output at the bottom of the absorber, the solvent is therefore enriched in
acid gas according to one or more of reactions 1.1 to 1.6: we speak of rich amine. At the top
of the absorber, the gas has been stripped of its undesirable components C 0 2 and/or H2S.
The rich amine is then pre-heated by a heat exchanger then fed into the top of a regener-
ation column. In this part of the unit, the solvent is raised to high temperature by the reboiler,
which releases the dissolved acid gases. This is due to the fact that the equilibrium of reac-
tions I . 1 to 1.6 are shifted to the left at high temperature and low pressure. At the liquid out-
put of the regenerator, the solvent is hot (about 120 "C) and contains little or no acid gas: we
speak of lean amine. The solvent is then cooled by the heat exchanger then sent back to the
top of the absorber to start a new cycle. The acid gases are collected at the top of the regen-
erator, where they can be sent for suitable processing.
In such a complex unit, numerous pieces of equipment are exposed to equally numerous
types of corrosion. We can nevertheless adopt the classification proposed by Nielsen [ 1 171,
who identifies:
- wet acid gas corrosion,
- amine solution corrosion.
1.I
1.2 Mechanisms and parameters governing corrosion
in acid gas treatment plants
1.11.2.1 Acid gas corrosion

This first type of corrosion is encountered in all parts of the unit in contact with an aqueous
phase with a high concentration of dissolved acid gases C02, H2S, as well as NH, and HCN
for refinery units. This type of corrosion is found primarily in zones where the gaseous
phases have high concentrations of acid gases and where water may condense, mainly at the
bottom of the absorber and the top of the regenerator.
The C 0 2 and H2S corrosion mechanisms have been described in specific paragraphs of
this book ( 5 1.2 and 1.3). For more information, the reader can refer to the corresponding
sections.
For gas containing mostly C02, parts of the installation made from carbon steel may suf-
fer fast uniform corrosion, up to several mm/year. In the presence of HzS, this uniform cor-
rosion is generally delayed by the formation of a protective iron sulfide layer. A minimum
H2S/C02 ratio of 1/20 is often considered as sufficient to avoid risks of uniform C02 corro-
sion [8]. In the presence of H2S however, specific cracking phenomena may also be encoun-
tered (hydrogen embrittlement, HIC, SSC, etc.). In the presence of HCN and/or NH,, the
risks of cracking are also increased.
1.11.2.2 Corrosion by amine solution

Generally, alkanolamines are not intrinsically corrosive, since they associate both high pH
and low conductivity. They may nevertheless become corrosive when they absorb C02 or
H2S. Furthermore, since the treatment units operate in semi-closed circuit, the solvent may
become enriched with possibly corrosive degradation products.
No consensus has yet been reached concerning the mechanisms of corrosion by amine
solutions. The models proposed vary depending on the type of amine (in particular, primary,
secondary and tertiary), the H2S/C02 ratio in the gas to be treated, possible presence of oxy-
gen either as contaminant in the circuit or as component of the input gas (e.g. C 0 2 capture in
fumes). For more information on a particular case, the reader may refer to the relatively
extensive bibliography on this subject [71; 72; 102; 103; 1171.
We may nevertheless identify some major parameters governing the corrosivity of acid
gas chemical solvents:
- Type of amine
Most of the alkanolamines frequently used in gas treatment are not intrinsically corro-
sive. They become corrosive, however, in the presence of CO, or H2S, and when the
concentration of degradation products increases. In service, classification of amine
corrosivity has been clearly determined and recognised. Primary amines (MEA,
DGA) are the most corrosive, secondary amines (DEA) slightly less and tertiary ami-
nes (MDEA) exhibit the lowest risks of corrosion [43; 62; 71-74; 149; 1511.
- Amine concentration
The amine concentration is generally accepted as having an influence on corrosion.
Excessively high amine concentrations should generally be avoided. Nevertheless, the
results obtained from the few laboratory studies conducted on the effect of amine
concentration on corrosivity vary widely, between a marked effect [71; 1491 and a
moderate or null effect [81; 1481.
- Acid gas loading (moles of acid gas per mole of amine)
The acid gas loading is defined as the quantity of acid gas absorbed by a defined quan-
tity of solvent and is often expressed in moles of acid gas per mole of amine. Increasing
the acid gas loading increases the corrosivity of amine solutions [42; 71; 1491.
- Temperature
Temperature generally has an extremely important effect on corrosion phenomena
since most electrochemical reactions involved are thermally activated. It is common
practice in industry to consider that the rate of corrosion is doubled when the opera-
ting temperature increases by 10 "C to 20 "C.
For gas treatment units, the effect of temperature is relatively difficult to asses on an
individual basis. Temperatures vary widely in the installation, with extreme values
ranging from 40 "C in the absorber up to 130 "C in the reboiler. However, these tem-
perature variations have a significant effect on the chemistry of the solution, in parti-
cular the acid gas loading. Taking into account both the loading and the temperature,
we may consider that the main corrosion risks are encountered in areas with high loa-
ding and high temperatures [44; 711. These conditions are generally found in the rich
amine line after the heat exchanger and up to the regenerator input.
9 45
- Degradation products and contaminants

A distinction must be made between basic and acidic degradation products.
Basic amine degradation products mainly result from chain reactions between amine and
C02, for example the following compounds: HEOD (3-(2-hydroxyethyl)-2-oxazolidone),
BHEP (N,N’-bis(2-hydroxyethyl)piperazine), THEED (N,N,N’-tris(2-hydroxyethyl)ethy-
lenediamine). The studies on corrosivity by these degradation products date back a num-
ber of years, the general conclusion being an absence of specific corrosivity [43; 731.
Most acidic degradation products result from reactions with oxygen. The main products
include salts of oxalic, glycolic, formic and acetic acids, which are stronger than carbonic
acid. As a result these salts are not thermally regenerated in the process, hence their name:
Heat Stable Salts (HSS). The effect of these products on corrosion has been well docu-
mented through laboratory tests; they increase corrosion of carbon steel [128; 129; 1441.
- Solvent flow rate
The solvent flow rate and conditions favourable to turbulence (gas flash, gas injection
zones, etc.) may cause risks of erosion-corrosion. This type of corrosion is specific to
carbon steels, since stainless steel grades are far more resistant. Lastly, this type of
corrosion is probably aggravated when the content of degradation products becomes
too high: as indicated above, some of these products have a chelating effect on iron
and may favour more efficient and faster dissolution of the protective deposits
exposed to erosion [8; 32; 42; 1171.
1.I
1.3 Equipment concerned by corrosion
This section describes the specific corrosion risks for the main equipment in gas treatment units.
1.11.3.1 Absorber
The absorber may suffer several types of corrosion.
Wet acid gas corrosion may develop at the bottom of the absorber and on the first plates, if
the walls are not wetted sufficiently by the solvent: in this case, water may condense and
become loaded with acid gases. Sour service units are prone to risks of hydrogen embrittlement.
Risks of erosion-corrosion may also be encountered. In particular, the high flow rate at
gas inlet may lead to turbulence and impingement of solution against the walls, creating con-
ditions favourable to this type of corrosion. The same phenomenon is observed on the plates
and in case of excessive flow rates.
For H2S treatment units, specific risks of amine stress corrosion cracking (ASCC) are
also possible, especially in the lower part of the absorber where the loading is highest. Post
weld heat treatment is then essential to reduce these risks [8].
1.I1.3.2 Rich amine lines

Corrosion risks are especially high in this section where the amine is loaded with acid gas.
Corrosion-erosion is the most frequent risk encountered with carbon steel lines subjected to
high flow rate or flow disturbance. In particular, up to the flash drum, the solvent is pressurised
46 Chapitre I Main corrosion phenomena encountered in oil and gas produciion
and highly loaded with acid gas, and there is a high risk of degassing, which may aggravate the
turbulence effects. Similarly, between the rich/lean amine exchanger and the regenerator, the
risks of degassing remain high and are combined with a higher solvent temperature.
1.11.3.3 Richllean amine exchanger

This equipment is exposed to a wide range of highly specific corrosion risks.
On the rich amine side, the risks of erosion-corrosion mentioned in the previous para-
graph still remain, especially if the rich amine inlet has been badly designed.
When stainless steel plate exchangers are used, the main risks are stress corrosion crack-
ing (especially at welds or in case of repairs) and crevice corrosion.
Sour service units are prone to risks of hydrogen embrittlement on the rich amine side of
the exchanger, if it is made of carbon steel.
1.11.3.4 Regenerator and acid gas outlet (condenser, reflux drum)

The solvent at the top of the regenerator is still rich and already at high temperature. The
intrinsic corrosivity is therefore very high and there is a serious risk of erosion-corrosion in
case of turbulence. If there is no significant turbulence in the medium, extensive uniform
corrosion of carbon steel is frequently observed. For this type of corrosion, it would also
appear that the risks are greater in sweet service units (only C02), where fast uniform corro-
sion has been observed.
Wet acid gas corrosion is another major risk, especially at the top of the regenerator and
in the acid gas outlet lines. The condenser is also highly sensitive. Experience has shown
that keeping the gas flow rates above 8 m/s limits these risks considerably by preventing
accumulation of condensates.
For sour service units, hydrogen embrittlement may occur at the top of the regenerator
and in the acid gas outlet lines, in case of inappropriate choice of metal (non sour service
carbon steel) or heat treatment (failure to carry out post weld heat treatment).
1.11.3.5 Reboiler
Due to the high temperatures, the reboiler is relatively sensitive to corrosion. The risks are
elevated with solutions containing high concentrations of degradation products. If the regen-
erator fails to operate correctly (insufficient stripping), solvent still loaded with acid gas may
be brought up to the reboiler, significantly increasing the risk of corrosion. Excessive tem-
peratures also represent a recognised risk factor.
1.11.3.6 Lean amine lines

An extensive survey launched following the explosion of an absorber in 1984 detected cases
of amine stress corrosion cracking (ASCC) in the lean amine lines, due mainly to failure to
carry out post weld heat treatment [ 125; 1261.
A case of erosion-corrosion has been reported for an MDEA unit in Indonesia [ 1321,
possibly due to an excessive lean loading (a> 0.02).
Another case is reported for an MDEA unit, where very severe corrosion of the lean
amine parts developed just a few months after starting the unit [89]. This case would seem to
have been caused by very fast degradation of MDEA to form bicine, due to the presence of
oxygen in the gas to be treated, at a concentration of 90- 100 ppmv.
1.I
1.4 Examples of corrosion by acid gas solvents
Bonk et al. [44] recently described an interesting case of corrosion in acid gas treatment
units. In sweet service units (only CO,), highly corrosive conditions were encountered in the
zones where the solvent exhibited high loading and high temperatures, i.e. in the bottom of
the absorber and at the top part of the regenerator. The conditions were such that very fast
uniform corrosion was observed on the AISI 410 type stainless steel trays, as well as fast
corrosion of the carbon steel regenerator shell (Figure 1.33).
Figure 1.33
a) Corrosion of the carbon steel shell in the upper part of a sweet service unit
regenerator b) Corrosion of AISI 410 stainless steel trays of a sweet service
unit regenerator.
Feedback found in the literature is summarised in Table 1.3. Other feedback specific to
refinery gas treatment plants has recently been published by the European Federation of
Corrosion EFC 46 publication [20].
1.5 Prevention of corrosion in acid gas treatment units

1.I
This section summarises the various solutions to control or limit corrosion risks in alkanola-
mine acid gas treatment unit.
8
Table 1.3 Summary of feedback on corrosion in amine units.
Material and type of corrosion I Causes I Ref.
Hydrogen embrittlement (SOHIC) or [94; 112;

CS - Cracking and mechanical failure Amine Stress Corrosion Cracking (ASCC), 125; 126;
arising non PWHT welds. 132; 1451
CS -Uniform corrosion at bottom of absorber
Galvanic coupling with copper deposits
from the corrosioninhibitor t661
CS - Erosioncorrosion at bottom of absorber Turbulence at the raw gas inlet [70; 721
AISI 410 - Uniform corrosion of the plates Higher corrosivity of sweet services units in
high temperatureand high loading [44;
[94; 1 12;
CS - Stress corrosion (ASCC) No post weld heat treatment 125; 126;
132; 1451
CS - Erosion-corrosion Excessive flow rates and acid gas flash [44; 70;
72;
[94; 112;
CS - Amine Stress Corrosion Craclung (ASCC) No post weld heat treatment 125; 126;
132; 1451
CS - Erosion-corrosion High temperatures and turbulence [44; 1001
Turbulence and acid gas flash from too high [70; 72;
CS - Erosion-corrosion and pitting lean loading 1321
3 16L and 254SMO - Failure
of the exchanger trays
Possible case of stress corrosion [44; loo]
Regenerator
CS Amine StressCorrosion Cracking (ASCC) I No post weld heat treatment I 11321
I
~
CS - Erosion-corrosion of the internal parts High corrosivity of the rich amine [44;70;
I
72: 1001
I 2
High HSS contents -Acid water

CS - Serious uniform corrosion
condensation zones [66; 761
AISI410 - Uniform corrosionof the trays Corrosive conditions specific to sweet units,
due to high loading and high temperatures [44; 1001
AISI 304L -Uniform corrosion of internal
parts and shells Specific of a DGA unit 11461
Reboiler
CS -Uniform corrosion and erosion-corrosion Turbulence, high concentration [44; 92;
of degradation products 1001
CS Amine Stress Corrosion Cracking (ASCC) No post weld heat treatment [94; 1 12;
125; 1261
~
CS - Erosion-corrosion Too high

- lean loading
- -11321-
CS - Erosion-corrosion Significant amine degradation due to
the presence of oxygen in the raw gas 1891
CS = Carbon Steel
9 49
Recommendations for the various operating parameters are described in the first paragraph.
Then the use of corrosion inhibitors and of corrosion monitoring methods are discussed.
Lastly, relevant metallurgical and design choices are examined in the light of the recom-
mendations found in the literature.
1.11.5.1 Operating conditions of the units

For every major parameter likely to influence the corrosivity of amine solutions, the follow-
ing limits are proposed to reduce the corrosion risks:
- amine concentration (% by weight) and loading (leadrich) (moles of acid gas per
mole of amine)
MEA: 15%-20% (lean < O.l/rich < 0.45)
DEA: 40% (lean < O.OS/rich < 0.40 to 0.85 depending on the authors)
MDEA: 55% (lean < O.Ol/rich < 0.55)
- temperature at reboiler
< 130 "C
- flow rate in the amine lines
< 1.8 m / s
- HSS and other impurities (ppm weight)
bicine < 250 ppm
oxalate < 250 ppm
formate < 500 pprn
acetate < 1 000 ppm
HSS total < 5000 ppm
chloride < 500 ppm
Note that the aim of these recommendations is to limit the corrosion risks of plants made
mostly from carbon steel. In some cases, design options using stainless steel grades may
enhance some of these parameters, especially the loading and flow rate.
1.11.5.2 Use of corrosion inhibitors

Use of corrosion inhibitors is often recommended when the operator wants to minimise
investment costs and make most components from carbon steel.
We may mention in particular the family of film-forming amines which bind to the metal,
creating a protective barrier layer. These inhibitors are therefore extremely sensitive to turbu-
lence and are generally inefficient in pipes subject to high flow rate, for example. The other
large family of inhibitors used in gas treatment consists of heavy metal salts, e.g. chromium
and vanadium. They have a highly oxidising effect, favouring the formation of a protective
layer of Fe203. These inhibitors are inefficient in the presence of H2S, when other less pro-
tective surface compounds are formed. Moreover, most of these metals are ecotoxic, which
tends to limit their use.
Chapter 2.2 of this book provides a more detailed description of the various families of
inhibitors and their action modes.
1.I
1.5.3 Corrosion monitoring
Corrosion monitoring systems are generally recommended to control corrosion in gas treat-
ment plants. A complete range of monitoring tools is proposed in § 2.3.
Figure 1.34 illustrates the recommended zones for corrosion monitoring systems [ 1 181.
Absorbei
&l
Figure 1.34
Recommended corrosion monitoring points (CMP), source [ 1 181.
1.I
1S.4 Choice of appropriate metallurgies
The prevailing philosophy when designing gas treatment plants consists in giving priority to the
use of carbon steel [86] with a corrosion allowance. A traditional rule of thumb consists in a 3 mm
allowance associated with an acceptable corrosion rate of less than 100 prdyear, for a lifetime of
30 years. This is generally possible, provided that the recommendations given in § 1.1 1.5.1 in
terms of amine concentration, loading rate, degradation product concentration, etc. are observed.
Post weld heat treatment is critical to prevent stress cracking, especially for installations treating
gases containing H2S. In this case, use of sour service steel grades is also mandatory.
However, it may be worthwhile using stainless steel grades in those parts of the plant
exposed to extremely corrosive conditions. This allows operating at higher loading and
higher flowrates, as well as easier solvent swapping. Table 1.4 lists the metallurgical choices
proposed in the literature for the various parts of a gas treatment plant. Sweet and sour ser-
vice plants are discussed separately.
Table 1.4 Metallurgies recommended for the various parts of a unit.
Component Sweet service Sour service Ref.
Shell cs 1711, ~ 1 8 1
CRA cladding at the top [861
cs I cs 1401
Intemals CS or CRA 1711, ~ 1 8 1
CRA (304 or 316) I CS or CRA (304) I 1401
I Regenerator I
CS = Carbon Steel
CRA = Corrosion Resistant Alloy
Lastly, we may mention studies [44; 1001 which demonstrate that greater use of stainless
steel grades may yield a substantial operational advantage, for example by pushing up the
loading past 0.5 to 0.7 moles of acid gas per mole of amine, values impossible to reach with
carbon steel plants.
1.12 CORROSION BY CRUDE OIL CONTAINING NAPHTHENIC ACIDS
1.12.1 Equipment concerned by naphthenic acid corrosion
Crudes produced from fields in Russia, Venezuela, India and Angola, for example, contain
carboxylic (also called naphthenic) acids. These acids have saturated cyclic structures with
one or more carboxyl groups. Their general chemical formula is R-[CH2] ,-COOH where R
is normally either a cyclopentane or a cyclohexane and n is only rarely greater than 12. The
molecular weights (and boiling points) of naphthenic acids vary over a large range of values.
The abundance of naphthenic acids in a crude depends on the diagenesis of kerogen. Matu-
ration of crude oil results in a decrease in molecular weight and an increase in thermal stabil-
ity of the acids [ 1081. These acids are corrosive at temperatures close to boiling point: corro-
sion occurs from 170 "C. Refining plants are therefore concerned by this corrosion:
atmospheric distillation and vacuum plants and their equipment, for example pumps, fur-
naces, transfer lines (especially bends), heat exchangers, condensers, vacuum column. In
1999, the NACE work group T8-22 produced a review and a compilation of the literature
discussing naphthenic acid corrosivity of hydrocarbon feedstocks [35]. This type of corro-
sion affects carbon and low alloy steels, stainless steels and some nickel alloys.
1.12.2 Mechanisms and parameters governing naphthenic acid corrosion
In addition to naphthenic acid concentration,the presence of hydrogen sulfide affects the corro-
sion mechanisms. Three types of mechanism are proposed for naphthenic acid corrosion [34]:
- Type I, a corrosion mechanism due exclusively to the naphthenic acids, where sulfur
compounds, if present, have little or no effect;

- Type 11, for which sulfidation is accelerated by the presence of acids;
- Type 111, for which naphthenic acid corrosion is inhibited, to a certain extent, by the
sulfur containing compounds.

Competition is observed between the attack due to naphthenic acids and the sulfidation
generated by hydrogen sulfide, according to the following equations:
- direct acid attack on iron: Fe + 2RCOOH @ Fe(RC00)2 + H2 (1.7)
- corrosion due to hydrogen sulfide: Fe + H2S t)FeS + H2 (1.8)
- attack of iron naphthenate by H2S: Fe(RC00)2 + H2S @ FeS + 2RCOOH (1.9)
(this reaction regenerates naphthenic acid, causing further corrosion).
The interdependent parameters affecting this type of corrosion are:

- Naphthenic acid concentration: crudes with TAN (Total Acid Number) greater than
0.5 and refined fractions with TAN greater than 1.5 are potentially corrosive. The
TAN is not the only parameter to be taken into account, however: the type of acid
(and its boiling point) and the presence of hydrogen sulfide are important parameters;
- Acid types: increasing the number of [CH& groups up to n = 3 in the series of naph-
thenic acids studied by Turnbull et al. would tend to increase the corrosion rate. For
acids of high molecular weight, steric hindrance due to their long carbon chain would
be unfavourable to absorption and consequently would slow the formation of soluble
iron naphthenates and hence the corrosion rate [ 1471;
- Sulfur content and fluid flow rate: crudes with significant sulfur contents (2% to 3%)
may form a protective layer of iron sulfide which reduces naphthenic acid corrosion,
if the film is not removed by erosion [91];
- Temperature: the temperature range 220 "C-420 "C is the most critical, although cor-
rosion at temperatures of 180 "C is mentioned in the literature [35];

- The metallurgical composition of the steels is also an important parameter: stainless
steels containing at least 3% Mo offer the greatest resistance [91].
1.12.3 Example of naphthenic acid corrosion
Figure 1.35 shows the corrosion of a low alloy 5 Cr-0.5 Mo steel (UNS K41545) bend
located at the outlet of a distillation plant furnace. The temperature was 360 "C, the feed-
stock had a TAN of about 3 and its flow rate was estimated at 80 m / s at bend inlet. In this
zone of high turbulence, the 5 Cr-0.5 Mo steel suffered extensive corrosion-erosion by the
naphthenic acids present in the feedstock.
Figure 1.35
Example of naphthenic acid corrosion [91]
1. I 2.4 Naphthenic acid corrosion prediction models
After compiling corrosion data, the API proposed in document 581 (“Base resource docu-
ment - risk based inspection”) [29] indicative values predicting the corrosion rates of vari-
ous steels according to temperature, feedstock sulfur content and TAN. Figure 1.36 below
shows an example of carbon steel corrosion prediction. As with the failure example pre-
sented in paragraph 1.12.3, however, the hydrodynamic flow conditions of the feedstock
may have a significant effect on the corrosion rates.
2.50
L
m
(L,
,X 1.25
E
E
v
a,
c
9
c
0
.-
v)
0.50
0
0
0.25
1 2 3 5 6
Total acid number (mg KOH/g)
Figure 1.36
Model for prediction of naphthenic acid corrosion of carbon steel,
source API RP 581 [29].
1. I 2 3 Prevention of naphthenic acid corrosion
To prevent naphthenic acid corrosion in distillation plants, several solutions are available
depending on the feedstock acidity rate:
- To adjust the operating conditions to limit the temperature and fluid flow rate;
- At distillation inlet, to mix the naphthenic crudes with non-corrosive feedstocks to
reduce the average TAN by about 0.2-0.5 mg KOH/g. If the TAN is not too high, the
sulfur content can be increased provided that this does not disturb the downstream
processing operations;
- The addition of corrosion inhibitors may also be effective. Soda was the first inhibitor
to be used. Formulations based on phosphate ester, thiophosphorated and more
recently sulfur compounds are currently proposed [ 1 10; 1 191;
- During the construction or revamping of equipment, to choose a metallurgy adapted
to the acidity of the feedstocks to be treated. Steels with increasing chromium and
9 55
molybdenum contents offer enhanced corrosion resistance (Figure 1.37). For the most
severe conditions, stainless steel AISI 317L (UNS S31703) that contains over 3%
molybdenum exhibits the greatest resistance [50; 83; 90; 911.
100 I
50 -
-kl 20-
(u
-
$- 10
g
._ 5 -",9:"
-
.--
._ 2 - 1-3Cr
E - 4-6 Cr
v
a,
1
c
0.5 - 9Cr
.-In
5 0.2
.-
In
- 12Cr
g 0.1 -
s 0.05 - 18/8
S content: 0.6 wt%
0.02 -
0.01 I I I I I I
Figure 1.37
Comparison of corrosion resistance of the main steels for a crude of TAN = 2,
source [141].
1.13 CORROSION DURING THE FORMATION OF POLYTHIONIC ACIDS
1.13.1 Equipment concerned by polythionic acid corrosion
During shutdowns, polythionic acids may form on the equipment surface by reaction between
iron sulfides, water and oxygen. These acids may cause intergranular cracking of austenitic
stainless steels (AISI 300 series) and austenitic alloys [alloys 600 (UNS N06600) and 800
(UNS N08800)l. If the latter alloys have been sensitised, these cracks may propagate entirely
through the wall. This type of cracking mainly affects solid austenitic stainless steel equip-
ment or austenitic stainless steel cladding: weld overlay coatings are less sensitive.
Austenitic stainless steel equipment operating at temperatures between 400 "C and
8 15 "C and containing sulfur products is concerned. Furnace tubes, heat exchangers, pipes
in hydrotreatment and FCC plants and cokers, can be particularly affected.
1.13.2 Mechanisms and parameters governing polythionic acid corrosion
Polythionic acids are formed during shutdowns, by reaction between iron sulfides, the atmo-
spheric oxygen and some liquid water (humidity) according to:
x FeS -t H 2 0 + (5 + x) 0 2 H2Sx06 + xFe0 (2 < x < 5)
These polythionic acids cause intergranular attack of sensitised stainless steels. Cracking
may propagate very quickly and cross the entire thickness of the wall within a few hours,
residual stresses inside the steel being sufficient for its propagation. External mechanical
stresses accelerate the crack propagation speed.
Some austenitic stainless steels are sensitised by prolonged periods at temperatures
between 400 "C and 8 15 "C, as shown on Figure 1.38 below for stainless steel AISI 304
[ 1041. Prolonged periods at these temperatures may cause precipitation of chromium car-
bides at the grain boundaries together with a reduction in chromium content in the zones
adjacent to this precipitation. The chromium-depleted zones become sensitive to intergranu-
lar corrosion phenomena (see paragraph 3.5.2 for further details).
1100 2012
- 1000 -
a
Coherent
0
S3
! 600 -
I
E
Time (h)
Figure 1.38
Stainless steel 304 sensitisation temperature ranges, source [ 1041.
1.13.3 Example of polythionic acid corrosion
Figure 1.39 is a photograph of the inside of a stainless steel AISI 32 1 (UNS S32 100) furnace
tube from a hydrodesulfurisation unit: cracks opening out onto this side are present, flame
side. Metallographic examination of a cross-section of the tube shown on Figure 1.40 clearly
indicates the intergranular path followed by this cracking. We observe precipitation of chro-
mium carbides at grain boundaries in this localised zone on the flame side, whereas
intergranular precipitation cannot be detected on the side opposite the flame. These furnace
tubes had been annealed but had not undergone a stabilisation treatment ( 2 to 4 hours
between 850 "C and 900 "C).
Figure 1.39
Cracking by polythionic acids of an austenitic stainless steel 321 furnace tube
from a hydrodesulfurisation unit.
Figure 1.40
Metallographic section of cracking by polythionic acids of an austenitic stainless
steel 321 furnace tube from a hydrodesulfurisation unit.
58 Chapitre I Moin corrosion phenomena encountered in oil and gas production
9
1A3.4 Prevention of polythionic acid corrosion
The main prevention methods concern the plant shutdown procedures andor the metallurgi-
cal choices.
- During unit shutdowns, neutralisation procedures can be implemented to eliminate the
polythionic acids by injecting alkaline solutions. Detailed information concerning

these procedures is provided in NACE recommendation RP 0 170 [ 161;
- Austenitic stainless steel grades stabilised with titanium AISI 321 (UNS S32100) or
niobium AISI 347 (UNS S34700) and stabilised austenitic alloy grades (alloys 825
(UNS N08825) and 625 (UNS N06625)) offer enhanced resistance to polythionic acid
corrosion. Chemical stabilisation treatment of 2 to 4 hours between 850 "C and 900 "C
increases the resistance of stabilised austenitic stainless steel (including the welded
zones) [39; 881;
- Austenitic stainless steel overlays, especially AISI 347 overlays (UNS S34700), offer
good corrosion resistance [107].
1.14 DECARBURISATION BY HIGH TEMPERATURE HYDROGEN ATTACK
1.14.1 Equipment concerned by high temperature hydrogen attack
Carbon and low alloy steel refining plants operating above 220 "C and under gaseous hydro-
gen pressure are subject to High Temperature Hydrogen Attack (HTHA), in particular
hydrotreatments, hydrocrackers, reformers and hydrogen production units [49].
1.14.2 Mechanisms and parameters governing high temperature hydrogen attack
Hydrogen recombines with the steel carbides (cementite Fe3C) to form methane, which
weakens the mechanical characteristics of the metal and may cause cracking (intergranular
cracking may develop since the methane cannot diffuse).
There are two types of high temperature hydrogen attack: surface decarburisation and
internal decarburisation.
High temperatures and low hydrogen partial pressures favour the first mode; the second
mode develops mainly at more moderate temperatures under high hydrogen partial pressures.
Suvface decarburisation: The generally accepted mechanism is based on migration of
carbon to the surface where it combines with hydrogen to form a gaseous compound. Unlike
internal decarburisation, surface decarburisation does not lead to the formation of microc-
racks, but reduces mechanical strength and increases ductility.
Internal decarburisation: Internal decarburisation is related to dissociation of molecular
hydrogen on the surface then diffusion of atomic hydrogen into the steel where it reacts with
carbon to form methane. The methane formed cannot diffuse out of the metal and tends to
accumulate at grain boundaries. This generates high stresses in the metal resulting in the for-
mation of microvoids, then microcracks which join up to form cracks or blisters depending
on the case.
To prevent the formation of methane, metallurgical choices involve the replacement of
iron carbides by carbides more stable with respect to hydrogen such as chromium, molybde-
num, titanium, vanadium or niobium carbides (alloyed steel addition elements). In the
HTHA sensitivity ranges, low alloy steels and even stainless steels are therefore chosen.
The API 94 1 Nelson curves [ 171 shown on Figure 1.4 1 indicate the domains where low
alloyed Cr-Mo steels can be used. The limitation of each low alloy steel application,
depends on the H2 partial pressure and the temperature. These curves are based on plant
feedbacks and they are regularly updated.
Hydrogen partial pressure (MPa absolute)

3450 6210
800
700
600
1.OCr-0.5Mo steel e
2
500 5
0,
F
400
300
200
5000 9000 13000

Hydrogen partial pressure (psia) Scale change
Figure 1.41
~
Curves extracted from API RP 94 1 - [ 171
1.14.3 Example of high temperature hydrogen attack
Photograph 1.42 illustrates a high temperature hydrogen attack of a low alloy 0.5 Mo steel
(UNS K11820) bend. This bend was installed on a catalytic reforming unit operating at
450 "C and 12 bars. The unit had been built according to the API 941 curve applicable to the
construction (version 1967). Based on feedback reporting decarburisations under conditions
assumed to be not sensitive for this steel grade, when API 941 was revised in 1990, the
0.5 Mo alloy steel curve was superimposed with that of carbon steel.
Figure 1.42
High temperature hydrogen attack of a 0.5 Mo steel bend from a catalytic
reformer.
1.14.4 Prevention of high temperature hydrogen attack
To prevent high temperature hydrogen attack, a low alloy steel grade or a stainless steel
must be chosen according to API 941 recommendations [17], applying a safety margin of
15 "C to 30 "C on temperature and 50 psi on pressure [lo].
For old equipment made from 0.5 Mo low alloy steel, high temperature hydrogen attack
sensitivity parameters have been introduced relating the incubation time, temperature and
hydrogen partial pressure.
Pv = log (PH2)+ 3.09 lo4 x T x (log(t) + 14)
with:
pH2 Hydrogen partial pressure kg/cm2
T Temperature K
t Time hour
This parameter was adopted in API RP 581 (Risk Based Inspection) to assess the proba-
bility of damage by high temperature hydrogen attack [29].
1.14.5 Hydrogen-induceddisbonding of stainless steel overlays
Some equipments operating at high temperature under hydrogen pressure are protected by
an internal overlay of austenitic stainless steel. These overlays can be produced by roll bond-
ing, explosion cladding, welding or even lining. They are used on hydrodesulfurisation units
where the base metal is chosen for its resistance to the high temperature hydrogen attack and
for its mechanical characteristics at high temperature. The overlay offers good resistance to
high temperature sulfidation.
Disbonding is the decohesion of the austenitic overlay from the base metal. There is in
fact a large difference in the solubility and the diffusion of hydrogen between the two mate-
rials: the hydrogen diffusion coefficient in austenitic stainless steels is much lower than that
in ferritic steels. This results in an oversaturation of hydrogen at the interface and a possible
decohesion of the overlay from the base ferritic steel (Figure 1.43). To assess the sensitivity
of the overlays to these disbonding phenomena, laboratory tests can be conducted under
conditions determined by numerical simulations [5 11.
I-
I
2,,4 Cr-IMo base steel-
Cl
High-pressure
high-temperature
hydrogen gas
i31
2
-0
25
0‘
i:
._
r m
mE
ma,
g:
5 8
Figure 1.43
Diagram showing the distribution of hydrogen in the wall of ferritic steel equi-
pment with austenitic steel overlay.
1.14.6 Hydridation of titanium equipment
Hydrogen reacts with titanium alloys to form titanium hydndes Ti,H. Precipitating inside the alloy,
these hydrides increase the hardness considerably and lower the ductility, causing the titanium
alloy to become embrittled. Hydrogen penetration in titanium alloys occurs in different ways:
- under gaseous hydrogen atmosphere, above 175 "C,

- also under conditions of cathodic overprotection in aqueous medium for potentials
below 900 mV/ECS or in solutions heavily loaded with H2S and temperatures of at
least 70 "C [ 101.
Titanium alloys must therefore not be used under hydrogenating conditions.
1.15 HIGH TEMPERATURE OXIDATION
1.I
5.1 Equipment concerned by high temperature oxidation
For temperatures above 530 "C, all equipment in contact with an atmosphere containing
oxygen or steam and for which oxygen activity prevails, is concerned. High temperature
oxidation creates a layer of oxides on the metal surface, causing a generalised reduction in
the thickness of the sound metal. Combustion systems, furnaces and boilers are primarily
concerned.
1.I
5.2 Mechanisms and parameters governing high temperature oxidation
During oxidation, metals are converted into the metal oxide according to the following
reaction:
xM + z/202 - M,O, where M is a metal
xMa + yMb + z/202 -

Mixed oxides of metals Ma and Mb may also form according to:
Ma,MbyO,
All steels and alloys used to manufacture equipment react with atmospheric oxygen,
forming a more or less protective oxide layer [ 1051. The main parameters governing high
temperature oxidation are:
- the temperature: for carbon steels, oxidation starts at 530 "C,
- the alloy composition and in particular the content in elements such as chromium,
silicon and aluminium,

- the oxygen or steam partial pressure. Steam is a more powerful oxidising agent than
gaseous oxygen.
1.I
5.3 High temperature oxidation prediction models
Data from various sources are available to assess the high temperature oxidation rate of the
main steels under air [29; 1051.
Figures 1.44 and 1.45 below provide estimated values of oxidation rates.
2.0,
I I --e Carbon steel 1
Figure 1.44
Estimated oxidation rates of carbon and low alloy steels under air (source: [29]).
5 1.2
h
1.4
- AlSl304
2?
1.0
v
0.8
e
.-c 0.6
m
0.4
0
0.2
n
600 700 800 900 1000 1100 1200
Temperature ("C)
Figure 1.45
Estimated oxidation rates of stainless and alloy 800 steels under air (source: [29]).
1.15.4 Example of high temperature oxidation
The example illustrated on Figure 1.46 concerns an furnace tube made from 5 Cr-0.5 Mo
low alloy steel (ASTM A335 grade P5). The temperature of the outer skin in contact with
the air reached 750 "C locally (the steel was chosen for a temperature of 625 "C). The outer
oxide layer has flaked off locally, reducing the thickness by about 0.25 mm/year.
Figure 1.46
Oxidised outer surface of a 5 (3-0.5 Mo steel furnace tube.
1.I
5.5 Prevention of high temperature oxidation
The oxidation resistance of an alloy depends on the formation of an adherent surface layer of
stable oxide(s) forming a barrier as impermeable as possible in one direction to the penetra-
tion of gas molecules from the environment and in the other direction to the diffusion of
metal ions from the underlying alloy. The lower the density of the vacancy or interstitial
defects (small differences from stoichiometry) in the oxide layer is, the greater the efficiency
of the barrier is. The presence of sufficient quantities of certain elements, such as chromium
or aluminium, reduces the oxidation rate due to the formation of a protective layer of
chromite or alumina. For steels, the optimum chromium content is between 18% and 30%,
for nickel alloys the optimum chromium concentration is about 30% to 50%. Aluminium
contents of 4% to 5% associated with rare earths will be sufficient to create a protective alu-
mina layer at temperatures higher than 900 "C. If the aluminium concentrations are too high,
however, hardening intermetallic phases will develop, making the alloy less ductile. In con-
trolled content, silicon may also help to increase the protective nature of the oxide layer
without affecting the mechanical characteristics of the material.
1.16 HIGH TEMPERATURE SULFIDATION
1.16.1 Equipment concerned by high temperature sulfidation
Above 250 "C, feedstocks containing sulfur compounds (H2S, mercaptans, etc.) may gener-
ate corrosion by forming a layer of metal sulfides on steels and copper or nickel alloys,
resulting in a uniform loss of thickness.
All refining units treating sulfur feedstocks may be affected by high temperature sulfida-
tion, especially hydrotreatment, FCC, visbreaking, vacuum distillation units and cokers.
1.I6.2 Mechanisms and parameters governing high temperature sulfidation
High temperature sulfidation is a reaction between the metal and the sulfur atmosphere,
resulting in the formation of metal sulfides.
For steels, the reaction is: Fe + H2S Fel-,S + xFe + H2
in the presence of chromium, in addition to Fel-,S, mixed sulfides such as FeCr2S4 may form.
For nickel alloys Ni + H2S __Lc Ni,-,S + xNi + H2
and the formation of mixed nickel-chromium and nickel-iron sulfides
The main parameters governing this type of high temperature attack are [52; 53; 1381:
- The composition of the steel or nickel alloy, which governs the formation of a more or
less protective sulfide layer;

- The content in sulfur compounds (crudes may contain up to 5%) and H2S in the feed-
stock. Due to the temperature, most of the sulfur compounds decompose into H,S;
- The presence of hydrogen which by synergy with the sulfur containing compounds
accelerates sulfidation by, amongst other things, converting the organic sulfides
present in the feedstock into H2S;
- The temperature, which favours corrosion.
6.3 High temperature sulfidation prediction models

1.I
Models have been developed to predict corrosion rates in the presence and absence of gas-
eous hydrogen.
In the absence of gaseous hydrogen (H2 pressure below 50 psia), the McConomy curves
shown on Figure 1.47 are used for carbon, low alloy and austenitic stainless steels.
In the presence of hydrogen, Couper and Gorman curves can be used to determine the cor-
rosion rates of carbon, low alloy and austenitic stainless steels in the presence of two typical
feedstocks (naphtha or gas oil). An example of a prediction curve is given on Figure 1.48.
Temperature ("C)
260 290 315 340 370 400
500 525 550 575 600 625 650 675 700 725 750 775
Temperature ( O F )
Figure 1.47
McConomy curves for prediction of high temperature sulfidation in the
absence of hydrogen (source: [I 1 I]).
1.16.4 Example of high temperature sulfidation

Figure I .49 is a macrographic image of a carbon steel pipe (initial thickness 6 mm) located
in the by-pass of a feedstock stripper in a hydrodesulfurisation unit. The temperature was
about 380 "C to 390 "C and the H,S content of the feedstock about 2% molar (absence of
gaseous hydrogen). After 6 years of service, an uniform sulfidation corrosion had com-
pletely reduced the thickness of the walls in the hottest zones. The sulfidation rate of 1 mm/
year corroborates the predictions of the McConomy curves shown on Figure 1.47. The use
of a low alloy steel containing 9% chromium (UNS K81590) should have been recom-
mended for the planned lifetime of the equipment.
1A6.5 Prevention of high temperature sulfidation

Choosing a steel (or nickel alloy) containing sufficient chromium will prevent uniform high
temperature sulfidation corrosion. For the most severe conditions, 18 Cr- 10 Ni austenitic
stainless steels are used, either as solid steels or more generally as cladding or weld overlays
for large equipments. More information on these overlay techniques is provided in
Chapter 2.2 of this document.
Temperature ("C)
260 315 370 425 480 540
10
=
E
& 0.1
Y
0.01
0.001
400 500 600 700 800 900 1000 1100
Temperature ( O F )
(1 mpy = 0.0254mm/y)
Figure 1.48
Couper and Gorman curves for prediction of high temperature sulfidation of
carbon steel in the presence of hydrogen (source: [53]).
Figure 1.49
Carbon steel pipe corroded by internal sulfidation after 6 years at 390 "C.
I.I7 CARBURISATION, COKING, METAL DUSTING
In oil refining processes, conversion of feedstocks into targeted compositions of hydrocar-

bons is carried out under high carbon activity atmospheres, causing various types of attack
on metal equipment: coking, metal dusting and carburisation. Coking leads to the formation
of carbonated deposits on the metal surface, which may cause head losses and limit heat
exchanges. Metal dusting can be described as wastage causing pitting, uniform corrosion or
substantial local loss. Carbon diffuses into the metal which disintegrates, resulting in the for-
mation of metal particles (dust), carbides and coke on the surface. Diffusion of carbon into
the metal may also lead to carburisation through the formation of stable metal carbides.
High temperature carbon attack affects units with high carbon activity: steam cracking,
steam reforming, catalytic reforming, thermal hydrodealkylation and cokers. Furnaces and
reactors are highly prone to metal dusting.
1.17.1 Coking
1.17.1.1 Catalytic and pyrolytic mechanisms
Depending on the temperature range, several mechanisms are responsible for carbon depos-
its called coke on the surface of numerous metals and alloys. Coke comes from the decom-
position of hydrocarbons [33].
Catalytic heterogeneous mechanism between 400 "C and 900 "C: a network of carbon
filaments (nanotubes) is catalysed by the iron and/or nickel present on the surface of the
tubes and reactors. Figure 1S O illustrates a catalytic coke deposit and a coke filament with a
metallic catalytic particle at its end.
Non-catalytic heterogeneous mechanism between 500 "C and 900 "C: the coke forma-
tion reactions are generated by coke precursors (such as aromatic and unsaturated com-
pounds) on active sites of the surface.
Figure 1.50
Images of catalytic coke filaments.
Non-catalytic homogeneous mechanisms at temperatures above 700 "C: these radical

reactions in gas phase lead to the formation of high molecular weight polyaromatic com-
pounds. These pyrolytic mechanisms occur mainly in steam cracking furnaces.
1.17.1.2 Example of pyrolytic coking

During operation, the internal walls of steam cracker tubes are covered with a pyrolytic coke
deposit which must be periodically burnt off during decoking. Figure 1.51 is a photograph,
after a long period of operation, of a steam cracker furnace tube made from ASTM HP40
modified heat-resistant steel (UNS 594224) cracking naphtha with steam to form ethylene.
The coke deposit is thicker than the steel tube itself.
Figure 1.51
Steam cracking furnace tube with an internal deposit of pyrolytic coke.
1.17.1.3 Prevention of coking

Coke deposits can be limited by metallurgical solutions or injection of coking inhibitors. A
layer of chromium or aluminium oxide on the surface prevents the formation of catalytic
coke: chromium- or aluminium-rich alloys or coatings can be used [47]. Another solution is
to inject small quantities of sulfur compounds (HZS, DiMethylDiSulfide) with the feedstock
(in catalytic refining processes, less than 1 ppm to preserve catalyst activity) [ 1301.
7.2 Metal dusting

1.I
1.17.2.1 Metal dusting mechanisms
Hydrocarbon molecules are chemisorbed on metal crystallites. Formation of these metal
crystallites or dust causes localised and sometimes uniform attack of the equipment,: this
process is known as metal dusting. Despite their nanometric size, due to removal of a large
number of particles and the associated surface carburisation, this phenomenon may cause
significant loss of thickness and perforation of the walls.
Figures 1.52 and 1.53 show the various consequences of the formation of metal particles
and the growth of graphite filaments, respectively for a reduced or oxidised steel surface.
70 Chapitre I 9 Main corrosion phenomena encountered in oil and gas production
Particle of iron
Graphite
Fe,C
v
1) Surface carburisation 2) Graphitisationof 3) Decomposition of
the surface the cementite
Fe,C
Fe + C (diss.)
/ Fe + C (diss.) /
4) Carbon enrichment 5 ) Superficial carburisation 6) Growth of the

of the iron particles of the iron particles graphite filament
Figure 1.52
Metal dusting mechanism on a reduced iron surface [45].
- 1) Initial state 2) Carburisation and fragmentation

of the oxide (VFe30, > VFe3C)
3) Iron carburisation
Fe + C (diss.)
kA
Graphite Fe + C (diss.)
Graphite / 1
c /
4) Graphitisation of 5) Decomposition of 6) Growth of the filament

the surface the cementite
Figure 1.53
Metal dusting mechanism on an oxidised iron surface [45].
1.17.2.2 Example of metal dusting

Figure 1.54 illustrates deterioration by metal dusting of a gas burner made from heat-resis-
tant ASTM HK 40 steel in a reduction unit [SO]. An H,-CO-C02-H20 atmosphere is heated
to 900 "C. A metal dusting inhibitor, DMDS, had to be injected but due to a construction
error, one burner was not protected by injection of DMDS. Metal dusting caused pitting
corrosion on zones where the chromium oxide layer did not provide sufficient protection
(chromium contents locally too low), especially near the welds.
-
2 cm
Figure 1.54
Metal dusting of ASTM HK40 steel gas burners in a reduction unit [80]
1.17.2.3 Prevention of metal dusting

The main solutions are similar to those described in paragraph 1.17.1.3 to limit coking:
- inject sulfur compounds such as H2S or DMDS in the feedstock,
- increase the partial pressures of the oxidising gases (steam, CO) to favour the forma-
tion of a protective oxide layer,

- choose alloys or coatings with sufficient chromium or aluminium contents to generate
protective chromium or aluminium oxide layers,

- carry out surface strain hardening and use steels of fine grain microstructure to favour
the formation of a protective oxide layer.
1.17.3 Carburisation
1.17.3.1 Carburisation mechanisms

Carbon from the coke deposited on the surface of metals can diffuse inside the alloy where it
stays in solution in the alloy microstructure (up to its solubility limit) or forms carbides
located mainly at grain boundaries.
X M + YC - M,C,
Also in the presence of hydrocarbons or carbon oxides, one or more elements on the
alloy surface may be converted into carbides according to reactions such as:
XM + 2yCO t)MXCY+ y e 0 2
XM + 2yCH4 fi, MxCy + 2yH2
For a given temperature, the carburisation tendency increases with the ratios (PCO)2/
PC02 and PCH4/(PH2)2. These ratios have critical values below which the opposite reac-
tions occur, i.e. decarburisation.
Unlike the action of High Temperature Hydrogen Attack (HTHA), carbon input in carburis-
ing atmosphere causes a significant reduction in the plasticity of the alloy, sometimes even
completely eliminating any plastic strain capacity, This has a considerable effect on the
mechanical behaviour of the metallic material, becoming highly sensitive to thermal variations.
Temperature and carbon activity (which depends on the hydrocarbon, CO and hydrogen
partial pressures) accelerate the carburisation kinetics. On the opposite, high oxygen and sul-
fur partial pressures decrease the rate of carburisation [ 1051.
1.17.3.2 Example of carburisation

The example illustrated on Figure 1.55 concerns a regenerating reforming furnace tube made of
5 Cr-0.5 Mo low alloy steel (ASTM A335 grade P5, UNS K41545). Temperatures of 750 "C
were reached locally (the steel design temperature was 625 "C). On the metallographic images
taken in cross-section throughout the thickness of a very hot zone of the tube, we observe pre-
cipitation of numerous carbides throughout the entire thickness, especially on the inside (feed-
stock side) where the carbon content reaches 4% instead of the initial 0.15%. Even on the out-
side, the carbon content quadrupled due to difhsion of carbon and precipitation of carbides.
Outside: carbon content 0.8% Zone at mid-thickness Inside: carbon content 4%
Figure 1.55
Metallographic cross-sections of a 5 Cr-0.5 Mo carburised steel furnace tube.
1.17.3.3 Prevention of carburisation

An non porous surface layer of oxides may be beneficial since it limits carbon penetration.
At low P02, these layers are difficult to form. Under certain conditions, Cr203 may not be
stable, whereas A120, and Si02 are stable. These oxide layers can either be generated by
selective preoxidation of alloys with sufficient chromium, aluminium or silicon contents or

deposited as coatings.
Elements such as silicon, niobium and tungsten increase the resistance to carburisation.
The effect of nickel, which has a low affinity for carbon, is generally beneficial.
1.I8 MOLTEN SALT CORROSION
1.18.1 Equipment concerned by molten salt corrosion
Some compounds, such as Na2S04, KzSO4, KC1 and V205, present in combustion or pro-
cess gases may deposit on the surface of metallic parts as liquid condensates which attack
the protective oxide layers [ 1051. The main equipment and processes concerned include fur-
naces burning fuels containing alkali salts or vanadium compounds and processes involving
thermochemical conversions of lignocellulosic biomass (pyrolysis furnaces, gasifiers) for
the production of second-generation biofuels.
1.I8.2 Mechanisms and parameters governing molten salt corrosion
As indicated in Table 1.5, alkali salts (KCl, K2S04, NaCl, Na2S04, etc.) and vanadium
oxides (V205) which have low melting points may be present in liquid state during combus-
tion or gasification processes.
KCI NaCl I Na2S04 I K2S04 I "2% I

Melting point ("C) 1 772 80 1 884 1069 69 1
In liquid state, these salts are highly corrosive since they convert the protective metal
oxide layer into the metal sulfate and/or chloride [104; 1231. Since this is an electrolytic
medium where ionic charge transfers occur, this type of attack is extremely fast.
Fez03 + 3Na2S04 + 3/202 + 3 s o 2

-
The iron oxide layers can be attacked in a number of ways, e.g.:
Fe2O3 + 6KC1+ 3/202 + 3 s 0 2 3K2S04 + 2FeC13
2Na3Fe(S04)3
Fe203 + 3K2S04 + 3/202 + 3s02 2K3Fe(S04)3
1.18.3 Example of molten salt corrosion
The images on Figure 1.56 show the morphology of the attack on a heat-resistant steel
exchanger 800H (UNS NO88 10) at 900 "C due to the presence of Na2S04 in the reaction atmo-
sphere. Portions of the outer surface have been attacked in the zones where the molten salts
(sulfates in this case) have been able to condense, creating veins that attack nearly the all thick-
ness of the tube. Surfaces where no molten salt was deposited have remained totally intact.
Figure 1.56
Na2S04 corrosion of an 800H steel exchanger tube:
corroded surface - cross-section - metallographic image of the corroded zone.
1.18.4 Prevention of molten salt corrosion
Chromium seems to be the most efficient alloy element with respect to this type of corro-
sion. Increasing the chromium content by 20% to 30% in a nickel base alloy reduces the
corrosion rate by a factor of 5 [ 1041.
For steels and cobalt-based alloys, 25% to 30% chromium seems to be the optimum
content, although the alloy is not completely immune to attack from molten salts. Cobalt
alloys are more resistant than nickel-based alloys with respect to molten salts, but they are
less resistant to oxidation.
To limit this type of corrosion, apart from seeking a more suitable metallurgy, chemical
compounds may be injected to prevent the formation of sulfates which, in liquid state, attack
the protective metal oxides. By chemical injection, the alkaline compounds can be converted:
- Either into mixed potassium-calcium or potassium-magnesium sulfates with higher
melting points, which will be in solid state during thermochemical or combustion ope-
rations. In the presence of sodium sulfate, injection of lime or magnesia leads to the
Chapitre I Muin corrosion phenomena encountered in oil and gas production
9 75
formation of more stable double sulfates Na2S04-2(CaS04) or Na2S04-2(MgS04)

with higher melting points [313;
- Or into non-corrosive liquid oxides which form a protective surface deposit when they
solidify on the surface. Adding tungsten (ammonium tungstates) or molybdenum
(ammonium molybdates) salts to the feedstock results in the formation of non-corro-
sive tungstates (Na2W 4 0 3, K2W 6 0 9 ) or molybdates (Na2M0207, K2M04OI3)
which may protect the steel surfaces [ 1361.
Similarly, for vanadium oxides (V205), adding magnesia (MgO) in a ratio M g N = 1,5
results in the formation of a mixed oxide (3Mg0 V2O5) of melting point above 1191 "C
[ 1051.
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2
Prevention of corrosion and degradation
of metallic materials used in the petroleum industry
This second section of the book discusses the various techniques implemented to protect the
materials most frequently used in the petroleum industry against corrosion. Protection con-
sists of two aspects, firstly appropriate selection of the metallic material and secondly proper
design of the equipment to control the various corrosion risks. If this first approach does not
guarantee the overall integrity of the unit or equipment or if the resulting investment is too
high (CAPEX), protection must be provided by applying a coating (inorganic or organic),
injecting chemical formulations inhibiting corrosion into the corrosive medium, or applying
cathodic protection (even anodic for a limited number of applications).
The last paragraph of this section deals with corrosion detection, control and monitoring.
The choice of corrosion control, evaluation and inspection methods used to set up possible cor-
rective actions is of vital importance to guarantee the reliability and safety of the equipment.
2.1 CORROSION PREVENTION BY APPROPRIATE SELECTION

AND DESIGN OF MATERIALS AND EQUIPMENT
Several interdependent criteria are involved when choosing the material that will be used to man-
ufacture equipment (or part of equipment) operating in corrosive environment whose main oper-
ating parameters are known (e.g. concentration or pressure of the corrosive agents, temperature,
flow rate, mechanical stresses in service) and for a planned service lifetime of the equipment.
2.1.1 Data concerning the corrosion type and propagation rate

The first aspect taken into account is the corrosion type: localised or uniform. Localised cor-
rosion is taken to mean damage affecting only part of the material: pitting, crevices, craters,
cracking, blistering, galvanic coupling. Uniform corrosion damages the entire surface and
leads to a more or less homogeneous reduction in wall thickness. The various signs of corro-
sion are described in more detail in section 3 of this book. The reader may also refer to the
IS0 standards defining the various corrosion categories [ 1601.
84 Chapitre 2 Prevention of corrosion and degradation ofmetallic materials
- Risks of localised corrosion: the material (chemical composition, mechanical charac-

teristics, microstructure, welding modes, heat treatments) is chosen to minimise or
prevent this corrosion. For example (non-exhaustive list):
choice of a stainless steel composition not sensitive to pitting corrosion,
choice of a carbon steel composition (with controlled sulfur and phosphorus
contents) not sensitive to blistering and hydrogen-induced cracking,
choice of a low alloy steel not sensitive to high temperature hydrogen attack (with a
proper chromium and molybdenum content),
choice of a stainless steel composition not sensitive to a chromium depletion of
grain boundaries (sensitisation) during operation at high temperature (low carbon or
stabilised stainless steel) and heat treatment for chemical stabilisation of stabilised
stainless steels in order to prevent intergranular cracking corrosion,
application of heat treatment to relax internal stresses (produced during welding or
when shaping the part) to prevent stress corrosion,
coupling of materials of similar electrochemical potential to avoid galvanic corro-
sion if they are immersed in an electrolyte,
etc.
- Risks of uniform corrosion: an estimate of the corrosion rate (CR) is required at
design stage to determine a corrosion allowance thickness (CA) which ensures that
the material is sufficiently thick at end of life (D) to withstand the various mechanical
service stresses (pressure, etc.).
CA (mm) 2 CR (mm/year)*D(year)
As a general rule the corrosion allowance CA is no more than 6mm. When CR
> 0.25 mdyear, the conclusion of the financial analysis is generally either to change the
material grade or, depending on the media, apply cathodic protection or a corrosion inhibi-
tion treatment or coating. For some equipment, the 6 mm corrosion allowance may prove
too expensive, in which case it may be necessary to review the metallurgical choice.
The data used to assess uniform or localised corrosion are obtained from:
- Curves and models validated by the profession. Numerous examples and references used
in the petroleum and process industries are provided in the first section of this book;
- Results of specific corrosion tests conducted in laboratory or full scale tests. In this
case, it is essential to ensure that the test conditions are representative of the industrial
operating conditions;
- Feedback from field experiences obtained under the same operating conditions.
2.1.2 Control of operating parameters
It is essential to control the operating parameters in order to prevent corrosion risks. In the
first section of this book, we examined the influence of the main operating parameters on the
corrosion mechanisms encountered in the petroleum and process industries. In service, it is
vital to set up instrumentation and regulation as well as corrective action plans to avoid any
slips which could be disastrous for the equipment integrity. These corrosion detection,
Chapitre 2 Prevention of corrosion and degradation of metallic materials 85
monitoring tools and methodologies are described in paragraph 2.3 of this second section.
The main critical operating parameters are:
- Temperature of the corrosive fluids and the equipment (in particular fiunaces, boilers, heat
exchangers, etc.) since most corrosion processes are thermally accelerated. Temperature
(and pressure) also govern the thermodynamic state of the corrosive compounds. For exam-
ple, following an accidental temperature rise, solid alkaline salts may change to highly cor-
rosive liquid state (as described in paragraph 1.18). Inversely, following a temperature drop,
inorganic acids such as HCI may change from gaseous to liquid state: the non-corrosive gas
is now a highly corrosive liquid, resulting in metal wastage in just a few hours;
- Concentration and partial pressure of the corrosive agents: increasing these parame-
ters generally increases corrosion rates;

- Mechanical stresses (hydrostatic pressure, stress cycles, etc.) applied on the metallic
materials. Even if these variations do not affect the physical integrity of the equip-
ment, the materials may become sensitive to stress corrosion or corrosion fatigue;
- Fluid flow hydrodynamic conditions. Increasing the flow rate may cause erosion-corrosion
and cavitation phenomena. The opposite is true for some materials, where conditions under
which corrosive products stagnate may generate increases of the sensitivity to localised
corrosion (e.g. pitting corrosion caused by chlorides on stainless steel surfaces);
- Presence of solid particles likely to cause attacks by erosion-corrosion, by conti-
nuously removing the natural surface layer protecting the metallic material.
2.1.3 Equipment design

Well-designed equipment with suitable geometry may prevent some forms of attack such as
crevice corrosion, galvanic coupling and corrosion-erosion damage.
Figure 2.1 provides some examples of bad configurations creating liquid retention zones
which may result in crevice corrosion:
I
I
+
Pipe wall
Crevices
[?
n n ,--Seal weld
crevides
Crevice at screewed joint
Figure 2.1
Examples of designs resulting in crevice corrosion (source: [269]).
Assemblies where metallic alloys of different corrosion potentials are placed in direct
contact are possible sources of galvanic corrosion, as shown on Figure 2.2. This type of cor-
rosion risk is generally prevented through the use of electrical insulation with a non-con-
ducting polymer gasket (as long as electrical shunting via external components such as
brackets doest not make the insulation ineffective):
Metal A ---,
Bad configuration Good configuration
Figure 2.2
Example of design resulting in galvanic coupling corrosion.
To avoid erosion phenomena, bottlenecks or sudden obstacles on the pipes should be

avoided, such as an overlap seam weld as shown on Figure 2.3 or a radius of curvature
which is too small.
Flow Erosion
directiont T damaae
Turbulent
Bad configuration Good configuration
Figure 2.3
Examples of design resulting in corrosion-erosion (source: [269]).
In environments where stress corrosion cracking could occur, stress-relieving heat treat-
ment should be performed to zones with high internal stress such as welds or zones which
werre highly strain-hardened during the manufacturing the equipment.
2.2 USE OF COATINGS, CORROSION INHIBITORS

OR CATHODIC PROTECTION
When control of operating parameters or equipment design fails to provide efficient corro-
sion protection, other solutions must be considered, such as use of coatings, inhibitors or
application of cathodic protection. These protection modes can be used alone or combined.
Anticorrosion protection can be applied before the equipment is put into service (by apply-
ing a coating or cathodic protection) or when it is in service (by applying cathodic protection
or injecting inhibitors), depending on operating conditions and costs. Coatings may also pro-
vide resistance to erosion or abrasion and act as thermal insulation.
2.2.1 Protection by coatings
The term coating generally refers to the class of organic coatings and paints, including the
composite liners, and the class of inorganic coatings, including metallic and cement-based
coatings. Before describing each class of coating, we will summarise the main principles
governing the anticorrosion protection provided by coatings [ 168; 202; 203; 2061.
2.2.1.1 Principle
A coating acts as a physical barrier isolating the metal from the corrosive medium and, theo-
retically, preventing the transfer of corrosion promoters (water, ions, chemical agents, etc.).
The success of this type of protection depends to a large extent on the choice of materials
forming the coatings and the quality of application. Protection by coating is fully efficient if
the coating has no defect and is perLectly impermeable to the corrosive media. Unfortunately,
it is impossible to achieve these conditions with an organic coating and penetration of the cor-
rosive medium through to the metal must be considered. Note, however, that organic coatings
are generally far less permeable to ionic species than to water. The resistance of the electro-
lyte penetrating the coating is therefore much higher when it reaches the metal surface than
the resistance of the external electrolyte and the corrosion current is reduced accordingly.
Another type of protection is based on the use of sacrificial coatings. Placed in electrical
contact with metal, these coatings form an anode. As a result, the metal becomes totally
cathodic and is therefore protected against corrosion. This is the case with zinc, for example,
for galvanised steel. This is also the principle of zinc or magnesium-rich organic primers.
Lastly, some coatings may inhibit corrosion reactions on the metal surface through the
action of active compounds in the coating capable of dissolving and reacting with the sub-
strate to form a protective oxide film on the metal surface. This is the case of traditional
chromate or lead-based anticorrosion primers, recently prohibited on massive scale due to
their toxicity. New anticorrosion primers, based on phosphate, silicate, titanate or molybdate
are now commercialised.
Apart from coating formulations and traditional paints, involving the above-mentioned
anticorrosion mechanisms, recent studies have led to the class of smart coatings, generally
formulated with encapsulated active agents [201]. When a smart coating cracks, the
88 Chapitre 2 Prevention of corrosion and degradation of metallic materials
9
encapsulated anticorrosion active agents or polymerisation agents are released as the crack
propagates, inhibiting corrosion or protecting the bottom of the crack. This will possibly
heal the crack, thereby attenuating the corrosion effects [222; 2601.
2.2.1.2 Organic coatings and paints

Numerous publications have described organic coatings and paints in detail: their chemistry and
composition, surface preparation methods and application methods. The reader is recommended
to refer to the books mentioned as references [ 1711, [205; 2231 on the subject. Paints, character-
ised by conversion of a liquid product when applied on a substrate into a solid film after drying,
generally form a class separate from coatings. The main definitions are detailed below.
A. Definitions
Organic coatings are composite materials consisting of an organic matrix (polymer) loaded
with pigments and fillers. Applied on a metallic substrate, they adhere to the support, in
principle due to chemical and mechanical phenomena. Several coatings may be applied one
after the other to get the various functions required. For example, a three-layer coating sys-
tem for external protection of buried or underwater pipelines consists of a highly adherent
primer in contact with the steel, a mechanically resistant product on the outside and an inter-
mediate adhesive product to bond the outer layer to the adherence primer.
Organic coating products include paints, liquid, paste or powder substances which,
applied on a support, form a solid and adherent film after drying. For more information,
especially on the vocabulary of paints, the reader can refer to European standard I S 0 EN NF
4618 [AFNOR T36-001, October 1999 edition, “Paints and varnishes - Terms and defini-
tions”]. In terms of raw materials, a paint is a mixture of fillers and pigments in suspension
in a non-volatile liquid binder, possibly containing solvents and other specific substances.
The binder, the essential element of a paint, consists of macromolecular products (polymers
or prepolymers) which will form the film. Solvents are organic or aqueous liquids (pure or a
mixture) which generally dissolve the binders. They help to adjust the viscosity of the prod-
uct to be applied. A wide variety of fillers and pigments is incorporated in the formulations
to reduce the cost andor adapt the properties of paints. For example, it is recommended to
add lamellar pigments such as micaceous iron oxides, glass flakes and nanocomposite clays
to improve the barrier properties of coatings and paints. The average length of the path taken
by molecules (water, oxygen, etc.) diffusing through the coating is increased and the perme-
ability reduced, provided that there is good adherence between the fillers and the matrix.
Over the last few years, numerous studies have been dedicated to replacing organic sol-
vents by water to reduce the Volatile Organic Compound (VOC) content of paints, in
response to new regulations. Similar efforts are also underway to reduce the quantity of sol-
vents in traditional paints. Low-solvent paints, known as “high solids” due to their high dry
extract, are formulated with this aim in mind. The field of application of powder paints,
which are absolutely solvent-free, is therefore developing [ 1871.
Paints are classified according to how the liquid product is converted into a solid: evapo-
ration of solvents, oxidisation or polymerisation. They are applied using different methods,
depending on the paint viscosity. Fluid products are generally applied by brush, roller,
Chapitre 2 Prevention ofcorrosion and degradation ofmetallic materials 89
immersion or spraying. Powder paints are applied using two methods, fluidised bed powder
coating (where the part heated to a temperature above the powder melting point is dipped in
the paint) and electrostatic powdering followed by curing.
9. Main polymers
Numerous polymers are used in the composition of coatings and paints. The thermal stabil-
ity of coatings and paints under continuous exposure, which is generally limited to well
below 200 "C, is due to the fact that the polymers are organic, i.e. based on carbon chemis-
try. The short-term resistance is higher, but rarely exceeds 350 "C.
Polymers can be classified into two categories depending on their response to temperature
increase [24 11. Thermoplastic polymers generally consist of more or less interpenetrating lin-
ear or branched macromolecular chains. They soften reversibly when heated until they
become liquid, and are generally soluble in solvents. Note that semicrystalline thermoplastics
exhibit locally structured crystalline zones (crystallites), as opposed to the disorganised amor-
phous zones. The elastomer and thermosetting polymers have a covalent three-dimensional
network architecture composed of chemically cross-linked macromolecular chains. The net-
works are infusible and insoluble. They are obtained by the formation of a chemical bond
between high molecular weight linear or branched polymers, or by polymerisation of low
molecular weight prepolymer components having functionalities greater than or equal to two.
Thermoplastic polymers frequently used as coatings include polyolefins (polyethylene,
polypropylene, etc.) and polyamides. The more expensive fluorinated polymer coatings are
much appreciated for their chemical and temperature resistance. The thermosetting plastics
which include epoxy resins, acrylic resins, polyesters and polyurethanes are frequently used
in the composition of anticorrosion coatings. Silicone-based high temperature paints are also
used when the other coatings are no longer efficient.
C. Surface preparation
Surface preparation of the support is extremely important, since it governs the wetting and
the adherence of the coating on the substrate. The adherence mechanisms, detailed for
example in the books [ 170; 2451 are based on chemical and mechanical phenomena highly
dependent on the degree of cleanliness of the substrate (elimination of solid deposits, rust,
dust, grease and soluble salts) and its roughness (surface structure). The surfaces are pre-
pared by projecting abrasive particles (sand or grit blasting) or stripping with ultra-high
pressure water (several hundred bar). These operations are designed to increase the number
of reactive sites between the metal entities (oxides and hydroxides) and those of the coatings
(acid groups, hydroxyls, etc). They also prevent pollution of the interface which impairs the
efficiency of the coating protection mechanisms and leads to blistering [203; 2731.
D. Application examples
Organic coatings and paints are generally applied on the outer surface of metallic infrastruc-
tures (protection against the ambient environment). Anticorrosion protection is particularly
important for buried structures (pipelines) and underwater structures (pipelines, ships and
offshore production platforms). Organic coatings may also be applied, however, inside tanks
9
dedicated to the storage of corrosive effluents and inside transport pipelines (especially for
purposes other than anticorrosion). Concerning gas transport pipes, the internal coating may
yield a substantial benefit in terms of reduced internal losses at the walls [ 1791.
The example of external protection of petroleum effluent transport pipelines will be
developed below in greater detail, since numerous types of coating have been used for this
purpose. Pipe anticorrosion external coatings have evolved over the years as new organic
materials and application methods have become available. Note that this protection mode is
always accompanied by a cathodic protection system (see paragraph 2.2.2) for buried or
underwater pipelines. Despite the precautions taken during surface preparation and applica-
tion, pipe coatings may have local defects, due for example to mechanical damage of the
coating during transport or when laying coated tubes.
Originally, hydrocarbon coatings (based on coal-tar pitch from distillation of tars and on
bitumens from distillation of oil) were widely used for outer protection of buried pipelines,
and especially parts of structures not visible or buried. These coatings were generally applied
hot in thick layers (about 5 mm). Oil bitumen coatings are still used for offshore pipelines at
temperatures below 60 "C when they are weighted down by a layer of concrete. Research
studies have been conducted on the ageing mechanisms of these coatings, still in use on sec-
tions of the oil and gas effluent transport network [200]. Currently, epoxy resins which poly-
merise when mixed with, typically, amine or amide hardeners form paint binders widely used
for external protection of pipes, due to their high adherence on metallic supports. Readers can
refer to the specialised book [FBE: Foundation for pipeline protection, Kehr] [214] which
deals with this subject in detail, providing numerous applied examples. In the United States,
the United Kingdom and the Anglo-Saxon countries, epoxy resins are applied in a single-layer
coating of several hundred microns thick. In Continental Europe, epoxy paints, used as adher-
ence primers for three-layer type external coating systems, are applied in thinner coats (between
60 pm and 150 pn),generally as a powder paint, so called fbsion bonded expoy (FBE) [2 141.
E. Problems encountered
Anticorrosion protection provided by coating is generally impaired if defective (areas with
no or very thin coating). Coatings such as epoxy resins are brittle and easily damaged. Sin-
gular points (corners, edges, etc.) and zones where coated parts are joined together are also
potential problem sites, especially if another application method is involved or even another
coating technology. Defects are likely to develop at cutbacks of coated pipes, where the cor-
rosive agents in contact with the metal tend to diffuse laterally along the metal-coating inter-
face. To limit these defects, apart from careful selection of the welded joint system with
respect to the type of coating, the quality of support surface preparation and the quality of
the coating application are crucial and must be certified by a recognised inspector [ 1911.
The long term performance of the organic coatings (even fault-free) is also critical.
Exposed to harsh environments, these coatings are expected to last for several decades.
Coatings in service on overhead pipes must be inspected regularly, whenever possible, to
limit the risks of collateral damage. For example, cases of massive disbonding of undam-
aged three-layer coatings have been observed during inspections on pipes in service, without
generating corrosion however, since the rate of renewal of the corrosive species is too low
thanks to the fact that the coating remained pressed against the steel [246; 255; 2561.
Diffusion of water to the interface through the undamaged three-layer coating system, which
occurs relatively rapidly with respect to the pipe lifetime (Figure 2.4), could be responsible
for the loss of adhesion of the primer epoxy resins [226; 2591. Reversible phenomena such
as plasticisation of the resin by water and differential swelling between the resin and the
metal may be put forward, as well as irreversible phenomena such as hydrolysis of the epoxy
resins, which occurs above temperatures of 50 "C for some compositions [262]. The effect
of residual stresses in the three-layer coating, related to application process by extrusion of
the polyolefin-based layers, has also been put forward [ 1781.
Figure 2.4
Results of peeling at 2 1 "C obtained on undamaged three-layer coatings aged
in deionised water and scarified just before peeling: (a) cohesive failures in the
adhesive after 10 days at 20 "C and 60 "C (mean peeling forces = 36 kN/m);
(b) steel/epoxy primer adhesive failure after 49 days at 60 "C (mean peeling
force = 6 kN/m) [261].
In conclusion, the performance of a coating (applied correctly on a properly prepared

surface) depends on several criteria:
- Adhesion of the coating on the metallic substrate in initial state;
- Barrier properties of the coating with respect to the molecular species to which it is
exposed. Note that the permeability of a material to a molecular species is an intrinsic
property, product of the diffusion coefficient and the solubility. The rate of permeation
through the coating is proportional to the permeability and inversely proportional to the
coating thickness (case of a thermally activated, traditional diffusion process);
- Durability of the coating and of the coating-substrate adhesive bonds, in particular
resistance to chemical damage such as hydrolysis. It is also an intrinsic property
related to the chemical nature of the materials;
- Resistance to mechanical damage, such as that caused by accidentally dropping a tool
onto the coating during an inspection, and during service under the effect of differen-
tial substrate-coating swelling (due to temperature cycling or plasticisatioddeplastici-
sation of the organic coating).
We must also point out that it is extremely difficult to estimate the long-term performance of
a coating system, especially since the contents and specifications of coating products and paints
change permanently, which limits feedback. Returning to the above example of three-layer
coatings, the qualificationtests include dry adhesion measurements as well as cathodic disbond-
ing resistance measurements, but the adhesion properties of undamaged three-layer coatings
plasticised by water are generally not evaluated [259]. The qualification tests must be adapted to
the service conditions, in terms of environment and duration. These qualification tests must also
meet industrial constraints, however, hence the notion of accelerated ageing. This remark raises
the question of the accelerated ageing tests representativity. These tests are relevant if they
implement the ageing mechanisms of a coating in a given application, but this assumes that the
ageing mechanisms, which are often complex, have been identified [234]. While the debate on
the issue continues, the best way to guarantee that a coating is efficient is to involve and train all
the various players: suppliers/manufactrs/customers/inspectors/scientists.
2.2.1.3 Composite liner

Consisting of a resin, fillers and reinforcing materials, a composite liner is a thick coating (at
least 1 mm) applied to protect the inside of tanks against corrosion or contamination [158].
This type of protection is similar to that provided by organic coatings, since it prevents
contact between a corrosive medium and a metallic structure.
We will take the example of the wash tank of a catalytic reforming regeneration loop in
refineries. In the wash tank partially filled with Raschig rings, acid vapour (just neutralised
with excess soda) from the reforming unit comes into contact with mineralised water at
ambient temperature injected in counter-current. The operating conditions (temperature/
pressure) in the tank are typically 60 "C/4 bar. The design conditions are 80 "C and 10 bar.
The acid vapour composition may nevertheless reach a molar CO2 content of about 20%, the
HCl content remaining less than a few ppm. Under the design conditions, the partial pres-
sure of C02, which is a highly corrosive species for iron (see paragraph 1.2 in this book),
may reach 2 bar. According to the literature [188], the C02 corrosion rate (at 2 bar) of
unprotected carbon steel is 3 m d y e a r at 40 "C, reaching 9 mm/year at 60 "C. In view of the
high carbon steel corrosion rates under the tank operating conditions, it is essential to use a
coating which acts as an efficient, long-term barrier against the corrosive species. According
to feedback, the epoxy paints (thickness < 1 mm) traditionally used as anticorrosion coating
for reforming wash tanks do not protect the steel efficiently over long periods of time. One
explanation put forward is their brittleness during maintenance phases, resulting in damage
to the coating (numerous cracks in the paints during inspection). The damaged zones of the
tank steel represent zones of preferential attack by C02.
A Stratified Glass fibrehinyl ester Resin (SGR) of total thickness approximately 4 mm
has been recommended, comprising an anticorrosion primer, various resin coated glass rein-
forcements and a final resin layer about 2 mm thick. The main factors governing the perfor-
mance of an anticorrosion coating in the short and long terms have been considered: surface
preparation and application quality, durability of the component materials under the exposure
conditions, resistance to mechanical damage and barrier properties. Due to the similarities
between epoxy resin and vinyl ester families, the annual flow rate of C 0 2 through a 4 mm
thick epoxy-amine coating was calculated under the tank design conditions, i.e. 7.5.10-5 g/
cm3 on the basis of C02 solubility and difhsion coefficients measured on epoxy resins
[ 1921. This flow rate induces an acceptable carbon steel corrosion rate of 0.8 pm per year.
Chapitre 2 Prevention of corrosion and degradation of metallic materials
9 93
2.2.1.4 Inorganic coating

Inorganic coatings include those made from metals, heat-resistant compounds (oxides, car-
bides, nitrides) and cement.
Metallic coatings, consisting of a metal layer resistant to corrosion in the medium con-
sidered often provide additional mechanical resistance (against abrasion or against friction).
They are said to be cathodic or anodic due to their protection mechanism, which depends on
the position of the protective metal in the corrosion potential scale (refer to paragraph 3.2 for
further information). The difference in behaviour of these two protection mechanisms is
very important in case of defects (such as pores) in the coating. With a coating which is
more noble (cathodic) than the substrate with an open porosity, the substrate (anode) will
locally corrode; this damage cannot generally be observed on the surface of the coated part.
This type of attack is therefore very insidious. In contrast, when the deposit is less noble that
the substrate, the opposite phenomenon is observed, with the deposit acting as an anode in
this case: it corrodes (acting as sacrificial anode) while the substrate is protected.
Metallic coatings can be applied using techniques classified into the following categories:
thermal spraying, physical or chemical vapour deposition techniques, electroless plating,
immersion in liquid metal and electrodeposition.
A. Thermal spraying
Thermal projection refers to deposition by detonation, deposition by flame spraying and
deposition by plasma spraying, which produce very similar microstructures. Ideally, the par-
ticles of a pulverulent material melt completely during spraying (but do not sublimate), then
flatten and solidify on striking the substrate surface. The solidified particles are more or less
flat depending on the state of fusion and the surface wettability, while their microstructure
depends on the rate of cooling. The coatings, built up by stacking lenticular particles,
contain cavities due to degassing, contraction of the material or topographic effects.
B. Vapour deposition [225]

Cathodic sputtering, which is a Physical Vapour Deposition (PVD) technique, can be used
to deposit a large number of metals, alloys and heat-resistant compounds. In a vacuum
chamber containing a gas such as argon under low pressure, a voltage of about 2000 V is
applied between the target (negative pole containing the chemical elements to be deposited)
and the substrate (positive pole). A plasma is formed. The electric field accelerates the
plasma ions (Ar' if argon is used) which will collide with the target: these collisions eject
atoms from the target which are then deposited on the substrate.
In Chemical Vapour Deposition (CVD) techniques, a mixture of gases containing a vola-
tile chemical compound of the metal to be deposited is used in the presence of a reducing
gas such as hydrogen or methane. As this mixture of gases is introduced into the reaction
chamber, the volatile compound is reduced on the surface of the substrate to be coated,
forming a deposit. These CVD techniques, which generally require high temperatures
(800 "C to 1 000 "C), can be used to deposit heat-resistant compounds (oxides, carbides,
nitrides, borides).
C. Electroless plating
During electroless plating, the metallic ions to be deposited, dissolved in the solution, are
reduced by a reducing agent on the surface of the substrate which acts as catalyst. Unlike
electrodeposition, electroless plating also applies to insulating substrates such as ceramics
and polymers. The example of electroless plating most frequently implemented in the petro-
leum industry is chemical nickel plating (also known as the Kanigen process): Ni2+ ions are
reduced in aqueous solution by hypophosphite ions H2PO:. An Ni-P coating is formed. Heat
treatment (in the region of 500 "C) applied to this type of coating may considerably increase
its hardness and adhesion due to the formation of Ni-P-Fe intermetallic compounds at the
internal coating-steel interface.
D. Immersion in a liquid metal

This technique is used to coat steels with zinc: the substrate is immersed in a bath of molten
zinc (above 420 "C); a zone of Zn-Fe interdiffusion also forms, ensuring good adhesion of
the deposit.
E. Electrodeposition
This technique is used to deposit metals such as nickel, copper, chromium and zinc, as well
as their alloys, on a conducting substrate which is then placed as cathode in an electrolyte
cell containing the ions of the metal to be deposited (together with various complexing
agents and buffers).
2.2.1.5 Cladding
Cladding is the combination of two metallurgies. It is applied by roll bonding, weld overlay
or explosion technique. This type of solution offers a compromise between different proper-
ties. One provides chemical inertia, for example, the other mechanical strength. This tech-
nology is typically applied to pipes to protect specific parts against erosion (surface attack
due to impact of debris) or abrasion (surface attack due to friction of another moving part).
In the refining industry, this technology is frequently used for hydrotreatment reactors to
provide inexpensive protection against internal corrosion by sulfidation: stainless steel clad-
dings are used to protect low-alloy steel ferrules, instead of making ferrules out of solid
stainless steel which would exhibit lower mechanical properties.
A. Roll bonding
Roll bonding consists in feeding sheets of the base metal and the plating metal simulta-
neously through the rolling mill.
B. Weld overlay
In the weld overlay technique, the noble metal is deposited as continuous weld seams over
the entire surface of the base metal. The main welding techniques used are Submerged
Arc Welding (SAW), Electro Slag Welding (ESW), Gas Tungsten Arc Welding (GTAW)
and Shielded Manual Arc Welding (SMAW). Two layers of different types are generally
specified to create the overlay required for hydrotreatment reactors. The first layer, made
from high-chromium stainless steel (AISI 309L, UNS S309003), reduces the effects of chro-
mium dilution from the overlay to the base metal during welding. The second layer, in con-
tact with the process fluid, consists of stabilised austenitic stainless steel [niobium in grade
AISI 347 (UNS S34700), or titanium for grade AISI 321 (UNS S321000)]. The ferrite con-
tent is an important parameter in this second layer: it must be greater than 3% to avoid hot
cracking and less than 8% to prevent loss of ductility, reduce hydrogen accumulation and
avoid low cycle fatigue cracking.
C. Explosion cladding
The energy required to bond the two sheets is obtained by the shock wave and pressure (sev-
eral GPa) generated by detonation of an explosive. This technique does not generate a tem-
perature increase in the centre of the metal or any metallurgical conversion which would
impair the corrosion resistance (e.g. chromium depletion of the grain boundaries).
2.2.1.6 Anticorrosion cements

Cements can be used to protect the metallic walls against corrosive attack. Cement coatings
are generally sprayed on and secured by metal anchoring points welded to the wall. The
cement coating is generally about 50 mm thick. They are virtually impermeable to water and
hydrocarbons. In addition, they generally offer excellent erosion and abrasion resistance.
This type of coating is used for example to protect carbon steel tanks against wet H2S
corrosion.
2.2.1.7 Surface treatments

Surface treatments are used to obtain a conversion layer by reaction of the metal with a cho-
sen medium. Chemical modification of the surface increases the corrosion resistance.
A. Anodising
Anodising is carried out to increase the natural metal oxide by anodic oxidisation. For alu-
minium alloys, the metal is immersed in a suitable solution (e.g. sulfuric acid) and a voltage
of 10 V to 20 V is applied for a few minutes. Anodising is also used to increase the thickness
of passive films on the surface of metal parts benefiting from this natural protection (stain-
less steels, titanium, tantalum, zirconium). For stainless steels, the treatment - which is also
known as passivation - consists in dipping the metal into a solution of nitric acid.
B. Phosphating
Phosphating is applied to low alloy and carbon steels. The metal is immersed in a solution of
phosphoric acid causing corrosion of the iron and precipitation of iron phosphates on the
surface. This type of protection is used, for example, to protect carbon steel equipment dur-
ing transportation. Protection is only efficient up to 120 "C, since the iron phosphates
formed decompose above this temperature.
2.2.2 Cathodic protection of structures

2.2.2.1 Principle
Since electrochemical corrosion is due to flow of a current between anode and cathode, it is
sometimes beneficial to cancel this current and completely convert the metallic structure to
be protected into a cathode, thereby protecting it against attack. This technique is known as
cathodic protection. The current applied can be produced by a DC generator and supplied by
more or less consumable anodes (scrap steel, ferrosilicon, graphite) or inert anodes (plati-
num-plated titanium, mixed metal oxide coated titanium Ti/MMO), which is, for example,
generally the case for onshore pipelines. The dissolution current of a sacrificial magnesium,
aluminium or zinc alloy anode may also be used to provide cathodic protection. Offshore
pipelines, for example, are protected by sacrificial anode clamps connected every 100 m to
200 m during laying. Cathodic polarisation of the metal lowers the metal/solution potential
so as to bring it within the immunity zone (Figure 2.5).
STEEL STATE
IN SEA WATER Cell at the steel surface with an
electrolyte and an oxidizing agent
am -0.55 Fe-, Fez++ 2e- (anode)

O2 + 2 HzO + 4e- * 4 OH- (cathode)
5
p -0.80
h
-
Cathodic protection
-Removal of the iron
-
.-ca
-1.05
-
by sacrificial ande
(less noble metal as Zn)
by impressed current
Figure 2.5
States of steel in seawater according to the potential scale.
When Cathodic Protection (CP) is applied on a metallic structure, the substrate oxidation
reaction (Equation 2.1) is unfavoured. In this case, the reduction reactions occur at the metal
(cathodic zone): reduction of oxygen (Equation 2.2) and/or reduction of protons (Equation 2.3).
At very low potential, reduction of water occurs (Equation 2.4).
Oxidation of the metal (corrosion): Fe w Fe2+ + 2e- (2.1)
Reduction of oxygen: O2 + 2H20 + 4e-- w 4 OH- (2.2)
Reduction of protons: 2H+ + 2e- w H2 (2.3)
Reduction of water: 2H20 + 2e- a H2 + 2 OH- (2.4)
2.2.2.2 History of offshore and onshore applications

Cathodic protection of metallic structures, whose history has been documented and
described in detail by M. Roche [254], dates back to the 19'h century. Cathodic protection is
now systematically applied to metallic structures, both buried (pipelines, tanks) and
Chapitre 2 Prevention ofcorrosion and degradation of metallic materials 97
submerged (pipelines, offshore infrastructures, ships, etc.). The reader can refer to a special-
ised document [243]. Cathodic protection is also implemented, though less frequently, to
protect internal seawater circuits and steel in concretes.
Cathodic protection can be combined with an anticorrosion organic coating, which con-
siderably reduces the current required for cathodic protection or the weight of the sacrificial
anodes, compared with the cathodic protection necessary to protect the entire area of the
uncoated structure. Use of a coating will therefore be taken into account when designing
cathodic protection under given service conditions. It is essential to ensure, however, that
the coating, if damaged and exposing the metal, is not too sensitive to cathodic delamination
phenomena. The consequences of these phenomena, whose mechanisms have been exten-
sively studied in the literature [176; 219; 2581, are to increase the cathodic current demand
or the rate of consumption of the sacrificial anodes over time. As for coatings used without
cathodic protection, adhesion is a key parameter when choosing a coating to be applied on a
structure which will be placed under cathodic protection; adhesion must be evaluated under
conditions - potential, exposure medium, dissolved oxygen, electrolyte flow and duration -
simulating the service.
2.2.2.3 Problems encountered (design, checks of cathodic protection

and cathodic overprotection,shielding, monitoring)
To ensure that the entire installation is at the correct potential, the cathodic protection volt-
age must actually reach all bare steel surfaces exposed to the surrounding medium. The
installation must therefore be properly designed and maintained to limit failures of the
impressed DC power supplies and replace the sacrificial anodes on proper time. Design of
cathodic protection must be carefully studied, especially for a complex structure, since the
distribution of potentials at each point on the structure may vary considerably. The risk is
that certain zones where the IR drop with the groundbed is too significant would be under-
protected. This may be the case for example in soils, when the land dries, increasing the
electrolyte resistivity and reducing the range of the cathodic protection. Cathodic protection
design models have been developed as support during the initial design phase.
Another risk associated with the combined use of an organic coating and a cathodic pro-
tection system is the shielding of the cathodic protection current, if the organic coating
exhibits high electrical resistivity, which is the case of polyolefins, for example, and if it is
thick. This risk may lead to highly critical situations in case of substantial disbonding of the
coating from the steel if the locally damaged coating allows electrolyte to come into contact
with the metallic substrate in a zone remote from the defect, where cathodic protection is no
longer effective [209; 270; 2711.
Application of the cathodic protection must be monitored during service in order to avoid
situations where there is no more protection, but also situations of overprotection. In practice,
it may be difficult to check the potential applied: cathodic overprotection may occur when the
potential is too negative for impressed current systems using a magnesium electrode. Cathodic
overprotection is accompanied by the production of hydrogen, which exposes the steel to a
risk of hydrogen embrittlement. Overprotection also increases the risk of cathodic disbonding
of coatings near the defects, exposing the metal. For onshore facilities, cathodic protection
98 -
efficiency is generally controlled by periodic checks at the potential measurement points,

together with records of potential measured using permanent electrodes distributed in the crit-
ical zones, possibly transmitted to a remote monitoring system. Cathodic protection measure-
ment techniques are continuously being improved, to eliminate the problem of IR drop
between the reference electrode and the structure controlled. The measurements taken when
cathodic protection is applied are in fact subject to error, due to the IR drop between the refer-
ence electrode and the structure controlled. The higher the land resistivity, the greater the dis-
tance between the reference electrode and the point to be controlled, and the greater the
cathodic current density (e.g. at coating defects), the greater the error. The most well-known
means of correcting the IR drop is to take measurements using the ordoff method. Cathodic
protection monitoring is a major issue and improvements are made on a regular basis: to check
the true effectiveness of cathodic protection on buried structures, in particular, intensive meth-
ods operating with stray or telluric currents as well as remote monitoring and the use of cellu-
lar and satellite telecommunication are being developed [254]. The best way of guaranteeing
the effectiveness of cathodic protection is to rely on qualified personnel whose skills have
been demonstrated by a certification system, complying with standard EN 15257 for example.
2.2.3 Corrosion inhibitors
2.2.3.1 Principle
Added to the corrosive medium in small doses, corrosion inhibitors are compounds which
modify the electrochemical reactions without taking part themselves in the reactions. There
are numerous types of inhibitors and inhibition mechanisms. The main reaction mechanisms
used to classify inhibitors include adsorption, passivation, film precipitation (precipitation of
complexes on the metal surface), elimination of a corrosive agent (applicable in closed sys-
tems such as elimination of oxygen using scavengers). A given inhibitor is often associated
with several action mechanisms. Inhibitors are in fact specific to a type of alloy and a type of
medium. In liquid media, they are said to be cathodic, anodic or mixed, depending on
whether they act more especially on the cathodic reaction, anodic reaction, or both at the
same time by reducing the current density of the reaction(s) concerned, as indicated on
Figure 2.6 (see paragraph 3.2 for more detailed information).
Some anodic inhibitors may have a passivating effect, i.e. participate in the formation of
a passive, protective surface layer. The effect of this type of passivating inhibitor is illus-
trated on the simplified polarisation curves shown on Figure 2.7.
Inhibitors can also be added in gas phase: adsorption and/or formation of protective sur-
face layers govern their action mechanisms.
The degree or efficiency of inhibition characterises the decrease in corrosion rate due to
the presence of the inhibitor. It depends on the inhibitor concentration (c) and is generally
expressed by:
(corrosion rate in absence of inhibitor - corrosion rate in presence
of a quantity c of inhibitor)
YOefficiency = 100 x
corrosion rate in absence of inhibitor
/
\ /
\
\\ //Without
\ /
Figure 2.6
Influence of an anodic, cathodic or mixed inhibitor on simplified polarisation
curves and on the corrosion potential.
Figure 2.7
Influence of a passivating anodic inhibitor on the simplified polarisation curves
and on the corrosion potential.
In petroleum production, the aim is to achieve efficiencies of at least 80% [239]; effi-
ciencies of more than 99.9% can be obtained if the inhibitors are correctly selected.
2.2.3.2 Liquid phase inhibitors

We have seen that these inhibitors affect either one or both of the corrosion reactions.
A. Anodic and passivating inhibitors

These inhibitors are mainly used in neutral medium to form or promote the formation'of a
protective film which inhibits anodic dissolution of the metal. These inhibitors must be
injected in sufficient concentrations since otherwise, they may accelerate anodic dissolution.
100 -
Anodic inhibitors can be classified according to their corrosion inhibition action mecha-
nism:
- Oxidising inhibitors such as chromates CrOZ-, nitrites NO, or the less efficient moly-
bdates MoOZ- and nitrates NOT. Due to their toxicity, however, these inhibitors are
only recommended for systems and circuits with no discharge to the exterior
(e.g. closed cooling water circuits);
- Inhibitors acting as buffers to maintain a high pH near the surface, to facilitate passi-
vation. Basic salts such as silicates, borates, carbonates or phosphates can be used to
stabilise the pH in neutral or alkaline medium.
B. Cathodic inhibitors
Cathodic inhibitors control corrosion by reducing the cathodic reaction by adsorption of
chemical compounds (cathodic poisons) or by formation through precipitation or polymeri-
sation of a film-forming a layer preventing diffusion:
- Sulfide or selenide type cathodic poisons adsorb onto the metallic surface whereas
compounds containing arsenic, bismuth and antimony are reduced, forming a metallic
layer. Adsorption of these compounds may also favour hydrogen penetration in steels,
causing Hydrogen-Induced Cracking (HIC) or Stress Corrosion Cracking (SCC), as
described in paragraph 1.3 of this book;
- Precipitation or polymerisation agents generate the formation of a protective film which
reduces the cathodic reaction rate. In neutral and alkaline media, this occurs when scale
deposits of calcium and magnesium carbonates precipitate on the metallic surface. Inor-
ganic salts such as silicates, borates or phosphates may also have this cathodic effect.
Polyphosphates (NaP03), and organophosphophates are also included in this category.
C. Mixed inhibitors
Numerous inhibitors, mainly organic formulations, are capable of reducing the rates of
anodic and cathodic corrosion reactions. Their efficiency is closely related to their ability to
adsorb onto and cover metallic surfaces. Their adsorption depends on their structure, the
charge of the metallic surface and the type of electrolyte.
The organic inhibitors are composed of numerous formulations: aromatic molecules,
linear or branched chain macromolecules, etc. They contain a non polar, hydrophobic part
consisting mainly of carbon and hydrogen atoms and a polar hydrophilic part consisting of
one or more functional groups such as amines (-NH2), mercaptans (-SH), hydroxyls (-OH),
carboxyls (-COOH), phosphates (-PO3) or their derivatives (addition information on the
functional groups is provided in Table 2.1). The inhibitor is attached to the surface by its
hydrophilic functional group, while its larger non polar part partially blocks the active
surface, as shown on Figure 2.8.
a. Examples of basic compounds used to inhibit corrosion in petroleum production .
The inhibitors have a long hydrocarbon chain (12 to 18 carbon atoms) and a nitrogen- and
oxygen-based functional group, as indicated in Table 2.2. The hydrocarbon chain makes
these additives partially soluble in crude oil: the chain also attracts hydrocarbons in the
9 101
Metal
Fonctional group
Non polar part
Figure 2.8
Adsorption of an organic inhibitor in aqueous medium [225].
Table 2.1 Chemical compositions of the functional groups of organic inhibitors (source: [240]).
Structure Name Structure Name
-OH Hydroxy -CONH, Amide

-cx- -yne -SH Thiol
-c -0-c - epoxy -S- Sulfide
-COOH Carboxy -s=o Sufoxide
-C-N-C- Amine -c=s- Thio
-NH2 Amino -P=O Phosphonium
-NH lmino -P- Phospho
-NO, Nitro -AS- Arsano
-N=N- N - Triazole -Se- Seleno
fluid; the film formed by these hydrocarbons on the metallic wall may also play a role in
inhibiting corrosion.
In petroleum production, inhibitors are also classified according to their solubility, dis-
persibility in water and/or in crude oil:
- water-soluble inhibitors quaternary amines, amine salts, imidazoline salts,
- crude oil-soluble inhibitors: for example long chain primary amines, imidazoline,
fatty acids, phosphate esters.
Table 2.2 Basic chemical compositions of some inhibitors used in petroleum production (source: (2391).
Chemical compound Structure
Primary amine R-CHZ-NH,
0
II
Amide Rl-CH2- C -NH-R,
ImidazoIine
Quaternary ammonium ion
,(o-cH,-cH,+,oH
Polyethoxylated amines R-N
‘ ( 0 -CH, -CH, $,OH
b. Examples of inhibitor injection modes in petroleum production

Inhibitors can be added by continuous injection, batch injection or a mixture of both:
- Continuous injection: after several hours of pretreatment with an overconcentration of
products, a constant quantity of inhibitors is injected throughout the lifetime of the

equipment;
- Batch injection: a larger quantity of inhibitor is injected periodically, with no continu-
ous injection. A pig is generally run through to clean the pipe walls before injecting
the batch. The batch injection frequency depends on the concentration of the inhibitor
which desorbs, this quantity being determined by analysing the product in the effluent
at the exit of the effluent and by monitoring the corrosion rates;
- Mixed treatment: periodic batch treatment is carried out, together with maintenance
by continuous injection of a small quantity of inhibitor.

c. Other associated functions in anticorrosion formulations
Corrosion inhibition additives are often associated in formulations with other chemical
compounds, for example to limit deposits, to break up emulsions and to neutralise acid
compounds:
Antimineral deposit additives to prevent clogging of wells, oil tubings and water coo-
ling circuits. These additives prevent precipitation of calcium and magnesium carbo-
nates and barium sulfates: They are based on film-forming fatty amines, condensed
phosphates, organophosphates, organic polymers and polyaspartates. Sometimes they
also have corrosion inhibiting properties;
9 103
- Antideposit and antifouling: refining processes may be particularly affected by deposits

from side chemical reactions (polymers, coke), especially in heat exchangers. Antide-
posit additives are often based on antipolymerising and oxygen scavenging compounds;
- Neutralising agents to reduce corrosion by increasing the pH of the aqueous solution
which may condense, for example in atmospheric distillation column heads. Although
ammonia has been widely used and remains an inexpensive solution, it may cause
ammonium chloride deposits, as well as fouling and under deposit corrosion. Organic
liquid neutralisers have been developed to prevent the formation of ammonium chlorides.
Table 2.3 illustrates the anticorrosion, antideposit and neutralising functions sought for
various refining processes.
Table 2.3 Applications of anticorrosion, antideposit and neutrabing formulations in the refining industry [204].
Corrosion Neutralising
Unit Process flow Anticlogging inhibitor
crude feedstock
atmospheric column head X X
Distillation
vacuum column head X X
steam injection
Coker coker feedstock X
debutaniser column head X X
Alkylation
depropaniser column head X X
fractionation column head X
compressed wet gas X
FCC
debutaniser column head X
depropaniser column head X
hydrodesulfurated feedstock X
hydrodesulfurated effluent X
Catalytic light product stripping column head X
reformer
prefractionation column head X
hydrogen feedstock stripper
reactor feedstock X
Hydrocracker
debutaniser column head X
2.2.3.3 Gas phase inhibitors

These inhibitors are conveyed by gas pathway up to the metallic walls to be protected.
Amongst the gas phase inhibitors used, two types of additive can be identified depending on
the temperature range of the application.
A. Inhibitors providing temporary protection against atmospheric corrosion

They are generally organic compounds with high vapour pressure which, after transport in
gas phase, adsorb onto the metallic surface and protect it against atmospheric corrosion. The
various chemical compounds used include amines (triethylamine, hexylamine, dibenzy-
lamine, isopropylamine, etc.) and organic carbonates (monocyclohexylamine, ethylamine
carbonate, etc.). Amine-based compounds vaporise without molecular dissociation and only
dissociate on the surface of the metal to be protected when they come into contact with liq-
uid water [164].
B. Inhibitors to avoid some types of high temperature corrosion

Most film-forming amine-based inhibitors are used to solve problems of liquid-phase corro-
sion up to their stability limit of about 175 OC. For applications at higher temperatures, inor-
ganic or organometallic formulations are used to transport protective alkaline earth and/or
metal sulfides, phosphates or oxides, for example, to the metallic walls. The following
examples concern applications of corrosion inhibitors during high temperature refining
operations. These inhibitors form, for example, a phosphate or sulfide ester-based protective
layer on the metal surface:
- Inhibition of corrosion by the naphthenic acids present in some crudes during distilla-
tion operations (a more detailed description of naphthenic acid corrosion is provided
in paragraph 1.12). Phosphate ester or thiophosphorated compound-based additives
are proposed to limit this type of corrosion [232; 2381;
- Inhibition of corrosion by metal dusting and clogging by catalytic coking. (also refer
to paragraph 1.17): injecting small quantities of sulfur compounds (H,S, DiMethylDi-
Sulfide) in the feedstocks blocks the activity of iron particles which catalyse coking
and metal dusting of steels [257].
2.3 CORROSION DETECTION, CONTROL AND MONITORING
2.3.1 Introduction
In the oil and gas industry, corrosion control tools and inspection strategies are required to
guarantee equipment integrity and reliability.
To prevent catastrophic failures, optimise inspection activities and limit repair costs, sig-
nificant effort has always been invested in the development of corrosion monitoring tools
[217; 2481. For example, inspection practices have become much more efficient through, in
particular, the use of risk evaluation strategies, which lead to improved inspection planning.
Thanks to continuous progress in inspection tools, the data obtained to assess corrosion is
now more useful and more accurate, e.g. reduction in wall thickness and in situ conditions
(temperature, pH, etc.). This type of information provides a means of evaluating the overall
condition of the equipment or the various parts and predicting lifetime via corrosion models,
when available.
In total interaction with the process conditions, corrosion evaluation must be considered as
input data for global management of industrial equipment and installations. On-line corrosion
monitoring, i.e. permanent, real-time recording [2 131, firstly prevents unplanned stoppages
and, secondly, the data collected can be merged or correlated with process variables [ 195; 2 131
in order to take decisions more rapidly. Due to the progress made in the fields of automation
and computer technologies as well as recent improvements in the corrosion monitoring tools
themselves, it is now possible to meet most of these new corrosion measurement requirements.
This paragraph provides a non-exhaustive overview of the various tools available for
corrosion detection and monitoring in the oil and gas industry, from the simplest tools to the
most recent developments and trends.
The first section is dedicated to real-time monitoring techniques, i.e. those requiring no
process interruption. We will make a distinction between techniques requiring intervention,
e.g. recovery of coupons, and those which can be carried out completely on line, since they
can be installed permanently, automated or even managed remotely.
The techniques in this category can also be classified according to their relations with
corrosion:
- electrochemical means are available to record the actual corrosion taking place, due to
electronic transfers,
- specific tools are also available to determine the corrosive power, i.e. the severity of
the conditions faced by the structure; these measurements generally concern the
corrosive medium, but measurements may also be taken with galvanic probes.
These two types of monitoring provide instantaneous corrosion data, either directly on
the phenomenon or indirectly, i.e based on the potential risks. Although some electrochemi-
cal methods are essentially qualitative, they are nevertheless valuable to identify the active
corrosion mechanisms, especially in case of local attack.
Some techniques also provide quantitative corrosion measurements based on property-
induced variations (weight loss, electrical resistance), but only cumulatively; as a result,
they can only be used to monitor damage over a relatively long period, since the corrosion
intensity can only be appreciated through the rate of variation of the variable recorded or in
reference to a previous value.
The second section describes the methods used for inspection and, in particular, tools
belonging to the family of non-destructive methods. A subsection will be dedicated to pipe-
line inspection, a very special activity due to the use of pigging. The last subsection will deal
with Risk-Based Inspection (RBI).
2.3.2 Corrosion control methods

This category includes all the techniques which do not necessarily require shutdown of the
installations concerned (even if this may be the case), as opposed to inspection methods
which, by definition, are employed during scheduled shutdowns.
We will make a distinction between direct methods, used to detect corrosion as it is actu-
ally happening, and indirect methods generally based on the cumulative effects of corrosion,
either due to modification of a property (weight, electrical resistance) or of an induced con-

sequence (e.g. hydrogen production).
In the first case, corrosion intensity can be monitored in real time and expressed as a cor-
rosion rate, provided that prior calibration has been carried out. This is essentially the case
with electrochemical methods, which take direct measurements of the electronic transfer
responsible for metal consumption: they will be discussed in paragraph 2.3.2.2 on direct
methods.
The response time of cumulative methods is much longer, since the property concerned
must be modified sufficiently with respect to the accuracy of the sensors used. Conse-
quently, the measurement taken is necessarily an average, which means that trends can be
monitored but not short-term effects, induced for example by occasional modification of the
installation operating conditions.
2.3.2.1 Indirect methods
A. Corrosion coupons [ 189; 2 171

This is the oldest and most widely used method of monitoring corrosion in industrial instal-
lations. In the petroleum industry, it is still the basic tool to evaluate corrosion for all acces-
sible equipment. The principle, which is extremely simple, consists in placing coupons made
from the same alloy as the equipment in contact with the aggressive medium (as a compari-
son, coupons made from more or less resistant alloys can also be inserted). The coupons are
inserted for a specific period, typically several months, after which they are removed and
examined. They are generally inserted on simple devices (Figures 2.9 and 2. lo), with the
following considerations:
- firstly the need to access the chosen location, which may involve adapting the installa-
tion (e.g. a special flange),

- secondly, the need to minimise the impact on operation of the installation and on the
corrosion phenomenon itself, especially by galvanic coupling or geometric confine-

ment problems.
Spacers Nut and

f , Coupons / lock nut
Figure 2.9
Example of corrosion coupon rack [ 1591.
+ I 1-1
Figure 2.10
Example of Dutchman corrosion coupon rack [159].
An equivalent uniform corrosion rate can then be calculated from the sample weight
loss, using a simple analytical formula:
V = - (K . AM/(p . S . t))
where: V: corrosion rate (pm/year)
AM: sample weight variation (mg)
p: alloy density (g/cm3)
S: area of the sample exposed to the medium (cm2)
t: exposure duration (h)
K: adimensional coefficient (= 8 . 76 . 106, with the units used for the other terms)
This formula is included in standard ASTM G1-03 [161] which also describes the sam-
ple cleaning and weighing procedures.
Metallographic examination may confirm the presence of uniform corrosion and, other-
wise, reconsider the corrosion rate calculated. Physico-chemical analyses (e.g. X-ray dif-
fraction analyses of the corrosion products, analyses of chemical elements present in the
cracks) are then conducted on the coupons to identify or corroborate the mechanisms
responsible for metal attack.
Some coupons are specifically designed to study certain forms of localised corrosion,
such as crevice or pitting corrosion.
Apart from its simplicity, the main advantage of this technique is the fact that the cou-
pons are highly representative of the installation material, since they can have the same com-
position and metallurgy and even similar surface condition, if necessary. The coupons may
also include portions of welded joints produced using a suitable process.
108 Chapitre 2 Prevention ofcorrosion and degradation of metallic materials
The composition of medium is also the same as that actually seen by the equipment mon-
itored and there is no limitation to its electrical conductivity. In addition, good representa-
tiveness is obtained, both as regards the corrosion deposits and more generally the degrada-
tion process seen by the installation.
There are also numerous restrictions:
- The coupons can only be installed in accessible locations, making them unsuitable for
underwater applications and, unless a removable rack is used, the equipment must be
shut down to remove them;
- The corrosion measurement may be biased not only by localised corrosion but also by
the positioning of the coupons and by the possible effect of disturbing factors such as
multiphase flow, turbulence, and areas of aqueous phase condensation, which may
lead to incorrect interpretations;
- The coupons are unable to indicate changes in corrosion over time; consequently, they
are of no use to solve problems requiring operator reactivity;

- Lastly, due to their small size, corrosion coupons are unable to take into account the
effects of solid-liquid heat transfer, which may bias their behaviour compared with
the more massive metal walls.
Coupons have been developed to evaluate specific types of corrosion. The variants pro-
duced for specific degradation problems include:
- Crevice corrosion coupons: the various geometries available [ 155; 1571 (ASTM G48
and G78) are based on different principles to initiate a crevice (differential aeration,
local pH, anodekathode surface area ratio). The choice must be made in view of the
actual risks involved; coupons used on oil fields are generally installed on electrically-
insulated supports whose geometry is adapted to the equipment (reactor or pipeline:
Figures 2.3.1 and 2.3.2);
- Galvanic corrosion coupons composed of different electrically-coupled metals [ 1561
(ASTM G7 1) with variable anode/cathode surface area ratios; apart from dissolution
of the anode, this type of coupon can be used to study the risk of cathode embrittle-
ment by the hydrogen produced during the corrosion reaction;
- Stress corrosion coupons: the devices used to produce the stress (C-ring, U-bend) are
small and relatively simple so that they remain easy to handle and insert; the drawback,
however, is that failure rarely occurs since the stress tends to relax spontaneously as
corrosion develops, and careful examination is required to detect the cracks.
B. Electrical resistance probes [207; 215; 2 171

These probes monitor metal consumption by measuring the electrical resistance, which
increases as the cross-section of the consumable coupon decreases [265]. These coupons can
provide remote, instantaneous information on corrosion development, upon request [242].
Most of the strong and weak points of this technique are the same as those of traditional cor-
rosion coupons, but since the corrosion rate can be measured, corrosion can be monitored on
a far more regular basis.
The main limitation concerns temperature, which affects electrical resistivity. Compen-
sation is therefore required in case of significant temperature variations.
Provided that this precaution is taken, the technique exhibits relatively good sensitivity,
typically 0.1YOon the thickness variation detected. This accuracy nevertheless remains
insufficient to monitor highly fluctuating corrosion conditions, and electrical resistance
probes must be considered primarily as long-term monitoring tools designed to measure the
cumulative effect of corrosion.
In addition, this type of device requires a power supply, which may represent a signifi-
cant limitation for some applications involving explosion or flammability risks. Anti-defla-
gration devices are necessary in this case, possibly incurring substantial extra costs.
Moreover, the “coupon” is not examined afterwards (since it is consumable) and there-
fore provides no indication on the corrosion mechanism involved: it is therefore essential to
ensure beforehand that the active phenomenon is uniform corrosion, since otherwise the
information collected will be worthless.
The information collected will be highly representative since the coupon is subjected to
the actual process conditions, and the technique imposes few limitations on the electrical
conductivity of the medium (except for highly conducting media such as molten salts or liq-
uid metals). Care must nevertheless be taken to keep the coupon electrically insulated to
avoid problems of galvanic corrosion due to accidental contact with a metallic part.
Although the geometry of the “consumable” part of the electrode may vary, long prod-
ucts suitable for resistivity measurements are often used (wires, tube, thin strip). Numerous
products are available to carry out this type of measurement, to suit the application condi-
tions or specific monitoring requirements. For example, flush probes are used to monitor
corrosion related to thin films in pipes with two-phase flows [162; 1891.
For some applications, where access is difficult or impossible (e.g. deep offshore), sev-
eral probes of different characteristics can be used, some with higher sensitivity, others with
longer lifetime [ 1961.
Despite the disadvantages described above, corrosion measurement by electrical resis-
tance probes is one of the most widely used techniques on oil fields [194].
Different versions, marketed since the mid- 19903, have contributed to this continued
success. The most well-known are:
- FSMTM(Field Signature Method) intended for pipelines [221]: suitable for a wide
range of applications, this method can be used to produce an electric potential map,
while offering the enormous advantage of being non-intrusive [263; 2741. Capable of
operating at temperatures up to 400 “C, its use can be extended to refinery installa-
tions [ 1651. Dedicated software calculates the corrosion rate and produces a 3D pro-
file of the metal loss [ 166; 1671;
- High-sensitivity tools such as the MicrocorTMsystem by Cortest Inc. [215-2171 and
the CEIONTMsystem by Cormon [ 172; 173; 1841, which can calculate corrosion rates
over shorter periods thanks to more advanced electronics. For temperature compensa-
tion, the first system uses a relative measurement (by comparison with a reference
sample), while the second proposes numerical correction.
Research conducted by Li et al. [227] aims at further improving the sensitivity of resis-
tive sensors, in order to install instruments on equipment operating under moderate corrosion
9
conditions. The special geometry of these Thin Film Electrical Resistance (TFER) sensors
involves a highly sophisticated manufacturing process. A secondary advantage of this
increased sensitivity is faster response time than for current products. Lastly, it may be pos-
sible to adapt the method to detection of localised corrosion using a multiple-line pattern
configuration.
C. Chemical analysis [ 189; 242; 2781

Although highly indirect, global and requiring “off line” analyses, this method is worthy of
attention being based on a simple principle. It is relatively easy to implement since no instru-
mentation is required, apart from a sampling valve. It can be used for all types of equipment
containing or conveying aqueous fluid (tanks, transfer lines, treatment units, distillation units,
various utilities, etc.), especially in petrochemical plants and refineries where it is considered
as an additional but valuable technique to obtain semi-quantitative corrosion information.
The principle consists in analysing the metallic ions solubilised in the fluid following
corrosion. In practice, the element considered is nearly always iron, the majority component
in most metal alloys: more reliable results can be obtained since the analyses are conducted
on high content values.
The disadvantage with iron is that precipitates form under certain pH or temperature con-
ditions frequently encountered in the petroleum industry. These precipitates will not be
taken into account in the analysis and the corrosion will be underestimated. Determination
of manganese content has therefore been proposed, especially for applications in the pres-
ence of H2S [233].
The ion content measured is directly proportional to the weight of metal consumed. Con-
sequently, knowing the area of metal affected and provided that there is no other source for
the metallic ion considered, it is theoretically possible to calculate a corrosion rate. The main
application of this technique is more global, however, to monitor corrosion trends, detect
anomalies (sudden variations) or check the efficiency of a protective measure (addition of
inhibitors, coating, etc.)
Samples are sent to the laboratory where a number of analysis methods are available to
determine the metallic ion contents:
- atomic absorption spectroscopy,
- atomic emission spectroscopy, used more and more routinely, in particular ICP-MS
(inductively coupled plasma mass spectroscopy),
- colorimetry, using light absorption by metallic complexes formed using reactants (this
method can also be applied on the field).
This technique has two main limitations: it provides global, essentially qualitative infor-
mation and the corrosion rate estimation is not obtained immediately (time must be allowed
for analysis).
D. Hydrogen probes [ 189; 242; 2651

Dating back to the 1990’s, this non-intrusive technique provides continuous information and
offers a vast potential for petroleum equipment.
Chapitre 2 Prevention of corrosion and degradation ofmetallic materials 111
Its principle is based on the fact that the quantity of hydrogen produced during corrosion
is proportional to the intensity of the reaction and that the hydrogen can be collected and
measured to calculate the corrosion rate.
Hydrogen is generated by the cathodic component of the electrochemical corrosion reac-
tions occurring in non-oxidising acid medium. The method is therefore ideal for sour service
applications (presence of H2S) especially pipelines and pressurised containers.
Since the hydrogen produced penetrates steel rapidly and diffuses easily through the
metallic walls, this property can be used to monitor from the outside the intensity of the cor-
rosion occurring on the inside.
This is not the only configuration since intrusive use is always possible, with in this case
the probe consisting of a thin steel tube, immersed in the medium (or flow). This tube con-
tains a cylindrical rod to form an annular space. Molecular hydrogen, recombined after
atomic diffusion into the tube from the outside, builds up in this annular space, raising the
pressure which can then be measured easily with a sensor. The rate of pressure increase pro-
vides an indication of the corrosion intensity on the outer surface of the tube.
The same pressure measurement principle is applied for non-intrusive use in refining
[190], with in this case a patch being attached to the outer wall of the equipment
(Figure 2.1 1). This patch creates a volume where hydrogen produced by corrosion on the
process side builds up. The method is extremely simple, but the drawback is that the actual
area concerned by the corrosion producing the hydrogen collected is unknown. It is even
possible that this area could change over time (formation or disappearance of corrosion
deposits). The information collected is therefore primarily qualitative: it can be used to
detect substantial modifications in corrosion intensity (change of slope on the pressure
curve) but not to determine a corrosion rate directly.
Figure 2.11
Hydrogen patch probe [ 1901.
Other external hydrogen probes are based on an electrochemical principle to quantify the
hydrogen collected (Figure 2.12). After diffusing through the wall, the hydrogen is quanti-
fied by the intensity of the current required for its oxidation. An electrolytic cell is used (the
electrolyte is an acid solution) fitted with electrodes, one being a stainless steel working
electrode which produces the oxidation current. A sheet of palladium (inert material) is
inserted between the equipment wall and the electrolytic detection cell to normalise the flow
of hydrogen, like the permeation cells used in laboratory (Devanathan type).
Stainless steel electrodes
90% sulfuric acid
pipe wall
Figure 2.12
Diagram of a hydrogen patch probe [190].
This detection technique has a number of limitations:

- temperature limitation, especially for the electrolytic version,
- complexity of the system for this version and limitation inherent to extended use on
equipment in service (reliability, maintenance, infrastructure, cost),
- need for high rate of diffusion into the wall, which rules out the use for austenitic alloys,
- for the quantity detected to be representative of the corrosion intensity, a sufficient pro-
portion of the hydrogen produced by corrosion must penetrate the steel instead of being
released on the inside; this assumes the existence of poisons preventing molecular recom-
bination on the steel surface, which in practice limits its benefit in situations with H2S.
E. Optical sensors
These methods [ 1691 take advantage of the progress made in the field of optical fibres, for
telecommunication applications, and they are worthy of interest since they represent a useful
addition to the range of existing techniques. In addition, they solve many of the electricity
supply problems encountered with traditional methods, a significant advantage for installa-
tions which are remote, difficult to access or subject to special safety constraints (ATEX).
Optical fibres also offer extended lifetime under special conditions (humidity, fluctuating
pressure and temperature) or aggressive conditions (chemical inertia) and good insensitivity
to electromagnetic interference.
These optical methods are all indirect since they detect a consequence of corrosion as
opposed to the actual phenomenon. The property most frequently monitored with optical
fibres is their strain under the effect of corrosion. There are several possible configurations.
Optical fibres, especially Fibre Bragg Gratings (FBG), behave as strain sensors capable of
detecting strain or curvature variations.
Developed by the Canadian company FOX-TEK [235] the system, which consists of a
spiral-wound optical fibre strain gauge attached to the outside of the equipment, can detect
very small wall thickness variations. The system is therefore non-intrusive, a big advantage
for numerous applications, whether in petroleum production (buried pipelines) or refining
installations [235].
The strain is measured with respect to an internal reference not exposed to the aggressive
environment. Development of corrosion can therefore be monitored, provided that tempera-
ture correction is made (for HT processes, limited to about 250 "C) since the thermal expan-
sion of the fibre must be taken into account.
Like all non-distributed control systems, the main disadvantage with this strain gauge is
that it provides local information.
Distributed measurement systems for corrosion detection based on fibre optical measure-
ment are also available [ 174; 224; 2501. They may involve several principles, but the most
widely used consists in coating the fibre with a corrosion-sensitive metallic layer. When the
metallic layer has been corroded away, some of the light injected down the fibre escapes
from the point considered, reducing the intensity of the reflected light. In addition, this point
can be located by analysing the travel time of the light signal.
Another possibility is to use a fibre Bragg grating, stressed by the coating (or plating).
The strain induced is detected when the coating has thinned down or completely disap-
peared. The zone concerned along the fibre can be located.
These systems are used mainly as alarms since, once corrosion has been detected, the
device provides no further information. Since the metallurgy of the material forming the
coating is different from that of the installation, the main problem with this device is that it
could react differently with respect to corrosion.
Warning signals on damage to pipeline networks, in particular the appearance of leaks, can
be obtained by installing distributed optical measurement devices. For example, special coat-
ings (concept proposed by the company Luna Innovations) can be used to detect chemical
species or variations (in humidity or pH for example) around the fibre, located near the pipe.
The company SensorTran has designed a leak location system based on detection of very
slight temperature variations, but the principle still relies on induced strain measurement.
IFP has also developed a system called CODA (Corrosion Optical Detection and Alarm)
[ 1981, which provides a local indication of corrosion progress based on a measurement of
the refractive index of light at the end of the optical fibre. The end of the fibre is placed in a
sealed cavity which is closed by a corrosion coupon. When the coupon disappears or starts
to leak, liquid enters the cavity, causing a sudden change in the local refractive index. The
1 I4 -
change of index can easily be detected by inexpensive, traditional optical measurement

means (laser diode, photo-diode, coupler). The robustness of the concept and its ability to
detect corrosion from a distance of several hundred metres, via the optical fibre, were vali-
dated through an industrial demonstration carried out on large-size equipment.
The system has several limitations: local measurement, intrusive device (contact with the
corrosive medium necessary) and single-use alarm type operation, although the corrosion
coupons can be replaced to a certain extent.
In addition to its simplicity, the associated reliability and low cost, there are numerous
advantages:
- Versatility: suitable for numerous configurations (including a standalone version with
built-in, high-autonomy power supply) and a wide range of equipment, even when
access is difficult;
- Adaptability: the coupon material can be chosen to be fully representative of the
installation, including its metallurgical composition and surface roughness;

- Safety: no electrical components are required near the instrumented equipment;
- Ability to monitor corrosion progress, by installing several sensors with coupons of
different thicknesses (different alarm levels).
F. Acoustic emission (AE) [ 1751

This well-known technique consists in recording and analysing the acoustic signals emitted
by active degradation phenomena, by interpreting them with respect to the cause. Ceramic
piezo-electric sensors are used, which convert the elastic waves received into recordable
electric signals. In principle therefore, this technique would appear highly suited to detection
during service, especially due to its high sensitivity. This is also its main drawback however,
since it is strongly disturbed by all the background phenomena, always abundant in an
industrial environment. This makes it difficult to identify the relevant signals and extract any
information that could be used for preventive monitoring.
Consequently, the technique is not implemented permanently and is mainly reserved for
control and inspection purposes, generally during installation shutdown phases. In this case,
it is often combined with hydraulic or pneumatic testing, during which the external noise
sources can easily be controlled or filtered from the acquired signal [175]. The principle
consists in stressing the equipment and recording the signals emitted by any emissive phe-
nomena, for example crack initiation or propagation. The method is widely used for closed
equipments (storage tanks, pressurised devices) since it is non-intrusive: sensors positioned
on the outer wall record signals emitted by phenomena occurring either on the inside or
within the thickness of the material. The technique can be used not only to detect but also to
locate evolving defects, in order to produce maps of localised corrosion or leaks, for exam-
ple at the bottom of storage tanks. The main emission sources (due to corrosion) are located
by triangulation between several sensors.
In the field of corrosion, Acoustic Emission (AE) is generally employed as an external
preinspection method intended for equipment which are difficult to open or dismantle, such
as storage tanks or process units [ 1831. In the latter case, installations are not shut down sys-
tematically, provided that the relevant signal can be extracted from the background noise.
Next Page
Chapitre 2 Prevention of corrosion and degradation ofmetallic materials 115
Higher frequency sensors can be used to identify the signal due to corrosion, but their range
remains limited to a maximum of about 1 metre.
Although acoustic emission is primarily used for inspection, it can also provide warnings
of active corrosion [249] - including localised corrosion (pitting, crack) - and may be
included in an integrated monitoring approach as a tool for early detection of corrosion [ 1771.
G. Measurement of factors leading to corrosion

Instead of monitoring the progress of corrosion through its effects, one method widely used
in the petroleum industry for aqueous medium consists in measuring the factors promoting
corrosion, especially the corrosivity of the solution in contact with the equipment [242].
Measurements can be taken on samples, as with chemical analysis described above: they
should preferably be taken on line, not only to obtain a fast measurement but also and above
all to avoid disturbing the medium.
Measurement of temperature is also important since the processes responsible for corro-
sion are thermally activated. This is also true for pressure which has a major impact on the
acidity of process aqueous solutions. Pressure affects the pH via solubilisation of acid gases
such as C02 and H2S, present at sometimes high concentrations in oil and gas products. The
contentration of these gases depends on the origin of the crudes and the treatments carried
out to eliminate them: it is therefore especially critical for equipment located upstream (on
oil and gas fields, well equipment, petroleum pipes, processing units) where these gases are
in contact with production water. Probes capable of operating under severe conditions of
temperature (100 "C or more) and pressure (up to several tens of bars) are available for
continuous pH measurement. When the conditions are too severe, sampling remains a valid
solution. In this case, the pH measurement is corrected using formulae based on thermody-
namic equilibria: pH = f (T, P, % C02, % H2S).
Salinity and oxygen content are also important parameters when determining corrosion
risks, especially for passivable alloys such as stainless steels. The stability of protective pas-
sive layers composed of oxides is sensitive to the presence of chlorides and to the electro-
chemical nature of the medium (reducing or oxidising).
With pipes, the erosive action of the fluids transported must also be taken into account.
This effect, which increases with the rate of flow, amplifies the corrosion risks due to two
mechanisms (see also paragraph 3.3.7):
- synergy between chemical and mechanical effects, during the corrosion process,
~ degradation of the protective layers formed by corrosion, since some deposits may
provide good protection.
This is particularly important for materials protected by a passive layer or by coatings
since, once this protective surface layer has been eliminated, consumption or perforation of the
wall may occur rapidly in some critical zones which are subjected to high forces by the fluids
(bends, nozzles, regions of turbulence). Pressure sensors or flow sensors measuring the fluid
speed or flow rate should therefore be positioned in the immediate vicinity of these zones.
These measures are all relatively straightforward to implement and the data produced
can be read immediately, allowing action to be taken rapidly in case of potential problem. In
Previous Page
addition, numerous suppliers offer a wide range of systems with advanced post-processing
and recording functions.
The main difficulty when using these techniques is the required knowledge of the corro-
sion mechanism involved and of its quantitative consequences on the degradation of the
materials selected [277]. It is in fact essential to identify the potential phenomena before-
hand and, for the alloys concerned, define the operating window to be applied with respect
to the parameters measured. Short of complete immunity, which is always difficult to guar-
antee, a prediction model using the history of the corrosivity factors is required, in order to
obtain a conservative estimation of the corrosion generated.
In conclusion, note that some of the above parameters determining corrosion severity
(temperature, flow rate) are directly related to the processes and therefore controlled by the
operators, even though there is generally little freedom for adjustment. Other parameters are
only impacted by the operating conditions and a thorough knowledge of the relations
between these two parameter families may act as a basis for mutual alarms. A drop in pH for
example could result from - or equally well be responsible for - a malfunction (incorrect
process regulation) or a sign of damage.
2.3.2.2 Direct methods

Direct methods are intended to detect, and generally monitor, corrosion as such and not one
of its symptoms. We will not discuss high temperature corrosion (oxidation, carburisation,
sulfurisation, etc.) here, since to our knowledge, very few methods of this type are adapted to
these conditions. Indirect methods are therefore used in this case, such as corrosion coupons,
acoustic emission recording and wall thinning monitoring by a suitable control method.
Direct methods to monitor low- or medium-temperature corrosion in the presence of an
electrolyte are available. In this case, the degradation mechanism is based on electronic
transfer and so, electrochemical methods are used to measure these exchanges.
The main techniques in this category will therefore be described below, some providing
quantitative information on the corrosion rate and on its variation over time. The shortcom-
ing with these methods is that they all require a sufficiently conducting medium.
A. Corrosion potential measurement [ 1891

In a given medium, the simplest measurement consists in recording the corrosion potential,
i.e. the potential difference between the installation material and a reference electrode. This
corrosion potential measurement can be used to quantify the risk of corrosive attack by locat-
ing the structure concerned with respect to domains of electrochemical activity or immunity.
The principle, which consists in maintaining a metallic part in an immunity domain by adjust-
ing its electrochemicalpotential, forms in fact the very basis of cathodic protection.
Although less widespread in practice than the polarisation methods described below,
measurement of potential is extremely useful to detect the transition of a material from pas-
sive to active state in a changing environment. For instance, the passive layer of stainless
steels may be destabilised by the presence of chlorides or reducing elements. In this case, the
material becomes reactive, according to Pourbaix diagrams (potential-pH diagrams
9 117
discussed in paragraph 3.2.3.5), and starts to corrode. Pourbaix diagrams, in conjunction

with potential-pH values, can be used to predict immediately whether corrosion is likely to
occur. Drawn up for a large number of alloys using thermodynamic equilibria between
oxides and ionic species [247], these diagrams provide no information on corrosion kinetics.
In addition, the temperature must also be specified since they depend on this parameter.
Integrated electrode systems have been designed to monitor the potential of a structure with
respect to a reference electrode and to follow at the same time the pH of the medium. However
these systems are still limited by their ability to withstand the environmental conditions.
B. Galvanic probe [ 18 1; 182; 2201

This technique is based on the principle of the electric cell, since it consists in monitoring
the amount of current flowing between two electrodes immersed in a known electrolyte.
This measurement determines essentially the corrosivity of the medium and its evolution
over time. However, if the anode is made from the same alloy as the structure of interest,
then an estimation of the degree of corrosion can be determined. In this case, the probe must
be positioned near the structure so that it is exposed to conditions representative of those
prevailing on the surface of the equipment. In addition, if a deposit is formed, modification
of the active surface changes the conditions for the corrosion rate calculation conditions
(true area ratio different from initial ratio).
Apart from coupons, this is the simplest method available to monitor corrosion. Probes
have a fast response time, from a few seconds to a few minutes and are now highly sensitive
thanks to Zero Resistance Ammetry (ZRA) technology. ZRA uses a current-to-voltage con-
verter in order to eliminate the effects of resistance perturbations. By doing so, it provides a
voltage output strictly proportional to the current flowing between the electrodes. Very weak
phenomena can therefore be recorded.
Apart from being intrusive, the main disadvantage of this system is that it is disturbed by
external phenomena affecting the current measured, independently of corrosion (temperature,
electrolyte conductivity, etc). It is therefore difficult to obtain reliable quantitative informa-
tion on the corrosion rate. Consequently its main purpose is more to detect the presence of
corrosion and, in this respect, it provides excellent results, including for localised corrosion.
C. Electrochemical polarisation [ 189; 2651

Unlike the simple measurement of potential, polarisation studies can be used to characterise
a material-medium pair by scanning the current-potential (i-E) domain. Different versions
are available, depending on how the following two parameters are imposed or varied:
- potentiostatic: potential kept constant, evolution of the corrosion current,
- galvanostatic: current imposed, potential recorded,
- potentiodynamic or galvanodynamic: the curve i = f(E) is plotted while varying one of
the parameters and recording the other; this current or potential scanning can be car-
ried out at constant speed or in stages.
The complete curve, produced by backward and forward scanning, can be used to deter-
mine parameters which are characteristic of the alloy behaviour in the environment studied:
corrosion potential, pitting potential, repassivation potential, transpassivity domain. This
118 Chapitre 2 Prevention of corrosion und degradation of metallic materials
method is frequently used to characterise the behaviour of stainless steels with respect to
localised attacks.
Although they are sometimes used on equipment in service, the variants of this method-
ology are mainly intended for laboratory studies, since by nature they are unsuitable for
monitoring real structures. Not only is this technique intrinsically “not passive”, but in addi-
tion the material must be brought, even temporarily, under effective conditions of corrosion,
which is always a risk. The high currents or potentials applied may also irreversibly modify
the material-medium interface, by polarising the metal, which biases the measurement and
involves frequent replacement of the electrode.
Electrochemical polarisation is mainly useful to provide complete information about the
“corrosion system” under study and in this respect it should be considered more as a control
method. Regular recording of the current-potential curve can detect a change in the above charac-
teristic potentials, which would indicate a modification of the conditions imposed on the equip-
ment: temperature, composition of the medium, etc. Like most electrochemical methods, its
primary function is therefore to monitor the corrosivity of the medium with respect to the alloy.
For example, it represents a means of checking the efficiency of a chemical inhibition treatment.
D. Linear Polarisation Resistance (LPR) measurement

The LPR technique provides a fast, accurate estimation of the instantaneous rate for uniform
corrosion [267]. It is therefore perfectly adapted to routine monitoring of installations exposed
to corrosion, and to the prevention actions deployed, such as for example injection of inhibi-
tors whose efficiency can be measured rapidly. It can be implemented in the petroleum indus-
try in sufficiently conducting multiphase systems (i.e with low hydrocarbon content). There-
fore, to obtain a reliable measurement it is important to prevent fouling of the electrodes,
which is not always possible when crude oil is present. Consequently, this technique is mainly
reserved for aqueous electrolytic environments: cooling systems, various utilities [242].
The linear polarisation resistance method consists in applying to the metal very small volt-
age variations (typically less than 30 mV) above and below its rest potential. Over this narrow
range in the vicinity of the rest potential the current response obtained is linear. The polarisa-
tion resistance (Rp), defined as the slope of this current-potential curve, is therefore constant.
Moreover, according to the Stern-Geary equation [272], Rp is inversely proportional to the
instantaneous corrosion rate, at least under certain conditions: unique anodic and cathodic
reactions, both respecting a simple activation model, stable corrosion potential, negligible
electrolyte resistance. The latter condition is critical to avoid underestimating the corrosion
rate, due to neglecting the IR drop in the solution. To avoid this problem, a device combining
LPR with a current-interrupted galvanostatic polarisation method has been proposed [23 11.
Rp = B/ico, with B = (p,pc/2.3(p, + p,))
where i,,, is the corrosion current and pa and pc the Tafel coefficients, discussed in
paragraph 3.2.3.6
The device consists of three electrodes [ 1891 (Figure 2.13); [220]:
- the working electrode made from the material concerned (same as the equipment to be
monitored),
9 1 I9
- an inert counter-electrode to transfer the current to the electrolyte,

~ a reference electrode to measure the potential of the working electrode.
Being intrusive to allow exposition to the real corrosion medium, it is installed using
adapter flanges. Numerous commercial devices are available, equipped with adapted and
automatable acquisition systems, to which alarm systems can be added in case of excessive
corrosion rate. The measurement quality largely depends on the quality of the associated
measurement electronics.
Figure 2.13
Typical polarisation resistance measurement probe a) general configuration
b) installation in a pipe connection fitting c) installation in a welded line
d) installation in a pipe T [ 1891.
E. Harmonic Distortion Analysis (HDA)

This is an improved version of the previous method, providing more accurate determination
of the uniform corrosion rate [ 1951. The electrode system is essentially the same, the only
differences being the shape of the current perturbations applied and analysis of the signals
recovered, which involves more complex mathematical processing.
A low-frequency sinusoidal current is applied to the electrodes and the effective instanta-
neous resistance of the solution (Rs) is determined by harmonic analysis of the retrieved sig-
nal. This resistance is used to calculate the true value of coefficient B, involved in the Stem-
9
Geary equation. A more accurate corrosion rate can therefore be calculated using the polari-
sation resistance Rp, as measured by LPR. These two complementary methods are generally
combined in modem control equipments.
The accuracy provided by the HDA method is particularly interesting in the context of
process control and equipment management.
Inter-Modulation Distortion (IMD), a variant of the HDA method, is also worth mention-
ing: it consists in polarising the system by injecting a composite current, formed by superim-
posing two sinusoidal signals. Analysis of the current response provides a direct estimation
of the corrosion current and of the Tafel slope coefficients. IMD requires less in-depth signal
frequency analysis than HDA (limited to the second harmonic). It can only be applied, how-
ever, if the coefficients of the anodic and cathodic parts are different; this method has not yet
reached the stage of experimentation on site.
F. Electrochemical Impedance Spectroscopy (EIS)

This technique is also known as the “AC impedance measurement”. Its main use is found in
laboratories due to sometimes lengthy acquisition conditions and also because interpreting the
records requires a certain degree of skill which is not always available on industrial sites [ 1891.
From the electrochemical point of view, EIS can be considered as an extension of the
methods mentioned above (LPR, HDA) and in fact uses the same type of sensors (system
with two or three electrodes). The main difference is that it is a spectroscopic method, which
consists in recording the electrical response of the system of electrodes when subjected to
variable current excitations [242]. The electrochemical measurement is taken by injecting a
variable frequency AC signal. This frequency scanning is carried out discontinuously (in
stages at predetermined values) over a wide range, typically 7 or 8 decades. Acquisition
times for low-frequency measurements are very long, sometimes even prohibitive in prac-
tice. The measurement mode is either potentiostatic or galvanostatic.
The recorded response is converted into electrical resistance and is expressed by separat-
ing the resistive component (real part) from the capacitive component (imaginary part). This
signal is then plotted according to traditional complex number representations, i.e. Nyquist
or Bode diagrams (Figure 2.14). Some phenomena or types of behaviour stand out more
clearly on these representations.
The main advantage of EIS is that it can be used to analyse corrosion mechanisms or to
identify the behaviour of subassemblies on relatively advanced systems. This is the case in
particular of coated structures for which the behaviour of the substrate, the coating, their
interface and the electrolyte, if any, can be identified individually. Measurement is still pos-
sible even if the electrolyte conductivity is low, which is an intrinsic advantage compared
with the DC methods [185]. Due to its ability to work on very poorly conducting media, this
method is highly suited to studying painted structures and coatings. It can be used to monitor
their degradation through impedance parameters, characterise their protective nature and
monitor the phenomena occurring underneath them: accumulation of species which have
diffused through them, formation of substrate reaction products, etc. [220].
EIS is also frequently used to evaluate the corrosion rate [ 1941. The charge transfer resis-
tance value, assimilated to the polarisation resistance Rp, is extracted from the Nyquist
G
2
8
6.0~10'
4 . 0 ~10'
1 10 OOO Hz
j o 0
lo o o o
looHz
0.0
100 OOO Hz
I I I I
\y O
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O
",plHZ,
0.0 2.0~10' 4.0~10' 6.0~10' 8.0~10' 1 . 0 ~ 1 0 ~1 . 2 ~ 1 0 ~ 1 . 4 ~ 1 0 ~
Real part/Q
Q)
20 g
40
sg:
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u)
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n
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100
l m 10m 100m 1 10 100 1k 10k 100k 1M 10M
FrequencyIHz
Figure 2.14
Representation of impedance as a) Nyquist and b) Bode diagram.
diagram and the corrosion current is then predicted, as with the LPR method. In view of the
time required for the measurement (at least several tens of minutes), use of EIS is only justi-
fied for a very poorly conducting medium.
G. Electrochemical Noise
This technique refers to an entirely passive methodology, which consists in recording only
the spontaneous fluctuations in potential (EPN) and current (ECN) generated by corrosion at
the metal-electrolyte interface of a three-electrode system [266]. This combination of two
quantities is advantageous since it provides complementary data:
- variations in potential provide information on the thermodynamic equilibrium of the

system with respect to the corrosion risk (regions of the Pourbaix diagram),
- fluctuations in corrosion current provide information on corrosion kinetics, even if
kinetics is never used as such in process control due to the fact that other methods
such as LPR are more appropriate.
In addition, frequential analysis of the signals provides indications on the active type of
corrosion, by making in particular a distinction between uniform corrosion and localised
corrosion (pitting, SCC). EN is more suited for localised corrosion, since the severity of the
attack can be evaluated by examining certain parameters such as the number or the form of
the transient phenomena recorded.
Furthermore, a pitting factor can be calculated automatically by simple statistical analy-
sis of the current records. This factor is defined as the integral over a given time of the ratio
between the standard deviation of the corrosion current fluctuations and the mean value of
this current.
The three-electrodes measurement system which is generally used, consists of two iden-
tical working electrodes and a reference electrode. In control applications in the field, a
metallic reference pseudo-electrode, identical to the other two and made from the alloy to be
evaluated, is used for practical reasons [195] [199; 230; 237; 2831.
Like LPR and HDA, electrochemical noise is an on-line real-time corrosion monitoring
technique powerful enough to be integrated in a process control system [2 121.
Due to the difficulty in interpreting the signals and to the calibration problems, however,
the results of measurements taken on site remain essentially qualitative. EN must therefore
be considered as a complementary method, which skilled operators can use to identify signs
of localised attack (destabilisation of the metallic surface) from the mass of data collected.
Other advantages include the fact that since no current is injected (the metal is at the free
corrosion potential), EN is insensitive to the artificial polarisation effects of the electrodes,
observed with other electrochemical methods. This aspect also represents a safety factor for
installations sensitive to electrical risks.
Lastly, EN allows corrosion detection in low-conductivity media and real-time monitor-
ing of the process [2 181.
Its main disadvantages and limitations include:
- weakness of the signals recorded, creating the need for high-sensitivity equipment,
- difficulty in signal interpretation, requiring sophisticated algorithms to extract mea-
ningful information from the records. Progress has been made, however, especially to
detect crevice and corrosion problems under deposit [264].
In conclusion, measurement of electrochemical noise is an interesting method since vir-
tually no other technique is capable of providing the same type of information. Its operating
conditions are difficult to transpose from one item of equipment to another and the data
acquired must be considered with caution. It nevertheless remains a powerful tool to detect
the appearance of localised corrosion, even though the data is more expressed as a risk
(increased probability, favourable conditions) than as the direct and quantitative sign of cor-
rosion. Its fast response time allows correlation with operating variables of the equipped
installation [237; 2791, which is extremely useful for active monitoring of the corrosion pro-
cess under industrial conditions.
H. Multi-array sensors (MAS)

A system comprising several electrodes, coupled together via an external circuit in order to
keep them at the same potential and arranged as a regular geometric network, is known as a
Coupled Multielectrode Array Sensor (CMAS) [284]. Figure 2.15 shows some examples of
CMAS probes which can be installed on all types of installation, like the electrode systems
used for the other electrochemical control methods.
Figure 2.15
Multielectrode array sensors [284].
The main advantage of this technique is that it allows real-time localised corrosion mon-
itoring, according to a measurement principle which consists in recording the potential dif-
ferences between the anodic parts and the cathodic parts of the metallic surface [284]. A
multichannel recorder and extremely sensitive measuring instruments are required to detect
very low potential drops, corresponding to corrosion currents as low as lo-'* Amperes. A
single corrosion current can be determined from the information collected using the multi-
electrode sensor, either by only considering the most anodic current or by applying more
complex statistical rules. The more or less heterogeneous nature of corrosion on the sensor
surface can also be found: it is quantified by the ratio between the maximum corrosion rate
and the mean rate (these rates are themselves calculated from the currents measured). Given
certain assumptions, it may even be possible to calculate a penetration rate of localised
attacks.
In the petroleum industry, the main advantage of this technique is that it operates in oil-
water mixtures and in solutions containing H2S. Although generally used in pipes and tanks,
it is a potentially useful tool for a wide range of applications since, unlike the other electro-
chemical methods, the electrodes do not have to be immersed in an electrolyte [ 2 8 5 ] . It can
also be used to measure corrosion in wet gases, salt deposits, corrosion deposits and bacte-
rial films, as well as under coatings. Although the electrodes can be manufactured from
more or less noble alloys, most of the applications mentioned concern carbon steels. It can
also be applied in severe environments with high temperatures or pressures.
This monitoring technique is therefore extremely interesting since it provides a great

deal of information and can be adapted to numerous situations, especially phenomena gener-
ating very low currents [244; 2751. It is not devoid of limitations, however.
Firstly, due to its operating principle (all cathodic reactions must be referred to the most
anodic site), the method underestimates the true corrosion rate of the metal and the solutions
proposed to overcome this effect are still far from being satisfactory.
As with other techniques based on measurement of extremely low currents, the equip-
ment is complex and considerable care is required during implementation to avoid external
disturbance and background noise. In the special case of MAS, installation is made difficult
due to the number and small size of the electrodes as well as the numerous possible sources
of artefacts. Even the advocates of the technique agree that formation of crevices at the elec-
trode-insulation interfaces is a problem which may disturb the phenomena and bias the
results in case of corrosion-resistant alloys.
1. Probes dedicated to bacterial corrosion

Bacterial activity is a critical issue in media exposed to natural water, whether fresh water or
seawater: water injection circuits, cooling circuits, offshore structures, buried pipes. While
microorganisms may be responsible for fouling, due to formation of biofilms on the walls,
they also cause various types of damage due to corrosive attack. This type of corrosion
alone, known as Microbial Induced Corrosion (MIC) or biocorrosion, would be responsible
for 5% to 10% of the corrosion-related costs: its mechanisms and main prevention methods
were discussed in paragraphs 1.5 and 3.4 of this book. However, it is worth mentioning here
some systems which are classified as electrochemical methods but are specifically dedicated
to this type of attack.
In the search for solutions to detect and monitor bacterial corrosion, one particular inte-
grative approach [2 111 uses a combination of several electrochemical methods. We will
restrict ourselves to two examples describing studies which also adopt a quantification
approach, but are based on special and novel technologies:
a. Development of sensors to detect biofilms and the corrosive risk [ 197; 2801
Detection is obtained using a gold electrode on which biofilm development occurs. Modifi-
cation of the interface potential or of the mass transfer is recorded by considering the limit-
ing diffusion current.
Corrosion is evaluated with a system composed of concentric electrodes made from the
material under investigation. After artificially initiating pitting by applying an external cur-
rent, the risk of microbial corrosion is determined by analysing the coupling current flowing
between the short-circuited electrodes.
b. Development ofa field instrument, known as CFG MIC Sensop
This instrument (Figure 2.16) has more or less the same objectives: real-time indication of
microbial flora density and in situ monitoring of corrosion under biofilm.
Intended for carbon steel equipment, this system is used to check the efficiency of bio-
cide-base treatments. Its principle is the same as that of an electrochemical cell, where the
development of corrosion artificially initiated on a small anode is observed. Two versions

are available: single-electrode when the pipe acts as a cathode, dual-electrode for pipelines
under cathodic protection.
The strong points put forward are ease of.installation and the entire peripheral logistics,
configured for field use: remote control and data acquisition, ATEX version, integrated
post-processing, relatively high energy autonomy.
For petroleum applications, its main disadvantage could be the probe becoming clogged
due to the presence of crudes.
Figure 2.16
CFG MIC Sensor@.
2.3.3 Detection and inspection methods

The techniques and methodologies described in this section are all implemented when the
installations concerned are shut down. These preventive interventions designed to protect
both personnel and equipment also aim at optimising maintenance budgets (repairs, replace-
ments) through planning. Consequently, they fall in the category of preventive maintenance
policies set up by operators and carried out during scheduled shutdowns, at a minimum fre-
quency generally defined by regulations.
2.3.3.1 Non-destructivetesting methods [ 163; 175; 189; 242; 2651

These techniques are generally carried out to inspect metal parts in order to assess their
overall integrity and evaluate their ability to perform their function. Despite specificities,
most are well suited to the detection of corrosion phenomena and their physical symptoms:
loss of thickness, cracks, crevices. Since the parts under investigation are neither destroyed
nor even partially altered by control, they do not have to be replaced when they exhibit no
critical anomaly. A good knowledge of the phenomena involved is required to evaluate this
criticality when reading the results, especially as regards the harmfulness of defects and their
evolution kinetics.
126 Chapitre 2 Prevention ofcorrosion and degradation of metallic materials
For the various techniques described, we will simply mention their main characteristics,
conditions of use, advantages and limitations.
A. Liquid penetrant inspection

This technique is applied to parts of the equipment that are easy to access. It consists in
revealing surface-breaking flaws difficult to detect by simple visual examination. The sur-
face to be inspected is covered by liquid dye capable of penetrating into the very fine flaws.
After rinsing off the excess, the dye within the flaws is drawn to the surface by applying a
developer. Very fine flaws can therefore be made visible, if necessary by observing the part
under suitable lighting ( e g ultraviolet).
Liquid penetrant inspection is easy to implement, requires little equipment, is inexpen-
sive and can be used to inspect large surfaces quickly, while providing precise information
on the location and length of the flaws. It can therefore be performed under all circum-
stances on a wide range of parts, including those of complex shape. Observation is carried
out directly on the part and not on an intermediate support, which simplifies inspection and
reduces delays, even though thorough inspection is still required to ensure that all the flaws
are detected.
Drawbacks include the fact that only surface-breaking flaws can be detected and, even
for them, the depth information is highly indirect: the “volume” of the flaw, and therefore its
depth, can only be assessed by the area of the visual indication on the surface, making inter-
pretation difficult. In the field of corrosion, this technique reveals only fine, localised flaws
(pitting, exfoliations, intergranular corrosion) and cannot detect loss of thickness by uniform
corrosion. In addition, the surfaces must be cleaned thoroughly before applying the pene-
trant, which may prove difficult or even impossible in the presence of adherent corrosion
products whose porosity would distort the result. The surface condition of the metal may
also bias the observation result, making the interpretation more subjective. Liquid penetrant
inspection is therefore primarily considered as a pure detection method providing little
quantitative information and which must be associated with other techniques.
B. Borescope
Rather than a technique on its own, it must be considered as a visual inspection aid for inac-
cessible areas. Depending on the equipment investigated, it may not be possible to examine
the surfaces exposed to corrosion, especially internal surfaces. Dismantling cannot always
be considered for technical or financial reasons and, in this case, the borescope is a valuable
tool. Consisting of an optical fibre and lenses which reproduce an image of the surface at its
tip, this tool allows fast inspection of areas which are inaccessible by other means. Bores-
copes are available in different diameters (between 6 mm and 13 mm) and different lengths,
some being up to 2 metres long. The tip is more or less sophisticated in order to provide an
image with different directions of view with respect to the optical fibre axis: forward,
oblique, 90” and even backwards. A lighting device may also be fitted to illuminate the area
inspected.
Like all visual inspection methods, the borescope allows only surface examination.
Image quality is not as good as with direct access and considerable skill is required to obtain
good interpretation. Lastly, sufficient access points should be planned right from the design
stage and carefully distributed to allow access to zones considered as sensitive. This is not
always possible due to size or configuration constraints, however, and in particular old
devices do not have borescope access points.
C. Magnetic inspection methods

We will discuss in turn magnetoscopy and eddy currents, bearing in mind that Magnetic
Flux Leakage (MFL) is described in paragraph 2.3.3.2 dedicated to intelligent pigs.
a. Magnetoscopy
Magnetoscopy is able to detect surface or near-surface defects. The part inspected is covered
with magnetic particles, or with a fluid containing these particles, then subjected to a mag-
netic field, wholly or partially. The magnetic fluid then builds up at the defects or around
surface defects, producing a more visible indication. Since this is a visual method, it can be
combined with special lighting or the borescope technique mentioned previously.
Applied mainly in petrochemistry for detection of cracks, this technique can also be used
to perform inspections under water, e.g. inspection of offshore structures and subsea pipe-
lines. Implementation is more difficult in this case, however, especially since surface prepa-
ration such as grinding is often required to allow efficient detection.
The main limitation of magnetoscopy is that the equipment must be made from a ferro-
magnetic material, which excludes the austenitic alloys frequently found in petroleum appli-
cations subject to corrosion.
The sensitivity of the method depends on the orientation of the defects with respect to the
direction of the field lines. Moreover, the distance of the defect from the surface may also
affect the detection sensitivity. The method remains largely qualitative as regards estimating
the size of defects with respect to depth.
b. Eddy currents
The physical principle on which this technique is based is slightly more complex (more indi-
rect) than magnetoscopy. Although different and requiring another type of instrument, the
symptoms of the defects are as easy to detect. Once again, a strong magnetic field is applied to
the part under investigation. This time however the field is variable, inducing currents which
are in phase opposition in two adjacent sections of the material. A defect, located in front of
one of the coils creates an imbalance between the two currents, thereby revealing its presence.
Due to the physical principle involved, the technique is restricted to electrical conduc-
tors, a minor constraint for corrosion monitoring. Not all metals exhibit the same conductiv-
ity, however, which has an impact on the type and quality of the result. The response mea-
sured in the field must therefore be compared with a reference made from the same alloy.
The eddy current measurement technique is suitable for cylindrical and very long parts,
such as pipes and nozzles. With parts of more complex shape, however, implementation is
difficult and the results are harder to interpret. This is partly explained by skin effects, limit-
ing the maximum depth that can be examined, and the fact that detection sensitivity largely
depends on the distance between the coil and the surface of the part.
128 -
Chapitre 2 Prevention ofcorrosion and degradation ofmetallic materials
Due to its global nature, the method cannot be used to identify which side of the metal is
affected by the defects, but the side exposed to corrosive conditions is generally known.
Nonetheless, the method can operate through insulation parts, a major advantage for petro-
chemical and refining equipment. In this case, its main purpose is to detect uniform attacks.
Operating across a large temperature range (up to 500 "C), it may also be used on equipment
in service with no need to wait for complete cooling.
One of the main problems with this technique is that the interpretation of signals for
flaws characterisation is difficult, and it is even harder to extract quantitative information.
As part of routine monitoring, however, and provided that the operating conditions are
highly reproducible (as well as the conditions ensuring good detection sensitivity), eddy cur-
rent inspection represents an efficient way of checking that no defects have appeared
between two inspections.
D. Ultrasonic inspection
This technique is further discussed in the paragraph dedicated to intelligent pigs for pipe-
lines (paragraph 2.3.3.2), which presents its advantages and drawbacks.
The method consists in sending high frequency (20 kHz to 15 MHz) ultrasound waves
- mechanical vibrations, unlike light or x-rays - emitted by a piezoelectric transducer
through the thickness of the part. There are volume waves, which have either longitudinal
mode or transverse mode, and guided waves (Rayleigh or Lamb waves). Guided wave ultra-
sonic inspection is a fast global inspection technique for tubular structures [ 1751.
The detection principle of volume waves is as follows. When there is a discontinuity in
the wave path, part of the energy is reflected back from the sides of the flaw. The reflected
signal is then converted into an electrical signal by the transducer. Information concerning the
location and, depending on their orientation, the size of flaws such as plane cracks can be
determined. The same principle can also be used to measure wall thicknesses, and therefore
thinning by corrosion, via the travel time of the signal which is reflected by the opposite side.
Ultrasonic inspection can detect flaws throughout the volume of the metal intercepted
and provides quantitative information which is interpreted and then compared with generally
standardised acceptability criteria. The method is extremely sensitive to the relative orienta-
tion of the flaws and to the incident ultrasonic beam. It can be used at temperatures up to the
operating limits of the piezoelectric sensors.
Finally, note that contactless alternatives have been developed to avoid the need for a
coupling medium between the transducer and the part: with electromagnetic coupling, using
eddy currents, or with aerial coupling, involving low-frequency signals.
E. Imaging techniques
These methods are based on different physical principles which we will now discuss.
a. Radiographic imaging
The detection of flaws is based on the difference in photonic absorption of X- or y-rays by
comparison with the material. The projected image of the defects is formed on a film placed on
the side of the part opposite the source. The source determines the type of radiation: X-rays are
created by a high-voltage generator, y-rays by a radioactive isotope such as iridium 192. Isoto-
pic sources are easier to transport, being more compact, and therefore more adapted for use on
site. The type of source chosen depends more on the thickness to be inspected, however.
The method offers very good geometric resolution and an excellent detection capacity at
depths of up to several centimetres. For corrosion monitoring on industrial installations, radi-
ography involves little special preparation, such as for example removing the pipe insulation.
It is therefore frequently used for inspection on sites, although there are numerous drawbacks:
- no indication as to the depth of the defect, unless images can be obtained from several
different angles,
- image interpretation requiring special expertise,
- relatively high cost due to the sources, the consumables and the difficult operating
conditions,
- delay required to develop the films after exposure,
- safety issue for operators, imposing very strict execution procedures.
The recent emergence of digital radiography has partly solved the last three points by
introducing reusable supports requiring low exposure times and consequently reducing the
radiation doses necessary.
b. Ultrasonic imaging
Application of this technique has led to the development of the Time-Of-Flight Diffraction
(TOFD) method, based on the interaction of the ultrasonic waves with the contours of the
physical discontinuities inside the metal part (edges or ends). A large volume is covered due
to the divergent incident beam and to the wide-aperture sensors. The entire thickness of parts
can therefore be inspected in a single scan, leading to time savings. In addition, the results
are obtained in real time, even if a digital reconstruction is then required to produce the
images (B-scan, C-scan).
TOFD can detect and size fine flaws such as cracks, whether or not surface-breaking,
and can be used for in-service inspection. It may sometimes be used as an alternative to radi-
ography, but the quality of the results obtained is largely dependent on the operating condi-
tions, especially the quality of coupling with the metallic surface inspected.
One major advantage of the method is that, under certain conditions, flaws can be moni-
tored over time, especially those due to corrosion. This can be achieved by comparing
images, ensuring the reproducibility of the operating conditions. Compared with other
inspection techniques, this reproducibility is a key aspect of TOFD, largely due to its
straightforward implementation. The images may be difficult to interpret, however, and
skilled operators are required.
c. Thermographic imaging
This method is also based on perturbation by geometric discontinuities of a flow injected
into metal parts, but in this case a heat flow is used. Any anomaly modifying the heat flow
through the material results in a local temperature variation on the output side. An external
heat source can be used, but the method also applies to structures which are hot during oper-
ation. Consequently, there is no need in this case for an additional heat input or access to
both sides of the metallic wall to be inspected.
Contactless inspections are conducted with a high-sensitivity infrared camera (measuring

to a fraction of a degree), to obtain images of the temperature variations caused by the under-
lying flaws. It is important to ensure that the heat source is homogeneous to avoid artificial
differences in the temperature distribution, which could lead to incorrect interpretations.
Pulse thermography is a variant based on rapid heating of the surface with a very power-
ful quartz lamp or hot air gun. In this case, detection is based on transient temperature
change, not on direct temperature measurement. Local loss of thickness will therefore result
in faster thermal stabilisation at higher temperature than areas not affected by corrosion.
When interpreting the signals, however, care must be taken to interference phenomena
which may modify the heat flows: thermal bridges, irregular geometry, deposits.
This method can be applied to check the integrity of coatings, especially for non-surface-
breaking flaws. For example, flaws such as blistering or disbonding modify the thermal dif-
fusivity, which is easily detected with this technique.
The cost of equipment is prohibitive, however: apart from high sensitivity in temperature
measurement, expensive components are necessary to guarantee the extremely fast response
times needed.
F. Acoustic emission inspection

This technique has already been discussed in the section dealing with inspection (4 2.3.2.2).
We will therefore restrict ourselves here to a few indications as to its field of application in
corrosion control. Readers may also refer to the database created by CETIM, INSA-Lyon
and UTC to obtain a list of the studies conducted in this field [ 1801.
By definition, the method is only suitable for detection of active damage since it picks up
the acoustic signals produced by corrosion. Since these emissive phenomena are greater
when the equipment is subjected to mechanical stresses, the main applications of acoustic
emission concern equipment under pressure or during testing.
In aqueous corrosion, emissive phenomena may either be of electrochemical origin,
related to the evolution of corrosion products or be produced during hydrogen release. The
technique may also be implemented to monitor dry corrosion, produced by aggressive gases at
high temperature. This latter application is more recent, however, and is faced with a number
of practical problems, such as the need for a waveguide to couple the sensor to the structure.
It is primarily used in the detection of cracking corrosion, especially stress cracking cor-
rosion (Figure 2.17 of [ 175]), although applications to less energetic phenomena (uniform
corrosion, pitting) have emerged.
This technique has proved highly efficient with the following corrosion situations:
- detection of initiation and kinetic monitoring of cracking corrosion propagation,
- location of active sources by comparing the times required to reach two different sensors,
- monitoring of acoustic activity to characterise the extent of damage,
- identification of corrosion mechanisms from their acoustic signature (by comparison
with existing data),
- correlation of acoustic intensity with operating parameters of installations andor cor-
rosion prevention measures.
9 131
140
I
(I) 120
z
s
U
a
100
c
80
5
-
0
60
40
: 20
0
Figure 2.17
Use of acoustic emission to detect corrosion [ 1751.
In the petroleum industry, this technique mainly finds application in the refining sector,
to inspect storage tanks, pipelines and pressurised equipment. In the ~O’S,however, it started
to appear in the upstream petroleum sector, including offshore [276].
2.3.3.2 Intelligent pigging [186; 193; 253; 2811

Dating back to the 1960’s, this equipment was developed with the precise objective of
inspecting long-distance pipelines, more efficiently and faster than inspection from the
outside, without having to open or dismantle them. These ILI (inline inspection) tools,
known as “pigs” or “pistons” in the gas industry, run inside the pipes, being pushed either
by the fluids conveyed (lines in service), water, or possibly compressed air (dry air or
nitrogen).
These articulated tools are composed of several compartments, including one which
contains the measuring equipment used to detect and characterise defects from corrosive or
mechanical origins: loss of thickness, cracks, dents, leaks. The other compartments are
modules for data acquisition and recording (electronic and computing) as well as battery
modules to provide power (Figure 2.18).
Historically, the first intelligent pigs developed were electronic calliper tools used to
locate areas of damage on pipelines. Their primary purpose was soon extended to the detec-
tion of corrosion-induced thickness loss, then finer defects, located on the surface or in the
wall thickness.
,Odometer
ery vehicle
Wheels for alignment

\
Transducers Ultrasound
supports transducers
Figure 2.18
XTraSonic intelligent pig [28 11.
Calibration tools are used to check for example that oil and gas pipelines have not
become obstructed by the formation of deposits or accumulation of debris. Their main pur-
pose is therefore to check pipelines before sending other pigs.
These calibration tools are based on a simple technology implementing displacement
sensors (LVDT) to measure the deflection of articulated fingers as they pass over roughness.
The sensitivity and accuracy of this type of device is typically less than or equal to the pipe
diameter. Note that more sophisticated tools combining dynamic measurements such as
vibrations, inclination and differential pressure are now available [236].
Two measurement technologies are used in the field of flaw detection (the eddy current
method has now virtually been abandoned). These are detection:
- by Magnetic Flux Leakage (MFL), and
- by Ultrasonic Tool (UT),
with their variants and improvements which increase the spatial resolution. These two
techniques are described later in this book.
Apart from generally internal flaws of metallurgical origin, the defects that intelligent
pigs try to locate and characterise are related to the operating conditions. They can be
divided into 4 categories:
- purely geometrical defects: dents, ovalisation, notches, tool impacts,

- loss of thickness: by corrosion, wear or tearing,
- cracks: due to fatigue or corrosion,
- leaks: final stage of one of the previous processes.
Typical wall thicknesses that can be checked extend from 3 mm to about 20 mm, and
routine systems exist for diameters between 15 mm and 100 mm, with restrictions related to
the technologies implemented, but also special cases located outside these limits. For a par-
ticular application, information can be obtained from the numerous suppliers and service
providers.
A. Magnetic flux leakage [228; 229; 2531

The principle consists in using powerful magnets to generate a magnetic field which satu-
rates the wall of the pipeline (Figure 2.19). If there is a defect in the wall, some of this field
leaks out, the leakage being picked up by the sensor in the pig. A volumetric estimation of
the flaw detected can then be determined by calculation. Since the sensor only detects an
interruption in the field lines by defects perpendicular to them, two configurations have been
developed to take into account the different defect orientations:
- systems generating axial fluxes for the mostly transverse defects,
- systems with circumferential fluxes for the axial defects.
Pipe wall
Steel bristles
Magnets -+
-
Ferromagnetic flux --+
return piece
Figure 2.19
MFL inspection principle [253].
The first are by far the most frequently used and are available in a range of versions
offering more or less high resolution. This resolution depends on the relative orientation of
the defects with the lines of flux. Equipment specifications indicate flaw detection threshold.
For example, very high resolution equipment will respect the following criteria [253]:
- minimum detection depth: 5% of the wall thickness,
- width detection threshold: 1/4 of the thickness internally, 100% of the thickness externally,
- dimensioning capacity: flaw size 2 5% of the wall thickness.
MFL offers the following advantages over ultrasonic inspection:

- ability to operate without a liquid medium, hence its use for gas pipes,
- less sensitivity to problems of deposits, which explains why it is chosen for pipelines
conveying paraffinic crudes.

As a general comment, we can say that this robust and reliable technology is also the
most widely used in-service inspection tool for oil and gas pipes. It is well suited to detec-
tion of metal wastage by corrosion. It is less accurate than ultrasonic inspection, however,
for detection of plane and highly localised flaws (cracks and pitting).
The major disadvantage with this technique is that it is unable to provide a direct mea-
surement of the thickness loss: the results and interpretations must generally be validated by
external measurements (e.g. ultrasound) at the points of most suspect indications collected.
In conclusion, we must also mention the efforts currently underway concerning the
inspection of offshore pipelines, due to increasing water depths and the associated financial
stakes. Statoil and Pipetronix for example are working on a joint project to develop equip-
ment of this type dedicated to thick, very long pipelines (Magnescan XHR), the main objec-
tive being to detect initiation of internal corrosion.
B. Ultrasonic inspection (US) [228; 229; 252; 2531

The basic measurement principle is well known: it consists in emitting acoustic signals
towards metallic surfaces and then in measuring the reflections produced. In the case of pipe-
lines, the thickness can be calculated using the signals reflected by the internal and external
surfaces. The distances are determined from the travel time, the propagation speed being
already known (for a given signal and medium of propagation). Lack of material on either sur-
face of the pipe can therefore easily be detected (Figure 2.20). The extent of the zone affected
and the depth of damage can then be visualised graphically using the records obtained.
Pigs capable of measuring local thickness losses are available for inspection of pipelines
over a wide range of diameters, from 150 mm up to more than 1 metre.
A sufficient number of sensors must be installed around the pig in order to cover the
entire pipe circumference. These sensors take measurements at regular intervals along the
pipe, the spacing between two successive sections examined being configured according to
the speed of the pig (generally 1 to 2 m/s). At these speeds, current instruments can take
measurements virtually every millimetre (1.5 mm spacing with the TRAPIL XtraSonic
system). The number of sensors around the pig depends on the pipe diameter. In all cases,
several hundred sensors are required (Figure 2.18) to obtain a circumferential location accu-
racy of approximately one degree of angle. Instruments of this type have been developed
8 135
Internal metal loss External metal loss

\ \
Wall
thickness
Stand-off
E
E 20
Stand-off
I I I I J.1 I I I I I ,
100 200 300 400 500 600 700 800 900 1000 1100
Length (mm)
’
Wall thickness
= 5
100 200 300 400 500 600 700 800 900 1000 1100
Length (mm)
Figure 2.20
Ultrasonic measurement principle [253].
following the progress made by the on-board electronics in terms of data acquisition, pro-
cessing and storage capacities: high-frequency measurements (about 1 kHz) are collected at
the same time as position, data (longitudinal and angular), in order to produce a mapping of
the records (Figure 2.21):
- B-scan: representation across the thickness of the pipe, obtained for each sensor,
- C-Scan: image across the developed surface, recreated using all the records obtained.
The C-scan reconstruction also takes into account the angular rotation movement of the
pig as it runs along the inside of the pipe. Note that for considerations of space availability
within the compartments, the intelligent pigs are fitted with transmitter-receiver sensors per-
manently switching from one mode to the other.
For volume flaws, current equipment is capable of achieving detection thresholds of less
than one millimetre in depth and of several millimetres on the intercepted surface.
Ultrasonic inspection is considered as the best crack detection technique since any free
surface, such as the wall of a crack, is a good reflector for sound waves. Obviously, the
detection quality largely depends on the relative orientation between the flaws and the inci-
dent beam: detection is maximum when they are perpendicular and very low when they are
b L26.22 m
' 122.82 In
Figure 2.21
Typical display of ultrasonic mapping [253].
nearly parallel. To be adapted for all possible situations in terms of flaw orientation, inclined
devices appeared on the market [282]. They proved extremely efficient to detect Stress Cor-
rosion Cracking (SCC) responsible for penetrating cracks generally orthogonal to the main
pipeline axis.
The first onboard systems were introduced by Pipetronix. Their basic configuration
allows them to detect all types of axial crack (due to fatigue, corrosion or hydrogen embrit-
tlement) in the base metal and in the longitudinal welds.
For butt welds, most prone to flaws since carried out in the field, the sensors are arranged
at 45" with respect to the pipe generator since, in this case, the flaws are generally axial.
With this measurement principle, cracks at least 1 mm deep can currently be detected, pro-
vided that they are long enough (about 30 mm) and wide enough (0.1 mm).
Other types of flaw can be detected using ultrasonic methods: pitting (at least 5 mm
diameter), craters, grooves or dents (at least 2 mm deflection).
The main advantage of ultrasonic inspection tools is their ability to provide quantitative
information on continuous flaws over the entire pipeline wall. In addition, the geometric
accuracy is better than with magnetic measurements, as regards detection threshold as well
as flaw dimensioning and location.
Apart from its accuracy, another point in favour of ultrasonic inspection is its long-term
“validity” allowing installations to be monitored over long periods of time [251]. Since the
measurements taken using this technique are not biased, it is possible to refer to previous
measurements, even if operating or surrounding conditions have changed, in order to moni-
tor damage phenomena with very slow kinetics.
In addition, various types of numerical processing can be carried out easily to calibrate
records taken at large intervals, especially if the geometrical data contained in these records
is in 3D.
Another major advantage of US inspection compared with the competing methods is its
higher probability of flaw detection. This can be explained by the fact that there is redundant
inspection of the surface: measurements are taken on the same zone by several sensors (up
to 6), thereby minimising the risk of flaws remaining undetected.
The main drawback with ultrasonic inspection for continuous pipeline monitoring is the
need for a liquid medium to transport the sound waves. This makes implementation more
difficult in numerous situations, for example in gas pipes. In some liquid effluents, however,
the use of special systems such as Long Range Guided Wave Ultrasonic (LRGWU) testing
can be considered to screen the line without the need to interrupt operation [229].
2.3.3.3 Inspection plans and RBI [208; 2 10; 2681

Risk-based inspection is a practice borrowed from the nuclear industry and later extended to
other heavy industrial sectors, including the petroleum industry and petrochemistry, in order
to optimise the cost-efficiency (or cost-safety) ratio for monitoring of installations.
Our intention here is not to provide details on how to prepare and conduct this type of
inspection, especially since abundant literature is available: in the petroleum sector, readers
can refer to API 580, for example, which explains and describes the procedure to inspect
fixed equipment and effluent transport pipes. All the main inspection and certification
organisations (e.g. Bureau Veritas and DNV) also publish useful information on RBI. We
will simply provide a reminder of its general principles and its relation with the Corrosion
Management Systems (CMS).
RBI can be applied to all sorts of heavy equipment, including structural components and
pressure vessels, both onshore and offshore. Its main objective is to process as efficiently as
possible the risks of damage that can be monitored by conducting inspections or analyses.
RBI must therefore be considered as part of a preventive management approach, promoting
maintenance over repair and providing guidelines to help set up an optimum organisation to
monitor these installations.
This approach is based on means that can be divided into two categories:
- a framework and methodological tools to build and sustain the approach,
- expertise on the installations themselves (their structure, history, operating conditions,
etc.) and knowledge of the degradation phenomena likely to affect them.

Concerning the risks specifically related to corrosion, the second point is the responsibil-
ity of the inspection departments, supported by the operating managers. For each type of unit
or device concerned, experts implementing RBI require a good knowledge of the possible
138 Chapitre 2 Prevention of corrosion and degradation oj'metallic materials
types of corrosion (mechanism, type and symptom, influencing factors, evolution kinetics,
potential consequences, etc.) and of the operating situations favouring corrosion, while taking
into account the specificities and limitations of the inspection tools.
RBI has two objectives:
- focus efforts on those assemblies and zones with the "highest risk", which implies that
they must first be identified,

- select and employ the most suitable inspection tools, which involves a thorough
knowledge of non-destructive techniques.

Since the inspection technologies have already been described, we will now discuss the
first point, starting with the notion of "risk". Risk is defined as the product of the gravity of
an event and of the probability of the event occurring. The risk intensity can therefore be
represented graphically on Probability-Consequence diagrams which provide a framework
for initial classification of the units. Although the consequences taken into account are pri-
marily related to safety, they may also include the incidence on downstream equipment or
on the overall process, financial impact, environmental risks.
Time must also be taken into account to define the frequencies of inspections and pre-
ventive actions. This means that the evolution kinetics of the degradation phenomena must
be either known or at least conservatively estimated. The kinetics can be obtained by relying
on the expertise of corrosion specialists responsible for the equipment considered, but also
on the empirical knowledge of operators, and especially on the data collected more or less
continuously and automatically (recordings, readings, alarms) concerning the degradation
phenomena.
It is important to capitalise on this knowledge base which must remain accessible
throughout the life of the industrial units. It is also essential to update this information and
re-evaluate the risk level after each inspection, which implies modifying the rules for subse-
quent inspections.
As part of a corrosion management procedure, RBI can be summarised as a set of tools,
knowledge and good practices providing answers to the three fundamental questions inher-
ent to inspection scheduling: What (which equipment)? How (which techniques)? When
(what frequency)?
Apart from the generic approach described above, in practice RBI is based on computer
software allowing users to deploy the methodology rigorously and easily. The risk calcula-
tions are automated according to protocols complying with applicable statutory recommen-
dations. They include several types of data:
- general data and data on the design of the actual equipment,
- inspection data or data concerning previous damage,
- data concerning the materials: composition, treatment and implementation,
- data concerning the main operating conditions (temperature, pressure, medium).
RBI offers the operators numerous advantages:

- improved knowledge of critical factors and risks incurred,
- greater reliability of installations and operating conditions,
- improved safety for personnel and for the environment,

- development of an operational knowledge base including numerous data sources

(equipment, operating conditions, degradation modes, inspection strategy and results,
maintenance actions),
- cost reductions in various areas:
inspection and maintenance (through programming and proper allocation of resources),
repair and replacement (through reduction of damage and thanks to preventive action),
productivity (through reduction of accidental shutdowns and possible postponement
of statutory shutdowns).
In addition to rigorous inspection practices, based on powerful inspection tools adapted
to each situation, the success of the RBI approach depends on:
- meticulous management of all documents (definition, update and archiving),
- efficient circulation of information between all players involved, both internal and
external (subcontractors, advisory organisations),

- and strong commitment from employees and management, on the site and throughout
the company, supported by active training programs and formal adoption of the RBI
approach in a corrosion monitoring policy.
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3
Fundamentals on metallic alloys and corrosion
The first paragraph in this third section deals with the basic information concerning the main
metallic materials used in industrial processes and in the petroleum sector: alloy structures,
mechanical behaviour and the main alloy families which find application in the petroleum indus-
try.The second paragraph describes the various corrosion modes and mechanisms discussed in
the first section of this book. Lastly, other damage modes are mentioned: metallurgical transfor-
mations due to high temperature ageing. The chapters in this section will provide the non-spe-
cialist reader with basic information on metallurgy (structure, families of metallic alloys used in
the petroleum industry) and corrosion, making the first chapters of the book easier to understand.
3.1 BASIC INFORMATION CONCERNING THE METALLIC MATERIALS USED

IN THE PETROLEUM SECTOR, THEIR STRUCTURE AND PROPERTIES
To obtain a better understanding of the reactivity of metallic materials with respect to corro-
sion, we will first examine the metallurgical structure of alloys, then the resulting mechanical
properties before describing, in the last paragraph, the main families of metallic materials used
for industrial processes and in the petroleum sector. For more information, the reader may also
refer to the bibliography indicated at the end ofthe chapter [316; 320; 321; 330; 333; 350; 3521.
3.1.I Structure of metallic alloys
Due to their chemical, physical or mechanical properties, most pure metals are unsuitable
for industrial applications. Deliberate or accidental addition of one or more elements to a
pure metal may significant modify its properties. Metallic elements (Cr, Ni, Mo, Cu, etc.) as
well as other inorganic elements (C, S, N, 0, P etc.) may be added. The mixtures obtained
are known as metallic alloys.
The properties of alloys depend mainly on:
- their overall chemical composition,
- their physico-chemical constitution: the type, composition and proportion of the
constituents,
148 Chapitre 3 Fundamentals on metallic alloys and corrosion
- their microstructure (distribution of constituents),

- their mechanical state characterised by some specific constraints related to crystalline
defects at atomic scale (dislocations, macles, etc.) and to chemical heterogeneities.
Depending on their manufacturing process and their subsequent treatments (mechanical,
thermal, chemical), alloys are in equilibrium or non-equilibrium state.
3.1.1.1 Crystallographic structures of alloys

In solid state, metallic alloys consist of numerous small crystals (grains) that have a diameter
of a few microns. These crystals can be oriented in all spatial directions (isotropic medium)
or have preferential orientations (anisotropic) due for example to the solidification or form-
ing (rolling) conditions: in this case, the alloy has a texture and its properties are also no
longer isotropic (Figure 3.1).
The crystals are characteristic of the alloy structure: they may all have the same compo-
sition (single-phase alloys) or correspond to different phases. Each crystal consists essen-
tially of metallic ions forming a pattern periodically repeated in all three spatial directions.
The crystal can be defined as a regular stack of cations which can be considered as hard
spheres tangential to each others. The unit cell is the elementary structure repeated infinitely
throughout the crystal, forming a lattice. A crystal system is defined by the parameters of the
unit cell (length of edges, angles) and the arrangement of the metallic ions (Figure 3.2).
Nearly all metallic alloys crystallise in one of the following three systems:
- Body-Centred Cubic system (BCC): the unit cell is a cube (edge of length a) with the
centres of the metallic ions not only at the comers but also at the centre of each elementary
cube (Figure 3.3). The coordination number (number of first neighbours) of each ion is 8.
a-iron, chromium, tungsten, molybdenum and vanadium crystallise with this structure.
Other ions can fill two types of interstice in this system. The largest interstices are the
tetrahedral holes [centres located in the faces, coordination numbers (d2, aJ4, O ) ]
Figure 3.1
Metallic alloy crystals.
Chapitre 3 Fundamentals on metallic alloys and corrosion 149
Grain Grain boundary Grain
Figure 3.2
Metallic alloy crystals and unit cells.
Iron a Iron y
Body-centred cubic Face-centred cubic
Figure
- 3.3
Cubic structures.
9
which can be occupied by atoms of radius 0.126a. There are 12 tetrahedral interstices
per unit cell (Figure 3.4). The smallest interstices are the octahedral holes (centres
located in the middle of the edges and in the centre of the faces) which can be occu-
pied by atoms of radius 0.0.067a. There are 6 octahedral interstices per unit cell;
- Face-Centred Cubic system (FCC): the unit cell is a cube (edge of length b) with the
centres of the ions at the comers and the centres of the faces (Figure 3.3). The coordi-
nation number of the FCC system is 12. Examples of elements with this crystal sys-
tem include y-iron, nickel, copper, aluminium and lead. The largest interstices are the
octahedral holes (centres located in the middle of the edges and in the centre of the
cube) which are surrounded by 6 atoms arranged at the comers of a regular octahe-
dron. There are 4 per unit cell, which can be filled by spheres of radius 0.146b. The
smallest interstices are tetrahedral since each centre is surrounded by 4 atoms located
at the corners of a tetrahedron: their centres are in the middle of each of the 8 small
equal cubes into which the unit cell can be divided. There are therefore 8 per unit cell,
which can be filled by spheres of radius 0.08b;
- Hexagonal Close-Packed arrangement (HCP): the unit cell is a rhombus-based right
prism, but the hexagonal-based right prism which is three times bigger is generally
considered as the conventional cell (Figure 3.5). The centres of the metallic ions are
organised in three layers, the top and bottom layers containing six ions at the corners
of a hexagon and one atom at the centre of each hexagon, the middle layer containing
three ions at the centres of the 3 non-adjacent equilateral triangles at half way between
the top and bottom layers. The coordination number is 12. Magnesium, titanium,
cobalt, zinc crystallise with this lattice. The interstices of the hexagonal close-packed
arrangement are the same as those of the FCC system: there are 6 octahedral interstices
(the largest) per hexagonal prism.
0.067a
4&
.---- I \A/
0.126a
Figure 3.4
Interstices of the body-centred cubic structure.
Chapitre 3 Fundamentals on metallic alloys and corrosion
9 151
(1100)’
[21lo] [lolo] [1120]
Figure 3.5
Hexagonal close-packed structure.
In alloys, metals can be found:

- In pure state: when alloying two metals without any combination taking place, the
atoms of one metal may be too large with respect to those of the main metal: the large
atoms cannot penetrate the lattice of the base metal and the metals separate;
- In combination: the metal (or sometimes non-metal) added is generally incorporated
into the crystal lattice of the base metal, resulting in a solid solution (Figure 3.6)
which is an intimate mixture where the atoms of the alloyed metals are assembled in a
unique crystal lattice. There are three types of solid solution: in substitution1 (the
solute ions are similar in size to those of the solvent metal and are distributed ran-
domly in the nodes of the lattice, such as for example nickel in the y-iron lattice and
chromium in the a-iron lattice); ordered (the solute ions replace those of the solvent
Substitution Insertion Well-ordered
Figure 3.6
Types of solid solution.
metal and are distributed in an ordered manner in the nodes of the lattice); and inser-
tion (the solute atoms such as carbon, hydrogen, nitrogen are small enough to fill the
empty interstices between the atoms in the unit cell).
The alloys may also contain definite compounds, whose atoms are present in relatively
simple and well-defined proportions. Examples of definite compounds include carbides
(e.g. cementite Fe3C), nitrides and sulfides (MnS).
Compared with the crystallography models which have just been described, real crystals
contain imperfections which have beneficial or negative impacts on some of their properties
(Figure 3.7):
- point imperfections such as impurities (foreign atoms which deform the network by
substitution or insertion) and vacancies (holes created when the normal position of an
atom is not occupied),
- line imperfections such as dislocations (screw, edge or mixed) which are disturbed
regions of a crystal situated between two parts which fit perfectly but have been
shifted relative to the other,
- planar imperfections such as grain boundaries, interfaces between two phases or twin
boundaries.
Vacancies
Interstitial
Figure 3.7
Lattice imperfections: vacancies and screw dislocation.
3.1.1.2 Alloy equilibrium diagrams

Alloys do not generally solidify at a specific temperature: under fairly slow cooling, solidifi-
cation starts at temperature T1 and finishes at temperature T2: there is no solidification point
but a solidification interval. The solidification diagram is the area bounded by temperatures
T1 and T2 which depend on the alloy composition. The line of temperatures T1 when solid-
ification starts is called the liquidus and that when solidification ends is called the solidus. In
solid state, the physico-chemical constitution of an alloy may undergo changes revealed by
sudden variations in one or more of its properties. The transformation points and their posi-
tions depending on the alloy composition form the transformation lines. An equilibrium dia-
gram includes the following information: liquidus, solidus and transformation lines.
Equilibrium diagrams form the basis of all rational studies of alloys. Given the chemical
composition of an alloy, the diagram indicates its constitution at all temperatures, provided
that the alloy is in its equilibrium state: this assumes extremely slow heating or cooling. How-
ever, the equilibrium diagram provides no indication concerning the micrographic structure.
To produce the equilibrium diagrams of an alloy, we must know the Variance (V) of the
chemical system in equilibrium, i.e. the number of equilibrium factors that can be arbitrarily
varied without varying the number and type of the system phases:
v=c+2-(p
- C is the number of independent constituents (number of pure simple bodies present in
the alloy),
- cp is the number of phases (homogeneous parts of the system).
Number 2 represents the two factors, pressure and temperature, but since the effect of
pressure variations is imperceptible, we consider a reduced variant Vr:
Vr=C+l-cp
Application to a Binary Alloy (BA)formed from two solid solutions with eutectic:
The alloys of metals A and B will form solid solution a if they have a high content in A
and a solid solution p if they have a high content in B. The liquidus and solidus corresponding
to the solid solution a start from the melting point of pure A and the liquidus and solidus cor-
responding to the solid solution p start from the melting point of pure B (Figure 3.8). The two
branches of the liquidus intercept at E. Three phases exist at this point: the liquid and two
solid solutions a(e,) and P(e2). The reduced variance is then zero Vr = 2 + 1 - 3 = 0 and equi-
librium can only exist at a specific temperature. The triple point E is called the eutectic point.
For this alloy composition, corresponding to point E, at temperature T, we obtain equi-
librium: Liq E H solid solution a(el) + solid solution P(e2) f n calories.
A B
Figure 3.8
Transformation diagram of a Binary Alloy (BA) formed from two solid solutions
with eutectic.
9
Solidification occurs at constant temperature T, by simultaneous formation of two solid

solutions a(e,) and P(e2). The eutectic alloy is therefore a mixture of these two solutions, the
ratio of their masses being given by the inverse segments rule:
mass el/mass e2 = Ee2/Eel
Solidification for other compositions of the alloy BA:
a) alloys for which 0 < B (?A)< el: the solid solution a is the only constituent,
b) alloys for which el < B (YO)< E: the two constituents of the solid solution a ( e l ) and
the eutectic,
c) alloys for which E < B (%) < e2: the two constituents of the solid solution P(e2) and
the eutectic,
d) alloys for which e2 < B (%) < 1: the solid solution p is the only constituent.
A eutectic triple point may also be found in transformation lines of the alloys (in the
solid domain): this is the eutectoid point.
3.1.I
.3 Application to the Fe-C diagram
We will apply the notions discussed in the previous paragraphs to the iron-carbon equilib-
rium diagram (steels sufficiently annealed) which is the basis of metallurgy and heat treat-
ments for steels. There are two Fe-C diagrams: an iron-cementite (Fe3C) diagram, which
corresponds to a metastable state, and an iron-graphite diagram, which corresponds to a sta-
ble state: the two diagrams partially overlap.
A. Iron-cementite diagram
A simplified diagram is given on Figure 3.9 for carbon contents below 6.7%. We observe
the presence of a eutectic (called ledeburite) at 1145 "C for 4.3% C and a eutectoid (called
pearlite) at 725 "C for 0.85% C. The various zones are:
Zone I: liquid + austenite mixture (y-iron with carbon inserted in the FCC unit cell)
Zone 11: liquid + proeutectic cementite mixture
Eutectic line at 1 145 "C
Zone 111: austenite with variable carbon content in insertion
Zone IV: austenite + cementite
Zone V: austenite + ledeburite + proeutectoid cementite
Zone VI: primary cementite + ledeburite + proeutectoid cementite
Zone VII: ferrite (BCC a-iron which dissolves little carbon) and austenite
Eutectoid line at 72 1 "C. The following domains lie below this line:
- 0 < C < 0.85%: proeutectoid ferrite + pearlite (hypoeutectoid steels),
- 0.85% < C < 1.7%: proeutectoid cementite + pearlite (hypereutectoid steels),
- 1.7% < C < 4.3%: proeutectoid cementite + eutectic cementite + pearlite (hypoeutec-
toid white cast irons),

- 4.3% < C < 6.7%: proeutectic cementite + proeutectoid cementite + eutectic cemen-
tite + pearlite (hypereutectoid white cast irons).

C%
Figure 3.9
~
Simplified iron-cementite diagram.
B. Ordinary annealed steels

These are Fe-Fe3C alloys which also contain small quantities of other elements (including
Mn, S, P) as combinations or inclusions. They are composed of ferrite + hypoeutectoid
pearlite or pearlite + hypereutectoid cementite. Pearlite has a two-phase lamellar structure
(alternating lamellae of ferrite and cementite).
The transformation points of ordinary steels correspond to the intersection of the vertical
representing the steel composition with the transformation lines on the diagram. In practice,
the transformations are very slow. These points are extremely important for heat treatments
(Figure 3.10).
Ac, corresponds during heating to the start of the reversible pearlite (ferrite + Fe3C) H
austenite reaction. Transformation occurs progressively from Acl to Ac3. When cooling,
austenite starts to transform at Ar3; transformation of eutectoid austenite ends at Arl. For
hypereutectoid steels (C > 0.85% C ) point Ac3 is replaced by point Ac,,. The transforma-
tion interval is Acl-Ac3 or Acl-Ac,,.
.4 Steel heat treatments: time-temperaturetransformation diagram

3.1.I
Heat treatments, which consist of heating and cooling operations, are carried out to change
certain properties (mechanical, corrosion resistance, etc.) of an equipment to make it more
suitable for its purpose. Traditional heat treatments include quenching, tempering and
annealing.
@
' \'\
0.85 C content ("10)
Figure 3.10
Transformation points of ordinary annealed steel.
A. Quenching
Quenching is carried out to improve steel toughness (this property is described in more
detail in paragraph 3.1.2). It consists of:
- heating the steel to a temperature 8,,known as the quenching temperature, when aus-
tenitisation occurs,
- maintaining the part at temperature 8,: the temperature is maintained long enough to
ensure thermal homogeneity throughout the equipment,

- cooling by immersion in a suitable medium, rapidly enough to avoid transformation
corresponding to the constitution predicted by the equilibrium diagram. The quenched
state is characterised by the presence of non-equilibrium constituents (martensite,
troostite or austenite).
Continuous Cooling Transformation (CCT) diagrams have been developed to indicate
the composition of the steel after quenching: they can be used to monitor the austenite
decomposition mechanism as a function of the cooling rate.
Figure 3.1 1 is an example of a cooling diagram for steel 42C4 (AISI 5 140). The transfor-
mation (start and end) temperature ranges are given as a function of the logarithm of the
time during cooling at various rates from an austenitisation state. The CCT diagrams also
provide indications of the steel hardness obtained after these cooling operations:
- Very fast cooling (lines 1 to 3): from 3 10 "C, we observe exclusive but not necessarily
complete transformation of the austenite into martensite (lines M50 and M90 corres-
pond respectively to a transformation of 50% and 90% of the austenite into marten-
site). Martensite is an oversaturated solution of carbon in ferrite with expanded lattice
whose unit cell is not cubic but tetragonal;
0.44 0.80 0.31 0.013 0.03 0.46 0.96 0.05 0.18
900
800
ACl
AC2
700
600
-g 500
?
c
e
Cl
+$ 400
1 min 2 min 15min 1h 2h 4h 8h 24h

CCT Diagram of steel 43 Cr4 (42C4)(Atlas IRSID)
Figure 3.1 1
Cooling transformation diagram for steel 42C4 (AISI 5140) (Atlas IRSID).
- Relatively fast cooling (lines 4 to 9): we observe the formation of an intermediate

structure, bainite, which has the same phases as pearlite (ferrite and cementite), but a
fine morphology, often in the form of needles. After cooling, we observe the presence
of martensite and bainite (lines 4 to 6) for fast intermediate rates and the presence of
bainite and ferrite for slower rates (lines 7 to 9);
- Slow cooling (lines 10 to 12): we obtain a fenito-pearlitic structure with lamellar
pearlite (equilibrium structure) and low hardness.
B. Tempering
After the hardening treatment, steel is often harder than needed and generally too brittle for
its application. Hardening is therefore followed by tempering, which consists in heating the
steel to a temperature below Acl, holding it at that temperature for the required length of
time, and then cooling it fairly quickly.
C. Annealing
This treatment consists in heating the steel to a temperature generally above Ac3 (or Ac,,)
then cooling it slowly at a rate less than the critical quenching rate. The metal is brought to a
state of physico-chemical and structural equilibrium. The non-equilibrium states resulting
from previous heat or mechanical treatments are removed.
3.1.I.5 Metallurgicaltransformations during steel welding operations

Steel welding operations involve heat cycles which generate different microstructures in the
heat-affected zones. As shown on Figure 3.12 below, various structural transformations may
occur in the weld, affecting its mechanical properties and corrosion resistance.
Taking the example of steel 42C4 (AISI 5 140) whose CCT transformation diagram was
detailed in the previous paragraph, we obtain the following microstructures after welding:
- Zone 1: base metal which has the initial steel structure depending on the heat treat-
ments applied (ferrito-pearlitic, bainitic or martensitic structure);

- Zone 2: the temperature remained below Acl (760 "C). The microstructure remains
unchanged but precipitation of carbides and coalescence of the precipitates may occur;
- Zone 3: the steel temperature has been raised to between Acl (760 "C) and Ac3
(790 "C). Austenite has formed and has retransformed into pearlite, bainite or marten-
site depending on the cooling rate;
- Zone 4: the steel temperature has been raised to between Ac3 (790 "C) and 1 100 "C.
Only austenite has formed: depending on the cooling rates, different structures may be
obtained, as shown on Figure 3.1 1;
- Zone 5: the steel temperature was raised to between 1 100 "C and its melting point
(about 1 500 "C), well above that of the standard austenitisation treatments. A high
grain size can be obtained.
.6 Influence of the various addition elements on steel properties

3.1.I
The steel properties (mechanical strength, corrosion resistance) can be modified and adapted
by incorporating other elements in the iron-carbon mixtures.
9 159
HAZ
(heat affected zone)
Initial state of the base metal \
I \
\ i
\ \
\ 1\100°C
‘\ 1
‘ A,,
~ 6 0 0 ° C A,,
Figure 3.12
Microstructural modifications in a welded zone.
A. Influence on the equilibrium diagrams and the non-equilibrium states

Each element has a dominating tendency either to dissolve in the ferrite or combine with the
carbon to produce a complex carbide replacing the cementite.
If we classify the main addition elements in the following order:
Ni - Si - A1 - Mn - Cr - W - Mo - V -Ti
- the first three dissolve only in ferrite,
- from manganese, there is an increasing tendency for the elements to form carbides.
These elements are all soluble in austenite at high temperature and they modify the solid
state transformation points of the steel.
Some elements reduce the range of austenite existence and increase the ferritic range:
known as the alphagenous elements, they include Cr, Si, Al, W, Nb, Mo, Ti and V.
Conversely, other elements widen the austenite range: known as the gammagenous ele-
ments, they include Ni, Mn, Co and Cu.
Elements W, Mo, Ni, Cr, V and Mn have an increasing tendency to lower the tempera-
ture at which martensite forms, while Co and A1 increase this temperature.
B. Action of addition elements on steel properties

Table 3.1 below summarises the effects of the addition elements on the structural and
mechanical properties.
Table 3.1 Influence of addition elements on steel properties.
Key: W sharp increase 2 increase

Y sharp decrease Y decrease
3.1.2 Mechanical behaviour of metallic materials
3.1.2.1 Introduction
This aim of this section on mechanical behaviour is to provide a few basic notions to readers
not familiar with this subject. These few pages will obviously not suffice to cover or explain
in detail this vast domain, which is nevertheless fundamental in the use of materials.
In this section, we will first describe the tensile test which provides an introduction to the
basic notions on mechanical characteristics and behaviour of metals (9 3.1.2.2).
We will then give a an overview of the strain, damage and fracture mechanisms
( Q 3.1.2.3 to 3.1.2.5).
The various types of mechanical stress and behaviour are discussed in 9 3.1.2.6.
The mechanical tests most frequently used, after the simple tensile test, are discussed in
9 3.1.2.7, especially characterisation of creep, fatigue, hardness, resilience and toughness
with some notions on,fracture mechanics.
Further knowledge on the behaviour and mechanical characterisation of metals can be
obtained in several books [327-329; 332; 3381.
3.1.2.2 Tensile test

We will describe the simple tensile test to illustrate fundamental mechanical behaviour and
demonstrate the characteristics used to quantify this behaviour. This test, conducted on all
materials and especially metals, has been documented in numerous standards. The test
machines are said to be universal since they can be fitted with various assemblies and acces-
sories in order to subject the materials to a wide range of mechanical stresses which will be
described in this chapter. As first illustrations, Figure 3.13 shows diagrams and photographs
of test machines (in tensile configuration) and Figure 3.14 shows photographs of test setups.
Tensile stress is obtained by vertical displacement of the crosshead or a hydraulic cylin-
der. A sensor records the displacement and a load cell records the stress applied to the spec-
imen (the sensor is generally fitted on the crosshead above the upper grips holding the spec-
imens). One or more extensometers can be fastened to the specimen to measure the strains
more locally and more accurately.
Other
potential
positions
for load cell
Upper grip
Lower grip
Testing machine Hydraulic testing

wich mechanical drive machine
(screw in the frame)
Figure 3.13
Universal mechanical test machines (shown here with tensile devices).
Figure 3.14
Tensile tests (a: on a steel cable with an extensometer, b: on a dumbbell prismatic
1fiu
specimen, c: on a steel specimen partially immersed in a corrosive environment -
in this case H 2 0 + H2S, d: temperature test in a chamber placed on the machine).
Stress Necking
(T = F/So Start of necking
I n
‘0 I
0.2 % f ES f EM
f
ESR Am A,
Figure 3.15
Typical tensile test (stress-strain curve and standard specimen).
The notions of elasticity, and therefore yield strength (also called elastic limit), as well as
plasticity, necking and failure are illustrated on Figure 3.15 which shows a tensile stress-
strain curve and a traditional specimen geometry. This test is generally interpreted by using
the “engineering” curve (§ A below) but the notion of “true” curve (9 B below) may be
employed for more in-depth studies.
Tensile tests have been described in numerous standards and vary depending on the
materials and the standardisation organisations. We will only provide a few references
(specific to metals): European standards NF EN 10002 [3 141, NF EN 10319 [3 lo]; interna-

tional standards I S 0 6892 [299], IS0 783 [313], IS0 15579 [312]; American standards
ASTM E8M [286], ASTM E21 [288].
A. Engineering tensile curve (“engineering” characteristics)

The example of “engineer*ing”or “nominal”stress-strain curve we provide here can be used
to deduce the “engineering” or “nominal” characteristics (a “true” stress-strain curve
deduced from this data will be explained below).
So and 1, correspond to the cross-section and length of the specimen at the start of the
test. The tensile force F increases continuously and produces an elongation A1 = 1 - I,. By
definition, the stress (in MPa) and the strain (dimensionless but often expressed in%) are
F Al
defined by: o=- and E=- .
SO lo
We identify on this curve:
- the elastic region OE with reversible strains,
- the plastic region EM with homogenous, permanent or irreversible strains,
- the plastic region MU with propagation of localised strain called necking, U being the
ultimate point corresponding to failure of the specimen,

- if unloading is carried out from point S, we follow a curve parallel to OE resulting
into permanent or irreversible strain ESR.

Generally, the total strain is the sum of the elastic (reversible) strain and the plastic
(irreversible) strain. The material reaching point S has therefore undergone a total strain
ES = E~ + ESR and retains the remanent strain &SRafter unloading. On subsequent reloading,
the material will exhibit elastic behaviour, with the same slope up to point S, then plastic
behaviour along curve SM.
Other mechanical characteristics that can be obtained from this test:
- The yieldpoint (or proportionality limit): Re is given by point E which marks the end of
the linear section where o is proportional to E, whose slope is Young’s modulus E. The
-
constitutive law is the relation between stress and strain in this elastic region: o = E E;
- Point E is therefore the end of elastic strain and the start of the plasticflow or strain.
This point may be (especially with mild steels) followed by a plateau with a series of
discontinuities (corresponding to the appearance of plastic deformation bands known
as Piobert-Luders bands), in this case the standard defines three additional elements
(Figure 3.16):
an upper yield limit Re,,
a lower yield limit Re,,
and the length of the section Ap;
- The offset yield point is given by point Y (Figure 3.15). Since point E is sometimes
difficult to identify, a conventional limit has been defined, where a line parallel to OE
(elastic section) shifted by 0.2% (generally, corresponding to a permanet or unrecov-
erable plastic strain of 0.2%) cuts the curve. This offset yield strength or proof stress
is denoted RpO.2;
- The maximum or ultimate strength: at point M the stress R, (in MPa) or OUTS corre-
sponds to the maximum load Fm supported by the specimen: R, = F,/So;
- The permanent set under maximum load is denoted A,;
- The total elongation under maximum load is denoted E,;
- The permanent strain after fracture is denoted A,;
- The total elongation after fracture is denoted EU;
t
Upper yield point ReH
Lower yield point Re,
Figure 3.16
Upper and lower yield points.
- The necking Z (in%) is used to quantify the reduction in diameter (which does not
always appear), knowing that S, is the minimum ultimate cross-section of the speci-
men (at the fracture after necking): Z = ___. so - SrJ 100;

SO
- The Poisson’s ratio v is the ratio of the transverse strain ~2 (in a plane normal to the
load F) to the axial strain E~ (in the direction of the load F) v = - E ~ / E(see
~ Figure 3.17).
Special extensometers are required to measure E~ and E ~ .

Table 3.2 below compares the mechanical characteristics of various metallic materials.
B. True stress-straincurve
We observe that the definition of (engineering) stress o =F/So, which is divided by the
initial cross-section So, does not correspond to the true stress in the cross-section S which is
Ov = FIS.
1
F
2 L3 Here: c p = E~
I = lo (1 +
v = - & p I E, J.
F
Figure 3.17
Tensile strain and Poisson's ratio v (in this case E~ = E ~ ) .
Table 3.2 Examples of mechanical characteristics of metals.
Examples of mechanical Young's Yield Tensile Failure Poisson's

characteristics of metals modulus strength strength elongation ratio
E (GPa) (MPa) Rm (MPa) El,% V
Steel 210 200-400 350-600 15-30 0.3

Special steels 210 500-1 300 700-1 800 10-15 0.3
Stainless steels 195 180-240 400-700 20-40 0.3
Aluminium alloys 70 100-500 200-600 5-30 0.35
Titanium and alloys 110 500-1 000 600-1 200 8-50 0.34
SG cast irons 100 200-600 350-900 2-25 0.29
Aluminium (annealed) 60 20 60 40 0.33
Copper (annealed) 130 20 200 30 0.34
Similarly, the (engineering) strain E = AMo, which refers to the initial specimen dimen-
sion is not representative of the true strain of a volume element which is the sum of the ele-
mentary elongations undergone by the material and which can be written for a specimen
The relation between true strain (E") and engineering strain (E) is therefore: E~ = ln(1 + E).
If we postulate conservation of volume during the plastic strain (v = OS), assuming that
the transverse strains are equal, and if we consider the material before the appearance of
necking, we obtain the following relation between cross-section and strain: S/So = I/( 1 + E)
and between true stress and conventional stress: crV = (T (1 + E).
The curve [true stress (TV = f(engineering strain E)] shows the “strain-hardening” of the
steel.
The curves have for example been described (at least partially) using the Ludwik
(T + a . E,” or Hollomon (T = K . E,” relation where “n” is called the strain-hardening
= (TO
exponent or index.
3.1.2.3 Elastic and plastic strain mechanisms in metals

A. Elastic strain in metals
Metals consist of an assembly of crystalline microstructures. “Elastic” strain occurs at
atomic scale by deformation of the crystal unit cells, without the atoms actually changing
neighbours. Consequently, only the distances between atoms or the angles may vary. This
geometric phenomenon is therefore reversible. In metallic materials, however, little purely
elastic strain is observed: about 0.2%.
As we saw during the tensile test, the elastic range (section OE on Figure 3.15) is charac-
terised by a parameter intrinsic to each material called the modulus of elasticity or Young’s
modulus E (E is the slope of the [(T-E] curve and the elastic constitutive law is (T = E . E). The
other important characteristic is the yield point or elastic limit (point E on Figure 3.15).
B. Plastic or permanent strains

Beyond the elastic limit, irreversible (permanent) strain mechanisms develop. We are now
in a region of “plasticflow”.While elastic strains of materials are generally very low, this is
not true of “plastic” strains which may reach several tens or even hundreds of %.
Plastic strains only occur if flaws are present in the (po1y)crystalline structures. For
examples, flaws at atomic level (substitution, insertion or vacancies which distort the crys-
talline network), at grain boundaries or at twinned crystals, and especially the presence of
dislocations which, due to their motions, represent the main mechanism of intragranular
plastic strain.
Dislocations are the result of atom stacking faults naturally present when the crystals form.
There are two types of dislocation, edge dislocation and screw dislocation, which are schema-
tised in the crystal lattice on Figure 3.18. The number of dislocations may increase dramatically
during high strain, making their motions more difficult and causing “hardening”. The disloca-
tion density varies from about 10 km/cm3 to 1O7 km/cm3 in highly strain-hardened metals.
The above diagrams show that the faults are created by translation of the upper part of
the crystal in case of edge dislocation, or a local rotation in case of screw dislocation.
Through highly localised movements around the dislocation line, the motion of dislocations
allows the entire structure to deform. These motions, which can be broken down into two
components: glide and climb (see diagrams below on Figure 3.19), allow high plastic defor-
mations in crystalline structures.
Edge dislocation Screw dislocation
Figure
- 3.18
Schematic views of edge and screw dislocations (shown here in a simple cubic
lattice).
f- f- f-
a) Dislocation glide by a shear stress effect
- - - - - -4- - -
b) Dislocation climb due to diffusion of vacancies or atoms
Figure 3.19
Diagrams showing the glide (a) and climb (b) motions of edge dislocations.
3.1.2.4 Damage and failure mechanisms

During plastic deformation, irreversible phenomena appear in multiphase and polycrystal-
line structures. Creation and motion of dislocations inside grains are the main mechanisms,
even through they are accompanied by more macroscopic phenomena such as crystallo-
graphic slips and shears in the grains or at the grain boundaries.
Defects initiation may for example be attributed to dislocation stacks which create a
microcrack in a previously homogeneous medium. Inclusions, however, form the most fre-
quent initiation sites. These inclusions and the metallic matrices surrounding them have a
wide range of shapes and properties. Decohesions may be observed at the interfaces as well
as fragmentation of inclusions which are too brittle. We might then expect that these decohe-
sions and fragmentations lead to the opening of microcavities or creation of microcracks
(see Figure 3.20). By propagation and/or coalescence, these damage initiation sites may
lead to macroscopic flaws which can propagate and cause total failure.
Apart from inclusions, grain boundaries and boundarie junctions, irregularities and
external surface defects (scratches, roughness, sharp edges, corrosion, etc.) also represent
preferential damage initiation points.
Inclusion Microcavity Microcracks Fragmented
Figure 3.20
Illustrations of an inclusion and damage initiation sites (microcavity or micro-
crack on grain boundaries or in the grain).
3.1.2.5 Ductile failure and brittle failure

Two types of failure, schematised on Figure 3.2 1, are generally identified:
- ductile failure, which involves high strains (at least locally) and often exhibits facies
with cups (ductile development of microcavities) and ductile tear and shear zones,
- brittle failure, which exhibits sharper, shiny facies (small facets in case of metals)
resulting from cleavage with transcrystalline (along the grain crystallographic planes)
or intergranular (in case of weak boundaries) propagations.
In practice, failures may exhibit brittle zones (trans- and intragranular) and ductile zones
simultaneously. Similarly, a distinction must be made between macroscopic behaviour
which may be brittle, for example, and “micro” mechanisms which may produce ductile
behaviour very locally.
Lastly, we must remember that the notion offailure is highly dependent on thejlaws (and
their size), whether they are internal or external. If there were no flaws, the materials would
be extremely strong. The strengths of carbon, glass, ceramic or polymer fibres with very
small diameters (about 10 pm) and containing very few flaws are much greater than those of
the usual metals.
Transgranular
cleavage
Inclusion
Microvoid
Ductile fracture Brittle fracture
Figure 3.21
Diagrams illustrating failures:
-on the left: ductile failure after creation of microcavities leading to cup facies,
- on the right: brittle failures by decohesion or cleavage.
Obviously, the propagation and failure modes are strongly influenced by the material
itself (composition, phases, microstructure, etc.), but the environment and the stress condi-
tions are just as important. This is a vast subject and we will only mention the main parame-
ters influencing failure:
- Material: high-strength steels are very often brittle (since the elastic limit is high, they
can work under high stress but with increased risk of brittle fracture). The notion of
brittleness has been quantified for over a century by impact tests (which will be des-
cribed later) and, for a given material, we can plot the ductilehrittle transition curve,
for example the resilience-temperature curve;
- Temperature: “all” materials are highly sensitive to this parameter, behaviour
becomes brittle as the temperature is lowered. Consequently, there is a “ductile/brittle
transition” characterised by a transition temperature defined using impact tests per-
formed at different temperatures for example. We must be extremely cautious, how-
ever, since this transition temperature remains dependent on the test conditions, in
particular on the specimen geometry and the impact speed;
- Stress rate: increasing the stress rate (application of force or strain) favours brittle
failures;
- Notch and specimen geometry: the stress is much greater at the bottom of the notch and
there is a stress concentrationfactor (KT function of the geometry). In addition, when

applying the mechanical stress, a confined plastic strain zone forms at the bottom of the
9
notch, increasing the triaxiality. The notch geometry therefore has a considerable influ-
ence on the “severity” of the flaw. The type of specimen and in particular its thickness
also affect the triaxiality and the increase in brittleness. These notions have very impor-
tant consequences on the methodologies of the “toughness” tests conducted in the field
of “fracture mechanics”;
- Environment: presence of a corrosive or embrittling environment (e.g. hydrogen in
steels) around the material, and in particular in the cracks, may make it more brittle.
3.1.2.6 Description of mechanical stresses and behaviours

The tensile test described in the previous paragraph, used to introduce notions on mechani-
cal behaviour and strain mechanisms in metals, is one of several mechanical tests. These
tests can also be used to determine intrinsic and/or important characteristics such as the
Young’s modulus, elastic limit, ultimate strength, etc. They demonstrate the limits (often
failure) of the materials, but they can also quantify the parameters used in the mechanical
constitutive laws (laws used for example to describe the evolution and relations between
stresses and strains and which are used in finite element calculation codes).
The following paragraphs outline the various types of stress, test and behaviour.
A. Types of mechanical stress

a. Tension/compression
Tensile (or compressive) stress on a specimen introduces uniform stresses in the material in
a cross-section normal to the stress direction (force F) as shown on Figure 3.22.
In the elastic range (small strains), the stress-strain relation is: (S = E * E.
i a=FIS
i U
_ _ _ S_ cr: normal
stress in the
cross-section S
T
F F
F
Figure 3.22
Tensile stress (on the left), compressive stress (on the right).
b. Shearltorsion
Figure 3.23 below shows objects subjected to shear stresses. In one case, forces T introduce
shear stresses in the material in cross-section S, which is a plane parallel to the direction of
forces T (in this case, the shear stress can be expressed simply: T = T/S). Torsion is another
9 171
T : uniform shear stress

withing the section S
. d : T
0=a/h
t = G.r.0
Figure 3.23
Shear stress (simple on the left, torsion on the right).
At the bottom: stresdstrain relations (small strains).
frequent configuration. In this case, a cylindrical specimen is subjected to a torque (or tor-
sion moment) at each end, which induces shear stresses in the planes normal to the torsion
axis (unlike the previous case, the stress state is not uniform throughout the cross-section).
As with tension, there is a simple relation between stresses and strains provided that the
material remains in the elastic range of small strains. We can therefore introduce a shear
modulus of elasticity denoted G.
The element of material subjected to shear stress (Figure 3.23) illustrates the stresdstrain
relation: z = G . d/h, (since angle y is small: dJh = tan y = y).
We note the relation: z = G y. -
For a cylinder subjected to torsion, the shear stress z at a distance r from the axis is there-
fore written: z = G . r . 8 (8 is the unit torsion angle, in this case equal to d h ) .
For small strains in the purely elastic range, the elastic constants discussed here and the
Poisson’s ratio v can related by:
E = 2 . G(v + 1)
c. Bending
The stress state produced by bending is more complex than tension or shear alone, since it
induces tensile, compressive and shear stresses in the material. This is illustrated on
Figure 3.24 for a specimen subjected to 3-point bending stress. The stresses in the specimen
A 4 points bending
The normal stress u

(tensile and compression) and the shear stress T
are maximal under the central C support Cantilever beam
Part under .
Built-in beam
tension ' ,
j
!
Shear stress in
parallel planes to
the neutral axis
I
I
j
Figure 3.24
Bending stress (3-point on the left and other arrangements on the right).
are not uniform, whether across the thickness or along the length. This type of stress has also
been documented in mechanical characterisation standards. It is nevertheless primarily used
for rigid materials andor materials with low failure strain or those more easily manufactured
as parallelepipeds (e.g. composite materials). Note that other bending geometries are possi-
ble, for example 4-point bending, dual cantilever bending, etc. Stress states in the specimens
nevertheless remain complex but with variants. With the 4-point bending test or the dual
cantilever test for example, the stress state is unusual since shear is zero between the central
supports, the tensile and compressive stresses are constant in all cross-sections normal to the
neutral axis and the shape adopted by this central section of the specimen is circular.
8. Some types of mechanical behaviour

The study of laws and behaviour, which involves mechanics, rheology and thermodynamics of
continuous media, is a vast, complex field. Our intention here is simply to give a brief reminder
of a few terms frequently encountered when describing mechanical behaviour - see Figure 3.25.
a. Elasticity
Purely elastic behaviour is reversible and instantaneous, there is no time factor. The law
describing linear-elastic behaviour (tension or compression) is the simplest and has already
been given: (r = E . E.
At small strains, metals can be considered as elastic.
p:::;ty
U
i/
Stress
Strain E
Elasticity
Stress
4
I
/'
9
I
Stress
0
Strain E
Viscoelasticity
Flactn nlastir
ctmin harrlnninn
,
Stress
4
I
.
&'-'
,
Stress
(7
:-*-%-Depend
/
~
Plasticity
173
Strain E
of the
strain rate
,
Strain E Strain E
Elasto-plasticity Visco-elasto-plasticity
Figure 3.25
Types of mechanical behaviour.
b. Viscoelasticity
Polymers are the most obvious example of materials exhibiting viscoelastic behaviour. Unlike
elasticity, the time factor plays an important role. The behaviour is reversible but the responses
always depend on the time and the strain or stress rate. Viscosity introduces mechanical
dumping which means, for example, that there is a phase difference between a sinusoidal force
applied to a viscoelastic solid and its strain response (notion of internal friction).
c. Plasticity
Under the effect of a stress less than a threshold (oJ, a solid exhibiting perfectly plastic behaviour
would have zero (or negligible) strain. Upon reaching this stress threshold oS,it would deform in
a stable manner, like a soil for example which remains in place when the stress is removed.
d. Elastoplasticity
In this case, linear elasticity is followed by purely plastic or plastic hardening behaviour.
The latter more realistic behaviour may apply to metals and alloys.
e. Elastoviscoplasticity (strain hardening)

By introducing a viscosity component, the responses will become much more complex and
strongly depend on the stress time and rates. This type of behaviour model can be applied to
metals and alloys for example at high temperatures.
3.1 -2.7 Types of mechanical test

We will now provide a brief description of the main types of mechanical test encountered.
Numerous tests are used to determine a certain number of parameters in order to characterise
the structures and also evaluate their lifetimes. Simple data such as Young’s modulus, elas-
tic limit, elongation at break, etc. are used, but much more complex test campaigns can also
be conducted, to evaluate fatigue or creep life for example, often in conjunction with tem-
perature “environmental” stresses andor aggressive fluids.
A. Monotonichelaxation tests
The mechanical tests most frequently carried out on all materials and described in numerous
standards are the so-called monotonic tensile tests. They consist in subjecting the specimen
to strain at constant rate and monitoring the stress response, as illustrated on Figure 3.26.
This type of test is frequently conducted in tension and the characteristics (elastic, at break,
etc.) that can be deduced were detailed in the first paragraph concerning mechanical behav-
iour. However, the principle of a monotonic test at constant strain rate applies to other types
of stress, for example compression or bending stress.
In a “relaxation” test (Figure 3.27), a strain is also applied and then held constant. Vis-
coelastic materials then undergo stress relaxation (the case schematised on Figure 3.27
exhibits a sharp stress drop rarely found in metals at ambient temperatures).
Stress
Strain E U
Time t Strain E
Figure 3.26
Monotonic test: imposed strain and stress response.
I-:\,
Stress
Strain E
IF!,
U
Time t
* b‘- Time t
Figure 3.27
Relaxation test: imposed strain.
B. Creeplrecovery tests
When conducting creep tests, the stress or force imposed is maintained constant. This type
of test is important in practice since numerous structures work under imposed forces (or
pressures). Figure 3.28 illustrates this test and shows that if this stress is reduced to zero,
recovery takes place and it takes the material a certain amount of time to return to its initial
dimension (viscosity effect); if plastic strain mechanisms have been activated, only partial
recovery will occur. The creep curve shows that creep may accelerate up to break (indicated
by a star on the curve).
Stress Strain
0
4
*
.......
&
4 Creep -
acceleration
-
Rupture
- l *
0 Time t 0 Time t
- OA=Loading
-
____
Creep
Recovery
......
Case with creep
acceleration then rupture
Figure 3.28
Creep test.
In practice, it is difficult to maintain stress rigorously constant. If the stress is imposed by

a hanging weight, the force is rigorously constant. During elongation, however, the cross-
section of the specimen is reduced slightly (Poisson’s ratio) thereby increasing the stress
slightly. Strictly speaking, the forced applied would have to be adapted to the geometric
evolution of the specimens, which can in fact be achieved using hydraulic test machines
slaved to strain measurements taken on the specimens. In case of very high strains, observed
for example during severe creep, the specimen may even undergo necking.
Creep tests can be conducted to compare materials, design a structure, determine consti-
tutive laws and evaluate lifetimes by long-term extrapolation [325]. Standards NF EN 10291
[300] and ASTM E3 19 [287] illustrates these tests. The creep curves can therefore be repre-
sented and interpreted in numerous ways. We will only give two examples here, which also
provide an opportunity to mention the 3 stages usually involved in creep.
The traditional creep curve [ E = f(t)] is often represented as on Figure 3.29 without plot-
ting the loading phase (OA on Figure 3.28); the time scale can be logarithmic. The graph
opposite shows the strain rate E which can be plotted against E, t or lg t.
I
Primary Secondary i Tertiary:
creep i creep ! creep i
!
!
A !
!
.a !
a ! b
c ! Time t o r lg t
Ec
!
._ !
E !
! !
! !
! !
!
I I Time t o r tg t
Figure 3.29
On the left: test with the three creep stages.
On the right: for a series of creep tests (in this case with 3 stress levels).
Metals exhibit the three creep stages presented here when the temperature is high enough
to activate the mechanisms leading to high strains (generally for T > 0.3 to 0.5 . Tmeltingpoint):
- Primary or transient creep: the strain rate E (or creep rate) decreases with time
(work hardening of the material). This is the normal type of creep observed at low
temperatures (T < 0.3 . Tmeltingpoint), the strain rate becomes very low (logarithmic
creep);
- Secondary or steady state creep: the strain rate E is constant over time. The plastic
strain mechanisms involved are mainly related to dislocations (with the creations and
motions of dislocations already present during primary creep, we observe grouping of
dislocations in cellular substructure in the grains, etc.);
- Tertiary creep: the strain rate increases and failure occurs. In particular at high tempe-
rature andor high stress, other mechanisms such as restorations, recrystallisation and
diffusion of atoms, slipping at grain boundaries, etc. are involved. As in a monotonic
tension test, necking may occur before failure.
Creep type characterisations are widely used for pipelines subjected to high internal fluid
pressure, the times required to reach bursting being recorded in tests conducted at different
pressures.
Creep is predicted using parametric relations between stress (or strain) at failure, temper-
ature and time. Larson and Miller proposed the following relation:
P applied stress (N)

T . c . log(@) T temperature (K)
P= with
1000 tr time at failure (hours)
C constant (for steels 18 < C < 28)
C. Combined stresses (multidirectional)

In practice there are obviously numerous cases where the stress on the element or on the structure
is not simple (e.g. only tension or torsion). Stress in cases of bending is complex (tension or com-
pression combined with shear). A few other cases will be mentioned below (see Figure 3.30).
- Tubes with internal (or external) pressure with axial tension (or compression): axial
stress can be applied by a traditional mechanical test machine, pressure stress is relati-
vely easy to apply using a hydraulic device. With an internal pressurised tank, end cap
effect will introduce (axial) tension in the cylindrical part in addition to (circumferen-
tial) tensile stresses due to the internal pressure. This is known as biaxial tension;
- Cylinder or tube under torsion with axial tension (or compression): a device, generally
hydraulic, can be added to a traditional machine to impose torque on the system under
test. Standard ASTM E2207 is an example [301];
- Plate under biaxial stresses: the test setups may become complex with the use of sev-
eral hydraulic cylinders, even superimposing normal and shear stresses;

- Specimen under triaxial compression: this type of test is used in particular in rock (or
soil) mechanics by applying hydrostatic and therefore triaxial pressure. Problems of

tightness must however be solved when the tests are conducted on permeable materials.
F F
Figure 3.30
Examples of multidirectional loading.
D. Cyclic stresseslFatigue
Fatigue tests are conducted to reproduce cyclic mechanical stresses as close as possible to
those encountered in service by the parts (mechanical loading mode, stress level, stress fre-
quency, etc.). The materials subjected to cyclic stresses that are often well below their elastic
limit will nevertheless fail after a certain number of cycles. Damage occurs progressively
inside the material and, locally, one point becomes the failure initiation zone. Cracking
propagates from this zone through the part up to final failure when the remaining material
can no longer withstand the stresses. This type of failure occurs at much lower strains than
those observed in the traditional monotonic tension tests, due to progressive cracking which
invades a large section of the part.
A part which has failed under fatigue generally exhibits 3 characteristic zones:
- An initiation zone, from where the crack starts. It often corresponds to a preexisting
flaw which may be located on the surface or inside the part (foundry, machining, wel-
ding flaws, or flaws caused by corrosion or various mechanical aggressions, etc.). The
initiation zone may also be created at the start of fatigue by accumulation microda-
mage (as we have seen for example with dislocations);
- A relatively flat and smooth propagation zone (in the plane of maximum stress) and
which under the microscope reveals a succession of striations calledfatigue striations;

- AJinalfailure zone which often corresponds to sudden tearing.
Fatigue tests can be conducted under imposed load or imposed strain.

Under high stresses when the metal switches periodically into plastic strain, the number
of cycles up to failure is low, a situation known as low cycle fatigue.
The various stress modes are observed in the fatigue tests: tension, compression, tension/
compression, bending, rotary bending, torsion as well as combined modes, in particular ten-
sion/torsion or bendingkorsion (static stress may be superimposed on cyclic stress).
Figure 3.3 1 illustrates stress cycles and the definition of alternating stresses. Periodic
stress is often sinusoidal but may include linear ramps, especially when using hydraulic test
machines.
Stress a
4 Ondulating load
arnaxi __ ,~ .......
am -
mean
a<O
Figure 3.31
Cyclic fatigue (stress-controlled in this case).
The fatigue test parameters are the minimum/maximum stress ratio R (R =c ~ ~ ~ ~ / c ~ ~

the frequency and the maximum stress.
To analyse the results, the most well-known endurance diagram is the S-N curve (Stress-
Number of cycles) or Wiihler curve: it displays the imposed stress levels (e.g. the maximum
stress) against the number of cycles to failure N, (generally a logarithmic scale). A large
number of tests must be conducted during the fatigue test campaigns since the results are
generally highly dispersed. For a given level of stress, therefore, the N, may extend over a
decade, a situation which is partly due to the experimental conditions but more especially to
the phenomena involved in crack initiation and propagation. Figure 3.32 shows an example
of this diagram and indicates the three fatigue regions:
- Low cycle fatigue: under high stresses generating plastic strains and small numbers of
cycles to failure (often from just a few cycles up to lo4 cycles);
- High cycle fatigue: failure still occurs, but the lifetime increases when the stress level
decreases;
- Fatigue limit, under which fatigue failure no longer occurs, is frequently observed; in
this case, the S-N curve extends towards a horizontal asymptote (this region often
(MPa) ornaxi
0 Broken sample
400 .............. ...
....... ..... @+ Not broken sample
\ (here with 5.1O’cycles)
......................................
\
m...\ a
P\ -----
--- Curve of endurance
\
300 ..................................................... Q~.X)..O...O
......
\
\
\
200
......................................................................
...............................................................................
_ _ _Endurance _____ limit___________-_-------_--.
\
- 0 -
......................................................................................................
*----
Oo\Q ......0.....0...............@+
0.....%Q-& .......0......
O.-O..-@+
104 1o5 106 1o7 108

lg N (cycle)
Figure 3.32
Fatigue: example of S-N (or Wohler) curve.
9
concerns numbers of cycles to failure Nr > lo7 or lo8). This asymptote is not always
the rule, however, especially when other damage such as corrosion occurs in addition
to mechanical fatigue.
Numerous standards and operating procedures, especially statistical, are available to
conduct the tests. Failure equiprobability curves (at go%, 50% and 10% survival) for exam-
ple can be plotted on the endurance diagram. The reader can refer to various articles and
books on fatigue: [323; 324; 326; 334; 341; 3461, and standards IS0 1099 [307], I S0 1143
[303] and ASTM E606 [306], ASTM E466 [289].
The fatigue study methodologies also apply to fracture mechanics. Fatigue cracking
tests may for instance use the toughness specimen geometries (CT and 3PB specimens
described on Figure 3.36) and several methods have been developed to monitor crack propa-
gation (optical, ultrasound, electrical measurements, etc.).
Lastly, we may mention the variable amplitude stress fatigue tests. The objective here is
to assess the behaviour of structures which are subjected to highly variable stresses during
service. Several methodologies are available and some test sequences have even been stan-
dardised in the aeronautical, automotive and petroleum industries.
E. Hardness
By definition, “hardness” is the resistance exhibited by a material to penetration by a harder
body. The principle consists in applying a constant force for a given time on an indenter of
well-defined geometry and measuring the dimensions of the indentation left by this indenter.
Although the hardness cannot be directly related to other properties of materials, we can
well imagine that there is a strong likelihood that a very rigid material will be “hard”. This is
not always true, however, for example a composite material with polymer matrix may be
very rigid in the direction of the fibres, without exhibiting the hardness of steel. Studies
establishing correlations between various properties (hardness, Young’s modulus, strength,
etc.) and conversion tables can nevertheless be found [304].
Hardness is highly sensitiveto the surface state which may quite different from the state of the
material at depths exceeding the penetration depth, a factor which must be taken into account. It
is also influenced by the experimental conditions, in particular the load application time, but also
the metal microstructure (grain size). The three most widely used tests are described below:
Brinell, Vickers and Rockwell hardnesses detailed in standards [290-293; 296; 3051. Figure 3.33
illustrates the principles of these three tests. A description of microhardness will follow.
a. Brinell hardness
The indenter is a ball of diameter D which is applied under a force F for a time t. The hardness
HB is the ratio of the mass applied divided by the area of indentation (spherical cap). It can be
calculated using the following formula:
The hardness HB must be given with the values of D (often 5 mm or 10 mm), the force F
(the mass F/g can be up to 3 000 kg) and the time t.
b. Vickers hardness
The indenter is a diamond pyramid with square base and a summit angle of 136". The definition
1 2F.sin68"
is similar to that of H,: Hv = -.
g d2
c. Rockwell hardness
There are two indenters (ball or cone with rounded tip), the measurement follows the follow-
ing sequence:
- application of a first light load (Fo = 98 N) which acts as origin,
- application of Fo + F 1,
- force F1 is released -+ the additional depth of penetration h is used to calculate the
Rockwell hardness (relation depending on the geometry and the force applied; there
are several Rockwell hardness values: A, B, C, D, E, F, G, K, N and T).
Carbide ball Pyramidal Sphere (1/16 ou 1/8") or diamond cone 120"

diamond (1 36") (rounded tip r = 0,2mm)
F F Fo Fo+ Fl Fo
Rockwell hardness
/
3
Hardness Hardness li
Brinell
Figure 3.33
Brinell, Vickers and Rockwell hardness tests.
d. Microhardness
A microhardness tester is used to take highly local measurements (about 100 pm2), in a spe-
cific phase for example. A Vickers type tip is used and the hardness tester is a microscope
used to measure the indentation after having applied very small loads (< 1 N). Figure 3.33
shows an indentation example. This test is conducted mainly in laboratory, unlike the
Brinell and Rockwell tests which are frequently implemented in workshops and on sites.
F. Impact strength tests

Scientists have been aware of the notion of the “brittleness” of materials for more than a
century and have developed tests capable of demonstrating it. The tests are “dynamic”, in
other words they use an impact (at speeds higher than the traditional tension tests for exam-
ple) in order to produce “sudden” failures. The Charpy impact test is the most well-known
example used to measure the impact strength of a material, expressed for example in J/m2 or
J/cm2 and described in international standards IS0 148 [294], I S 0 14556 [298] and ASTM
E23 [295]. The Charpy impact test is schematised on Figure 3.34.
This quick test uses specimens of reasonable size (10 x 10 x 55 mm3) with a V-shaped
notch (2 mm deep with a 0.25 mm notch radius) or a U-shaped notch ( 5 mm deep with a
1 mm notch radius). It is generally conducted using a pendulum equipped with a hammer
connected to an axis (very low friction) which strikes a specimen (on the face opposite the
notch) placed on 2 pads and therefore subjected to bending stress. On steels, the impact
speed is generally 5 m/s, the speed being determined by the fall height of the pendulum.
The three embrittling factors (external to the materials) are:
- increase in stress rate,
~ temperature decrease,
- increase in notch severity (essentially its “sharpness”).
The energy absorbed by breaking the specimen is calculated using the difference
between the initial height (start of hammer fall) and the climb height ([hl-h2] on the figure).
The energy is divided by the broken area and the impact strength is written (for the Charpy
V test): Kcv = WAS (Wr is the energy at break and S the area). Some improvements or
observations increase the quality of these interpretations:
- Although the test is quick and easy, the results are often highly dispersed. Consequently a
large number of specimens are required, especially to obtain the ductilehrittle transition. In
this case, batches of 5 to 10 specimens must be tested at numerous temperatures, for exam-
ple between - 50 “C and + 200 “C, the transition extending over several tens of degrees;
- Observation of fracture su@ces demonstrates that fracture generally starts (at the
notch tip) with a ductile tear region followed by a region dominated by brittle fracture
by cleavage, lastly terminal ductile tears are observed, sometimes with shear lips on
the sides. Quantification of the fraction of brittle facies with respect to the total area
also gives a relevant indication of the degree of brittleness;
- Test devices sometimes include an “instrunzente8’ hammer with a force sensor. The
impact curve (force against time, which may be a few millisecond) can provide a bet-
ter appreciation of the ductile and brittle natures, if the vibratory phenomena are cor-
rectly controlled. The initiation and propagation phases can therefore be quantified.
Propagation in case of brittle failure is characterised by low energy absorption. The
instruments may also indicate the force at which propagation starts;
~ By providing critical force values, the instruments also allow the use of fracture
mechanics methods in order to assess the “toughness”.
Impact tests other than the Charpy tests are also available, sometimes with weights fall-
ing vertically but often with pendulums such as the IZOD impact test, which uses the same
specimen as the Charpy V. In this case, however, the specimen is positioned vertically. The
lower half of the bar (up to the notch) is clamped and the upper part is struck 22 mm above
the notch by the hammer.
Other types of impact test have been designed to be more representative of applications,
e.g. impact with a weight falling onto a clamped sample, impact on a specimen under ten-
sion or even dropping the object to be tested from a height of several metres (automotive
fuel tanks). In addition to impact pendulums and devices with falling weights, hydraulic
machines have been developed to conduct well-instrumented mechanical tests at high
speeds, but obviously they are much more expensive.
Hammer
G: centre of gravity
I Impactspeed I
Figure 3.34
Impact pendulum and geometry of the Charpy impact test (on the left: diagram
of a Charpy impact pendulum and conventional specimen with V-shaped notch
and dimensions in mm on the right: photograph of a small impact pendulum).
~
The quantitative resilience values obtained with the various methods and with variable
geometries are not comparable. Although there are correlations and comparisons, these val-
ues cannot be used to calculate the loads that structures can support or for design purposes.
This is obviously the big criticism of resilience. It explains the emergence of fracture
mechanics towards the middle of the 20th century, which uses flaws (cracks, etc.) as main
parameters and which allows characterisation of materials (critical flaws, critical energies,
etc.) with toughness as new intrinsic property of materials.
9
G. Notions of fracture mechanics and toughness

Fracture was discussed in the previous paragraphs through its main mechanisms and from
the experimental point of view using tension tests and the impact test which characterises
impact strength. Parameters such as temperature, stress rate and presence of a notch were
already taken into consideration over a century ago.
Very sudden and catastrophic fractures have been observed, however, on large metallic
structures (generally at low temperature) such as bridges and the famous American Liberty
Ships of the Second World War. Built to a standardised, mass produced design to send sup-
plies to Europe, these ships relied extensively on welded sections (instead of rivets), allow-
ing fractures to propagate over long distances (more than 300 cases out of 2 700 ships built),
sometimes across the entire hull resulting in some ships splitting in two.
Towards the middle of the 20thcentury, the birth of ‘Facture mechanics” led to a greater
understanding of the notion offlaw, one of the main causes of fracture initiation, so permit-
ting quantification that is far more relevant and intrinsic to the material than impact strength,
through the use of a new characteristic: toughness. While impact strength can be used to
compare materials and evaluate their ductilehrittle transition, it cannot be used to calculate
critical loads on structures presenting flaws of known size. For given loads, fracture
mechanics can also be used to evaluate the critical sizes of flaws, in particular very narrow
cracks which develop during fatigue, for example. The nuclear, aerospace and petrochemi-
cal industries played a leading role in the development of fracture mechanics.
Numerous studies have been conducted on fracture mechanics and much progress has been
made over a period of more than half a century. A large number of books, publications and obvi-
ously standards have been published. We will only provide here a f m notions, dejnitions and
experimental examples with af a v references to books [331; 343; 3451 and standards NF EN IS0
12737 [302] and ASTM E208 [297], ASTM E399 [311], ASTM E813 [309], ASTM El221 [308].
The main point to remember is thatfracture mechanics provides a means of determining
relations between the load on a part, the geometry of the flaws (cracks) and the material
through a property known as toughness.
Fracture tests can be performed to determine toughness, but they must apply methodolo-
gies extremely rigorously (see standards) in order to obtain valid, relevant results. For more
complex parts and structures, the results of toughness tests can be associated with finite ele-
ment calculations.
Toughness tests are typically divided into 3 categories:
- tests based on linear elasticity fracture mechanics,
- tests based on elastoplasticity fracture mechanics,
- tests based on the local approach of fracture mechanics.
a. Linear elasticity fracture mechanics

The available energy rate or energy release rate is denoted G. If G exceeds a critical value,
the crack propagates (G 2 2y, y being a property of the material, surface energy), and rela-
tions exist to connect G to the load and to the crack. For example: if F is the applied force
1
and a C the compliance variation when the crack increases by area aA: G = - F2 - .
ac
2 aA
While the previous approach is based on energy, a parameter called the stress intensity
factor K has been determined by studying stresses at the tip of the crack. This factor (which
is not a stress concentration coefficient) is in fact the key parameter in fracture mechanics
since it simultaneously takes into account the geometries of the part, the crack and the load.
For a given value of K therefore, different parts or structures will have the same stress state
at the crack-tip.
Direct relations therefore exist between the stresses and the crack and load geometries.
Figure 3.35 illustrates a few examples which are also traditionally used in test geometries.
This figure also indicates the 3 crack stress modes traditionally used: mode I opening,
mode ZZ in-plane shear and mode ZZZ out of plane shear (shear perpendicular to the plane).
As the moment of crack propagation, the stress intensity factor K reaches a critical value
denoted Kc, the toughness, an intrinsic characteristic of the material. KI, KII, or K I I I ~can
be defined depending on the stress mode (I, I1 or 111). Toughness characterises the resistance
of a material to propagate cracks.
Mode I Mode II Mode 111
(5
a
2b na
K,=O-G - rg-
xa
[na 2 b ) cos Tb
K,= a&. cos'a

K,,= &a . cosa. sina
Figure 3.35
Fracture mechanics:
- at the top: fracture modes,
- examples of stress intensity factors K as a function of load, specimen and notch.
-
Toughness Klc is usually expressed in MPa tn1I2. Typical values range between 20 and
200 for steels, 10 and 50 for aluminium alloys and much less for concrete and plastics
(between I and10).
It is important to note that environmental conditions may signij'icantly affect toughness.
Stress corrosion and hydrogen embrittlement, for example, will lower the toughness of
steels sensitive to these types of corrosion.
Figure 3.36 shows two types of very widely used specimen (standard ASTM E399 and in
France NF A03-1SO) with their stress intensity factors K: the CT (compact tension) speci-
men and a 3PB (three-point bending) specimen (the same geometry can be used in Charpy
impact tests). To ensure that the tests are valid, the standard describes the conditions to be
respected (in particular the specimen dimensions - especially the thickness B - with respect
to the properties of the material and creation of a fine notch for example with fatigue pre-
cracking) and describes the analysis methods implemented to determine a critical load Pc
(start of crack propagation) which is used to calculate the toughness KIc.
The principles and methods of fracture mechanics may also be applied to fatigue tests to
monitor crack growth (Paris, Forman laws, etc.).
2t
W=2B
L=2W
a=B
W=28
H = 1,2B
D = 0,58
HI = 0,658
W1 = 2,5B
Figure 3.36
Toughness specimens (ASTM E399):
- onthe left: CT (compact tension) specimen
KI =-
- on the right: 3PB (3-point bending) specimen
KI=-[ l' 11,58 ( ;-

B f i
]I2 -18,42 (ZT'
- +87,18 (Zr2 (;r2 (;r2]
- -150,7 - +154,8 - .
b. Elastoplasticity fracture mechanics

When linear elasticity fracture mechanics conditions are no longer met and the material is
ductile, elastoplasticityfracture mechanics techniques can be applied to propose methods to
monitor stable propagation of a crack, then its instability. This characterisation is not intrin-
sic to the material but valid for a given thickness. We will simply mention the methods here:
R-curve method, Dugdalle-Barrenblatt model, J-integral and crack extension force JIc
(standard ASTM E813).
c. Local approach of fracture mechanics

To conclude our summary of approaches to predict fractures, we will now mention the local
approach: a criterion is defined locally according to fracture mechanisms (cleavage, cups,
etc.) and compared with the stress and strain states in the material, especially near flaws.
Experimentally, notched cylindrical (axisymmetrical) specimens are used (see Figure 3.37)
with several notch radii and a very carefully prepared surface to limit failure initiation from
surface flaws. In case of cleavage fracture, for example, a large number of tests is required.
The results are analysed using a Weibull law (generally applied to study statistical dispersions
of brittle fractures) in conjunction with finite element calculations to determine the stress states
at time of fracture.
Figure 3.37
Notched axisymmetrical specimen (large notch radius on the right).
3.1.3 Alloys used in the petroleum industry
This paragraph provides information on the main steels and metallic alloys used for equip-
ment in the petroleum industry. Firstly, note that the international standards most frequently
used in the petroleum sector to designate alloys are the:
- designation of the American Society of Testing and Materials (ASTM) and the Ame-
rican Society of Mechanical Engineers (ASME) which are close,
- designation of the American Iron and Steel Institute (AISI) and the Society of Auto-
motive Engineers (SAE) which are very similar,
- designation of the Unified Numbering System (UNS),
- designation of the Alloy Casting Institute (ACI),
- designation of the Copper Development Association (CDA),
- designation of the Aluminium Association (AA).
Readers will find further information about these standards in Appendix 1 of this
document.
Material specifications are also provided according to their applications by:

- The American Petroleum Institute (API) such as, for example, for oil and gas produc-
tion, API 5CT (steels for casings, tubings and liners), API 5D (steels for seamless drill
pipes), API 5L (steels for pipelines);
- European Standards such as, for example, specification EN10028 (steels for pressure
vessels), EN10027 (steels for simple pressure vessels), EN100275 (structural steels).
Obviously, this list is not exhaustive, since metallic materials find numerous applications
in the petroleum industry.
3.1.3.1 Ferrous metals (iron content > 50%)
A. Steels
a. Carbon steels
These steels are composed mainly of iron and carbon (maximum 1.5% in theory with less
than 0.4% for most carbon steels). Generally, increasing the carbon content of a steel
increases the mechanical strength (which is the intended purpose), but decreases the ductility,
increases the Ductile-Brittle Transition Temperature (DBTT) and decreases the weldability.
Tables 3.3 and 3.4 give the compositions and mechanical properties of a few carbon steels.
Table 3.3 Composition and mechanical properties of a few carbon steels.
1 ASTM 1 UNS 1 Composition (%)"

Yield Tensile
A285A KO 1700 0.17 C, 0.90 Mn 165 3 10-380 30

A53B KO3005 0.30 C, 1.20 Mn 24 1 415
A106B KO3006 0.30 C, 0.29-1.06 Mn, 0.10 min Si 241 415 30
a Single values are maxima, unless indicated otherwise.
Values at ambient temperature, the single values are maxima.
b. Killed carbon steels

A distinction is made between rimming steels and killed carbon steels: when they are cast,
rimming steels contain excess oxygen which continues to react with carbon, releasing a
large volume of carbon monoxide (CO) forming bubbles during solidification shrinkage
(blowholes). During rolling, these cavities close and the steel recovers its compactness. In
killed steels, the excess oxygen is removed and the resulting structure offers greater resis-
tance to hydrogen embrittlement.
Table 3.4 Composition and mechanical properties of a few API 5L carbon steels (steels for pipelines).
APISL Composition (%)"
A25 C1 I
A25 C1 I1
A 207
B 0.27 C, 1.15 Mn, 0.03 P, 0.030 S 24 1 413
X42 0.29 C, 1.25 Mn, 0.03 P, 0.030 S 289 413
X46 0.31 C, 1.35 Mn, 0.03 P, 0.030 S 317 434
X52 0.31 C, 1.35 Mn, 0.03 P, 0.030 S 358 455
X56 0.29 C, 1.25 Mn, 0.03 P, 0.030 S 386 489
X60 0.26 C, 1.35 Mn, 0.03 P, 0.030 S 413 517
X70 0.31 C, 1.35 Mn, 0.03 P, 0.030 S 482 565
X80 0.31 C, 1.35 Mn, 0.03 P, 0.030 S 55 1 620
c. Low alloy steels

Low alloy steels contain less than 10% of addition elements. Chromium, molybdenum a n d
or nickel are the main alloy elements of low alloy steels used in the petroleum industry.
Table 3.5 provides two examples of compositions and mechanical characteristics illustrating
this steel class.
Table 3.5 Composition and mechanical properties of a few low alloy steels
Yield Elongation
UNS Composition (YO)" Strength
(MPa)b
G4 1300
0.28-0.33 C, 0.80-1.10 Mn,
0.15-0.30 Si, 0.80-1.10 Cr,
0.15-0.25 MO
830' 965' 1 22' 1
G43400
0.38-0.43 C, 0.60-0.80 Mn,
0.15-0.30 Si, 0.70-0.90 Cr,
0.20-0.30 Mo, 1.65-2.00 Ni
860d 1020d 1 20d 1
' Values at ambient temperature. the single values are maxima.
'I inch diameter bars quenched in water from 860 "C and tempered at 650 "C.
I inch diameter bars quenched in water fiom 845 "C and tempered at 650 "C.
High Strength Low Alloy steels (HSLA)

High strength low alloys steels typically contain 0.07% to 0.12% carbon, up to 2% manga-
nese and small additions of niobium, vanadium and titanium (generally less than 0.1%).
HSLA steel is preferably manufactured by hot rolling, which increases the mechanical prop-
erties by refining the grain size. Addition of 0.1% to 0.2% molybdenum leads to the forma-
tion of a fine grain structure of acicular ferrite increasing the hardening effects by precipita-
tion of other addition elements. Some HSLA steels are also called “microalloys”, due to
their low content in addition elements compared with the main commercially available alloy
steels. Quantities as low as 0.10% of niobium and vanadium may significantly modify the
mechanical characteristics of 0.1% C-1.3% C steels. The addition elements are added to
modify the microstructure of carbon steels (generally composed of ferrito pearlitic clusters)
by forming an almost pure ferrite with a very fine dispersion of metallic carbides. This elim-
inates the effects of pearlite volume fractions on reduction of hardness, increasing the steel’s
mechanical strength by precipitation hardening and refining the grain size. Table 3.6 gives
the compositions and mechanical properties of a few HSLA steels.
Table 3.6 Compositions and mechanical properties of a few HSLA steels.
ASTM 1 UNS 1 Composition (TO)”

Yield
Strength
(MPa)b
class 1 290-345 435-485 1 21

I
0.13-0.37 Si, 0.36-0.79 Cr,
0.002-0.006 Nb, 0.12-0.53 CU,
0.02-0.09 V
689 795-930
1 l6

Chromium steels up to 9% Cr
These steels are used mainly for the construction of hydrogen pressure vessels to withstand
high temperature hydrogen attack. Chromium carbides are in fact insensitive to high tempera-
ture hydrogen attack (see paragraph 1.14). Presence of molybdenum and vanadium in solid
solution improves the high temperature creep resistance. 9 Cr-1 Mo steel, in particular, exhib-
its excellent behaviour with respect to high temperature oxidation (up to about 750 “C).
Table 3.7 gives the compositions and mechanical properties of a few chromium low
alloy steels.
Table 3.7 Compositions and mechanical properties of a few low alloy steels.
I 0.90-1.10 Mo, 0.25-1.00 Si I

9 Nickel steels from 2.5% Ni)

Addition of nickel increases the mechanical strength and in particular improves low-temper-
ature resilience (use for devices operating at low temperatures). They are widely used in
LNG units. 3.5% Ni steel can be used down to temperature of - 100 "C and 9% Ni steel
down to about - 195 "C. Table 3.8 gives the composition and mechanical tensile characteris-
tics of 9% nickel low alloy steel.
Table 3.8 Compositions and mechanical properties of a few nickel steels
, u. I J-U.3U 31, I 515 I 690-825

I *O
' Values at ambient temperature, the single values are maxima.
d. Stainless steels
Stainless steels contain sufficient quantities of alloy elements to generate a thin layer of
oxide on the surface which separates the metal and the electrolyte:
- Chromium is the main element which favours the formation of a passive film on the
surface. At a content of above 11%, the steel becomes stainless. This corrosion resis-
tance progressively improves with the chromium content;
- Molybdenum increases the action of chromium. Its content varies between 1% and
3%. The average content of 2% significantly improves the resistance to localised

corrosion;
- Nickel improves the resistance to acid corrosion, especially crevice corrosion;
192 Chapitre 3 -Fundamentals on metallic alloys and corrosion
- Nitrogen increases the passive layer and also improves the resistance to localised cor-
rosion. For certain grades, its content may reach 0.3%.
Stainless steels are classified according to their microstructure.
Martensitic stainless steels

These steels have a chromium content between 11% and 17% and contain little or no nickel
(Table 3.9). They can be hardened by heat treatment and exhibit high hardness but low ductility
and low resilience.
Table 3.9 Compositions and mechanical properties of a few martensitic stainless steels.

Typical values at ambient temperatures for annealed steel sheets
Fevritic stainless steels

These steels have a chromium content between 11% and 28% and contain no nickel. Unlike
martensitic steels, they cannot be hardened by heat treatment since no phase transformation
occurs at high temperature (Table 3.10).
Table 3.10 Compositions and mechanical properties of a few ferritic stainless steels.
-
Yield Tensile
AISI UNS Composition (%)" Strength Strength
(MPa)b (MPa)b W)
405 s40500 0.08 C, 11.5-14.5 Cr, 1.0 Mn, 1.0 Si,
0.04 P, 0.03 S, 0.1-0.3 Al 276 448 30
409 s40900 0.08 C, 11.5-1 1.75 Cr, 1.0 Mn, 1.0 Si, 241 448 25
0.045 P, 0.045 S, (6 x C)Ti
429 s42900 0.12 C, 14-16 Cr, 1.0 Mn, 1.0 Si, 276
0.04 P, 0.03 S 483 30
430 s43000 0.12 C, 16-18 Cr, 1.0 Mn, 1.0 Si,

0.04 P, 0.03 S 276 517 30
442 s44200 0.20 C, 18-23 Cr, 1.0 Mn, 1.O Si,

0.04 P, 0.03 S 310 552 20
446 s44600 0.20 C, 23-27 Cr, 1.5 Mn, 1.0 Si,

0.04 P, 0.03 S, 0.25 N 379 586 25
'' Single values are maxima, unless indicated otherwise.

I' Tvpiccrl values at ambient temperaturesfiw annealed steel sheets
Austenitic stainless steels

These steels have a chromium content of between 17% and 19% and contain 8% to 14%
nickel giving them an austenitic structure. High carbon grades (0.05% < C < 0.1%) are used
for their high temperature mechanical strength. Series S3XXXX steels (see Table 3.1 1) can
be hardened by cold working. This is the most widely used series of stainless steels.
Table 3.11 Compositions and mechanical properties of a few austenitic stainless steels.
Yield Tensile
AISI UNS Composition (YO)" Strength Strength
(MPa)b (MPa)b ("/.I
304 S30400 0.08 C, 18-20 Cr, 8-10.5 Ni, 2.0 Mn,
1.O Si, 0.045 P, 0.030 S
I 24, I 586 1 50
O.O8C, 16-18Cr, 10-14Ni,2.0-3.0Mo, 248 565 55

316 S3 1600 2.0 Mn, 1.0 Si, 0.045 P, 0.030 S
0.03 C, 16-18 Cr, 10-14Ni, 2.0-3.0 Mo, 234 558 55
316L S31603 2.0 Mn, 1.0 Si, 0.045 P, 0.030 S
0.08 C, 16-18 Cr, 10-14 Ni, 3.0-4.0 Mo, 276 586 50
317 S3 1700 2.0 Mn, 1.0 Si, 0.045 P, 0.030 S
0.03 C, 16-18 Cr, 10-14 Ni, 3.0-4.0 Mo, 241 586 55
317L S31703 2.0 Mn, 1.0 Si, 0.045 P, 0.030 S
0.08 C, 17-19 Cr, 9-12 Ni, 2.0 Mn, 207 586 55
S32100 1.O Si, 0.045 P, 0.030 S, (5 x C)Ti
0.08 C, 17-19 Cr, 9-13 Ni, 2.0 Mn,
S34700 1.O Si, 0.045 P, 0.030 S, 24 1 62 1 50
(10xC)5(Nb+Ta)
329 1 S32900
0.10 C, 25-30 Cr, 3-6 Ni, 1.0-2.0 Mo,
2.0 Mn, 1.0 Si, 0.045 P, 0.030 S
552 724 25
Single values are maxima, unless indicated otherwise.

Typical values at ambient temperatures for annealed steel sheets.
Austeno-ferritic (or duplex) stainless steels

These steels have a chromium content between 21% and 28% and contain only 4% to 9%
nickel (Table 3.12). Presence of molybdenum and nitrogen increases their resistance to loca-
lised corrosion. Their structure is composed of 2 phases in equivalent quantities: austenite
and ferrite.
Next Page
Table 3.12 Compositions and mechanical properties of a few austeno-ferritic stainless steels.
Yield Tensile Elongation

UNS Composition (%)" Strength Strength
(MPa)b (MPa)b ("10)
0.03 C, 21.5-24.5 Cr, 3.9-5.5 Ni, 0.05-0.60 Mo,
S32304 1.0 Mn, 1.0 Si, 0.04 P, 0.03 S, 0.05-0.6 Cu, > 400 670 > 30
0.05-0.20N
0.03 C, 21-23 Cr, 4.5-6.5 Ni, 2.5-3.5 Mo, 1.0 Mn, >450 800 > 25
s38103 1.0 Si, 0.04 P, 0.03 S, 0.08-0.20 N
~~
s31200 1 0.03 C, 24-26 Cr, 5.5-6.5 Ni, 1.2-2.0Mo, 1.O Mn,

1.0 Si, 0.04 P, 0.03 S, 0.14-0.20N
I > 450 I 800 I >25
s32550 1 0.03 C, 24-27 Cr, 4.5-6.5 Ni, 2.0-4.0 Mo, 1.0 Mn,
1.0 Si, 0.04 P, 0.03 S, 1.5-2.5 Cu, 0.10-0.25 N
I ,550 I 800 I >I5
s32750 0.03 C, 24-26 Cr, 6.0-8.0 Ni, 3.0-5.0 Mo, 1.0 Mn, > 550 800 > 15
1.0 Si, 0.04 P, 0.03 S, 0.24-0.32N
Typical values at ambient temperatures for annealed steel sheets.
e. Heat-resistant steels
These steels are designed to offer good mechanical characteristics at high temperatures and
good creep resistance. They are used above 600 "C and up to about 1 000 "C. They are rich
in nickel, chromium and addition elements Mo, Ti, Nb, Al, Si (Table 3.13):
Table 3.13 Compositions and mechanical properties of a few heat-resistant stainless steels.
1 I 1 I
ACI AS1 UNS Composition (Yo)"
I HC I 446 I 592695 I 0.5 C,26-30Cr,4Ni, l.OMn,2.0Si I 160 I 20 I

Typical mechanical properties at 875 "C.
Some types of equipment are manufactured by moulding or centrifuging (especially

oven tubes, manifolds, quenching exchangers).
Previous Page
f. Castiron
With a carbon content of over 2% (Table 3.14), cast irons are brittle and non weldable They
find limited applications in petroleum installations, mainly for pump equipment.
Table 3.14 Compositions and mechanical properties of a few cast irons.
Alloy 1 ASTM 1 UNS 1 Composition (“h)”

Tensile
Strength
(MPa)b
I Grey cast iron 1 (G3000)
A159 I F10006
I 3.1-3.4 C, 0.6-0.9 Mn, 1.9-2.3 Si 1 207
Ni-resist cast iron A436 (1) F41000 3.0 c, 1.5-2.5 Cr, 5.5-7.5 cu, 0.5-1.5 Mn, 172
13.5-17.5 Ni, 1.0-2.8 Si
3.0 C, 1.5-2.5 Cr, 0.5 Cu, 0.5-1.5 Mn,
Ni-resist cast iron A436 (2) F41002 18-22 Ni, 1.O-2.8 Si
172
Ni-resist cast iron A436 (5) F41006 2.4C,O.l Cr,0.5Cu,0.5-1.5Mn,

138
34-36 Ni, 1.O-2.0 Si
Ductile austenitic A439 (D2) F43000 3.0 C, 1.75-2.75Cr, 0.7-1.25 Mn,
cast iron 18-22 Ni, 1.5-3.0 Si 400
I Silicon cast iron I A518 I F47003 1 0.7-1.1 C, 0.5 Cr, 0.5 Cu, 1.5 Mn,
0.5 Mo, 14.2-14.75 Si
‘Single values are maxima, unless indicated otherwise
Typical values at ambient temperature, as moulded.
3.1.3.2 Non-ferrous metals

A. Copper and its alloys
Copper alloys exhibit good corrosion resistance and good ductility. Table 3.15 provides
some compositions of copper alloys.
a. Copper-zinc alloys: brass

Copper-zinc alloys generally exhibit excellent resistance to wet corrosion. They are sensi-
tive to selective corrosion by dezincification (zinc goes into solution and the brass becomes
brittle and porous). They are prone to stress corrosion in the presence of ammonia:
- standard brass (70 Cu, 30 Zn) for application in freshwater,
- admiralty brass (70 Cu, 29 Zn, 1 Sn UNS C44300) reserved for slightly saline water,
- aluminium brass (76 Cu, 22 Zn, 2 Al) often used for exchanger tubes in seawater,
since aluminium enhances resistance to cavitation and erosion.
b. Copper-nickel alloys
These alloys offer better erosion resistance than brass and are widely used for operation in
seawater (Table 3.15):
Cu-Ni 10 Fe 1 Mn (known as “90/10” UNS C70600) which exhibits good erosion resistance.
Cu-Ni 30 Mn 1 Fe (known as “70/30” UNS C71.500) which withstands higher fluid speeds.
They offer greater resistance to polluted water than aluminium brass and cupro-nickel90/10.
Table 3.15 Compositions and mechanical properties of a few copper alloys.
Yield Tensile
Alloy CDA UNS Composition (%)" Strength Strength
(MPa)b (MPa)b (%)
I
Commercial
Bronze 1 1
I
220 C22000 1 89-91 Cu, rem Zn
I
I
70
255 50
I RedBrass 1 I 230 C23000 I 84-86Cu,remZn I 70 276 55
I Brass I I
I
443
I
C44300 I
I
70-73 Cu, rem Zn,
0.9-1.2 Sn, 0.02-0.1 As
I
I
124 33 1 65
Naval Brass 1 464 ] (2446400 ] 59-62 Cu, remZn, 0.5-1 Sn I 172 400 50
+
86.5-93.8 Cu, rem Zn,
A'uminium 6 13 C61300 0.2-0.5 Sn, 6-8 Al, 0.5 Ni, 207 483 42
Bronze 3.5 Fe
Nickel 76-85 Cu, 0.3 Zn, 0.2 Sn,
Aluminium 630 C63000 9-1 1 Al, 4.0-5.5 Ni, 248
Bronze 2.0-4.0 Fe, 1.5 Mn
1 90/10Copper-
Nickel
1 706 1 c70600 1 86.5 C q l.OZn,9.0-11.0Ni,
1.O-1.8 Fe, 1.O Mn
1
70/30 Copper- c7 5oo rem Cu, 1.O Zn, 29-33 Ni, 138 372
Nickel 0.4- 1.O Fe, 1.O Mn
B. Nickel-basedalloys
Nickel alloys combine good mechanical and corrosion resistance properties. Table 3.16
gives some compositions of nickel-based alloys.
a. Nickel-copper alloys
These alloys (including N04400) are used in seawater at high circulation speeds (resistance
to cavitation and impacts) and for exchanger tubes in seawater desalination units. They
exhibit good resistance to chlorides and fluorides: it is the main material specified for use in
hydrofluoric acid environment.
b. Nickel-chromium-iron alloys
These alloys exhibit excellent resistance to oxidising or reducing atmospheres at high tem-
perature (up to about 1 000 "C). The most common grades are alloys 600 (N06600) and 625
(N06625).
c. Iron-nickel-chromium alloys
The basic grade is alloy 800 with Incoloy 800H (UNS N 08810) and Incoloy 800HT (UNS
N 088 1 1) variants for high temperature applications (Table 3.16).
9 197
Table 3.16 Compositions and mechanical properties of a few nickel alloys.
I 1 AISI UNS 1 Composition (%)"

1 Yield
Strength
(MPa)b 1 Tensile
Strength
(MPa)b 1 ("/.I I
200 NO2200 99 Ni, 0.4 Fe, 0.15 C 100-210 380-550 40-55
400 NO4400 63-70 Ni, 1.0-2.5 Fe, 0.3 C, 28-34 Cu 170-345 480-620 35-60
600 NO6600 72 Ni, 14-17 Cr, 6-10 Fe, 0.15 C 205-350 550-690 35-55
601 N06601 58-63 Ni, 21-25 Cr, rem Fe, 0.10 C,
1.O-1.7 A1 205-415 550-790 40-70
I 625 I I remNi,20-23Cr,5 Fe,8-10Mo,O.lOC,

3.15-4.15Nb
I 415-655 I 825-1 035 I 30-60 I
I I 718
8oo
NO7718
N08800
I 50-55 Ni, 17-21 Cr, rern Fe, 2.8-3.3 Mo,
0.08 C, 4.75-5.5 Nb, 0.65-1.15 Ti,
0.2-0.8 Al
30-35 Ni, 19-23 Cr, rern Fe, 0.10 C, 205-414 5 15-690 30-60
0.15-0.60 Ti, 0.15-0.6 A1
800H N08810 30-35 Ni, 19-23 Cr, rern Fe, 0.05-0.10 C,

0.15-0.60 Ti, 0.15-0.6 Al
I B-2 I N10655 I rem Ni, 1.0 Cr, 2.0 Fe, 26-30 Mo, 0.02 C I 525 I 960 I 53 I
c276 N10276 rem Ni, 14.5-16.5 Cr, 4.7 Fe, 15-17 Mo,
0.02 C, 3.0-4.5 W 360 790 61
rem Ni, 21-23 Cr, 18-21 Fe, 5.5-7.5 Mo,
G NO6007 0.05 C, 1.0-2.0 Mn, 1.5-2.5 Cu, 317 703 61
1.75-2.5Nb
I X I NO6002 1 rem Ni, 20.5-23 Cr, 17-20 Fe, 8-10 Mo,

0.05-0.15 C, 0.2- 1 .O W I 385 I 760 I 45 1
Single values are maxima, unless indicated otherwise.
Typical values at ambient temperatures,for annealed steel sheets
C. Cobalt alloys
Due to their high hardness, they are suitable for applications under erosion and abrasion
conditions. Stellite 6 (60 Co - 29 Cr - 5 W or UNS R30006) for example is used as a coat-
ing for valve seats and to provide protection against pitting in abrasive service.
D. Aluminium alloys
These alloys (density = 2.7) are three times lighter than steels. They are classified into vari-
ous families according to their alloy elements (series 2 000,3 000,5 OO0,7 000), as shown in
Table 3.17. Aluminium alloys retain good ductility at very low temperatures. Their mechani-
cal characteristics, however, drop significantly above 180 "C. They are mainly used for:
- brazed aluminium plate exchangers for cryogenic applications,
- their good resistance to aqueous phases of H2S and NH,.

But:
- they are sensitive to attack by molten metals (mercury embrittles aluminium alloys, as
described in paragraph 1.4),
- there is a possible risk of pitting corrosion for some grades in the presence of chlorides,
- precautions must be taken to avoid contact with a more noble metal (galvanic corro-
sion effect by formation of an electrochemical cell).
Table 3.17 Compositions and mechanical properties of a few aluminium alloys.
Yield Tensile Elongation

AA
Designation UNS Composition (YO)" $:if::t Strength Strength
(MPa)b (MPa)b (%)
1060 A91060 99.6 A1 min Temper 28 69 43
1100 A91 100 99.0 A1 min, 0.05-0.2 Cu Temper 34 90 45
Al rem, 0.1 Cr,
2024 A92024 3.8-4.9 CU, 1.2-1.8Mg, T4 324 469 19
0.3-0.9 Mn, 0.5 Si
A93003 A1 rem, 0.05-0.2 Cu,
3003 HI4 145 152 18
1.O-1.5 Mn, 0.5 Si
5052
I A95052
I
I
Al rem. 0.15-0.25 Cr.
0.1 Cu,'2.2-1.8 Mg, '
0.1 Mn
1 Temper 1 90 I 193 I 30
A1 rem, 0.04-0.35 Cr,

606 1 A96061 0.15-0.4 Cu, 0.8- 1.2 Mg, T6 278 3 10 17
0.15 Mn, 0.4-0.8 Si
A1 rem, 0.18-0.28 Cr,
7075 A97075 1.2-2.0 CU,2.1-2.9 Mg, T6 503 572 12
0.3 Mn, 0.4 Si, 5.1-6.I Zn
" Single values are mmima, unless indicated otherwise.
'?vpical values at anihient teniperatirre.
E. Titanium alloys
They are highly resistant to corrosion by seawater (plate exchangers on seawater-freshwater
cooling circuits) and are often specified in cooling systems when the service presents risks
of localised corrosion by chlorides. Their oxide layer provides excellent protection against
corrosion. They represent a good compromise between low density (d = 4.5) and high
mechanical characteristics, useful in offshore petroleum production applications (e.g. risers).
Table 3.18 gives some compositions of titanium alloys.
In addition, it is important to avoid coupling between titanium alloys and other metallic
materials (galvanic effect). Titanium alloys must never come into contact with anhydrous
chlorine (less than 1% water) or high pressure oxygen (combination with the alloy generates
a violent exothermic reaction with serious risk of inflammation). Methanol may also gener-
ate stress corrosion cracking in titanium and its alloys (in particular alloy Ti-6A1-4V UNS
R56400), as indicated in paragraph I . 10.
Yield Tensile
Alloy UNS composition ( O h ) " Strength Strength
(MPa)b (MPa)b ("/.I
Grade 1 R50250 Ti rem, 0.2 Fe, 0.18 0 24 1 33 1 30
Grade 1 R50250 Ti rem, 0.2 Fe, 0.18 0 24 1 33 1 30
Ti-Pd Ti rem, 0.3 Fe, 0.25 0,
Grade I R52400 0.12-0.25 Pd 345 434 28
Ti-6AI-4V Ti rem, 5.5-5.6 Al, 0.40 Fe,
Grade 5 R56400 0.20 0,3.5-4.5 v 924 993 14
3.2 BASIC INFORMATION CONCERNING THE MECHANISMS INVOLVED

IN THE CORROSION OF METALLIC MATERIALS
Corrosion is defined as being the physico-chemical interaction between a metal and its sur-
rounding environment leading to modifications of the metal properties and often a func-
tional degradation of the metal itself, its environment or the technical system they form.
Few metals are found in native state in nature. Some metals like gold and platinum are
thermodynamically stable and are found in metallic form, but very often most metals com-
bine to form oxides, sulfates, sulfides, carbonates or chlorides, which represent the main
types of ore. Reduced to the metallic state, in some environments they tend to return to their
thermodynamically stable form, the oxidised one. Depending on the thermodynamic state of
the corrosive environment (liquid or gas), return to stable state takes place according to
chemical, electrochemical or gas-phase (dry corrosion) processes.
For more information, the reader may also refer to the bibliography indicated at the end
of the chapter [335; 337; 347; 3481.
3.2.1 Information concerning the thermodynamic stability

of corrosion reactions
3.2.1.1 Free enthalpy of a corrosion reaction

Chemical reactions are generally represented by the relation C vi Ai = 0, where Ai represents
the chemical species involved in the reaction and vi the associated stoichiometric coeffi-
cients, positive for the reaction products and negative for the reactants.
Writing ni the number of moles of species Ai (ni > 0) and G the fotu1,freeenthulpy of the
system composed of the set of species Ai present, we define the extent of reaction and the
chemical potential as follows:
d(5) = d(ni)/vi 6 is the extent of reaction C vi Ai = 0.
pi = a G/a ni where p, represents the chemical potential of species Ai.
Since G(ni) is therefore a homogeneous hnction of degree 1, the total free enthalpy of
the system can be written: G = C ni pi.
By differentiating the previous equation, we obtain:
d(G) = d(C ni pi) = C ni d(pJ + C pi d(ni)
In addition, the definition of chemical potential implies: d(G) = C pi d(ni) which gives:
C ni d(pJ= 0 known as the Gibbs-Duhem relation.
As for G, we define the reaction free enthalpy denoted AGr which corresponds to the
energy difference between the reaction products and reactants represented by C vi Ai = 0:
AGr = X ni pi
The chemical potential pi of a species Ai can be separated into two parts according to the
relation:
pi = p? + RT Ln ai
where py represents the standard chemical potential of species A, (the standard state is
the physical state in which pure specie Ai is the most stable, at atmospheric pressure
(1 bar), for a given temperature),
and where ai represents the activity of specie Ai: the activity is the product of an activity
coefficient f and the concentration of the specie.
For a gas mixture, the activity of a gas i is: ai = fi Pi/P0,,where Po,i corresponds to the pres-
sure of specie i in standard state (in other words atmospheric pressure). Since pressures are
generally high in corrosion processes, the gases behave as perfect gases fi = 1 hence ai = Pi.
For a solution, the activity of a solute i (e.g. a salt dissolved in water) is: ai = fi ci/co,,
where co,i corresponds to the concentration of specie i in standard state (c,,i = 1) hence
ai = fi ci and since the solute is generally highly diluted ai = ci (in mole/L).
The activity of solvent i (e.g. water in the aqueous solution) or an alloy component is:
ai = fi Xi with the molar fraction Xi = Ni/CNi where Ni designates the number of moles of i
and CNi the total number of moles. For highly diluted solutions, the solvent activity is gener-
ally equal to 1.
The free enthalpy of reaction AGr becomes: AGr = A q + RT Ln K
With A q = C vi pio, Ln K = X pi ni Ln ai, i.e. K = nxi
A q is called the standard free enthalpy of reaction.
A chemical reaction is spontaneouslypossible if the total free enthalpy G decreases (so AG < 0),
reaching its minimum value when the system is at equilibrium, i.e. when the reaction occurs
“equally” in both directions. The minimum value of G corresponding to d(G) = 0 is expressed by:
d(G) = C pi d(ni) = 0
Using the definition of extent of reaction 6 for the equilibrium condition we obtain:
d(G) C vi pi d(Q = 0
1
Which finally gives at equilibrium:

Cvipi=AG,=O
Chapitre 3 Fundamentals on metallic alloys and corrosion 20 1
Substituting this result in the expression for free enthalpy of reaction, we obtain for the
system at equilibrium:
A q = - RT Ln K
The value of K = l78i is the reaction equilibrium constant.
3.2.1.2 Ellingham diagrams

It may prove u s e l l representing graphically for various oxides (as well as carbides and sulfides
which will not be discussed in the remainder of this paragraph) the evolution as a function of
temperature, of the standard free enthalpy of the reaction leading to their formation (standard
fiee enthalpy offormation) AGO for an oxygen partial pressure of 1 bar in the case of oxides.
This type of graph is called an Ellingham diagram (Figure 3.38 for various oxides). The
position of the oxides on this diagram can be used to compare their relative thermodynamic
stabilities.
The reactions represented are therefore all reduced to 1 mole of oxygen. The values com-
pared correspond to the standard free enthalpies of formation multiplied, for each oxide con-
sidered, by the stoichiometric coefficient “n” corresponding to the number of moles of oxide
formed for one mole of oxygen. The lower the position of an oxide in the diagram is, the more
-1 00
-300
f -500
.
E
2
0
-700
-900
-1100 1 I 1 I
Temperature (“C)
Figure 3.38
~
Ellingham diagram of various oxides.

stable the oxide will be. For example, since the curve of A1203 is below that of Cr203,alumin-
ium metal can reduce chromium oxide to form aluminium oxide and chromium metal.
If the free enthalpy of formation is negative, the corresponding metals must react spontane-
ously with oxygen. Two conditions must be met, however, for the equilibrium between metal, oxy-
gen and oxide to stabilise: firstly, the three phases must be in contact and secondly, the interfacial
reactions must be fast (which is not the case at ambient temperature since a thin, non porous layer
of oxide prevents oxygen penetration, but is true at high temperature where ion mobility is faster).
The oxygen partial pressure in equilibrium with the oxide and the metal is obtained
directly from the values indicated on Figure 3.38.
The standard free enthalpy AGO = - RT Ln K = RT Ln Po, since the oxygen activity is
equal to its partial pressure (ai = PO2)and the activity ai of a metal or a pure oxide is equal to 1.
3.2.2 Chemical corrosion in liquid phase

This type of corrosion by chemical attack leads to the dissolution of solid metals, for example:
- dissolution of a solid metal by a liquid metal: as described in paragraph 1.4, alumi-
nium can be dissolved by mercury,
- dissolution of metals in halides, e.g. lead in PbCI2,
- dissolution of metals in non aqueous solutions, e.g. aluminium in CCI,.
These highly specific corrosion mechanisms are rarely encountered. Metal dissolution
occurs more generally via electrochemical processes.
3.2.3 Electrochemical corrosion in liquid phase
3.2.3.1 Electrochemical reactions

Electrochemical corrosion corresponds to the formation, from metallic state, of ions going
into solution by an “anodic” oxidation reaction:
(Mlrnetal + (Mn+)solution+ n e- (3.1)
The ion initially formed is therefore monovalent in case of copper, divalent in case of
iron and nickel and trivalent in case of aluminium, titanium and chromium.
Reaction (3.1) is necessarily coupled with a “cathodic” reduction reaction:
(~x+q)solution+ (e-)metal+ (~ed+(q-I))solution (3.2)
The most common oxidising agents are:
- a water molecule according to the reaction H 2 0 + e- 4 1/2 H2 + OH- (3.3)
- H’ionsby H+ + e- + 1/2 H2 (3.4)
- dissolved oxygen by O2 + 4H’ + 4e-+ 2H20 (3.5)
or by 0 2 + 2H20 + 4e- -+ 40H- (3.6)
- the higher valence of a multiple valence ion, for example
Fe3+ + e- -+ Fe2+ (3.7)

Anodic and cathodic electrochemical reactions involve a charge transfer between the metal
(electronic conductor also called electrode) and an ionic conductor (also called electrolyte).
This also involves displacement.of electrons through the metallic mass between the anodic and
cathodic zones, thereby creating an electric current without the need for any external source.
3.2.3.2 Faraday's law

In an electrochemical reaction, when ni moles of a metal are oxidised, a proportional electric
charge Q passes through the metal (electrode)-electrolyte interface:
Q=nFni (3.8)
where F designates a universal constant called the Faraday constant F = 96 485 C/mol.
The (adimensional) number of charges n expresses the stoichiometric coefficient of the
Fe -
electrons in the anodic reaction equation. For the anodic dissolution of iron, for example:
n=2
Fe2++2e-
Differentiating equation (3.8) with respect to time, we obtain the usual expression of
Faraday's law for electric current:
I = d Q/dt = n F (dni/dt) (3.9)
where dni/dt represents an oxidation rate in moles per second.
The rate of the electrode reaction (corrosion) is proportional to the magnitude of the
electric current through the electrode-electrolyte interface. The corrosion rate is measured
in mol/m2s, A/m2, mg/dm2day, mm/year, mpy (milli incWyear). Appendix 2 provides a cor-
respondence table for these units.
3.2.3.3 Metal - electrolyte interface

Charge separation occurs when a metal is placed in contact with an electrolyte: electrons cannot
move more than 2 nanometres away from the metal under the attraction of the positive charges in
the electrolyte (metallic cations in solution, e.g, Fe2+). The charge distribution at the interface
depends on numerous factors: electronic properties of the metal, adsorption of water molecules or
hydrated cations and chemisorption of anions (e.g. chlorides in water) which, despite their nega-
tive charge, can adsorb on a negatively charged metal (thereby replacing water molecules on the
surface). The interface zone containing charge separation with conservation of electrical neutral-
ity is called the double electric layer. Figure 3.39 shows a diagram of the double layer (Helmotz
model). The double layer creates apotential dzflerence between the metal and the solution.
3.2.3.4 Electrochemical thermodynamic equilibrium

Thermodynamically speaking, each metal atom can be considered as an ion occupying a cer-
tain energy level stabilised by its electronic environment, which can be represented by its
molar chemical free enthalpy G c , ~ .
Layer of dipolar
water molecules
/ I
Helmholtz
layer
Figure 3.39
Helmotz model of the double electric layer.
In polar solvents, these ions may have a different energy level stabilised by the environment of
water molecules, which can be representedby its molar chemical free enthalpy G C ,(Figure
~ 3.40).
Due to thermal agitation, metallic ions tend to go spontaneously into solution if they can
cross the energy barrier formed by breakage of their electronic bonds. The difference
between the top of this energy barrier and GC,M represents the activation energy AG*
required for the metal to go into solution. However, presence of positive ions near the metal-
water interface and the corresponding excess of electrons on the metal surface create very
quickly a potential barrier tending to reverse dissolution. A dynamic equilibrium is then cre-
ated, which can be expressed by the following reaction:
M t)Mgf + ne- (3.10)
This equilibrium corresponds to a potential E representing the potential difference
between the metal M and the solution containing the ions Mi'. E is the reversible potential
of the electrode reaction. When this equilibrium is reached, the chemical free enthalpy dif-
ference AGc,r of the dissolution reaction (energy produced by the reaction) and the electrical
energy WErequired to cross the potential barrier E are equal (absolute value).
WE=nFE (3.1 1)
where F designates the Faraday constant F = 96 485 C/mol.
9 205
Free molar
Reactional step
Figure 3.40
Energy level indicating the passage of the metal into solution.
In addition, assuming that the activity of the metallic ions in diluted solution is propor-
tional to their concentration, the chemical free enthalpy difference of reaction 3.10 is written:
GS,C- GM,c = Gr,c = Gr,Co + RT ~n { W"+I/[MI I (3.12)
where Gr,co is the standard chemical free enthalpy of reaction ([M"+] = 1) at the temper-
ature considered, [MI the activity of the metal atoms in the metal (by definition equal to 1)
and [M"+] the metallic ion concentration in the solution (mol/L).
Equating relations (3.1 1) and (3.12) gives with [MI = 1:
nF E = Gr,co + RT Ln [M"'] (3.13)
i.e.: E = G,,co/nF + RT Ln [Mnf]/nF (3.14)
and putting Eo = Gr,co/nF E = Eo + RT Ln [M"+]/nF (3.15)
Relation (3.15) is called the Nernst equation of an electrode reaction.
Eo is the standard potential of the metal M electrode (potential of the metal in equilib-
rium with a solution of its ions of concentration equal to 1).
The reversible potential E cannot be measured directly. In electrochemical corrosion, however,
it is essential to know and compare the equilibrium potentials of various electrode reactions. The
equilibrium potentials E are therefore measured with respect to another electrode, called the refer-
ence electrode,at equilibrium and in electrical contact with the first electrode via the solution.
The arbitrarily chosen reference electrode is the standard hydrogen electrode. It consists
of an inert metal (platinum) immersed in a normal acid solution at 25 "C through which
hydrogen is bubbled at a pressure of one atmosphere. The inert metal (platinum) acts only as
electron donor and acceptor for the reaction:
2 Hf + 2e- H H, (3.16)
By convention, the reaction potential E, is taken equal to zero.

The voltage V measured between the metal and the reference electrode is (Nemst equation):
V = E = Eo + RT Ln [M"']/nF (3.17)
The standard potential Eo becomes equal to the standard potential of the metal M electrode.
The values of Eo determined in this way for various materials form the Nernst scale
which classifies metals according to their tendency to go into solution at 25 "C (Table 3.19).
Table 3.19 Standard potentials of electrode reactions with respect to the standard hydrogen electrode.
Equilibria Eo at 25 OC (V)
Au ts Au3+ + 3e- + 1.5
Pt tf pt2++ 2e- + 1.188
Ag H Ag+ + e- + 0.799
Hg tf Hg2+ + 2e- + 0.796
cuts cu2++ 2e- + 0.337
H2 tf 2H+ + 2e- 0
Pb tf Pb2++ 2e- - 0.126
Sn H Sn2+ + 2e- -0.136
MO tf M O ~ +
+ 3e- - 0.200
Ni tf Ni2+ + 2e- - 0.257

Fe tf Fe2++ 2e- - 0.440
Cr ts c?++ 3e- - 0.740

Zn ts zn2++ 2e- - 0.763
A I ts A I ~ ++ 3e- - 1.66
We can deduce from this ranking that metals such as gold, silver and copper which have
positive standard potentials will not be attacked by water since they oxidise less easily than
hydrogen. They are the so-called "noble" metals. This table is nevertheless imperfect, since
with some types of corrosion, the metal is not in equilibrium with its ions alone (which mod-
ifies its potential), or because a passive film forms on its surface (which also modifies its
potential by making it more noble).
In practice, the potentials are not measured directly with a standard hydrogen electrode
but using reference electrodes which are easier to use. Table 3.20 indicates the most com-
monly used reference electrodes and their potentials with respect to the hydrogen electrode.
3.2.3.5 Pourbaix diagrams: potential-pH equilibria

The reversible potential of numerous electrode reactions, in particular those involving
oxides, depends on the pH. The potential-pH or Pourbaix diagrams represent the reversible
potential calculated using the Nernst equation (3.15) as a function of pH. These diagrams
Table 3.20 Potentials of common reference electrodes with respect to the standard hydrogen electrode.
Reference electrode Electrolyte Reactions E (V)

saturated KC1 0.241
Calomel 1 MKCI Hg2C12+ 2 e- fs 2Hg + 2CI- 0.280
0.1 M KC1 0.333
Mercurous sulfate saturated K2SO4 HgSO4 + 2 e- t) Hg + SO:- 0.658
Silver chloride saturated KC1 AgCl + e- t) Ag + CI- 0.195
Copper sulfate saturated CuS04 CuSO4 +2 e- fs Cu + SO:- 0.316
Hydrogen H2S04 2H+ + 2e- t) H2 0.000
can be used to predict the thermodynamically stable species depending on the potential and
the pH.
For a given metal, this diagram is plotted taking into account the various possible
electrode reactions and chemical reactions. To illustrate this curve, the simplified Pourbaix
diagram for iron is given as an example (temperature = 25 "C, concentration of dissolved
species = 1o - ~mol/L).
Electrochemical equilibrium between a metal and its ions

M n + + ne- e M
Figure 3.41 line 6:
Fe H Fe2+ + 2 e- E (V) = - 0.440 + 0.0295 log [Fe2'],
i.e. with [Fe3'] = lod E(V)=-0.617
Electrochemical equilibrium between two ions of a metal

M n+ + me- e M (n-m)'
Figure 3.41 line 7:
Fe2+ + e- H Fe3+ Eo (V) = 0.77 1
Electrochemical equilibrium between a metal and one of its oxides

MOd2 + nHf + ne- H M + n/2 H 2 0
Figure 3.41 line 5:
3 Fe + 4 H 2 0 H Fe304 + 8 Hf + 8 e- E (V) = 0.085 - 0.059 pH
Electrochemical equilibrium between two oxides with different oxidation degrees

Figure 3.41 line 4:
2 Fe304+ H 2 0 H 3 Fe203+ 2 H+ + 2 e- E (V) = 0.221 - 0.059 pH
Electrochemical equilibrium in acid medium between an oxide and dissolved ions

Figure 3.41 line 1:
2 Fe3+ + 3 H 2 0 H Fe203+ 6 H+ log [Fe3'] = - 0.72 - 3 pH hence pH = 1.76
Figure 3.41 line 2:

2 Fe2++ 3 H 2 0 fs Fe203+ 6 H+ + 2 e-
E (V) = 0.728 - 0.1773 pH - 0.059 log [Fe2'], i.e.: E (V) = l .082 - 0.1773 pH
Figure 3.41 line 3:
3 Fe2++4 H 2 0 fs Fe30, + 8 H + + 2 e-
E (V) = 0.980 - 0.2364 pH - 0.0886 log [Fe2'], i.e.: E (V) = 1.512 - 0.2364 pH
Electrochemical equilibrium in alkaline medium between an oxide and dissolved ions
(there is no such equilibrium for our example)
Water stability field

The water stability field is also shown on Figure 3.41 by:
- dotted line a for the reversible potential of hydrogen
2 Hf + 2e- fs H2 E (V) - 0.059 pH
- dotted line b for the reversible potential of oxygen
O2 + 4 H + + 4 e - f s 2 H 2 0 E (V) = 1.23 - 0.059 pH
The region between lines a and b corresponds to the field where, from the thermody-
namic point of view, water is stable at ambient pressure.
-1.6
1.2
0.8
0.4
h
L
-m
.-c 0
c
a,
c
0
Q
-0.4
-0.8
-1.2
-1.6 ~ ~
0 2 4 6 8 10 12 14
PH
Figure 3.41
Simplified Pourbaix (potential-pH) diagram for iron.
Generally speaking, these two straight lines create three main regions:
- All metals whose equilibrium potential for an ion concentration of mol/L is
below the straight line (a) are attacked by water with release of hydrogen according to
the reaction:
M + n H,O H M"' + n OH-+ n/2 H,
- All metals whose equilibrium potential for an ion concentration of mol/L is
between lines (a) and (b) are only attacked in the presence of oxygen according to the
reaction:
M + n/4 O2 + n/2 H 2 0 w M"++ n OH-
- All metals whose equilibrium potential for an ion concentration of 10"mol/L is
above the straight line (b) are thermodynamically stable.
However, the surface oxides formed when a metal is attacked may protect the underlying
metal. In this case, the metal is passivated, the surface oxide layer being called the passive
film. When a metal is attacked by water at 25 "C, Pourbaix diagrams can therefore be used
to define the theoretical regions of immunity, passivity and corrosion of the metal consid-
ered, as illustrated on Figure 3.42.
However, since the Pourbaix diagrams are based purely on thermodynamic consider-
ations, they can only predict equilibrium states and theoretical reaction possibilities, provid-
ing no indication on their rates. Rates are determined using electrochemical kinetics, dis-
cussed in the next paragraph.
3.2.3.6 Electrochemical kinetics

Corrosion reactions include at least one anodic partial reaction and one cathodic partial reac-
tion, each including several steps as indicated on Figure 3.43.
Cathodic partial reaction:
The oxidising agent present in the electrolyte diffuses towards the surface of the elec-
trode where it reacts by accepting one or more electrons. The charge transfer reaction at the
metal-electrolyte interface occurs before or after a heterogeneous chemical reaction at the
interface or a homogeneous reaction inside the metal. Mass transfer phenomena generally
occur before then after the charge transfer reactions, affecting the concentrations of corro-
sion products and reactants at the interface. A contiguous diffusion layer is formed at the
interface. The concentrations of corrosion products and reactants in this layer is different
from those in the electrolyte (bulk).
Anodic partial reaction:
This reaction also involves a charge transfer at the interface, which corresponds to the
passage of a metal atom into solution as hydrated or complexed ion, with loss of one or more
electrons. The ion then diffuses in the electrolyte. Near the anodic surface, the concentration
of metallic ions generated by dissolution exceeds the concentration measured in the electro-
lyte; when it exceeds the saturation threshold, solid corrosion products precipitate out and
form a porous film. Under certain conditions (type of metal, pH, etc.) a thin, compact film of
protective oxides called the passive film may form.
9
Aluminium Nickel
PH PH
Chromium Copper
Figure
-
-
3.42
PH
Immunity
0
Passivity 1-
6
PH
Corrosion
Simplified Pourbaix (potential-pH) diagram for chromium, copper, aluminium

and nickel
14
Steps limiting the corrosion reactions:

The overall corrosion rate will be governed by the slowest reaction step. Three catego-
ries of corrosion reactions may be limiting:
- corrosion controlled by the kinetics of the charge transfer of anodic or cathodic reac-
tions at the metal-electrolyte interface (e.g. corrosion of steel in acids),
- corrosion controlled by the mass transfer rate (diffusion) of the oxidising agent or the
corrosion products (e.g. corrosion of steel in aerated neutral medium),
- corrosion controlled by the properties of the passive films (e.g. stainless steels in
water).
Double
Bulk
Diffusion layer .Ielectrolyte
I
- 1
Figure 3.43
Reaction steps during corrosion of a metal in liquid medium: (a) cathodic partial
reaction, (b) anodic partial reaction.
A. Corrosion controlled by charge transfer

a. Butler- Volmer equation
For electrochemical reactions, involving and limited by charge transfer at the electrode-
electrolyte interface, the corrosion rate is expressed in terms of current equivalent according
to Faraday’s law:
J=nFv (3.18)
with J: charge transfer current density (A/m2)
n: metal valence
F: Faraday constant (96 500 C/mol)
v: reaction rate (mol/s rn2>
If we apply this formula to the relation expressing the redox reaction representative of
metal corrosion,
Va
Red tj Ox + n e-
VC
we define an anodic reaction rate v, and a cathodic reaction rate v, corresponding

respectively to the current densities J, and J, (at electrochemical equilibrium we obtain in
absolute values v, = v, and J, = J,). The overall rate corresponds to the difference between
anodic oxidation rate and cathodic reduction rate:
J = n F (v, - v,) (3.19)
The reaction rates are proportional to the concentrations of the reacting species and
depend on the energy barrier corresponding to breakage of the atomic bonds (free activation
enthalpy) according to Arrhenius’ law:
i.e. for the anodic reaction: v, = kRedCRed exp(- AG,*/RT) (3.20)
and for the cathodic reaction: v, = kox Cox exp(- AGF/RT) (3.21)
where kRedand kox are constants, CRed and Cox the concentrations in reacting species,
AG,* and AG,* the electrochemical free activation enthalpy differences for the anodic and
cathodic reactions, R the perfect gas constant and T the temperature (in K).
The electrochemical free activation enthalpy can be broken down into chemical free acti-
vation enthalpy AG& (which is does not depend on the potential) and the charge transfer
electrical energy at potential A$ which is distributed, for the partial reactions, according to
the relations:
anodic partial reaction: AG,* = AGg,ch - a n F A$ (3.22)
cathodic partial reaction: AGE = AG& + (1 - a)nF A4 (3.23)
A$ represents the potential difference at the metal-solution interface and a the charge
transfer coefficient (0 < a < 1) which expresses the charge transfer ratio between the two
anodic and cathodic partial reactions.
Substituting relations (3.22) and (3.23) in the reaction rate expressions (3.20) and (3.21)
and using the current density expression (3.19), we obtain for the absolute values of the
anodic and cathodic current densities:
J, =n F kRed CRed exp(- AG;,,h/RT) exp(anF A$/RT) (3.24)
J, =n F kox Cox exp(- AGF,ch/RT) exp(- (1 - a)nF A$/RT) (3.25)
The electrochemical reaction rate v is given by v = v, - v, or, in terms of exchange cur-
rent density: J = J, - J,.
The electrode potential E is measured with respect to a reference electrode of constant
potential E r e Thus:
~
E = A$ - Eref (3.26)
Using relations (3.24), (3.25) and (3.26) and grouping the terms which do not depend on
the potential E into constants k,Redand k.ox we obtain:
J = J, - Jc = n F k ’ ~ C
~ dR exp(anF
~ ERT) - n F k‘, Cox exp(- (1 - a)nF ERT) (3.27)
with: k’i = ki exp(- (AG& +- Xi E,,f)/RT), XRed = - a n F et Xox= ( I - a)nF
When the redox reaction is in equilibrium, the exchange current density J (or the overall
rate v) is zero. This does not mean that “nothing is happening”, but only that the anodic and
cathodic partial reactions are equal, i.e. IJ,I = IJ,( = IJol.
9 213
JO is the exchange current density of the electrode reaction at equilibrium.

By definition, the potential E is then equal to the reversible potential Ere, of the electrode
as defined by the Nernst relation (3.17). Using the expressions of (3.27):
Jo = n F k’Red CRed exp(anF Erev/RT)= n F k’ox Coxexp(- (1 - a)nF EreV/RT) (3.28)
Introducing the expression of JOin (3.27), we obtain:
J = Jo[exp(a nF q/RT) - exp(( 1 - a)nF q/RT)] (3.29)
With q = E - Ere,, overvoltage or potential difference with respect to the equilibrium
value Ere, for which IJ,J = IJcI = (Jol,and J = 0.
Relation (3.29) is the Butler-Volmer equation of the electrode.
b. Tafel coefficients and lines

If the overvoltage q is sufficiently high, either the anodic or the cathodic reaction of relation
(3.29) soon becomes negligible. This is illustrated on Figure 3.44 which shows the evolution
in current densities J, J, and J, as a function of the potential E.
Figure 3.44
Evolution of current densities as a function of the potential (linear scale).
For an anodic overvoltage q,, we obtain: J = J, = Jo exp(a nF qa/RT) (3.30)

And for a cathodic overvoltage q,: J = J, = Jo exp(-(1 -a) nF qc/RT) (3.31)
In relations (3.30) and (3.3 l), we can define the anodic and cathodic Tufel coefficients by
respectively:
Pa = RT/a nF (3.32) and 0, = RT/(l - a)nF (3.33)
In this case we obtain:
qa = Pa Ln (J,/Jo) and qc = - P, Ln (JJJo)
Or, for the anodic branch:
log10 (Ja) = qa/(2,3 Pa) + loglo (Jo) (3.34)
And for the cathodic branch:

loglo (JJ = -Tc/(2,3 PC) + loglo (Jo) (3.35)
The Butler-Volmer equation expressing the overall current density can then be written
J = Ja + Jc = JO exp(q$Pa) - JO ex~(r\clPc) (3.36)
Relations (3.34) and (3.35) are the anodic and cathodic Tafel lines which describe the
anodic and cathodic limits of the general Butler-Volmer equation (3.29). The graph of loglo (J(
as a finction of E is frequently used to determine the kinetic parameters Jo, Pa and p,.
On a graph such as that shown on Figure 3.45, the intersection of the Tafel lines which
corresponds to IJaI = IJcI = lJol and to zero overvoltages qa and qc (at reversible potential)
allows graphical determination of the exchange current density at equilibrium.
The Tafel coefficients Pa and pcare given by the reciprocals of the gradients of these lines.
Log10 (Jcor) -
Tafel
cathodic zone I anodiczone
I I b E
Ere"
Figure 3.45
Anodic and cathodic current densities (absolute values) of an electrode reaction
(logarithmic scale).
c. Corrosion potential
A corrosion system generally consists of two coupled electrochemical reactions, one corre-
sponding to oxidation of the metal (M -+Mn' + ne-) and the other to reduction of the oxidis-
ing agent present in the solution (e.g. 2H+ + 2e- 3 H2), as illustrated on Figure 3.46 below.
Instead of the exchange current density at equilibrium JO and the electrode reversible
potential Ere", in this case we speak of corrosion current density J,,, and corrosion potential
Ecor: if there is no external current, the absolute values of the anodic dissolution and
cathodic reduction current densities are equal. The curve obtained is called a polarisation
curve. This curve (solid lines on Figure 3.46) is the sum of the reducing agent anodic curve
9 215
Ere, Ere,
Reducingagent Oxidising agent
Figure 3.46
~
Diagrammatic representation of a corrosion system (semi-log scale).
and the oxidising agent cathodic curve. As with a single electrode system, one of these reac-
tions soon becomes negligible on moving away from the potential Ecor,and the curve enters
the corresponding Tafel region.
d. Butler-Volmer equation applied to a corrosion system
The Butler-Volmer equation is applied to our corrosion system with a metal M as oxidising
agent and hydrogen as reducing agent. The total current density is the sum of the partial cur-
rent densities:
J = JM + JH = Ja,M + JcM + JaH + J c ~
JM = Ja,M + JcM = JO,M exp(qM@aM>- JO,M exp(qM&M)
JH = Ja,H + JcH = JO,H exp(qH/PaH) - JO,H eXP(qH&H)
In these equations, the overvoltages qMand qHare defined by:
qM= - Erev,M
qH= - Erev,H
At the corrosion potential (E = Ecor), the total current density J is zero and the contribu-
tion of JcM and J , , generally turns out to be negligible:
J = J,, + J,. = 0
In this case, the anodic and cathodic current densities are equal and correspond to what is
known as the corrosion current density Jcor.
Jcor = Ja,M(Ecor) = - J ~ H ( E ~ ~ r )
216 -
At the corrosion potential, applying Faraday's law (3.19), the metal corrosion rate is
therefore:
vcor = J c o h F = Ja,~(~cor)/nF
e. Polarisation resistance
If the overvoltage q is relatively low, the exponential terms in the Butler Volmer relation
(3.29) can be replaced by their series limited to the first order (ex = 1 + x and eCX= 1 - x).
We then obtain:
J = Jo [( 1 + a nF q/RT) - (1 - (1 - a) nF qIRT)]
1.e. J = Jo nF q (3.37)
We therefore obtain a linear relation between the current and the potential and, by
analogy with Ohm's law, we can define apolurisation resistance R,:
R, = RT/(Jo nF) (3.38)
The graph of Figure 3.46 and relation (3.38) form the basis of the electrochemical tech-
niques for experimental determination of corrosion rates.
B. Corrosion controlled by mass transfer

The relations we have determined so far and described by the polarisation curve shown on
Figure 3.43 implicitly assume that the phenomenon limiting the reaction rates is the charge
transfer process. This is not always true, however, and some reactions may, for example, be
limited by a diffusion phenomenon governing mass transfer near the electrode.
The diffusion flow of species i is expressed by Fick's law:
'pi = - Di grad Ci
1.e. with J = f n F q : J = f nF Di (Co - C,)/6 (3.39)

where 6 represents the thickness of the diffusion layer, Co the concentration of the spe-
cies in the solution and c, its concentration at the surface of the electrode. (The f sign
expresses the convention: anodic current positive and cathodic current negative.) If the con-
centration of the species is zero at the surface of the electrode, we obtain the limiting value
of current density:
Jlim = f nF Di Co/6 (3.40)
This is the case, for example, when the limiting phenomenon is transfer of dissolved
oxygen to the surface of the electrode. When, on the contrary, the concentration of the spe-
cies at the surface reaches saturation, the limiting value of the exchange current density is
given by:
Jlim= f nF Di (Co - C,,,)/S (3.41)
This situation corresponds to a reaction limited by transfer of corrosion products. In both
cases, this limitation is indicated on the polarisation curve by a current value which is inde-
pendent of the potential. This part of the curve is called the diffusion plateau.
3.2.4 High temperature gas phase corrosion

High temperature corrosion occurs in the absence of aqueous electrolyte when extensive dif-
fusion takes place in metallic alloys, typically at temperatures of more than 300 “C. This
type of attack is also called “dry” corrosion as opposed to “wet” corrosion, whose mecha-
nisms were described in the previous paragraph. Although aqueous electrolytes do not exist
at high temperature (except under supercritical conditions), the reactions remain electro-
chemical. It is the oxides, sulfides and other solid or liquid reaction products formed on the
surface of the metal which act as electrolyte due to their ionic conductivity.
At ambient temperature, when the diffusion coefficients are low, volumic diffusion in
solids such as oxide layers has no effect on corrosion kinetics. At high temperature, how-
ever, volumic diffusion and diffusion at grain boundaries are the dominant mechanisms
leading, for example, to the formation of oxide, sulfide and nitride layers. The overall rate of
the high temperature corrosion process is controlled by diffusion phenomena in the layers
resulting from corrosion and in the metallic alloy.
3.2.4.1 Main high temperature corrosive gases

The main gaseous compounds that can react at high temperature with the metallic alloys are:
- Oxygen (corrosion also discussed in paragraph 1.15 in the first section of this book)
when the temperature exceeds 300 “C to 400 “C. Oxides are formed, whose properties
xM + 2/2 O2 -
determine the kinetics of the reaction:
M,O, where M is a metal
The oxidation mechanisms will be described in more detail in the remainder of this
chapter.
-
-
xM+zH~O -
Water vapour, which also generates the formation of metallic oxides
MXO,+zH2
Sulfur and the sulfur containing compounds (see also paragraph 1.16).
Above 250 “C, feedstocks containing sulfur compounds (H$, mercaptans, etc.) may
generate corrosion by forming a layer of metal sulfides.
Fe + H2S -
With steels, for example, the reaction is:
-
Fe + 1/2 S2
Fel-,S + xFe + H2
Fe,_,S + xFe
Sulfur containing compounds in oil may also be converted into SO2 and SO, during com-
M+zS03
-
bustion for example. This is also true during combustion of sulfur compounds in coal:
3M+zS02
u
MS2+2M0,
MO,+zSO2
3 M + 2 SO2 + z 0 2 M(S04)2
Due to their low melting point, less than that of oxides, the sulfides and sulfates for-
ming on the surface of oxidised alloys may be in liquid state. In this case, they may
destabilise the oxide layer and cause accelerated corrosion (see paragraph 1.18).
9
- Gaseous chlorine
Under the action of this powerful oxidising agent, the metal is converted from the
metallic state into the metal chloride: M + z/2 C12 MCl,
In the refining industry, gaseous chlorine may be present at high temperature during
catalyst regeneration.
Metal chlorides exhibit low sublimation temperatures and can easily deposit in zones
downstream of the corrosion, causing plugging and heat losses. In the presence of
other salts, metal chlorides also favour the formation of highly corrosive liquid depo-
sits (see paragraph I. 18).
- Carbonaceous feedstocks
They can be responsible for several types of corrosion (carburisation, metal dusting)
known collectively as high temperature carbon attack. These corrosion types were
described in more detail in paragraph 1.17 of this book. Carburisation may attack
metal, according to the following reactions:
xM+yC MxCy
XM + 2yCO f~ MxCy + $ 0 2
XM + 2yCH4 t)MxCy + 2yH2
- Carbon dioxide
Gaseous C 0 2 may oxidise metals at high temperature according to the following reaction:
M + z C02 f~ MO, + z CO
The equilibrium of this reaction depends on the ratio Pco2/Pc0. For combustion gases
containing little CO, metal oxidation by gaseous C02 is favoured.
- Hydrogen
Steel decarburisation mechanisms by high temperature hydrogen attack were detailed
in paragraph 1.14 i? the first section of this book.
Fe3C+H2 3Fe+CH4
Some alloy elements form carbides more stable than iron carbide and their presence
avoids decarburisation of steels. On the Ellingham diagram of Figure 3.47, which
shows the standard free enthalpy of formation of carbides plotted against temperature,
we see that the values relative to chromium and molybdenum carbides are more nega-
tive than those of iron carbide, indicating greater thermodynamic stability.
3.2.4.2 High temperature corrosion mechanisms: oxidation and sulfidation

We will now examine the main high temperature corrosion mechanisms, in particular for
oxidation and sulfidation of metallic alloys.
A. Constitutive laws
The corrosion kinetics obey different constitutive laws depending on the metallic materials
and gaseous corrosive atmospheres. The high temperature corrosion rate is generally
measured by the variation in mass over time, which is often positive, as with oxidation and
9 219
100
r
-0
-E
Y
-J
-100
-300 L I I I
0 400 800 1200 1600
Temperature (“C)
Figure 3.47
Standard free enthalpy of formation of carbides against temperature.
sulfidation, the corrosion products remain on the metal surface, but sometimes negative
when volatile corrosion products are formed, e.g. during attack by gaseous chlorine. This
mass variation may be related to a variation in the metal thickness (th). This experimental
determination of the corrosion constitutive law may provide indications regarding the mech-
anism controlling it.
- Linear law: the mass increase is directly proportional to the corrosion time (constant
corrosion rate):
d(m,,,)/dt = K; and mCor= K; t (since at t = 0 mcor = 0)
where mcor designates the mass of corrosion products (e.g. oxides) formed per unit
area and K i a linear corrosion constant (kg/m2 s).
This type of linear law is generally characteristic of kinetics controlled by the inter-
face reaction;
- Parabolic law: The corrosion rate is inversely proportional to the mass of corrosion
products formed per unit area:
d(m,,,)/dt = Kp/mcor and mcor = (2 KP)112 t 112
where K, is a parabolic corrosion constant (kg2/m4 s).
This type of parabolic law is generally characteristic of kinetics controlled by diffu-
sion in the corrosion product;
- Logarithmic law:
d(m,,,)/dt = Ki/t mcor and mcor = mo + K;/Ln(t)
This logarithmic law is rarely encountered, but zinc oxidation, for example, obeys this
type of kinetics.
6. Oxidation mechanisms in gaseous phase

a. Characteristics of metal oxides
Metal oxides generally correspond to a compact arrangement of oxygen ions and metallic
cations, the latter being located on the tetrahedral or octahedral sites of the cubic network
formed by the oxygen ions. The oxides that are formed have generally a high melting point
(see Table 3.21) except for Moo3 and V20, which melt respectively at 795 "C and 690 "C
and which, in liquid state, may dissolve other oxides which normally withstand such high
temperatures.
Table 3.21 Properties of a few metal oxides.
Oxide Melting Boilingpoint Molar volume Pilling-Bedworth

point ("C) ("C) (cm3/mol) coeff.
"2O5 690 1750 54.2 3.25
Moo3 795 30.7 3.27
FeO (wustite) 1420 12.6 1.78
ci Fe304 (magnetite) 1538 44.7 2.1
Fe2O3 (haematite) 1565 30.5 2.15
NiO 1 990 11.2 1.70
coo 1935 11.6 1.78
ct A1203 (alumina) 2 015 2 980 25.7 1.28
Cr203 2 535 4 000 29.2 2.02
MgO 2 800 3 600 11.3 0.8
Since the molar volume of oxides is different from that of the corresponding metal, the
oxide layers formed during oxidation undergo tensile and compressive stresses which may
cause the layer to crack or lift off. This difference in molar volume is characterised by the
Pilling-Bedworth coefficient R ~ B :
RPB = voxd/(vM vM>
where Voxd and VM represent respectively the molar volumes of oxide and metal and vM
In principle, if R,,
-
the stoichiometric coefficient of the oxidation reaction:
V~M+Vo/202 MVMOVO
- 1, the oxide should protect the metal efficiently against corrosion.
b. Theoretical oxidation models

The Ellingham diagram introduced in paragraph 3.2.1.2 (Figure 3.38) can be used to predict
the thermodynamic stability of the oxides that are formed but provides no indication as to
the formation kinetics. Various models have therefore been developed to explain the growth
of oxide layers during high temperature oxidation. They include, depending on the differ-
ence in electrochemical potential between the metal-oxide interface and the oxide-gas inter-
face, the Wagner mechanism which models the growth of compact oxide layers on metals
and alloys exhibiting good resistance to oxidation due to their behaviour according to a par-
abolic law. This parabolic behaviour involves displacement of M"' cations and 02-anions
in the oxide, as schematised on Figure 3.48.
Figure 3.48
Growth of an oxide layer by diffusion of metal cations and oxygen anions.
Diffusion of cations generates pinpoint defects in the oxides such as interstitial cations or
cationic vacancies, as illustrated on Figure 3.49. To maintain electroneutrality, the electrons
and the holes move at the same time as the ionic faults.
By considering that the defects move by diffusion and migration, the flow of defects can be
quantified. In an oxide, the flow Ni of type i defects is proportional to their concentration ci,
their mobility ui and the electrochemical potential gradient d@/dy perpendicular to the surface:
Ni = - ci ui dfl/dy
Since the potential @ has a chemical component (pi) and an electrochemical component
(function of the potential a):@ = pi + zi F Q,
and using the Nernst-Einstein equations which relates the mobility u of a chemical spe-
cies i to its diffusion coefficient Di: Di = ui RT
the flow of each type i defect can be expressed as a function of the concentration gradient
and the potential gradient as follows:
Ni = - Di dci/dy - zi D ci ui d@/dy
This equation applies to all mobile defects in the oxide, but there is only an analytical
solution when just two types of defects move (e.g. for the pairs interstitial cations and elec-
trons, cationic vacancies and holes).
By interstitials By vacancies
Figure 3.49
Diffusion of cations by interstitials or vacancies in an oxide.
Based on this model, we can express the parabolic oxidation constant as a function of the
diffusion coefficients of defects in the oxide and of the defect concentration at the oxide-
metal or oxide-gas interface depending on the pair of defects considered.
C. Sulfidation mechanisms in gaseous phase

In the petroleum industry, above 250 "C feedstocks containing sulfur containing compounds
(H$, mercaptans, etc.) may generate corrosion by forming a layer of solid or liquid metal
sulfides. The enthalpy of formation of sulfides is generally lower than that of oxides, which
means that the bonding energy of sulfides is lower, resulting in a larger number of pinpoint
defects (vacancies, interstitials, etc.) and lower melting points than those of oxides (as indi-
cated in Table 3.22). In addition, nickel, cobalt, iron and chromium sulfides sometimes form
a eutectic (low-melting-point compound) with the base metal.
Table 3.22 Properties of a few metal sulfides.

9 223
Thermodynamic stability of the metal-sulfur system:

V M M + V ~ ~ S ~ MvMSV~
where vM is the stoichiometric coefficient of the sulfidation reaction.
The Ellingham stability diagram, which shows the difference in standard free enthalpy of
formation of a few metal sulfides, is given on Figure 3.50.
This diagram indicates that sulfides are less stable than oxides.
Thermodynamic stability of the metal-sulfur-oxygen system:
Under oxidising conditions, sulfur is present as SO2 or even SO3. Depending on the oxy-
gen and SO2 partial pressures, metal oxides and sulfides may form according to the follow-
ing reactions:
M + 1/202 MO
M+SO2 MS+02
MS+202 MS04
MS+3/202
MO+SO2+202 - MO+S02
MS04
-100
-400
-500
600 800 1000 1200 1400 1600
Temperature ("C)
Figure 3.50
Ellingham stability diagram, which shows the difference in standard free
enthalpy of formation of a few metal sulfides.
Low oxygen partial pressures favour the formation of sulfides, whereas a high partial
pressure leads to the appearance of oxides.
The various stability fields of oxides and sulfides as a function of Po and Pso2 for a
2
given temperature can be determined by thermodynamic calculations. Figure 3.5 1 provides
an example for the Ni - 0 2 - SO2 system at 727 "C. We therefore obtain phase stability dia-
grams comparable with the Pourbaix E - pH diagram used in aqueous corrosion.
+4
0
L
m
e
a
Q -4
0
0
1
NiO
-8
-12 ' I l l 1 I I I
Log P,b
l ar
Figure 3.51
Stability diagram for the Ni - 0, - SO, system at 727 O C .
3.3 THE VARIOUS FORMS OF CORROSION
After having described the main corrosion mechanisms, we will now examine the various
corrosion modes of metallic materials.
3.3.1 Uniform corrosion

This is the simplest and most well-known type of corrosion. A chemical or electrochemical
reaction occurs uniformly over the entire surface considered. Uniform corrosion takes place
in a homogeneous environment (no temperature, pressure or concentration gradient along
the interface) and when the behaviour of the metal itself is sufficiently homogeneous with
respect to this environment. This homogeneous behaviour may result from either intrinsic
homogeneity of the material due to absence of inclusions or structural defects, or to non-
selectivity of the environment with respect to these defects. In case of electrochemical corro-
sion, random alternation between anodic and cathodic sites is observed over the entire sur-
face. With dry corrosion, the surface undergoes uniform attack by the corrosive gas phase.
The corrosion rate is generally expressed either in terms of mass loss (Am) per unit area
and per unit time (after desquamation in case of an adherent corrosion product) or in terms
of thickness of metal corroded (Ath) as a function of time (rate expressed in mm/year or
milli inch per year - mpy).
Conversion of mass loss into thickness loss per unit time is carried out using the formula:
vcor (or CR) = Ath/t = A d ( p S t) or vcor (mdyear) = 87.6 Am/@ S t) with
Am: mass loss in mg
p: alloy density in g/cm3
S: total area of alloy exposed to the corrosive environment in mm2
t: corrosion duration in hours
To convert into milli inch per year use the relation: 1 m d y e a r = 39.4 mpy (for conver-
sion into other corrosion rate units, the reader can refer to appendix 2).
Depending on the uniform corrosion rate measured, the corrosion resistance classifica-
tion given in Table 3.23 is generally applied:
Table 3.23 Uniform corrosion corrosivity classification.
V,,, in mmlyear (mpy) Uniform corrosion resistance

V,,, < 0.05 (2) Excellent
0.05 (2) <V,,, < 0.1 (4) Good
I 0.1 (4) <Vror< 0.5 (20) I Poor I
V,,, > 0.5 (20) Bad
Depending on the uniform corrosion rate (especially if less than 0.25 mm/year), a over-
thickness allowance may be added, as indicated in section 2.1.1 of this book.
If reliable corrosion rates are available, uniform corrosion may therefore be taken into
account during equipment design and when analysing the data obtained from corrosion
monitoring.
3.3.2 Galvanic corrosion

This is one of the most common types of corrosion in aqueous medium. As its name implies, it
results from the formation of a cell (Figure 3.52) leading to heterogeneous attack. The anodic
(corrosion of the material) and cathodic (reduction of the oxidising agent) reactions occur in
2H++2e-
ou
-H,
2H,O + 0, + 4e- 40H

-+
l
I
Anode I Cathode
I
Figure 3.52
Diagram of a galvanic corrosion cell.
different zones and, unlike uniform corrosion, there is no alternation of anodic and cathodic
reactions on a given zone. As mentioned earlier, this selectivity of reactions is the result of
heterogeneity due either to the material (e.g. coupling of two alloys) or to the medium or the
physicochemical conditions at the interface (concentration cell, differential aeration).
3.3.2.1 Galvanic series of alloys

When describing the mechanisms involved in electrochemical corrosion, we saw that for a
given medium each metal can be characterised by its corrosion potential. “Galvanic series”
can therefore be established in order to classify for a given medium the various metals
according to their corrosion potential measured experimentally. Based on this information,
we can predict the direction of the cell which will be created upon electrical coupling of two
different metals. The corrosion rate of the less noble (lower corrosion potential) metal there-
fore increases and the corrosion rate of the more noble metal (higher corrosion potential)
drops to zero.
As an example, Figure 3.53 shows the galvanic series of the main metallic materials in
seawater.
Galvanic coupling can be exploited to fight corrosion by deliberate allowing one metal to
corrode while protecting another metal (cathodic protection): the material with the dominant
anodic reaction (sacrificial anode) protects the rest of the structure where the cathodic reac-
tion takes place.
3.3.2.2 Concentration cell

Since the corrosion potential is the result of an “equilibrium” between oxidation of the metal
and reduction of the oxidising agent contained in the medium, any local variation in the
composition of the medium could lead to a situation of galvanic coupling. This is the case,
for example, with attacks by concentration cells. Differential aeration is another example of
galvanic coupling due to a variation in the composition of the medium. When a steel part is
Active Noble
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Galvanic series of the main metallic materials in seawater.
immersed in a non-buffered neutral aqueous medium, corrosion increases in the poorly aer-
ated zones and, inversely, decreases in the well-aerated zones. The pH of the aerated
(cathodic) zones becomes higher due to reduction of oxygen leading to the formation of
OH- ions and favours passivation of the steel, as predicted by the Pourbaix potential-pH dia-
gram (Figure 3.41 of paragraph 3.2.3.5).
3.3.3 Pitting corrosion

Pitting corrosion designates local attack of a passive surface. It requires the presence of
aggressive anions in the electrolyte (especially C1-, Br- and I- ions) and an oxidising agent.
It results in the formation of small cavities (pitting) while the passive surface remains intact.
Although the quantity of corroded metal is very small, this type of attack sometimes results
in perforation of the parts affected within a very short period of time. The perforation kinet-
ics is generally difficult to predict.
Pitting is a very common type of corrosion, affecting a wide variety of materials such as
stainless steels as well as nickel, titanium, aluminium and copper alloys.
The pitting process consists of two steps: initiation, which occurs during local breakdown of
passivity, then propagation. Several mechanisms have been put forward concerning initiation:
- The film breakdown mechanism, which corresponds to cracks of mechanical origin
(scratches, punching, etc.) in the film, allowing the aggressive ions, which tend to
form complexes with the metallic ions, to access the metal surface;
- The penetration mechanism, which assumes transfer of the aggressive anions through
the protective oxide film up to the metal-oxide interface;

- The adsorption mechanism, which starts with the surface formation of complexes which
are transferred into the electrolyte faster than non-complexed metallic ions. Local
thinning of the passive film occurs until the bare metal is revealed, followed by pitting.
Growth takes place as soon as a pit has started to form and the local current density may
reach several tens of amperes per cm2 in the pit which is the electrochemical corrosion
anode. These current densities lead to a build-up of corrosion products and halides which
catalytically increase the oxide dissolution. Consequently, repassivation cannot occur and,
in the pit, hydrolysis of the metal ions leads to acidification as shown on Figure 3.54.
Electrolyte (pH 57) Electrolyte (pH - 7)
Figure 3.54
Pit initiation and propagation mechanisms.
9 229
The main parameters governing pitting corrosion are:

- the chemical nature and microstructure of the metal: in stainless steels, for example,
presence of molybdenum and nitrogen increases the pitting resistance,

- the surface state, and in particular large numbers of inclusions in the metal are prefer-
ential initiation sites,

- the temperature, which accelerates this type of corrosion,
- the electrolyte composition (halide contents and salinity).
3.3.4 Crevice corrosion

This type of corrosion has many similarities with pitting corrosion, which we have just
described. Like pitting corrosion, it primarily concerns passive alloys (stainless steels, tita-
nium and aluminium alloys, etc.) used in aerated media or containing an oxidising agent,
and generally in the presence of halides (e.g. chlorides). Crevice corrosion is encountered in
small confined spaces (hence its name of crevice corrosion) where the medium is stagnant,
such as the gaps between riveted plates, areas under deposits or seals (Figure 3.55 is an
example of geometry favouring crevice corrosion).
The attack mechanism is above all related to local modification of the medium
composition:
- In the first step, incubation, the oxidising agent disappears by reduction and can only
be renewed by diffusion, which is extremely limited due to the confined space. The
subsequent anodic reaction in the crevice (balanced by the external cathodic reaction)
leads to a build-up of corrosion products in the form of metallic cations. This step
takes place with no apparent noticeable damage;
- In a second step, anions (e.g. Cl-) migrate towards the crevice to maintain the electri-
cal neutrality. The phenomenon is then comparable to the one described for pitting
_-_-
Figure 3.55
Diagram of crevice corrosion.
corrosion with passivity breakdown by complexation and catalytic increase of oxide

dissolution;
- As with pitting, hydrolysis of the metallic cations then tends to change the medium in
the crevice into an anion-enriched acid solution (HCl, HF depending on the halogen
element). Since passivity can no longer be maintained, the material dissolves in active
state, leading to rapid propagation of crevice attack.
3.3.5 Intergranular corrosion
This type of corrosion is characterised by localised attack at grain boundaries in the material,
which form disordered zones compared with the more regular crystal lattice of the grains.
The grain boundaries contain numerous structural defects (vacancies, dislocations) promot-
ing precipitation of intermetallic phases or metallic compounds such as carbides, and segre-
gation of impurities in solid solution. Readers can refer to paragraph 3.1.1 for a more com-
plete description of the microstructure of metallic alloys.
Intergranular corrosion mainly attacks austenitic stainless steels which have been sensi-
tised after prolonged holding time at intermediate temperatures (600 “C to 700 “C), for
example during welding or under service conditions for reactors and refining furnaces. This
prolonged holding time leads to precipitation of chromium carbides Cr2,C6 at grain bound-
aries (Figure 3.56). Precipitation (which depends not only on temperature but also on the
holding time) causes, in the vicinity of the grain boundary, significant depletion of the chro-
mium content: the chromium content can be insufficient to form a passivating oxide layer.
Stainless steels exhibiting this characteristic are said to be “sensitised”.
For the refining industry, intergranular corrosion by polythionic acids is described in
paragraph 1.13.
Grain boundaries
Chromium depleted
Chromium carbide
Figure 3.56
Diagram representing sensitisation of a grain boundary in austenitic stainless steel.
3.3.6 Stress corrosion

Stress corrosion results from the combined action of mechanical stress (residual or applied)
and a medium which is aggressive with respect to the material. Taken individually, each fac-
tor is not likely to damage the structure. This type of corrosion, particularly insidious and
dangerous for installations, is characterised by the appearance of inter- or transgranular
cracks which generally propagate perpendicular to the largest principal stress, of residual
(bending, hardening, cold rolling, etc.) or thermal (expansion, pressure variation) origin or
inherent to the purpose of the equipment. Failure surfaces exhibit a brittle appearance and
the metal loss is generally very low.
Environment-that induced stress cracking of metallic materials includes the following
phenomena:
- stress corrosion,
- hydrogen embrittlement (this degradation mode was detailed in paragraph 1.3 on the
wet H,S petroleum environment),
- corrosion fatigue,
- liquid metal embrittlement (the liquid mercury environment and embrittlement of
aluminium alloys was discussed in paragraph 1.4).
Stress corrosion involves numerous factors, both mechanical and chemical. Figure 3.57
is a diagrammatic representation of the main elementary processes likely to occur.
1) Superficial reactions and transfers

2) Liquid phase transfers
3) Liquid phase reactions
4) Modification of the material properties
(dislocation, diffusion of species)
5) Mechanical ruptures.
Figure 3.57
Main processes involved at the bottom of a stress crack.
3.3.6.1 Stress corrosion mechanisms

Several mechanisms are proposed in the literature to account for stress corrosion.
Localised dissolution of the film which applies to passivated alloys:
This mechanism involves periodic breakdown of the passive film due to the creation of
slip steps on the material surface under the effect of creep. The exposed metal undergoes
high dissolution leading to reconstruction of the passive film. The crack propagates by
repeating the dissolution events whenever the mechanical conditions at crack tip are suffi-
cient to break the passive layer formed during the previous repassivation event. With this
model, the crack propagation rate will depend on the strain rate at the crack tip (passive film
breakdown frequency) and the metal depassivation and repassivation kinetics.
Corrosion-plasticity interaction
This type of model considers an indirect effect of anodic dissolution on the fracture process
which consists in a local increase of the material plasticity, favouringmobility of dislocations and
hydrogen diffusion. The dislocations (and possibly hydrogen) then build up at the boundary
between this very small softened zone and the hardened zone surrounding it at crack tip. When the
resulting stress exceeds a critical value, the softened zone fractures by cleavage, propagating from
the boundary between the two zones to the tip of the existing crack, as illustrated on Figure 3.58.
Defects Rupture by
stacking cleavage
Boundarv of \
Crack
1 2 3
Figure 3.58
Diagrammatic representation of the corrosion-plasticity interaction.
Brittle rupture by adsorption

This model is based on the assumption that adsorption of chemical species present in the
environment or formed at crack tip reduces the interatomic bond forces and therefore the
stress required for fracture by cleavage. This model has also been proposed for hydrogen
embrittlement (see paragraph 1.3) and for liquid metal embrittlement (see paragraph 1.4).
3.3.6.2 Corrosion fatigue

This phenomenon occurs under the combined action of the environment and cyclic mechan-
ical stress. It is characterised by a decrease in the fatigue strength of the material. Generally,
and in view of the dissolution and repassivation kinetics which are relatively slow compared
with the mechanical phenomena, this type of damage occurs on parts subjected to low-fre-
quency stress (oligocyclic fatigue), for example when structures undergo heating-cooling
cycles. The mechanisms put forward to account for corrosion fatigue are the same as those
described for stress corrosion.
3.3.7 Erosion-corrosion
Erosion corresponds to surface damage under the effect of impact of solid particles, drop-
lets, a jet or the action of turbulent flow. In the presence of electrolyte, simultaneous damage
by erosion and corrosion may lead to local thinning of the metallic material and to com-
pletely erode away the protective film, as schematised on Figure 3.59.
1 - Film erosion 2- Material corrosion 1- Damage evolution
Figure 3.59
Schematic representation of erosion-corrosion.
Cavitation-corrosion designates progressive degradation of the material under the com-

bined action of corrosion and implosion of cavitation bubbles. Cavitation, a well-known
phenomenon in fluid mechanics, is the formation of bubbles in a turbulent flow in a region
where the pressure of the liquid falls below its vapour pressure. When these bubbles reach a
region where the pressure is higher they implode, producing a shock wave which induces
local fatigue of the material and resulting in repeated breakdown of the passive film and loc-
alised attack.
3.4 BACTERIAL CORROSION
Microbial corrosion, also known as biocorrosion and Microbiologically-Influenced Corro-

sion (MIC), can be defined as corrosion in which the processes are initiated, facilitated or
accelerated by microorganisms with no modification of the basic electromechanical phe-
nomenon [3 19; 3531. Most cases of biocorrosion occur under biofilms and involve a range
of different materials and microorganisms. Sulfidogenic bacteria, iron-oxidising bacteria
and acid-producing bacteria are the main types of microorganism responsible for biocorro-
sion in the petroleum industry.
3.4.1 Biofilms and biofouling
In some cases, the biofilms responsible for biofouling in industrial equipment in contact
with water may account for the occurrence of corrosion. Broadly speaking, a biofilm con-
sists of a mixture of bacteria in a structured community, sometimes embedded in a viscous
matrix of exopolymers (Figure 3.60) [344]. The microbial composition of biofilms is varied,
like that of free-living planktonic microorganisms in the surrounding environment and
which form the biofilm. After agglutination on the surface of the support, the microbial cells
which have now become “sessile” can grow and form a network which controls the diffu-
sion of soluble compounds. The agents responsible for the formation of the viscous slime are
generally aerobic organisms which behave as “oxygen absorbers”. Very thin microbial lay-
ers (1 0 pm to 20 pm) composed of aerobic bacteria provide anaerobic conditions favourable
to the development and activity of strictly anaerobic bacteria. Sulfate-Reducing Bacteria
(SRBs) may therefore even be encountered in the most aerated water or soils, coexisting
with oxygen-consuming microorganisms. The microorganisms inside biofilms interact in
synergy. Microbial associations are created, where each group of bacteria benefits from the
presence of the other. Even though they do not play an active role in the corrosion process
directly, numerous unexpected types of microorganisms can be found in biofilms [3 171.
Methane producers, for example, may promote biocorrosion by providing suitable redox
conditions [355]. Note, however, that biofilms do not all have adverse effects and that some,
on the contrary, may actually protect the materials.
Figure 3.60
SRB biofilm on a corrosion sensor [344].
On Figure 3.60 the SRB biofilm covers the mild steel surface of an electrochemical
sensor developed for MIC detection. A: global view; B: detailed view.
3.4.2 Anaerobic corrosion by sulfidogenic bacteria
3.4.2.1 Microorganisms
Pitting is frequently observed following attack of mild steels by sulfidogenic bacteria. Mild
steel pitting is easily recognisable with its open pits filled with black corrosion products.
When the corrosion product is removed, the metal underneath becomes shiny and rusts rap-
idly on exposure to air. Corrosion pitting results from the excretion of corrosive metabolites
such as sulfides or acids. The excreted corrosion products may have a converse effect on the
metabolism of the microbial population. In particular, the Fe++ ions released from the metal-
lic surface may meet the iron requirements of SRBs and stimulate the growth and physiolog-
ical activity of the microorganisms responsible for corrosion [340].
SRBs are considered as the key players responsible for mild steel corrosion. They belong
to the “sulfidogenic” species which produce sulfides from compounds containing sulfur. In
the past, sulfidogenic bacteria were assimilated with SRBs alone. This type of bacteria is
strictly anaerobic, forming a coherent physiological group characterised by anaerobic respi-
ration of sulfates for energy production. In the current microbial classification, however,
based on the phylogenetic relations between microorganisms rather than their physiological
natures, SRBs are dispersed [3 181. Desulfovibrio desulfuricans, Desulfovibrio vulgaris,
species belonging to the genera Desulfobactev and Desulfomonas are the model SRBs of
biocorrosion.
Sulfidogenic facultative anaerobic bacteria have long been overshadowed by extensive
research on Sulfate-Reducing Bacteria (SRBs). They are now recognised as playing a key
role in damage to cooling systems, for example. Since SRBs are the only bacteria capable of
reducing sulfates, the sulfide cycle is initiated by SRBs, which reduce SO:- to S2-. Once
sulfide production has been initiated, sulfite (SO:-) and thiosulfate (S&) are generated
from S2- in the upper layers of the biofilm, by chemical oxidation [336]. The sulfurated
compounds supplied by partial oxidation of sulfides are then used by sulfidogenic faculta-
tive anaerobic bacteria such as Shewanella putrefaciens and Aeromonas species [342] or
also by SRBs. In oil pipelines, Thiosulfate-Reducing Bacteria (TRBs) with no sulfate-reduc-
ing capacity have even been detected after accidental introduction of air [339]. Note also
that sulfidogenic facultative anaerobic bacteria may form abundant biofilms on metallic
surfaces [3 151, since they develop by using Fe3+ or Mn4+ as electron acceptors.
3.4.2.2 Biocorrosion process

The current electrochemical aspects of biocorrosion by sulfidogenic bacteria have recently
been detailed [322].
A. Effect of bacterial H2S

During corrosion of mild steel, iron sulfides are formed when the H i s released by the bacte-
ria comes into contact with the metallic surface. Ferrous sulfides, especially makinawite, are
electrical conductors with low electrode overvoltage. When the localised deposits of ferrous
sulfide act as cathode in the galvanic cell with the metallic iron surface, biocorrosion may be
9
initiated from the discontinuities of the ferrous sulfate layer on the metal. In other words,
any accidental fracture of the iron sulfide coating may trigger a biocorrosion process [336].
B. Microbial depolarisation
Microorganisms were formerly believed to sustain the corrosion process by depolarising the
galvanic cell. Historically, the first analysis of the depolarisation process was formulated by
[354] and called the “Cathodic Depolarisation Theory” (CDT). According to this theory, the
biocorrosion process is maintained due to the ability of SRBs to capture hydrogen. Scientists
thought that elimination of hydrogen atoms by bacterial hydrogenase increased the cathodic
reaction rate. The general CDT mechanism is indicated in Table 3.24.
Reaction site Reaction

Anode 4 Fe ---+ 4 Fe++ + 8 e-
Cathode 8Hf+8e- 8H
Solution 8H2O 8H++8OH-
SRB SO,+8H S-+4H20
General reaction 4 Fe + SO:- + 4 H,O ---+ FeS + 3Fe(OH)2 + 2 OH-
Although SRBs are capable of using molecular hydrogen as electron donors, CDT is still
subject to debate. Numerous organic compounds are available in biofilms and can be used
preferentially by SRBs as carbon and energy sources. It is therefore possible that the use of
hydrogen by SRBs responsible for corrosion is not an essential characteristic and that the
role of bacterial hydrogenase in the electrochemical process has been largely overestimated.
3.4.3 Corrosion by iron oxidising bacteria
Filamentous ferruginous bacteria are responsible for the hollow hemispherical tubercules
frequently observed, “water” side, in steel equipment. They generate oxygen depletion in
these tubercules located on surface pitting [35 I]. Iron-oxidising bacteria use ferrous ions as
electron donors in an aerobic respiration process. Since only a small quantity of energy is
produced by oxidation of Fe2+, large quantities of Fe2+ are required for microbial growth.
The ferric ions obtained create large mucilaginous deposits of insoluble hydrates. Iron-oxid-
king bacteria may also oxidise Mn2+into Mn3+and create a brownish sludge of MnO,.
Iron-oxidising bacteria include heterotrophic and chemoautotrophic organisms. The
group of heterotrophic bacteria consists mainly of filamentous genera Leptotrix (class
“Betaproteobacteria”), Crenothrix (phylum “Bacteroides”) and Sphaerotilus (class “Betap-
roteobacteria”). The main species of chemoautotrophic organisms is Gallionella ferruginea,
which can utilise C 0 2 as sole carbon source. Gallionella prospers when the oxygen supply is
limiting, as in well water. Gallionella is a genus of the Gallionellaceae family, belonging to
the class of Betaproteobacteriu. It exhibits a typical morphology with a spiral stalk leading
to two bean-shaped cells. It exudes metal hydrate as twisted ribbons or pairs of filaments. It
tends to concentrate chlorides, with deposits rich in ferric and manganic chlorides acting as
dilute hydrochloric acid and causing uniform steel corrosion. Chlorides can create stress cor-
rosion cracking when the equipment is heated to more than 60 "C [35 11.
Iron-oxidising bacteria use molecular oxygen as electron acceptor and provide anaerobic
conditions favourable to SRBs growth. They have been observed to grow considerably
under the corrosive effect of SRBs in cast iron corrosion. Figure 3.6 1 is a diagrammatic rep-
Figure 3.61
Diagrammatic relations between sulfate-reducing bacteria and iron-oxidising
bacteria.
3.4.4 Corrosion by acidogenic bacteria
Like Crenothrix and Sphaerotilus, Thiobacillusferroxidans and Leptospirillumferrooxidans

are iron-oxidising bacteria. They exhibit a very high ability to oxidise sulfides into sulfates,
producing large quantities of sulfuric acid. If there are no neutralisation processes, the pH
may be lowered considerably and Thiobacillusferroxidans and Leptospirillum ferrooxidans
are capable of developing when the pH is less than 1. These two bacterial species are often
involved in damage to concrete and rebar.
3.5 OTHER DAMAGE MODES - AGEING OF METALLIC MATERIALS
In service, metallic equipment used in the refining and petrochemical industries may be
exposed for very long periods of time to high temperatures, above 300 "C. For some metallic
materials, this may lead to changes in their microstructure, thereby modifying their mechan-
ical properties andor corrosion resistance. Although initially resistant to the corrosive envi-
ronment, these aged materials may no longer exhibit the same resistance to the various types
of corrosion (chemical, electrochemical, gaseous). Microstructural changes in the most sen-
sitive materials must therefore be monitored throughout the all equipment lifetime. In this
paragraph, we will examine the main temperature ageing phenomena encountered in the
petroleum industry.
3.5.1 Embrittlement of low alloy steels
Some low alloy steels may be sensitive to two ageing phenomena: temper embrittlement and
creep cracking.
3.5.1.1 Temper embrittlement

The materials affected are Cr-Mo low alloy steels (between 2% and 9% Cr) and in particular
the quenched and tempered grade 2 1/4 Cr - 1 Mo UNS K21590 (with or without V) and
their welding zones.
Temper embrittlement is characterised by a decrease in steel ductility and an increase in
the ductile-brittle transition temperature. At ambient temperature, brittle intergranular cracks
may develop.
During prolonged exposure to temperatures between 375 "C and 550 "C (with maximum
kinetics around 470 "C), residual elements in the steel such as arsenic, antimony, tin and
phosphorus segregate at grain boundaries. Manganese and silicon would also contribute to
this type of embrittlement.
To reduce or even prevent this phenomenon, it is recommended to limit the contents of
elements P, Sb, Sn and As. The Bruscato factor X = (IOP + 5Sb + 4Sn + As)/l00 is used to
evaluate the sensitivity to temper embrittlement. Molybdenum seems also to limit this
embrittlement. The incubation time is generally long, but may be reduced by high contents
in some elements (e.g. phosphorus at concentrations greater than 0.015%).
This embrittlement is reversible and the state of the grain boundaries can be restored by
heat treatment above 600 "C.
Step cooling tests can be conducted to determine the sensitivity of a steel to this embrit-
tlement. Their aim is to simulate ageing: after a fixed holding time at a given temperature,
the specimen is cooled down to ambient temperature in several isothermal temperature steps
lasting a certain period of time (150 hours to 300 hours). Mechanical resilience tests are then
carried out to assess the impact of ageing and the sensitivity of the steel tested.
3.5.1.2 Creep embrittlement

The incubation time spans several years.
It affects Cr-Mo low alloy steels, in particular grades 1 Cr-1/2 Mo and 1 1/4 Cr-1/2 Mo
(UNS K11562). Grade 2 114 Cr-1 Mo (UNS K21590) is much less sensitive. A reduction in
ductility generates cracks in the Heat-Affected Zones (HAZ). Secondary cavities and cracks
develop at grain boundaries. Large grain sizes in the HAZs, generated for example by excessive
welding energies, promote the formation of cavities and cracks. The same is true when the stress
concentrations are very high in the HAZs. Impurities segregating at grain boundaries, especially
phosphorus, would favour this sensitisation. Post weld heat treatment at temperatures in the
region of 630-680 "C would limit the sensitivity of 1 Cr-1/2 Mo and 1 1/4 Cr-1/2 Mo steels.
The same applies when vanadium is present in steel.
3.5.2 475 "C embrittlement of stainless steels

This type of embrittlement concerns ferritic and austeno-ferritic stainless steels when they
are maintained for a few dozen hours between 320 "C and 550 "C, the phenomenon occur-
ring most rapidly around 475 "C, hence its name. This phenomenon embrittles ferritic and
austeno-ferritic stainless steels at ambient temperature due to an increase in the ductile-brit-
tle transition temperature.
The following factors are responsible for this type of embrittlement:
- Decomposition of ferrite into two phases, the iron-rich a phase and the chromium-
rich a'phase. Formation of the a'phase also results in a chromium depletion of the
surrounding region and sensitisation of the stainless steel (this phenomenon is descri-
bed in the next paragraph 3.5.2.3);
- Precipitation of a copper-rich E phase at grain boundaries;
- For austeno-ferritic steels containing molybdenum, precipitation of a molybdenum-,
silicon- and nickel-rich G phase.

Figure 3.62 gives an example of the microstructural modifications which appear during
475 "C embrittlement of a ferritic steel containing 17% chromium.
This problem can be prevented by the presence of cobalt and aluminium, which would
delay the decomposition of ferrite. In addition, the phases which precipitated during embrit-
tlement can be dissolved by restoration heat treatments around 800 "C.
3.5.3 lntergranular sensitisation of stainless steels
The intergranular corrosion phenomena were discussed in paragraph 3.3.5. This type of corro-
sion is caused by lower resistance of the grain boundaries due to their sensitisation during steel
ageing. Ferritic and austenitic stainless steels may be affected by this chromium depletion of
the grain boundaries after long holding times in the temperature range 425 "C to 870 "C. Due
to these long holding times, chromium carbides Cr2& precipitate at grain boundaries, signif-
icantly depleting the chromium content in the surrounding area (Figure 3.63).
Figure 3.62
475 "C embrittlement of a 17% Cr femtic stainless steel (after 300 hours ageing).
Figure 3.63
Intergranular sensitisation of a S3 1600 stainless steel after 80 000 hours ageing
at 550 "C [349]:
a) transmission microscope image of a grain boundary,
b) iron, nickel, chromium and molybdenum concentration profiles across a
grain boundary.
A sensitised austenitic steel, for example, may crack when polythionic acids form during
shutdowns of hydrotreatment units, as described in paragraph 1.13 of this book.
Austenitic stainless steel grades stabilised by titanium AISI 321 (UNS S32100) or nio-
bium AISI 347 (UNS S34700) exhibit low sensitivity to chromium depletion of its grain
boundaries. Maintaining these steels at high temperature will preferentially lead to the for-
mation of titanium or niobium carbides instead of chromium carbides, thereby keeping the
chromium content around the grain boundary high enough to withstand corrosion. Chemical
stabilisation treatment of 2 to 4 hours between 850 "C and 900 "C increases the immunity
of these stabilised austenitic stainless steels. Furthermore, if the mechanical design is not
limiting, choice of a low carbon austenitic stainless steel (C < 0.03%) AISI 304L (UNS
S30404) or AISI 3 16L (UNS S3 1603) may be considered.
3.5.4 Precipitation of intermetallic phases

Due to the high temperature (between 450 "C and 850 "C) and very long holding times, some
elements in metallic alloys may react together to form intermetallic compounds. The effect of
these compounds is to increase the mechanical resistance of the alloys and considerably
decrease their ductility. Depending on the metallurgies, various intermetallic compounds may
precipitate. The intermetallic compounds most frequently encountered are the (J phases
(FeCr) for austenitic stainless steels and the 7, y, 6 phases (Ni3A1, Ni3Nb) for nickel alloys.
Precipitation of (J phases (FeCr) in stainless steels:
This phase appears for austenitic and ferritic stainless steels in the temperature range
590 "C to 930 "C (the precipitation kinetics is fastest around 760 "C). Chromium, molybde-
num and silicon favour its appearance, carbon, nickel and manganese would delay it. The
Gow and Harder formula can be used to assess the sensitivity of stainless steels:
Cr + 4Mo + 3(Si-l)-16C < 1.7

Mn-1
Ni + ~
S
This phenomenon is also accelerated for highly strain-hardened stainless steels.
This phase can only be eliminated by dissolution during heat treatment at very high tem-
perature, between 1 000 "C and 1 100 "C.
Figure 3.64 below is a good example of this phenomenonwhich makes the steel twice as hard.
Figure 3.64
Sensitisation of the (3 phase of a S32100 stainless steel after 20 000 hours
ageing at 650 "C.
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Acknowledgements
Yves Chauvin took great interest in the subject of this book. I would like to express all my
warm thanks to him for doing me the honour of writing the preface, which clearly illustrates
the need to address the corrosion of metallic materials during both the R&D stage and dur-
ing operation of the industrial equipment and processes.
My thanks also go to the IFP General Management, its Scientific Management, the
Exploration-Production and Refining-Petrochemistry Business Units and the Applied
Chemistry and Physical Chemistry Division, which encouraged this work.
My special thanks to Philippe Ungerer, Scientific Director of IFP, Jacques Jarrin, Direc-
tor of the Applied Chemistry and Physical Chemistry Division and Patrick Boisserpe, of the
Information Mission, for their support and their sound advice.
This document is the fruit of research work in specific chemical environments and con-
siderable industrial feedbacks from the petroleum profession, including capitalisation of the
studies conducted at IFP. Thanks to all my colleagues, whether IFP members or not, who
participated directly or indirectly to this work. In particular, I would like to extend my
thanks to the contributors of this book:
Mrs Valerie Sauvant-Moynot paragraphs 2.2.1 and 2.2.2,
Mr. Bernard Dewimille paragraph 3.1.2,
Mr. Jean Kittel paragraphs 1.3 and 1.1 1,
Mr. Xavier Longaygue paragraph 2.3,
Mr. Remy Marchal paragraphs 1.5 and 3.4.
I would like to pay tribute to our predecessors, Bernard Le Boucher and Yves Lefebvre,
who initiated the work on corrosion at IFP.
I am grateful to Mrs Beatrice Fischer, Messrs. Xavier Lefebvre, Eric Prada and Marcel
Roche for their advice and the time they spent proofreading this document.
Finally, it would have been impossible to complete this book without the valuable contri-
butions of Mireille Darthenay for her support, Dominique Allinquant for the drawings and
Nathalie Toullec for compiling the bibliographic references.
Francois Ropital
Annexes
ANNEXE 1
International standards on designation
of metal materials
This appendix provides information on the international standards most often used in the
petroleum industry on the designation of alloys:
Al.l DESIGNATION OF THE AMERICAN SOCIETY OF TESTING

AND MATERIALS (ASTM) AND THE AMERICAN SOCIETY
OF MECHANICAL ENGINEERS (ASME) WHICH ARE VERY SIMILAR
The first part of the designation is a letter:

- A for ferrous metals,
- B for non ferrous metals,
- C for ceramics and concretes,
- D for other materials.
A letter S in front of this letter indicates the conformity with the ASME code.
The second numerical part characterises the family to which the material belongs but also
the manufacturing mode related to its use. The same material may therefore be designated
under different numbers, each being specific to the manufacturing andor use conditions.
The grade or type of material (that of the AISI nomenclature) is also indicated.
246 Annexe 1 International standards on designation of metal materials
Al.2 DESIGNATIONS OF THE AMERICAN IRON AND STEEL INSTITUTE (AISI)

AND THE SOCIETY OF AUTOMOTIVE ENGINEERS (SAE)
WHICH ARE VERY SIMILAR
A1.2.1 Carbon and low alloy steels
Carbon steels and low alloy steels are designated by a four digit number, where the first
two digits indicate the alloying elements and the last two digits indicate the amount of car-
bon, in hundredths of a percent by weight:
Carbon steels
1oxx I Plain carbon (Mn 1.OO% max)
1 lxx Resulfurized
12xx Resulfurized and rephosphorized
15XX Plain carbon (Mn 1.OO% to 1.65%)
Manganese steels
13xx II Mn 1.75%
Nickel steels
23xx 1 Ni 3.50%
25xx I
I
Ni 5.00%
Nickel-chromium steels
31xx Ni 1.25%, Cr 0.65% or 0.80%
32xx Ni 1.25%, Cr 1.07%
33xx Ni 3.50%, Cr 1.50% or 1.57%
34xx I Ni 3.00%, Cr 0.77%
Molybdenum steels
40xx I Mo 0.20% or 0.25%
44xx Mo 0.40% or 0.52%
41xx Cr 0.50% or 0.80% or 0.95%, Mo 0.12% or 0.20% or 0.25% or 0.30%
43xx Ni 1.82%, Cr 0.50% or 0.80Y0,Mo 0.25%

43BVxx Ni 1.82%, Cr 0.50%, Mo 0.12% or 0.35%, V 0.03% min
47xx Ni 1.05%, Cr 0.45%, Mo 0.20% or 0.35%
81xx Ni 0.30%, Cr 0.40%, Mo 0.12%
86xx Ni 0.55%, Cr 0.50%, Mo 0.20%
87xx Ni 0.55%, Cr 0.50%, Mo 0.25%
88xx Ni O X % , Cr 0.50%, Mo 0.35%
Annexe I 9 International standards on designation of metal materials 247
I 93xx I Ni 3.25%, Cr 1.20%, Mo 0.12%

94xx Ni 0.45%, Cr 0.40%, Mo 0.12%
91xx Ni 0.55%, Cr 0.20%, Mo 0.20%
98xx Ni 1 .OO%, Cr 0.80%, Mo 0.25%
46xx Ni 0.85% or 1.82%, Mo 0.20% or 0.25%

48xx Ni 3.50%, Mo 0.25%
50xx Cr 0.21% or 0.40% or 0.50% or 0.65%

51xx Cr 0.80% or 0.87% or 0.92% or 1.OO% or 1.05%
5oxxx Cr 0.50%, C 1 .OO% min
5 lxxx Cr 1.02%, C 1.OO% min
52xxx Cr 1.45%, c 1 .oo% min
Chromium-vanadium steels
61xx I Cr 0.60% or 0.80% or 0.95%. V 0.10% or 0.15% min
I Tungsten-chromium steels I
72xx I W 1.75%, Cr 0.75%
Silicon-manganese steels
92xx I Si 1.40% or 2.00%, Mn 0.65% or 0.82% or 0.85%, Cr 0.00% or 0.65%
High-strength low-alloy steels
9xx I Various SAE grades
I xxBxx 1 Boron steels I
XXLXX I Leaded steels
Al.2.2 Stainless steels
- 200 Series: austenitic chromium-nickel-manganese alloys,

- 300 Series: austenitic chromium-nickel alloys,
- 400 Series: ferritic and martensitic chromium alloys,
- 500 Series: heat resisting chromium alloys,
- 600 Series: martensitic precipitation hardening alloys.
248 Annexe I International standards on designation of metal materials
Al.3 DESIGNATION OF THE UNIFIED NUMBERING SYSTEM (UNS)
The Unified Numbering System ( U N S ) is a widely accepted alloy designation system. It

consists of a prefix letter and five digits designating a material composition. A prefix of S
indicates stainless steel alloys, C for copper, brass, or bronze alloys, T for tool steels, etc.
UNS series Metal type(s)

IAOOOOI to A99999 I Aluminum and aluminum alloys i
~ 0 0 0 toC99999
1 Copper and copper alloys
DO0001 to D99999 Specified mechanical property steels
EOOOO 1 to E99999 Rare earth and rare earth-like metals and alloys
FOOOOl to F99999 Cast irons
GOOOOl to (399999 AISI and SAE carbon and alloy steels (except tool steels)
I HOOOOI to H99999 I AISI and SAE H-steels 1
T O O 0 1 to 599999 Cast steels (except tool steels)
KOOOO 1 to K99999 Miscellaneous steels and ferrous alloys
ILOOOOl to L99999 I Low-melting metals and alloys 1
MOO001 toM99999 Miscellaneous nonferrous metals and alloys
NO0001 to N99999 Nickel and nickel alloys
PO000 1 to P99999 Precious metals and alloys
ROO00 1 to R99999 Reactive and refractory metals and alloys
s00001 to s99999 Heat and corrosion resistant (stainless) steels
TOO001 to T99999 Tool steels, wrought and cast
woooo1 to w99999 Welding filler metals
zoooo 1 to 299999 Zinc and zinc alloys
ANNEXE 2
Corrosion rate measurement conversion factors
mol/m’ s A/m2 pA/cm2 mgldm’ d mmlyear mPY

mourn’s 1 9.65 x lo4 n 9.65 x lo6 n 8.64 x lo5 M 3.15 x lo4 (Mip) 1.24 x lo6 (M/p)
A/m2 I .04 x 1 100 8.96 Mln 0.327 M/np 12.9 Minp
pA/cm2 I .04 x IO-’in 0.01 1 8.96 x Min 3.27 x Minp 0.129 Minp
mg/dm’d 1.16x10“/M 0.112n/M 11.2n/M 1 3.65 x lO-’ip 2.871~
mm/year 3.17 x p/M 3.06 npiM 306 np/M 27.4 p I 39.4
mpy 1.25 x p/M 120 np/M 1.2 x lo4 npiM 1.08 x lo3 p 0.0254 I
The units indicated in the first line of the table are obtained by multiplying the unit in the
first column by the corresponding conversion factor:
- M: atomic mass in g/mol,
- p: density in g/cm3,
- n: number of charges,
- mpy: milli inch per year.

Glossary
Acid gas treatment Process to remove COz and H2S acid gas from the gaseous effuents.
Alkylation Process by which a branched chain hydrocarbon, usually isobutane, is reacted
with an alkene to form compounds for blending to give gasoline with a high
octane number. The process employs either sulfuric acid or hydrogen fluoride
as catalyst.
Annealing heat Thermal treatment that consists to heat the steel at a temperature higher than
treatment Ac3 (or Accm) then to slowly cool it at a cooling rate lower than the critical
quench rate. A typical cooling rate is 100 "Cih.
Atmospheric Primary distillation of petroleum at atmospheric pressure for the purpose of
distillation obtaining petroligasoline, kerosine, gas oil, and heavier products.
Austenite Microstructure of iron that cristallises in the face centred cubic system.
Austenitising heat Thermal treatment that consists to heat the steel at a temperature higher than
treatment Ac3 and to maintain it during a sufficient time period.
Brittleness Loss of ductility of the metal due to chemical or physical modifications.
Carbon steel Steel mainly composed of iron and carbon (lower than 1.5% but lower than
0.4% for the majority of steel).
Casing Heavy steel lining used to prevent caving of the sides of a well, to exclude
unwanted fluids, and to provide means for the control of well pressures and oil
and gas production.
Catalytic Process for converting low octane gasoline fractions into higher octane stocks
reforming suitable for blending into finished gasoline raising the octane number from 40
to between 95 and 100.
Cladding A process of bonding two dissimilar metal sheets or plates, the covering metal
usually possessing greater corrosion resistance.
Catalytic cracking Cracking process that involves the use of catalysts that enable more extensive and
more selective conversion of heavier fractions to gasoline and middle distillates.
252 Glossary
Creep Time related high temperature strain of a metallic alloy due to a mechanical
stress (that can be its own weight).
Electrode Conductive material located in an electrolyte and through whitch the current is
colected or transfered in the electrolyte.
Electrolyte Liquid phase that contains the ions which move under an electrical field.
Fatigue Tendency for a metal to break under conditions of repeated cyclic stressing
considerably below the ultimate tensile strength.
Ferrite Microstructure of iron that cristallises in the body centred cubic system.
Fouling Clogging due to mineral or organic deposits
Heat Affected Zone of metal that is not melted during the welding or brazing operations,
Zone (HAZ) whose microstructure and properties are modified due to the heat effects of
these welding processes.
HIC Hydrogen induced cracking.
Hydrocracking Process carried out in the presence of hydrogen and with the aid of catalysts, in
which heavy hydrocarbons are cracked to significantly lighter products, with
process efficiencies and product qualities superior to those obtained with con-
ventional catalytic cracking.
Hydrotreatment Means of removing objectionable sulfur compounds from gasoline, by reaction
with them to form easily removable hydrogen sulfide.
Intelligent pigging In-line scraper (brush, blade, cutter, or swab) forced through pipelines by fluid
pressure, used to remove scale, sand, water, or other foreign matter from the
interior surfaces of the pipe. Pigs are also equiped with inspection tools.
Intergranular Local deterioration of a metallic material by a crack that takes place at the
corrosion grain boundary due to a reaction with the environment and to a sensibilisation
(depletion of a protective element against corrosion such as chromium).
Localised Local deterioration (pitting, crevice, crack) of a metallic material due to a reac-
corrosion tion with the environment.
Low alloy steel Steel with additionnal components whose contents are lower than 10%. Chro-
mium, molybdenum or (and) nickel are the main alloying elements.
Martensite High hardness microstructure of steel that crystallises in the quadratic system.
Merox process Process that transforms by oxidation mercaptans into disulfides.
Metal dusting High temperature deterioration of a metal under high carbon activity leading to
the destruction of the metal in "dusts".
Molten liquid Localised corrosion of a metallic material in contact with a liquid metal.
attack
Nickel alloy Alloy for which nickel is the main component.
Normalizing heat Thermal treatment that consists to heat the steel at a temperature higher than
treatment Ac3 (or Accm) then cooling it in air to a temperature substantially below Ac 1.
The cooling rate usually is in the range 500 to 1 000 "C/h.
Glossary 253
Passivity State of the metal for which the corrosion rate is reduced due to the formation
of a passive layer (thin protective oxide scale) on its surface.
Post weld heat Thermal treatment that consists to heat the steel at a temperature generally
treatment lower than Ac 1 during a sufficient period of time in order to lower the internal
stresses generated during the welding operations
Quench heat After austenisation, quick cooling by immersion in a dedicated liquid in order
treatment to avoid the transformations predicted by the equiblibrium diagram.
Refractory steel Steel that have high mechanical properties and good creep resistance at high
temperature.
Riser Connecting tubes between the platform and the sea bottom.
Sensibilisation Chromium carbide precipitation phenomenom at the grain boundaries, leading
to a chromium depletion around the grain boundaries that become more sensi-
ble to intergranular corrosion.
SOHIC Stress internal decohesion that is a specific form of HIC: it appears when stres-
ses are applied.
ssc Delayed rupture that appears in an aqueous medium containing H2S.
Stainless steel Steel containing enough alloying elements to generate on its surface a thin
oxide (passive) layer that seperate the metal from the electrolyte.
Steel Alloy for which the main component is iron and whose carbon content is lower
than 1.5%.
Strain hardening Increase in hardness and strength of a metal produced by plastic strain below
the recrystallisation temperature.
Stress corrosion Local deterioration by a crack of a metallic material due the combined effect of
a corrosion reaction and mechanical stresses on the metallic material.
Stress relieving Thermal treatment that consists to heat the steel at a temperature generally
lower than Acl during a sufficient period of time in order to lower the internal
stresses.
Sulfur unit Process for removing sulfur compounds contained in gaseous fuels.
Tempering heat Thermal treatment that consists to heat the steel at a temperature lower than
treatment Acl during a sufficient period of time then to quite fastly cool it.
Transgranular Local deterioration of a metallic material by cracks that take place through the
corrosion grains due to a reaction with the environment.
Tubing Steel pipe hung inside casing often supported only at the wellhead. The pipe
through which oil, or gas, or both are brought from the reservoir to the surface.
Uniform corrosion Deterioration of the all metallic surface due to a reaction with the environment.
Vacuum Distillation that takes place in a fractionating column at a pressure below
distillation atmospheric pressure. It is applied to the bottoms (residue) remaining from the
atmospheric distillation of crude oil.
254 Glossary
Weld overlay Process to desposit a corrosion resistant coating as continuous welding seams
on the all surface of the base metal.
Wellhead Equipment used to maintain surface control of a well. It is formed of the casing
head, tubing head, and Christmas tree.
INDEX
Index Terms Links
Acid
– carbonic 3
– hydrochloric 23 26
– hydrofluoric 30
– naphthenic 52
– polythionic 55
– sulfuric 27
Acid gas treatment 41
Acoustic emission 114 130
Activation energy 204
Activity (chemical) 200
Additive (see inhibitor)
Alcohol
– ethanol 40
– methanol 39 198
Alkaline
– carbonate 36
– caustic 34
– near-neutral 38
Alkylation 28 32 68
Alloy
– aluminium base 197
– cobalt base 197
– copper base 195
– nickel base 196
– titanium base 198
This page has been reformatted by Knovel to provide easier navigation.

Index Terms Links
Amine units 41
Ammoniac 25 29 36
103 195
Austenite 154
Bacteria
– acidinogenic 237
– oxidising 236
– sulfate-reducing (SRB) 16
– sulfidogenic 235
Bactericide 17
Bending 171
Biofilm 234
Borescope 126
Brass 195
Bronze 196
Butler Volmer equation 211
Carbon (high temperature carbon attack)

– carburisation 71
– coking 68 104
– metal dusting 69 71 104
218 252
Carbon dioxide CO2
– corrosion 3
– treatment 41
Cast iron 154 195 248
Catalytic reforming 23 59 68
92 103 251

Index Terms Links
Cathodic protection 19 96
Cement (anticorrosion) 95
Centrifuging 194
Chemical analysis of solutions 110
Chlorides 20 23
Chlorine 17 198 218
Coatings
– cladding 94
– composite liner 92
– organic and paints 88
– weld overlay 94
Coker 36 55 65
68 103
Coking (see carbon high temperature attack)
Concentration cell 226
Control - non destructive 125
Corrosion
– bacterial 16 233
– cavitation 233
– chemical 202
– crevice 20 85 229
– electrochemical 202 225
– galvanic 86 225
– high temperature 217
– intergranular 55 230
– pitting 20 228
– stress cracking 8 20 231
– transgranular 20 34 28
231
– uniform 224
Corrosion rate 224
Cost of corrosion XV

Index Terms Links
Coupons (corrosion) 106

Cracking
– intergranular 57
– transgranular 20 28
Creep 175
Cyanide 36
Decarburisation (see high temperature hydrogen

attack)
Deformation
– elastic 162
– plastic 162
Depassivation 21 232
Disbonding 61
Dislocations 14 148 152
166 231
Distillation
– atmospheric 13 23 52
103 251
– vacuum 23 65 251
Eddy current 127

Elasticity 172
Elastoplasticity 173
Electrical charge transfer 211
Electrical conductivity 108 117 217
Electrolyte 203 252
Ellingham diagram 201 218 223

Index Terms Links
Embrittlement
– at 475°C of stainless steels 255
– creep 239
– hydrogen 8
– temper 238
Energy level 203
Epoxy 89
Equilibrium diagram (alloys) 152
Erosion corrosion 86 233
Exchanger 7 13 23
30 43 46
52 74 85
196 198
Faraday law 203

Fatigue
Fatigue corrosion 232
Fatigue mechanical 177
Ferrite 154
Fluid catalytic craking (FCC) 34 55 65
103
Free enthalpy 199
Furnace 28 52 55
62 68 72
Galvanic serie 226

Index Terms Links
Hardness 180
– Brinell 180
– Rockwell 181
– Vickers 181
Harmonic analysis 119
Heat affected zone (HAZ) 159
Helmotz double layer 203
HIC 10 30 43
252
Hydrocracking 58 103
Hydrodynamic 4 8 21
29 32 54
85
Hydrogen attack at high temperature (HTHA)
– decarburisation 88
– hydritation 61
Hydrogen sulfide (H2S)
– corrosion 8
– embrittlment 8
– treatment 41
Hydrolysis of chlorides 23
Hydrotreatment 23 26 55
58 85 94
240 252
Impact strength 182

Impedance - electrochemical 120
Inhibitor 98
Intermetallic sigma phase 241

Index Terms Links
Iron carbon diagram 154
Liquid metal
– cadmium 15
– lead 15
– mercury 13
– zinc 15
Liquid penetrant inspection 126
Magnetoscopy 127
Martensite 156 252
Mass transfer 216
Mechanical damage 167
Mechanical stress 170
Mechanical tests tensile 174
Merox treatment 34 252
Metal dusting 69 71 104
218 252
MFL (Magnetic flux leakage) 133
Microstructure of metallic alloys 148
Molten salts 73
Necking 163
Nernst equation 205

Index Terms Links
Offshore 14 16 89
96 109 124
127 134 198
Optical sensor 112
Overvoltage 213
Oxidation
– electrochemical 202
– high temperature 62 217
Paint 88
Passivity 209 230 253
Phosphatation 95
Pigging 131
Pilling and Bedworth coefficient 220
Pipeline 3 8 16
20 38 88
96 133
Plasticity 173
Poisson coefficient 171
Polarisation - electrochemical polarisation 117 214
Polarisation resistance 118 216
Polyamide 89
Potential
– chemical 199
– corrosion 122 214
– reversible 204
– standard electrode 205
Pourbaix diagram 206 224 228

Index Terms Links
Prediction model
– Couper and Gordman (high temperature
sulfidation) 66
– McConomy (high temperature sulfidation) 65
– Nelson (high temperature hydrogen attack) 59
Probe - corrosion
– bacterial 124
– electrical resistance 108
– galvanic 117
– hydrogen 100
– multi array 123
Pump 3 9 50
195
Radiography 128
Reduction - electrochemical 202
Reference electrode 205 212
Riser 198 253
Risk based inspection (RBI) 137
Sacrificial anode 96
Sensitisation 56 230 239
SOHIC 10
SSC 10
Steamcracker 68
Steel 188
– austenitic stainless steel 193
– austeno-ferritic (duplex) stainless steel 193
– carbon steel 188

Index Terms Links
Steel (Cont.)
– ferritic stainless steel 192
– heat resistant (refractory) steel 194
– killed carbon steel 188
– low alloy steel 189
– martensitic stainless steel 192
– nickel steel 191
Sulfidation (high temperature) 65 218
Surface treatment 95
Tafel coefficient 213

Tensile test 161
Thermal treatment 168
– annealing 158
– austenitisation 156
– normalizing 252
– post welding 158
– quench 156
– stabilisation of stainless steels 57 84 240
– stress relieving 33 35 86
– tempering 158
Thermography 129
TOFD (Time of flight diffraction) 129
Torsion (mechanical) 170
Toughness 184
Ultrasound 128 132 134

Index Terms Links
Visbreaking 65
Viscoelasticity 173
Wagner mechanism 221
Yield strength 162

Corrosion and Degradation OF: Metallic Materials

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I F P PUBLICATIONS

Translated from the French

t Editions TECHNIP 2s rue Cinoux, 7501s PARIS, FRANCE

A Geoscientist’s Guide to Petrophysics

Acido-Basic Catalysis (2 vols.)

Petroleum Microbiology (2 vols.)

Physico-Chemical Analysis of Industrial Catalysts

Petrochemical Processes (2 vols.)

The Technology of Catalytic Oxidations (2 vols.)

- Marine Oil Spills and Soils Contaminated by Hydrocarbous

This book is a translation of “Corrosion et degradation des materiaux metalliques”

All rights reserved.

0Editions Technip, Paris, 2010.

Coupons Probes Inhibitors NDE Total

1.5.2.2 Construction of a non aggressive bacterial environment . . 17

1.10 Alcohol (methanol and ethanol) corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . 39

I . 15.4 Example of high temperature oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63

2.2.2.1 Principle ............................ 96

2.2.3.1 Principle .. ........................ 98

2.2.3.3 Gas phase inhibitors. ......... ......... 103

2.3.2.1 Indirect methods ............................... 106

2.3.3.3 Inspection plans and RBI .............................. 137

3.1 Basic information concerning the metallic materials used

of metallic materials ...................... 199

3.2.1.1 Free enthalpy of a corrosion reaction

3.2.2 Chemical corrosion in liquid phase ................. 202

Table 1.1 Lists of corrosive chemical environments detailed in Section 1

Corrosive environment Oil and gas Acid gas Refining

1.2 CARBON DIOXIDE CORROSION

1.2.1 Equipment concerned by C02 corrosion

1.2.2 Mechanisms and parameters influencing COz corrosion

Types of corrosion caused by carbon dioxide:

Main parameters injluencing carbon dioxide corrosion:

20 40 60 80 100 120 140

1.2.3 Example of CO2 corrosion

Heat exchanger on a refining unit:

1.2.4 Acidity and COz corrosion prediction models

1.2.5 Prevention of C02 corrosion

1.3 CORROSION BY WATER CONTAINING H2S

1.3.1 Equipment concerned by H2S corrosion

1.3.2 Mechanisms and parameters influencing H2S corrosion

Elongated blister associated with mid-wall HIC in a portion of pipeline [ 5 5 ] .

1.3.3 Selection of materials for use in H2S environment

1.4 CORROSION BY MERCURY AND LIQUID METALS

1.4.1 Equipment concerned by mercury corrosion

Mercury, in elementary state or as organometallic or inorganic compounds, may be present

1.4.2 Mechanisms involved in mercury embrittlement of aluminium

1.4.3 Example of mercury corrosion

1.4.4 Other metallic materials sensitive to liquid metal embrittlement

1.4.5 Prevention of liquid metal embrittlement

- Avoid entry of mercury in the refining circuits;

- Remove mercury from the gas by adsorption on beds of activated carbon or on

microporous adsorbants impregnated with elementary sulfur;

1.5 CORROSION BY THE BACTERIA PRESENT IN WATER, SOIL AND CRUDES

1.5.1 Stakes of biocorrosion in the petroleum industry

Biocorrosion, or Microbiologically Influenced Corrosion (MIC), concerns both the upstream

1.5.2 Means used to detect and combat biocorrosion

1.5.2.1 Use of non-corrodable materials

1.5.2.2 Construction of a non aggressive bacterial environment

1.5.2.3 Use of bactericides

Table 1.2 Biocides used in industrialwater supply networks (source: [153]).

I Name I Biocide activity Properties I Concentration