Commission of the European Communities

technical steel research

Properties and Service performance

ANALYSIS OF CURRENT PROBLEMS

CAUSED BY LOCALIZED CORROSION.
STUDY OF THEIR INDUSTRIAL IMPACT
AND PROPOSALS FOR ACTION.

Report
EUR 10607 EN
Blow-up from microfiche original

Commission of the European Communities

technical steel research

Properties and Service performance

ANALYSIS OF CURRENT PROBLEMS

CAUSED BY LOCALIZED CORROSION.
STUDY OF THEIR INDUSTRIAL IMPACT
AND PROPOSALS FOR ACTION.

M. POURBAIX
CEBELCOR
Avenue Paul Heger, Grille 2
B-1050 BRUXELLES

Contract No ECI-1273-B-7240-84-B
FINAL REPORT

Directorate-General
Science, Research and Development

1986

EUR 10607 EN

Published by the
COMMISSION OF THE EUROPEAN COMMUNITIES
Directorate-General
Information Market and Innovati on
L-2920 LUXEMBOURG

LEGAL NOTICE
Neither the Commission of the Eu ropean Commu nities nor any person acting
on behalf of the Commission is responsible for the u se which might be made of
the following information

ECSC-EEC-Euratom, Bru ssels Luxembourg

Summary
A statement is made about Che economic aspects of localized
corrosion, and problems presently existing in different industries
are reviewed.
Current knowledge about localized corrosion is described, particularly with regard to the electrochemical aspects.

Pitting

corrosion, crevice corrosion, stress corrosion cracking, hydrogen

cmbrittlement, intergranular corrosion and dealloying are considered.

Some applications of the knowledge are mentioned, notably

for vapour regenerators of nuclear reactors, heat exchangers in

stainless steel, copper pipes for vater distribution, copper aLloy
tubes for condensers cooled by sea water, research of corrosion
inhibitors, developing of new steels, ...
A vast program of joint action is proposed for fighting
localized corrosion.

This action vould include laboratory research

on "occluded corrosion cells" and practical applications of the

results as well as research on semi-industrial pilot installations
and on industrial installations.

Keywords
Localized corrosion - Pitting corrosion - Crevice corrosion Stress corrosion cracking - Hydrogen erabritt lenient - Ir.tergranular
corrosion - De-alloying- Nuclear reactors - Stainless steels Copper - Copper alloys.

- IVRsua

Aprs un expos sur les aspects conomiques de la corrosion

localise, on passe en revue les problmes de corrosion localise
existant dans diffrents secteurs d'activit industrielle.
On expose les connaissances actuelles relatives la corrosion
localise, particulirement en ce qui concerne leur aspect lectrochimique, en considrant succinctement la corrosion par piqres, la
corrosion caverneuse, la corrosion fissurante sous tension, la fragilisation par l'hydrogne, la corrosion intergranulaire et la corrosion
par dsalliage.

On cite quelques applications de ces connaissances

en ce qui concerne notamment les gnrateurs de vapeur de racteurs

nuclaires, les changeurs de chaleur en acier inoxydable, les canalisations en cuivre pour distribution d'eau, les tubes eri alliages
cuivreux de condenseurs refroidis par de l'eau de mer, la recherche
d'inhibiteurs de corrosion, la mise au point de nouveaux aciers, ...
On propose un vaste programme d'act-ion communautaire en vue de
lutter contre la corrosion localise, comportant des recherches en
laboratoire (principalement en ce qui concerne les "cellules de
corrosion occluses", des travaux sur installations pilotes semiindustrielles et sur installations industrielles ... et leurs applications pratiques.
Mots-clefs
Corrosion localise - Carrosion par piqres - corrosion caverneuse Corrosion fissurante sous tension - Fragilisation par l'hydrogne Corrosion intergranulaire - Corrosion par dsalliage - Racteurs
nuclaires - Aciers inoxydables - Cuivre - Aciers cuivreux.

- VZusammenfassung
Nach einer einfhrenden Darstellung der wirtschaftlichen Aspekte der rtlichen Korrosion wird auf die Probleme der rtlichen Korrosion in den verschiedenen Wirtschaftsbereichen eingegangen.
Der

aktuelle

insbesondere

Stand
der

Spaltkorrosion,

des

Wissens

auf dem Gebiet der rtlichen Korrosion,

elektrochemische

Aspekt,

Spannungsrikorrosion,

werden

dargelegt.

Lochfra,

Wasserstoffvereprdung,

interkri-

stalline Korrosion und Korrosion durch Entlegierung werden kurz beleuchtet.

Die

praktische

spielen
scher

Anwendung

aufgezeigt:
aus

leitungen

Kenntnisse wird anhand von einigen Bei-

Dampfgeneratoren

nichtrostendem
aus

dieser
Stahl,

Kupferlegierungen

von

Kernkraftwerken,

Wrmeaustau-

Brauchwasserleitungen aus Kupfer, Rohrvon

meerwassergekhlten

Kondensatoren,

Erforschung von Korrosionsinhibitoren, Entwicklung von neuen Sthlen usw.

Zur

Bekmpfung

der rtlichen Korrosion wird die Durchfhrung eines umfas-

senden

Aktionsprogramms

auf

Rahmen

Laborforschungen

(vor

Korrosionseiemente),

Gemein3chaftsebene
allem

Forschungen

vorgeschlagen, in dessen

ber die sogenannten abgeschlossenen

in Industrieanlagen und Pilotanlagen mit

industriehnlichen Bedingungen durchgefhrt ...und auch praktisch angewandt

werden sollen.

Schlsselwrter
rtliche

Korrosion

Lochfrakorrosion

- Spaltkorrosion - Spannungsri-

korrosion - Wasserstoffversprdung - interkristalline Korrosion - Korrosion

durch

Entlegierung

Kupfersthle.

Kernreaktoren

nichtrostende

Sthle

- Kupfer -

ANALYSIS OF CURRENT PROBLEMS CAUSED BY LOCALIZED CORROSION.

STUDY OF THEIR INDUSTRIAL IMPACT

AND PROPOSALS OF ACTIONS

by Marcel POURBAIX, Prof. Dr. Ir.

Honorary Professor of the "Universit Libre de Bruxelles",
Honorary Director - Advisor at the "Centre Belge d'Etude
de la corrosion", CEBELCOR (Belgian Center for the study
of corrosion)

CONTENTS

ES

1. ECONOMIC IMPACT OF LOCALIZED CORROSION

1.1. The characteristic economic aspects of localized

corrosion

1.2. Review of localized corrosion encountered in various

sectors of industrial activity

12

1.2.1. Extraction of mineral resources (crude oil,

natural gas, geothermics)

13

1.2.2. Metallurgy

14

1.2.3. Manufacture of paper pulp and paper

15

1.2.4. Treatment of food products

16

1.2.5. Oil refineries

16

1.2.6. Chemical industries

17

1.2.7. Maritime transport and applications in sea water

18

1.2.8. Air transport

21

1.2.9. Generation of electric energy (including nuclear

energy)

22

1.2.10. Transport, storage and distribution of natural

gas

23

1.2.11. Building industry

24

1.2.12. Medicine, surgery

25

2. CURRENT KNOWLEDGE OF LOCALIZED CORROSION

26

2.1. Definition and general description

26

2.2. Methods of study

28

2.2.1. Electrochemical bases of corrosion

28

2.2.1.1. Electrode potential

29

2.2.1.2. The electrochemical equilibrium.

The

first law of electrochemical thermodynamics

29

2.2.1.3. Affinity, overpotential, direction of

electrochemical reactions.

The second

law of electrochemical thermodynamics

31

2.2.1.4. Polarization curves

33

2.2.1.5. Other electrochemical methods of study

and control of corrosion

35

2.2.1.6. Experimental pH-potential diagrams and

"occluded corrosion cells"

36

2.2.1.6.1. Iron and non-alloy steels'

36

2.2.1.6.2. Alloy steels

43

2.2.1.6.3. Copper and copper alloys

47

2.2.1.6.4. Aluminium

49

2.2.1.6.5. Titanium

49

2.2.1.6.6. Tungsten

49

2.2.1.6.7. Molybdenum

50

2.2.2. Methods of analysis

5C

2.2.3. Study of corrosion phenomena due to mechanical

deformation

53

2.3. Initiation and propagation of localized corrosion

58

2.4. Pitting corrosion

61

2.5. Crevice corrosion

63

2.6. Stress corrosion

66

2.7. Hydrogen embrittlement

76

2.8. Intergranular corrosion

76

2.9. Corrosion by de-alloying

79

2.10. Localized corrosion models

80

3. APPLICATIONS OF CURRENT KNOWLEDGE OF LOCALIZED CORROSION

3.1. Electrochemical protection against localized corrosion

S3
84

3.2. Specifications for critical chloride content in secondary

circuits of nuclear reactors
3.3. Use of ferritic

86

stainless steel against corrosion of

support plates of steam generators in nuclear reactors

87

3.4. Inhibitors of localized corrosion

87

3.5. Steels resisting localized corrosion

89

3.6. Deformation induced cracking in nuclear reactors

90

3.7. Evaluation of sensitization to intergranular corrosion

93

4. RESEARCH REQUIRED

95

4.1. Laboratory research

95

4.1.1. Determination of general conditions for immunity,

generalized corrosion, pitting corrosion, perfect
passivity

and imperfect passivity of alloy steels

and their main constituents

96

4.1.2. Study of natural "occluded corrosion cells"

96

4.1.3. Study of

simulated "occluded corrosion cells"

97

4.1.4. Study of artificial "occluded corrosion cells"

98

4.1.5. Diffusion phenomena in "occluded corrosion cells"

100

4.1.6. Thermodynamic data

100

4.1.7. Industrial information and experiment precautions

100

4.2. Works in pilot installations

101

4.3. Works on industrial structures

102

4.4. Seminary sessions.

102

Recommendations. Publications

ACKNOWLED GEMENT S

102

INDEX OF TABLES

103

INDEX OF FIGURES

105

BIBLIOGRAPHY

109

FIGURES

123

AUTHOR INDEX

149

1. THE ECONOMIC IMPACT OF LOCALIZED CORROSION

1.1. THE CHARACTERISTIC ECONOMIC ASPECTS OF LOCALIZED CORROSION
In an imaginary situation where corrosion does not exist, materials
would be chosen for their mechanical

characteristics, their

price,their weight, their thermal and electric conductivity, the ease

with which they are used, etc., but not for their resistance (.o
degradation due to the environment.
In this imaginary situation without corrosion, one might often choose
steel for example for its price and for all of its mechanical characteristics (resistance, toughness, resilience ...), copper for thermal
exchange surfaces or for its good electric conductivity, or aluminium
when a combination of light weight and high electric conductivity is
needed.
But in the real situation where corrosion exists, the choice of
materials is particularly complex, because the number of environments
and of conditions that the materials may meet with is very large. Two
major families of materials are used for better resistance to
corrosion :
1. Noble materials, which maintain their surface in a metallic state
under a large range of operating circumstances (examples : gold,
iridium, platinum, rhodium, ruthenium, palladium, silver, osmium
... and some of their alloys)
2.

Passivable metals, whose resistance to corrosion is due to a

superficial film of a protective oxide (examples : tantalum,
niobium, titanium, zirconium, tin, copper, beryllium, aluminium,
chromium, stainless steel, nickel, nickel alloys, cobalt, etc ...)

This family of passivable materials is in principle subject to localized corrosion : when the film has a defect, localized corrosion
may occur at the place where the defect is present,

whereas the

-6 neighbouring surfaces remain passive.

This localized corrosion may take the form of pitting corrosion,
crevice corrosion, or stress corrosion cracking.
An easy way to list the costs of all of the corrosion phenomena,
inspired by a major study done in the United States (1, 2, 3) consists of locating and defining the following components.
1. Replacement of corroded equipment (reactors, machines, vehicles,
buildings ...)
2. Loss of products (through leaks or contamination)
3. Maintenance and repairs (re-welding ...)
4. Installed excess capacity (because of scheduled maintenance shutdowns, the hourly capacity of production must be increased to
reach programmed annual production)
5. Spare equipment (for example a reserve pump if the first pump is
corroded)
6. Protective measures against corrosion (special material,
inhibitors, paint, cathodic protection ...)
7. The cost of research, tests to combat corrosion
8. Design, special manufacture operations (for example : thicker
layers for corrosion, stress relieving thermal treatment ...)
9. Administrative costs (stocks, insurance ...)
Localized corrosion, which is the case that we are dealing with here ,
is particular from more than one point of view, as concerns the cost
components which have just been listed :

Localized corrosion generally results from a poor appraisal of the

properties of the materials or from aggresive conditions, or from a
lack of precautions during manufacture or commissioning, or again
from accident conditions during operation. By and large, localized
corrosion is an unforeseen event which is definitely in contrast with
generalized corrosion or with regular wear. The unforeseen character
of localized corrosion means that it is not possible to make economic
choices based on calculated life expectancies, and that it is not
possible to plan the period of maintenance and repair required.
What precedes shows that, for cases of localized corrosion which
still occur today, the components of cost indicated in 1 above
(replacement), 2 (loss of products) and 7 (research and development)
are particularly high.
By using simplified but valid reasoning, one can affirm that most
often, normal stainless steels of type AISI 430 (17% Cr), AISI 304
(18 Cr - 10.5 Ni) and AISI 316 (18 Cr - 10 Ni - 3 Mo) are used when
ordinary carbon steel is not suitable because of generalized corrosion. Stainless steels AISI 430, 304 and 316 are themselves subject
under certain circumstances to corrosion and generally this is a
phenomenon of localized corrosion. In these cases, the metallic
materials chosen to stop localized corrosion will usually be special
stainless steels (superaustenitic steels, austeno-ferritic steels,
superferritic steels), alloys with a high nickel content (Inconel,
Incoloy, Hastelloy ...) or titanium. The economic impact of localized
corrosion, with regard 'to the cost of special materials used to avoid
such localized corrosion (listed in point 6 above), can therefore be
estimated as a first approximation by the increase of cost due to the
use of these special materials (special stainless steels, nickel
alloys, titanium ...) rather than ordinary stainless steels like AISI
430, 304 or 316.
As an indication, table I gives comparative prices of metallic
materials to be considered when trying to avoid corrosion.

Table I : Indicative and compara tive pri

prices (June 1985)-of some materials
used for their resistance to corrosion
Indicative price per tonne

Materials

(1 to 2mm sheets)
Ecus

(June 1985)

Carbon steel

Price as compared

for the same thickne

0.2

AISI 304 stainless steel

Aluminium-magnesium (3% Mg)

2 620
2 570

1.0
0.3

Nickel 200

3 550 *
26 670

Tin

17 460

6.2

Monel 400

24 440

10.4

Inconel 600

26 670

11.0

Hastelloy B

66 670

29.8

Titanium

40 000

8.0

Tantalum

555 560

402.6

AISI 904L Stainless steel

6 820

2.6

AustenofertitiC
steel

6 360

2.3

3 600

1.3

Copper

stainless

Ferritic steel (26 Cr-lMo)

* The price of copper fluctuates widely.

to steel 304 per m"

1.4
10.2

Table II gives estimates of apparent consumption (production +

import - export) of some of these materials in the EEC.
Following the reasoning above, the annual increase in cost due to the
use of special stainless steels can be estimated at 25700 (6150 2620) Ecus/T = 91 million Ecus, where 6150 Ecus/T is the average
price for all the grades of special stainless steel used; in the same
way, the annual increase in cost due to the use of high nickel
content alloys is evaluated at 20000 (27800 - 2620) Ecus/T 0.60
= 302 million Ecus, where 27800 Ecus/T is an average price for the
entirety of high nickel content alloys, and

where the factor 0.60

takes into account the fact that a part of these alloys (estimated at
40%) is used, not to improve resistance to localized corrosion, but
to improve resistance to non-oxidizing acid medias; and, similarly,
the annual increase in cost of localized corrosion due to the use of
titanium can be estimated at 23000 (8 - 1) 0.40 2620 Ecus/T
0.40 = 67 million Ecus, where the factor (8 - 1) 0.40 takes into
account the additional cost of titanium as compared to stainless
steel for an identical surface and for a thickness of titanium equal
to 40% of what it would be for stainless steel in the same applica
tion (these figures are valid for condenser tubes in thermal power
plants), and where the last factor 0.40 takes into consideration the
part of the market in titanium metal reserved for chemical and ther
mal power plants, as opposed to cases (aviation for example) where
titanium is used for its low density or as a steel alloying element.
In all, the cost component of localized corrosion which is in direct
relationship to special materials used as a means of protection (i.e.
part of point 6 of the above list) can be estimated at 91 + 302 + 57
million Ecus per year, or 460 million Ecus per year.
The impact of the costs mentioned in 3 of the list above (repairs) is
generally low, because the remedial action is much more often likely
to be replacements rather than repairs, and the cost listed in 4

10
Table II : Apparent annual consumption in the EEC of materials used for
their resistance to corrosion

(estimations based on information gathered from the Eurostat EEC Statistic

from the Groupement de la Sidrurgie in Brussels, ALZ in Brussels, De Kri
company in Brussels, CreusotLoire Industrie in ChalonsurSane, the Cent
d'information des Mtaux

nonferreux

in Brussels, the Socit Gnrale c

Minerais in Brussels).
Materials, country, year

Apparent consumption
per year

Steel, all types together (ordinary, stainless)

FRG + GB + F + + NL + L + D + I + Ir, 1984

Stainless steels including

115.5 million tonne

special types

FRG + GB + F + B--+D + I + NL + S, 1984

flat, cold-rolled ferritic products

252 110

flat, cold-rolled austenitic products

783 700

flat, hot-rolled ferritic + austenitic products

156 900

long, bar products for molded parts

250 000

stainless steels, total :

1 442 700

special stainless steels (super austenitic,

superferritic , austenoferritic), EEC
cold-rolled,. EEC, 1984, about

10 000

hot-rolled,

15 700

EEC, 1984, about

special stainless steels, total

25 700

nickel alloys (monel, inconel, incoloy, hastelloy

used in an aqueous milieu (as opposed to atmospheres
at high temperatures) EEC, estimation 1984

20 0G0

in comparison : apparent consumption of steel (all types) for the United

States in 1984 : 91.95 million tonnes
abbreviations :

FRG : Federal Republic of Germany - GB : Great Britain -

F : France - : Belgium - NL : Netherlands : I : Italy - D : Denmark Ir : Ireland - L : Luxembourg - G : Greece - S : Spain

Table II (cont'd)

- titanium (metallic products)

EEC, 1980

23 000

- copper
FRG + GB + F + + NL + I + D + G, 1984

2 197 709

12-

(excess c a p a c i t y ) and 5 (redundant equipment) a r e g e n e r a l l y

tant,

inexis-

because of t h e unforeseen and a l w a y s " a c c i d e n t a l " c h a r a c t e r of

localized

corrosion.

To i l l u s t r a t e the economic impact of l o c a l i z e d c o r r o s i o n , we propose

t o d e s c r i b e l o c a l i z e d c o r r o s i o n which,

despite a l l

forecasting

and

because of a l a c k of knowledge or bad assessment s t i l l occurs today,

and which l e a d s t o r e p l a c e m e n t c o s t s ,
research,

l o s s of p r o d u c t s ,

shut-downs,

development ...

This approach i s

b a s e d on r e p o r t s of a c t u a l

c a s e s of

localized

c o r r o s i o n . D e s p i t e wide c o n s u l t a t i o n s , t h i s r e p o r t w i l l

probably

g i v e n u n d e r e s t i m a t e d a s s e s s m e n t s , e v e n i f c e r t a i n e x t r a p o l a t i o n s from
p r o d u c t i o n f i g u r e s can be made.
1.2 REVIEW OF LOCALIZED CORROSION ENCOUNTERED IN VARIOUS SECTORS OF
INDUSTRIAL ACTIVITY
An i n v e n t o r y of t h e main problems of l o c a l i z e d c o r r o s i o n encountered
i n v a r i o u s s e c t o r s of i n d u s t r i a l

activity

represents the t e c h n i c a l ,

and economic s i g n i f i c a n c e

social

i s i n t e r e s t i n g because
of

it

these

problems r e a s o n a b l y w e l l .
C e r t a i n of t h e v a r i o u s problems of l o c a l i z e d c o r r o s i o n not

specific

t o a t y p i c a l t y p e of i n d u s t r y may p a r t i a l l y be o m i t t e d from

this

i n v e n t o r y . For example, t h i s i s t h e c a s e f o r t y p i c a l l o c a l i z e d c o r r o sion in c e r t a i n environments l i k e atmospheric corrosion, corrosion in

sea w a t e r , or i n l i v i n g t i s s u e s .
To f a c i l i t a t e c l a s s i f i c a t i o n ,

t h e problems met with i n sea water w i l l

be t r e a t e d

called

in

the

section

"maritime

transportation

and

a p p l i c a t i o n s i n sea w a t e r " and a p a r t i c u l a r s e c t i o n c a l l e d "medicine,

s u r g e r y " w i l l d e a l w i t h t h e b e h a v i o u r of m e t a l s i n t h e human body.
The economic e f f e c t

of l o c a l i z e d c o r r o s i o n i n atmospheric

corrosion

13

does exist, but it is not considered fundamental as compared to other

applications, and atmospheric corrosion will not be discussed in this
report.
The sectors of industrial activity which will be treated have been
chosen for the extent to which localized corrosion affects them and
for their importance in technical activities within the EEC. They are :
- extraction of mineral resources (crude oil, natural gas,
geothermics)
- metallurgy
- manufacture of paper pulp and paper
- treatment of food products
- oil refining
- chemical industries
- maritime transportation and applications in sea water
- air transport
- generation of electricity, including nuclear energy
- transportation, storage and distribution of natural gas
- construction
- medicine, surgery
1.2.1. Extraction of mineral resources (crude oil, natural gas,
geothermics)
The corroding environment consists of water, generally containing
chloride, close to concentrations of sea water, and of COo and HoS
gases having concentrations up to 10 to 15%, and at variable
temperatures and pressures, for example about 150C and 50 bars, and
sometimes as high as 250C and 450 bars at the bottom of well shafts.
The first material used for tubing and casing is low alloy steel with
average mechanical resistance. In certain applications, this material
undergoes localized corrosion problems (HIC for hydrogen induced
cracking, stress corrosion due to H^S, SSCC for "sulfide stress
corrosion cracking) and generalized corrosion, located throughout the

-14

tubing in l o c a l hydrodynaraic conditions and circumstances separating

o i l and water.
To combat these phenomena, more and more s t a i n l e s s s t e e l s are being
used in the case of p a r t i c u l a r l y corrosive w e l l s i.e. in the presence
of s i g n i f i c a n t

q u a n t i t i e s of CO2, or CO2 and H^S. The s t a i n l e s s

s t e e l s used a r e m a r t e n s i t i c ,

ferritic,

austenoferritic

or even

superaustenitic s t e e l s , for a n c i l l a r y equipment on the top or in the

bottom of w e l l s h a f t s .
In t h i s c a s e , c o r r o s i o n problems t a k e on a l m o s t a l l t h e c l a s s i c a l
forms of l o c a l i z e d corrosion: p i t t i n g corrosion,
s t r e s s corrosion cracking. A f i r s t ,

very d i f f i c u l t

c r e v i c e corrosion,
question in t h i s

f i e l d i s to c o r r e c t l y e v a l u a t e t h e r i s k of t h e s e v a r i o u s t y p e s of
c o r r o s i o n and t o choose economical m a t e r i a l s which g u a r a n t e e t h e
required performance.
The t o t a l c o s t of a w e l l can be a s high as 50 m i l l i o n Ecus,, i n
d i f f i c u l t c a s e s l i k e t h e A r t i e , o f f - s h o r e or deep w e l l s ( 4 ) . T h i s
cost represents the p r i c e of a t o t a l f a i l u r e to c o r r e c t l y

evaluate

the material to be used, which could r e s u l t in rupture and the l o s s

of the lower tubing.
These same r i s k s of l o c a l i z e d corrosion ( p i t t i n g ,
...) e x i s t for s u r f a c e i n s t a l l a t i o n s

crevices,

: tanks, pipes,

cracks

separators,

pumps, heat exchangers . . . )

1.2.2. Metallurgy
The problems of l o c a l i z e d c o r r o s i o n i n h y d r o m e t a l l u r g y a r e more
s i g n i f i c a n t than in metallurgy u s i n g t h e r m a l r e d u c t i o n . Tanks used
for t r e a t i n g o r e s with a c i d s o l u t i o n s m i x t u r e s , and c o n c e n t r a t i o n
tanks in s t a i n l e s s s t e e l are exposed to corrosion by p i t t i n g ,

crevice

and cracking under s t r e s s when c h l o r i d e s and f l u o r i d e s are present in

the ore. Problems of t h i s type e x i s t in zinc and copper hydrometallurgy.

15 -

Certain i n t e r g r a n u l a r corrosions in welded s t a i n l e s s s t e e l tanks have

occurred in i n s t a l l a t i o n s for r e c u p e r a t i n g copper s c r a p , by r e d i s s o l u t i o n in a s u l f u r i c medium.
1.2.3. Manufacture of paper pulp and paper
Very serious problems of l o c a l i z e d corrosion caused by s t r e s s c o r r o s i o n c r a c k i n g of carbon s t e e l appeared i n 1979 i n t h e c o n t i n u o u s
d i g e s t e r s of p u l p for paper p a s t e . The environment i s very r i c h i n
c a u s t i c a l k a l i NaOH and NaS s u l f i d e and i t c o n t a i n s c a r b o n a t e s ,
s u l f a t e s and t h i o s u l f a t e s . The continuous d i g e s t e r s are l a r g e columns
which work a t 175C and 10 b a r s . After a d i s a s t r o u s e x p l o s i o n which
occurred in 1979, more than 150 continuous d i g e s t e r s were examined in
North America and Europe, and more than 60% of them showed s t r e s s
corrosion cracks near welds (5,6).
B l e a c h i n g paper p u l p i s c a r r i e d out i n an o x i d i z i n g

environment

containing c h l o r i n g d e r i v a t i v e s . S t a i n l e s s s t e e l i s widely used, but

with l o c a l i z e d c o r r o s i o n problems of p i t t i n g and c r e v i c e s ,

the

average l i f e expectancy of a bleaching tank in s t a i n l e s s s t e e l AISI

347 (18 Cr - 10 Ni, s t a b i l i z e d with Nb) i s t h r e e y e a r s and i t c o s t s
something on the order of 275 000 Ecus ( 7 ) .
The Technical Association of the Pulp and Paper Industry TAPPI e s t i mates t h e c o s t of c o r r o s i o n i n paper p u l p u n i t s l o c a t e d i n North
America a t 1.36 b i l l i o n Ecus. P r o b a b l y 60% of t h i s c o s t i s a t t r i b u t a b l e to t h e two major problems of l o c a l i z e d c o r r o s i o n d e s c r i b e d
above.
Another l o c a l i z e d corrosion problem has come up more r e c e n t l y ,
white l i q u o r s have become more r i c h in t h i o s u l a t e S2O0

since

: equipment

in s t a i n l e s s s t e e l AISI 304 (18 Cr - 10 Ni) s u f f e r s from s e v e r e

p i t t i n g corrosion caused by Na^SoOo ( 8 ) .

16

1.2.4. Treatment of food products

S t a i n l e s s s t e e l s a r e very w i d e l y used i n t h e agrofood i n d u s t r i e s ;
they r e s i s t food attack b e t t e r than o r d i n a r y s t e e l (or g a l v a n i z e d ,
cadmium plated or aluminium p l a t e d s t e e l ) , they conserve the f l a v o u r ,
they have a s u r f a c e which f a c i l i t a t e s c l e a n i n g and they w i t h s t a n d
cleansing products and d i s i n f e c t a n t s f a i r l y w e l l .
Dairies, breweries, sugar-refineries,

boiling tanks,

filling

a u t o c l a v e s consume

food cans and s t e r i l i z a t i o n

lines

for

large

q u a n t i t i e s of s t a i n l e s s s t e e l .
The c o r r o s i v e media are u s u a l l y c h l o r i d e s and may be acids (acid from
l a c t i c f e r m e n t a t i o n , a c e t i c , or p h o s p h o r i c a c i d s , c i t r i c a c i d ... )
or a c i d s w i t h high SO2 c o n t e n t ( f r u i t p u l p s ) . A c c i d e n t a l b a c t e r i a l
development may form l o c a l a c i d s . D i s i n f e c t a n t s a r e a g r e s s i v e t o
s t a i n l e s s s t e e l s : whether o x i d i z i n g , c h l o r i d e d or a c i d , they a r e
dangerous i f they a r e used i n too h i g h c o n c e n t r a t i o n , a t too high
temperature, for too long a time, or without subsequent r i n s i n g .
The corrosion problems met with are corrosion by p i t t i n g and crevice
of s t a i n l e s s s t e e l s and,

in equipment working a t high temperatures

and p a r t i c u l a r l y in c o n c e n t r a t o r s where e v a p o r a t i o n t a k e s p l a c e ,
s t r e s s corrosion cracking of a u s t e n i t i c s t a i n l e s s s t e e l s .
1.2.5. Oil r e f i n e r i e s
Stainless

steels

a r e used v e r y f r e q u e n t l y

in

desulfurization

processes because of t h e i r good r e s i s t a n c e to high temperatures and

high H2S content.
However, s e v e r a l cases of i n t e r g r a n u l a r corrosion under s t r e s s have
o c c u r r e d i n s t e e l 321 (18 Cr - 10 Ni, s t a b i l i z e d w i t h
during

plant

shut-down.

This

corrosion

titanium)

was a t t r i b u t e d

to

the

17

corrosive action of polythionic acids formed at room temperature by

reaction between deposits of sulfides, damp and air on steels made
sensitive during the welding of equipment.
This problem is one of the most serious corrosion problems in oil
refineries, after corrosion problems caused by the condensates of
atmospheric distillation towers for crude oil. It relates to the
installations for desulfurization, hydro-cracking and separation of
amines (9,10).
Oil refineries also encounter problems of localized corrosion which
are common to other types of industry : corrosion from heat exchangers, cracking corrosion of stainless steel under thermal isolation ,

1.2.6. Chemical industries

A study done by Du Pont de Nemours reports that, of all service
failures in a period of four years (1968 to 1971), 55.2% were due to
corrosion, versus 44.8% which were attributable to purely mechanical
causes. Of all of these failures, 28.5% were due to localized corrosion and 26.7% were due to generalized corrosion, erosion-corrosion,
corrosion by wear, at high temperature ... (11).
Nearly half of the incidents of localized corrosion were stress
corrosion cracking (13.1% of all failures), followed in order by
pitting (7.9% of the total) and intergranular corrosion (5.6% of all
total). Our experience, based on a large range of industries, indicates that crevice corrosion is to be placed between pitting and
intergranular corrosion in order of importance. For Monsanto, crevice
corrosion is even perhaps more costly than pitting corrosion and
stress corrosion cracking (12). Among the cases of corrosion reported
in a large chemical industry in the Federal Republic of Germany
between 1966 and 1972, 47,o were due to localized corrosion, 19% to

18

transgranular stress corrosion, 6% to intergranular stress corrosion,

11% to

corrosion by wear, 5% to corrosion by pitting, 4% to inter-

granular corrosion and 2% to hydrogen embrittlement (13).

The equipment affected the most are the reactors or conducts for hot'
chloride fluids, blowers for expansion compensation, hot thermally
isolated walls, heat exchangers, condensers, ...
Transitional periods of operation (pressure trials, start-ups,
stoppages ...) are often the cause of initiation of

localized

corrosion.
There are a large number of environment/material combinations in the
chemical industry which result in localized corrosion. Without mentioning all of the maritime or chloride media, which are very common,
one can note for ordinary steel : caustic environments, nitrate
solutions, liquid amnia, nitric and sulfuric solutions, H^S environments, carbonate solutions
derivatives, SO2 solutions

for copper alloys : ammonia and its

for nickel alloys : fluorhydric vapors,

caustic solutions, pure water at high temperature, phosphoric acid

prepared by dissolution of natural phosphates.
, The chemical industry in the United States estimates that the cost
it incurs every year due to stress corrosion is 40 million Ecus. This
cost would have to be slightly more than twice as much to take into
account other forms of localized corrosion as well. A very rough
estimate for Western Europe gives a cost for stress corrosion which
is somewhere between 44 and 118 million Ecus per year for the chemical and petrochemical industries (13).
1.2.7. Maritime transportation and applications in sea water
Of all the environments which create localized corrosion, sea water
is the most widespread : it affects all parts of ships, hulls,
condensers, ballasts, superstructures ..., off-shore installations,
buildings and industrial equipment located near shores, and in

19

particular cooling installations using sea water, desalination

plants, goods and equipment contaminated during maritime transport,
and the airplanes exposed to sea mists and then to important variations in humidity and temperature.
Copper alloys, stainless steels, aluminium alloys and steels with
high mechanical characteristics are the most exposed to localized
corrosion in sea water.

Stress corrosion cracking occurred at the chucks in brass or stainless steel tubes in the tubular heat exchange plates; the brass tubes
containining aluminium or cupro-nickel can be pitted in polluted sea
water; classic stainless steels AISI 316 (18 Cr - 10 Ni - 3 Mo) are
not reliable for condensers cooled in sea water because of pitting
corrosion and, particularly during shut-downs, crevice corrosion.
Grades of special stainless steels have been developed and are still
being tested to evaluate their behaviour with regard to various forms
of localized corrosion in sea water, for applications at moderate
temperatures (cooling) or higher temperatures (desalination).
Research and development is also going on pertaining to the operating
conditions for stainless steels so as to avoid a problem of localized
corrosion in sea water : control of circulation speed, elimination of
deposits, control of electrode potentials, measure of risk of localized corrosion.
A few examples of some problems illustrate the need for and the
interest from the economic point of view of a perfect knowledge of
all aspects of localized corrosion in sea water :
- corrosion of a condenser tube in a ship's boiler can stop the
ship. During a crucial period in the First World War, this type of
corrosion caused the British Admiralty more worry than war damage.
Research undertaken thereafter lead to the development of an
"admiralty brass" by the British Non Ferrous Metals Research
Association BNFMRA (76 Cu, 22 Zn, 2 Al with 0.02 to 0.06% As) which

20

was patented in 1927 and has remained standard material for heat
exchangers ever since.
A super oil tanker was totally stopped during its maiden voyage by
perforation of condensers made of copper alloys.The cause of these
perforations (presence of carbon on the inside of the tubes, as a
result of the cracking of drawing oil during annealing) was well
known for copper tubes in fresh water, but the risk in salt water
had been underestimated.
Exchangers in stainless steel which are cooled by sea water in
chemical plants, have been subject to crevice corrosion at the
joints of the water boxes, between the pressure tests and the
commissioning of the factory. The start-up of the factory was
delayed by three months.
Certain stainless steel components of a sea water cooling circuit
which included many ordinary steel parts behaved'well. On the basis
of this experience, the circuit was transformed entirely into
stainless steel : since then pitting and crevice corrosion have
increased. The presence of the carbon steel that had previously
been used, created a drop in the electrode potential of stainless
steel which stopped all localized corrosion - the users were unaware of this effect. This involuntary system of protection disappeared when the last part of the carbon steel circuit was eliminated.
Various tests of ship turbines are done in ports where water is
usually very polluted. These conditions are extremely unfavourable
for copper alloy condenser tubes. One can imagine that it would be
cheaper to undertake these tests in the docks where water has been
treated to oxidize and neutralize sulfurated pollutants.
One can still see specifications for martensitic stainless steel at
13% or 17% Cr, 4% Ni and some Mo for the shafts of seagoing
vessels. With these steels, pitting as large as a fist occurred in

21 -

s e v e r a l months. Other c l a s s e s of a u s t e n o f e r r i t i c s t e e l s , made

according to p a r t i c u l a r
properties,

make i t

specifications

possible

for t h e i r

metallurgie

to o b t a i n both t h e

mechanical

c h a r a c t e r i s t i c s and the r e s i s t a n c e to c o r r o s i o n d e s i r e d for

this

application.
- The d e s a l i n a t i o n

of

sea water

decarbonated

by

acidification

f o l l o w e d by d e g a s s i n g i s an e l e g a n t and common p r a c t i c e . But t h e

specific pH and aeration conditions at every moment during s e r v i c e
and shut-downs, and at every location of the i n s t a l l a t i o n must be
c o n t r o l l e d for proper behaviour of the material : poor functioning
of the degasser i s d i s a s t r o u s for s t a i n l e s s s t e e l , a c i d i f i c a t i o n
dangerous

for

imperatives

aluminium

bronze.

have been s e t

Very r e s t r i c t i v e

up to m a i n t a i n

the

is

operating

integrity

of

materials.
1.2.8. Air t r a n s p o r t
Two major problems of l o c a l i z e d c o r r o s i o n e x i s t i n a e r o n a u t i c s :
e x f o l i a n t c o r r o s i o n of aluminium a l l o y s used for a i r c r a f t

frames

(type AA7075), and s t r e s s c o r r o s i o n of high r e s i s t a n c e s t e e l s used

notably for landing gear (AISI 4340 or 4130).
These two problems are caused by chloride concentration with l o c a l
a c i d i f i c a t i o n phenomena.
P a r t i a l s o l u t i o n s have been found to these problems : thermal t r e a t ments T7 and T73 have replaced the T6 treatment for the a l l o y s Al-CuZn-Mg AA7075; the thermal treatment of AISI 4340 s t e e l has a l s o been
modified to decrease i t s hydrogen embrittlement, to the detriment of
i t s mechanical c h a r a c t e r i s t i c s .

But t h e s e problems s t i l l have an

i m p o r t a n t impact from t h e s a f e t y and c o s t s t a n d p o i n t . Some a s s e s s ments of the cost of these problems are a v a i l a b l e based on m i l i t a r y
s e c t o r s in t h e United S t a t e s (14), but for t h e moment they a r e not
e a s i l y transposed to problems of European c i v i l a v i a t i o n .

22 -

1.2.9. Generation of Electric Energy

(including nuclear energy)

Problems of localized corrosion in the sector of generation of electricity are not necessarily limited to nuclear power plants, but the
use of stainless steel is more widespread in nuclear power plants
than in power plants using fossile fuels, to decrease

transport of

radioactive corrosion products. It is true that there have been and

there still are a certain number of systematic localized corrosion
problems in nuclear power plants, and that there is particularly good
documentation from the technical and economic standpoint on these
problems.
The most expensive localized corrosion in the world, for the generation of electric energy, is the intergranular stress corrosion
cracking of tubes in AISI 304 steel near welded joints. This corrosion affects the boiling water reactors. Between 1974 and 1982, 300
cases of cracking were observed, which led to a loss in production of
about 2% per year. In 1982, 63% of the research funds of "Materials
and Corrosion Research'Program" managed by the Electric Power Research Institute EPRI, in the United States, were allocated to the
study of this problem, which shows its relative importance (15).
Other localized corrosion problems also appear on the same "Materials
and Corrosion Research Program" with these funds : stress corrosion
cracking of the joint tubulars in the BWR reactor tanks (13%), stress
corrosion cracking of turbine discs further to impurities in the
steam (CI, OH ...) (8%), stress corrosion cracking of PWR pressurized
water reactors (secondary water supply pipes, boricated water), localized corrosion in carbon steel ("denting") in the steam generators
of PWR reactors, and localized corrosion in condensers (15% in all).
The total cost of corrosion for nuclear energy in the United States
was estimated in 1982 at 0.68 billion Ecus. The analysis above
indicates that certainly 80% of this cost is due to localized
corrosion phenomena.

23 -

In 1978-1979 the steam generators of four PWR power plants were

replaced because of denting after 5 to 6 years of operation, whereas
the equipment was programmed for 40 years of service life. The cost
of replacing a steam generator is 125 to 250 million Ecus.
Recent examinations done in France have brought a new view to many
cases of localized corrosion : entirely accidental surface contaminations by sulfur or chloride compounds are responsible for more or
less disastrous incidents which are always very expensive. These
contaminations may be due for example to marking systems, to degreasers, or simply to the normally polluted atmosphere in workshops or
storage halls (16,17). Determining causes of localized corrosion is
likely to increase the strict compliance and quality of working
conditions in the nuclear industry and in other fields of the technology, at higher

cost but with increased security.

1.2.10 Transport of natural gas

A very serious accident, due to stress corrosion cracking, took place
in Louisiana on March 4, 1965. This accident was particularly worrisome because other indicents or other observations recorded since
that time lead us to think that the risk is fairly general. The
problem is one of intergranular cracking in various buried gas pipes
under stress; they are coated with coal-tar or asphalt and protected
cathodically. Most of the cracking took place less than 16 km after
the compression stations which raise the gas temperature up to 35 to
60C at the location of the cracks. The incidents occurred on the
average 14 years after installation of the pipes.
Very long studies of these cases of cracking, done by R.N. PARKINS,
indicated that in the carbonate-bicarbonate solutions produced by the
aging of the coal-tar, given the cathodic protection, and probably
the effect of a concentration by evaporation on the hot pipes, there
were spots under the coating or the calamine where the electrode
potential of the steel corresponds to the cracking conditions of the

- 24

These cases of corrosion showed the necessity of fully understanding

the localized corrosion processes, to be able in this case to establish the risky zones on existing networks of distribution of natural
gas, and to apply the remedies proposed up to date.
1.2.11. The building industry
A well-known localized corrosion problem in the building and public
works industry is the corrosion of reinforcing bars for concrete in
the presence of chloride additives or contaminants.
The prestressed cables in the concrete are exposed to localized
corrosion by hydrogen embrittlement. In practical technology, there
is still a lack of elaborate and complete recommendations covering
the state of the surface of the prestressed cables, the conditions
for storage, the control of their repair before injection into
sheaths and the nature of the injection composites.
Localized corrosion of aluminium beams and frames is an old and wellknown problem, whose economic impact can be considered small, because
of the means of protection used (anodisation

and

sealing,

maintenance).
Many types of localized corrosion affect water pipes in galvanized
steel and copper. The problems appeared distinctly in the 1960's for
copper (first in cold water, then also in hot water) and in 1965 for
galvanized steel (mainly in hot water).
Detailed studies of the problem of corrosion of copper pipes,made in
1960-63, have made it possible to understand the fundamental mechanism and to establish a method of control by simply measuring the
electrode potential (19, 20, 21). These studies were at the origin of
considerable progress in the understanding and

elimination of this

type of corrosion. However, although this has been understood for

more than twenty years, the problem of pitting corrosion in copper

25 -

water p i p e s i s s t i l l with u s . The c o n t r o l of t h e q u a l i t y of t u b e s

produced and d i s t r i b u t e d in the EEC countries and proper c o n t r o l of
t h e i r use could quickly eliminate t h i s problem e n t i r e l y .
1.2.12. Medicine, surgery
In bone surgery, there are problems of l o c a l i z e d corrosion of metal
i m p l a n t s which p e r h a p s do not bear on l a r g e numbers of t o n s , but
which are always very expensive and have a t t r a c t e d s c i e n t i f i c a t t e n tion which has broadened the scope of knowledge.
Among t h e m e t a l l i c m a t e r i a l s used as i m p l a n t s ( s t a i n l e s s s t e e l ,
t i t a n i u m and a l l o y s ^ , Cr-Co-Mo a l l o y s ...) 316 L s t e e l i s t h e l e a s t
e x p e n s i v e , but i t must be used o n l y f o r temporary i m p l a n t s which
serve for the time needed for r e c a l c i f i c a t i o n and no more. Very rapid
c r e v i c e corrosion takes place in the screw-plate assembly i n a u s t e n i t i c s t a i n l e s s s t e e l 316 L, and s t r e s s corrosion cracking takes place
on the e x t e r n a l coapters in m a r t e n s i t i c s t a i n l e s s s t e e l .
These problems have been w i d e l y i n v e s t i g a t e d s i n c e t h e end of t h e
1960's; the study of the r o l e of muscular metabolism, c h l o r i d e cont e n t , the oxidizing and buffer power of l i v i n g t i s s u e s along with the
t o x i c i t y of t h e c o r r o s i o n p r o d u c t s has brought u s e f u l

additional

knowledge pertaining to l o c a l i z e d corrosion and has led t o a b e t t e r

choice and use of m e t a l l i c implants and dental a l l o y s (22).

26

2. CURRENT KNOWLEDGE ON LOCALIZED CORROSION

2.1. DEFINITION AND GENERAL DESCRIPTION
The forms of localized corrosion considered are
- pitting corrosion
- crevice corrosion
- stress corrosion cracking
- hydrogen embrittlement
- intergranular corrosion
- corrosion by de-alloying

The first three types of localized corrosion mentioned take place in

cases where the metal is usually passive (this means covered with a
protective oxide) in its environment, but where the passive film has
local defects.
These defects may be due to certain ions (for example chlorides) or
to local defects in the protective oxide, which lead to pitting corrosion; the defects may be due to the phenomena of differential
aeration which causes destruction of the protective film in the nonaerated regions (under the deposits, in the recesses ...) and in this
case we talk about crevice corrosion; the defects in the oxide may be
due to rupture by mechanical stress and deformation, and this is
designated by the term stress corrosion, or cracking corrosion
induced by deformation.

Hydrogen embrittlement presents certain

characteristics which also apply to stress corrosion, but this more

particularly refers to the embrittling role of hydrogen, either by
its action on the liaison energy between atoms, or by the formation
of gaseous hydrogen within the material, forming blisters or cracks.
Intergranular corrosion is a preferential corrosion of grain boundaries or of the metal matrix around the grains, due to dissimilarity
in the composition of the matrix and the joints.

27

C o r r o s i o n by d e - a l l o y i n g i s t o a c e r t a i n e x t e n t an extreme case of
l o c a l i z e d corrosion, where one or s e v e r a l of the components of the
a l l o y are dissolved p r e f e r e n t i a l l y ,

g e n e r a l l y with redeposition of

another c o n s t i t u e n t .
A complete d e s c r i p t i o n of material/environment couples which cause
various types of l o c a l i z e d corrosion would be very long. By trying to
make a systematic presentation to show as many elements as possible
in a few general p r i n c i p l e s , one should underline the fact t h a t the
f i r s t three forms of l o c a l i z e d corrosion ( p i t t i n g corrosion,
corrosion,

crevice

s t r e s s c o r r o s i o n ) a r e , a s MONTUELLE (23) has put

it,

"diseases of the passive s t a t e " . They a r e thus produced in conditions

where the m e t a l l i c material i s p a s s i v e , i . e . where corrosion does not
occur because of the

formation of a p r o t e c t i v e outside l a y e r , and

where the p a s s i v i t y i s l o c a l l y d e f i c i e n t .

Passive conditions e x i s t

for example for unalloyed carbon s t e e l s in aerated a l k a l i n e s o l u tions,

for " s t a i n l e s s " s t e e l s in n e u t r a l s o l u t i o n s ,

alkaline solu-

t i o n s and c h l o r i d e - f r e e a c i d o x i d i z i n g s o l u t i o n s , for copper i n

n e u t r a l or s l i g h t l y acid s o l u t i o n s ,

for zinc in s l i g h t l y

alkaline

s o l u t i o n s l i k e bicarbonate s o l u t i o n s , for aluminium or zirconium in

essentially neutral solutions,

and for titanium in the presence of

most aqueous s o l u t i o n s , whether they are acid, n e u t r a l or a l k a l i n e .

Enemies of t h e p a s s i v e s t a t e , which i n t r o d u c e l o c a l d e f e c t s ,

are

c h l o r i d e s and f l u o r i d e s (and to a l e s s e r extent the other halogens),

geometric recesses (under i n e r t d e p o s i t s or under deposits of corros i o n p r o d u c t s , under j o i n t s , r i v e t s , b o l t s , a t t h e j o i n t s of mandrined tubes), blows, scratches and mechanical s t r e s s e s .
In t h e f o l l o w i n g p a r a g r a p h s
opportunity to p r o g r e s s i v e l y
phenomenon.

of Chapter 2, we w i l l
s p e c i f y each l o c a l i z e d

have t h e
corrosion

F i r s t , we must p r e s e n t a few b a s i c e l e m e n t s used t o study t h e s e

phenomena.

28

2.2 METHODS OF STUDY

2.2.1. Electrochemical bases of corrosion

The

study

of

corrosion

entails

a group

of

disciplines

electrochemistry, metallurgy, physics of m a t e r i a l s .

The r o l e of electrochemistry i s p a r t i c u l a r l y important in corrosion
phenomenon of metals and a l l o y s in the presence of an e l e c t r o l y t e ,
such as w a t e r . Thanks to t h e p i o n e e r work done on the s u b j e c t s i n c e
1923 by U l i c k R. EVANS (24) and s i n c e 1938 by C a r l WAGNER (25), a
v e r i t a b l e science of aqueous m e t a l l i c corrosion has been created by
many research teams working in various c o u n t r i e s , which has taken the
study of c o r r o s i o n and t h e f i g h t a g a i n s t i t out of t h e scope of
empiricism.
For t h i s reason, t h i s report devotes a v o l u n t a r i l y large share to the
electrochemical aspects of corrosion.
Below we r e c a l l some of t h e fundamental bases t h a t a r e used for
studying electrochemical corrosion; we w i l l successively consider :
- the electrode p o t e n t i a l
- the electrochemical e q u i l i b r i a
- the a f f i n i t y ,

o v e r p o t e n t i a l and d i r e c t i o n of

electrochemical

reactions
- the f i r s t and second law of electrochemical thermodynamics
- the p o l a r i z a t i o n curves
- other electrochemical methods of study and control of corroson
- the experimental potential/pH diagrams and the "occluded corrosion
cells".
Details

on

these

subjects

can

be

found

electrochemistry and corrosion (26, 27, 28).

in

treatises

on

29 -

2 . 2 . 1 . 1 . The electrode p o t e n t i a l
I t should be r e c a l l e d t h a t the e l e c t r o d e p o t e n t i a l E of a metal in
contact with an e l e c t r o l y t e (or more p r e c i s e l y the electrode poten
t i a l of an i n t e r f a c e between t h i s metal and t h i s e l e c t r o l y t e ) i s , in
size and sign, the difference in e l e c t r i c p o t e n t i a l between the metal
and a r e v e r s i b l e r e f e r e n c e e l e c t r o d e (hydrogen e l e c t r o d e , calomel
electrode,

s i l v e r c h l o r i d e e l e c t r o d e ...) on which t h e s t a t e of

thermodynamic equilibrium of a reference electrochemical reaction i s

reached. I t s h o u l d be u n d e r s t o o d t h a t t h i s r e f e r e n c e e l e c t r o d e i s
linked to the e l e c t r o l y t e by a siphon which opens up in the immediate
v i c i n i t y of t h e i n t e r f a c e ( f o r example a HABER-LUGGIN siphon or a
PIONTELLI siphon) and contains substances t h a t preclude the existence
of a diffusion

p o t e n t i a l between t h i s e l e c t r o l y t e and the s o l u t i o n

holding the reference e l e c t r o d e (for example an agar-agar gel s a t u

rated in KCl) (figure 1).
2 . 2 . 1 . 2 . The electrochemical equilibrium. The f i r s t law of e l e c t r o
chemical thermodynamics
For e v e r y e l e c t r o c h e m i c a l r e a c t i o n in which chemical s u b s t a n c e s
(metals, ions, oxides, s a l t s ..) and free e l e c t r o n s take part,

there

i s a value for the e l e c t r o d e p o t e n t i a l a t which the s t a t e of e q u i l i

brium of the r e a c t i o n i s r e a c h e d . The f i r s t law of e l e c t r o c h e m i c a l
thermodynamics expresses these equilibrium conditions :

for a reaction :

+ ne

= 0

(i.e. Fe = Fe++ + 2e )
aq

where M represents chemical substances, e

free electrons,

and

their stoechiometric coefficients, the equilibrium condition is :

(i.e.

- 23060 nEo = 0

(1)

where
" 23060

u ++ - Mu
*Te
Fe
aq
Eo =
46120

30 -

where the chemical potentials y

of the reacting substances are

expressed in calories and where the equilibrium electrode potential

Eo is expressed in volts (as compared to a standard hydrogen elec
trode - she).
The influence of the activity of dissolved compounds and the fugacity
of gaseous substances (M) on the equilibrium potential can be ex
pressed, at 25C, by the formulae :

Eo +

where

.
0 =

0,0591
U.OSiM

23060fl

lo

(M)

(i-e<

E o = Eo + 0 > 0 2 9 5

_ "'Fe"
" 46120

log (Fe

-20300
46120

)
^Q
'

where ES is the "standard equilibrium potential" of the reaction and

where u are the "standard chemical potentials1 of the reacting che
mical substances. Tables and thermodynamic data banks giving the
values of standard chemical potential

(or standard free enthal

pies of formation) exist for a large number of chemical substances,

and graphic representations of these electrochemical equilibria in
the form of potential/pH diagrams exist in the Atlas (29) and in
specialized works or articles dealing with various systems and at
various temperatures. These equilibria diagrams are currently being
treated by computer so that they will be available for any system,
any temperature and any concentration. There is a lack, however, of
much reliable data for substances dissolved at high temperature.
Information from these equilibrium potential/pH diagrams at 25C has
made it possible to draw figure 2 for 43 metals and metalloids in
contact with an aqueous solution free of substances that could form a
soluble compound or an insoluble salt with the element under conside
ration. Figure 2 shows theoretical conditions of immunity (where the
metal or metalloid is thermodynamically stable and therefore cannot

sh

- 31

be corroded), of passivation (where the thermodynamically stable form

is a solid oxide, which may or may not be protective) and of corrosion (where the thermodynamically stable form is dissolved in water
or gaseous).
2.2.1.3. Affinity, overpotential and the direction of electrochemical
reactions
The second law of electrochemical thermodynamics
The affinity A of an electrochemical reaction taking place on a
metal/electrolyte interface can be measured by the difference E-Eo
between the electrode

potential E of this interface

and

the

equilibrium potential Eo of the reaction, it being understood that

these potentials must both relate to the same physical-chemical
states of the reacting substances, the same temperature, the same
partial pressures (or fugacities) of gaseous substances, the same
concentrations (or activities) of dissolved substances :
= E - E0I

(in volts per faraday)

(2)

This affinity is the overpotential of the reaction.

Complications are very often met with in localized corrosion as a
result of the difficulty (or even impossibility) of correctly measuring the electrode potential E inside cavities in which the corrosion is taking place and the difficulty of accurately knowing the
composition of the solutions held in these cavities, where the volumes and the reactional surfaces are very small and hard to get at,
where the concentrations may be very high, or where the local reaction may change quickly, and where there are exchanges by diffusion
and convection.
In a general way, the direction in which an electrochemical reaction
can take place, which can be defined by the sign of its "reaction
current" i (positive in the case of oxidation and negative in the
case of reduction) can be expressed by the relation :

|(E - Eo) x i

(T|

32

which extends to electrochemical reactions the relationship

> 0

which was established by Th. DE DONDER for chemical reactions.

if E = E 0 , i = 0

Neither oxidation or reduction can take

place. This system is in thermodynamic
equilibrium.

if E > Eo, I > 0

Oxidation may take place, or there may

be no reaction (if the reaction is
irreversible); reduction is impossible.

if E < Eo, i < 0

Reduction may take place, or there may

be no reaction (if the reaction is
irreversible); oxidation is impossible.

Relation 3 which defines the direction of electrochemical reaction in

fact expresses the second law of electrochemical thermodynamics. The
speed of an electrochemical reaction is always, if not nil, of the
same sign as its affinity (or "overpotential") E E 0 .

Knowing the electrode potential E of a metallic surface in contact

with an electrolyte, and the equilibrium potentials Eo of all the
reactions which might take place on that interface, makes it thus
possible to predetermine in what direction (oxidation or reduction)
the reactions are possible or impossible.

Where affinity is not nil, the influence of electrode potential E on

the speed of the reaction i can generally be expressed by the TAFEL
relations :
E = a + log (i)

for oxidations

E = ' ' log (i)

for reductions

where the coefficients

a , ' , and ' can be determined by

polarization experiments done on the stirred solutions.

33

2.2.1.4. P o l a r i z a t i o n curves
The e l e c t r o c h e m i c a l b e h a v i o u r of m e t a l s and a l l o y s , including the
k i n e t i c s of t h e r e a c t i o n s ,

can be determined e x p e r i m e n t a l l y by

p l o t t i n g p o l a r i z a t i o n curves which show the r e l a t i o n s h i p between the

e l e c t r o d e p o t e n t i a l and the r e a c t i o n c u r r e n t s , i . e . , i n f a c t
affinity

the

of t h e r e a c t i o n s and t h e i r v e l o c i t y . These c u r v e s a r e

g e n e r a l l y easy t o i n t e r p r e t i f they a r e determined i n a s t i r r e d

s o l u t i o n and i f the e l e c t r o d e p o t e n t i a l corresponding to e q u i l i b r i a
of t h e water w i t h hydrogen ( p o i n t A) and w i t h oxygen ( p o i n t B) a t a
pressure of 1 atmosphere are indicated.
F i g u r e 3 g i v e s , as an example, a s c h e m a t i c r e p r e s e n t a t i o n of f i v e
t y p e s of c y c l i c p o l a r i z a t i o n

curves (traced with

successively

increasing and decreasing e l e c t r o d e p o t e n t i a l s ) determined p o t e n t i o k i n e t i c a l l y in oxygen-free aqueous s o l u t i o n s . Points A and i n d i c a t e

the equilibrium p o t e n t i a l s of hydrogen and oxygen r e s p e c t i v e l y a t 1
atmosphere a t

t h e t e m p e r a t u r e and pH under c o n s i d e r a t i o n

(for

example, r e s p e c t i v e l y - 413 and +810 mV r e f e r r i n g t o t h e s t a n d a r d

h y d r o g e n e l e c t r o d e - s h e a t 25C and pH 7 . 0 ) . P o i n t C i s

the

immunity p o t e n t i a l below which the metal or a l l o y i s in a s t a t e of

immunity, and consequently thermodynamically uncorrodible. Figure 3a
i n d i c a t e s general corrosion (with hydrogen e v o l u t i o n below p o t e n t i a l
A, and w i t h o u t hydrogen e v o l u t i o n above p o t e n t i a l A). F i g u r e 3b
i n d i c a t e s perfect behaviour with no corrosion, even i f the metal or
a l l o y i s used a s an e l e c t r o l y t i c anode (above p o t e n t i a l B), or an
e l e c t r o l y t i c c a t h o d e (below p o t e n t i a l A). In t h i s c a s e , t h e two
branches of the p o l a r i z a t i o n curve correspond simply to the r e l e a s e
of oxygen O2 (and perhaps ozone 0_and hydrogen p e r o x i d e H2O2) and
hydrogen Rn

on

an u n c o r r o d i b l e e l e c t r o d e .

F i g u r e 3c

c o r r o s i o n i n a r e d u c i n g environment w i t h f o r m a t i o n ,

indicates
above

the

p a s s i v a t i o n p o t e n t i a l P, of a p r o t e c t i v e oxide which makes the metal

passive in oxidizing conditions, but the p r o t e c t i v e oxide i s damaged
locally,

w i t h p i t t i n g , above t h e r u p t u r e p o t e n t i a l (or

pitting

p o t e n t i a l ) R. The e l e c t r o d e p o t e n t i a l whereby the e l e c t r o l y s i s curve

reaches zero value for the r e t u r n curve a t decreasing p o t e n t i a l s ,

is

34

the potential of protection against propagation of localized corro

sion, above which preexisting pits may expand and below which pits
do not expand. The behaviour of the metal or alloy is therefore
absolutely satisfactory below this protection potential, even if its
surface is locally damaged by pitting. Finally, figure 4e concerns a
metal (or alloy) which undergoes generalized corrosion in reducing
conditions, becomes passive above the passivation potential P, and
undergoes pitting corrosion above the rupture potential R. With
regard to

figure 4d, we have just shown that the pitting that is

formed continues to spread between the potentials R and "prot" and

stops spreading below potential "prot". The area of potentials
between "prot" and R can therefore be considered as an "imperfect
passivity area", and the area of potentials between "prot" and is a
"perfect passivity area" (which in practice is very important) where
the metal or alloy does not corrode, even if its surface has already
been damaged.
Between the passivation potential and the immunity potential C, the
passivating film can be dissolved by reduction, and generalized
corrosion takes place. Below the immunity potential C, the metal or
alloy is in a state of immunity, and once again

is uncorrodible.

Polarization curves like those shown in figures 4 can be traced

fairly rapidly using a "potentiokinetic" method, where, by using a
potentiostat, the electrode potential is continuously displaced up or
down. More accurate and more reliable polarization curves can be
obtained by using a "potentiostatic" method, which is more time
consuming, where the electrode potential is maintained constant at
various values for varying periods of time. Such experimental
methods, particularly if they are coupled with an analysis of
equilibrium diagrams, with a study of the state of the surface and
with chemical analysis, are the main tools for studying corrosion
problems, and generally can result in a perfect solution of those
problems.
These methods can also be used to draw up experimental potential/pH

35

d i a g r a m s which make i t

possible to specify

the

theoretical

equilibrium diagram, including useful k i n e t i c data. A few examples of

t h e s e e x p e r i m e n t a l diagrams a r e g i v e n i n s e c t i o n 2.2.1.6. of t h i s
report.
2.2.1.5. Other electrochemical methods of study and control of
corrosion
- Measuring and interpreting zero current electrode potentials (30)
is quite simple and particularly suitable to trace the real
behaviour of structures in use, and in many cases makes it possible
to obtain interesting conclusions.
- Measuring of polarization resistance (or, better, according to L.
CLERBOIS, the opposite, corrodence) proposed by M. STERN and GEARY,
which are also easy to use on real structures in operation,
indicate more or less accurately the instantaneous velocities of
corrosion.
- Methods using electrochemical impedence, proposed by I. EPELBOIN,
consist of adding a small increment of alternative potential at
variable frequency to various levels of electrode potential, and
analysing the resistive, capacitive, and inductive components of
the interface metal/solution. They are particularly useful in
studying the reactions which take place under surface films, and
for the study of defects in those films (30).
The analytical methods of electrochemical noise analyse the variations in electrochemical magnitudes (the potential E or current i),
in a certain spectrum of frequency, and are useful for studying
notably the phenomena of the initiation of localized corrosion.
It is useful to combine all of these methods with complementary tests
which vary according to the problems to be studied and the objectives
- combining mechanical stress, irradiation, evaporation cycles,
metallographic analysis, analysis of corrosion products, examination

- 36

of the s t a t e of the surface, ... We w i l l have the opportunity to come

back to t h i s question further on in t h i s report.
2.2.1.6. Experimental potential/pH diagrams and "occluded corrosion
cells"
The p o t e n t i a l / p H diagrams shown i n f i g u r e 2 a r e based on c e r t a i n
h y p o t h e s e s . They can be a good g u i d e for t e a c h i n g , r e s e a r c h and
corrosion c o n t r o l , but t h e i r s i g n i f i c a n c e ,

t h e i r v a l i d i t y and t h e i r

l i m i t s must be p r o p e r l y u n d e r s t o o d i n o r d e r t o use them. Most of

t h e s e diagrams s h o u l d be v e r i f i e d and improved

experimentally,

preferably by determining p o l a r i z a t i o n curves which, moreover, make

i t p o s s i b l e to i n c l u d e k i n e t i c d a t a i n t h e diagrams. F u r t h e r m o r e ,
experimental diagrams l i k e these can be h e l p f u l for studying a l l o y
behaviour.
In t h e d i s c u s s i o n t h a t f o l l o w s , we w i l l
publications

t h a t h a v e come o u t s i n c e

particularly refer

to

1 9 8 1 , a s we examine

a p p l i c a t i o n s of t h e n o t i o n s m e n t i o n e d a b o v e f o r d r a w i n g up
experimental potential/pH diagrams r e l a t i n g to a number of metals and
a l l o y s : i r o n and s t e e l s , c o p p e r , aluminium, t i t a n i u m ,

tungsten,

molybdenum. We w i l l a l s o discuss the "occluded corrosion c e l l s " , the

study of which i s very useful

for improving knowledge of l o c a l i z e d

corrosion phenomena.
2.2.1.6.1. Iron and non-alloy s t e e l s
a) Experimental potential/pH diagrams
F i g u r e s 4a and 4b

show t h e o r e t i c a l

conditions

for

corrosion,

immunity and passivation of iron a t 25C, by supposing r e s p e c t i v e l y

t h a t l e p i d o c r o c i t e yFeOOH and m a g n e t i t e FeoO a r e both p r o t e c t i v e
( f i g u r e 4a) and t h a t , as shown by many r e s e a r c h s p e c i a l i s t s , o n l y
l e p i d o c r o c i t e (very s i m i l a r to maghemite yFe20o) i s p r o t e c t i v e
gure 4b). Experiments made w i t h oxygen- and c h l o r i d e - f r e e

(fi-

stirred

s o l u t i o n s have l e d to p o l a r i z a t i r o n c u r v e s of t h e type shown in

37

f i g u r e 3c, which a r e r e p r e s e n t e d i n f i g u r e 5a (32). These make i t

possible to p l o t t h e e x p e r i m e n t a l

corrosionimmunitypassivation

diagram represented in figure 5b. One can see that the correspondence
between t h i s experimental diagram and the t h e o r e t i c a l diagram 4b i s
very good; p a s s i v a t i o n of iron in a c h l o r i d e f r e e s o l u t i o n i s t h e r e
fore t r u l y due to a f e r r i c oxide film yFeOOH (or Fe20), and magnetite
FeoO/ i s not p r o t e c t i v e .
P o l a r i z a t i o n curves drawn in figure 5a have made i t possible to p l o t
t h e t h r e e diagrams of f i g u r e 6,

which s c h e m a t i c a l l y

show

the

b e h a v i o u r of i r o n i n t h e p r e s e n c e of w a t e r , a t 25C. F i g u r e 6a
i n d i c a t e s the v e l o c i t y of reduction of water i n t o hydrogen (on non
passi vated m e t a l l i c iron) and v e l o c i t i e s of oxidation of water into
oxygen (on i r o n c o v e r e d with a p a s s i v a t i n g oxide f i l m ) . F i g u r e 6b
indicates

t h e v e l o c i t y of i r o n c o r r o s i o n . F i g u r e 6c, which was

obtained by superimposing figure 6b and the lower part of figure 6a,

shows both t h e v e l o c i t i e s of i r o n c o r r o s i o n and t h e v e l o c i t i e s of
hydrogen e v o l u t i o n . The bold l i n e in the corrosion area, which j o i n s
the points of i n t e r s e c t i o n of l i n e s p l o t t i n g the same values of iron
c o r r o s i o n and of hydrogen e v o l u t i o n , i n d i c a t e s t h e b e h a v i o u r of
e l e c t r i c a l l y i s o l a t e d iron, which corrodes according to the general
chemical reaction
+
Fe + 2Haq
"*" F eaq
tt
+ "2. , .
For example, a c c o r d i n g to f i g u r e 6c, a t pH 6, i r o n c o r r o d e s with

hydrogen e v o l u t i o n a t an e l e c t r o d e p o t e n t i a l of 0.52 v o l t s
speed of 10

and a

A.cm . G iven t h a t t h i s density of current corresponds

to the oxidation or reduction of 37.3 10

e q u i v a l e n t s mg per hour,

i r o n then c o r r o d e s a t a v e l o c i t y of 27.92 37.3 10

= 0.10 mgFe
2
per cm .h and hydrogen e v o l v e s a t a v e l o c i t y of 0.0037 mg
H., per
2
cm .hour.
Figures 7a and 7b show the results of polarization experiments
similar to those cited in figures 5a and 5b, but that were effected
2

in chloride solutions (10

molar, i.e. 0.35 g Cl

per litre). The

polarization curves shown in figure 7a are of types a, b, c or d in

figure 3, depending on the pH. It appears that this amount of

38

c h l o r i d e does not n o t a b l y modify t h e immunity c o n d i t i o n s (where

m e t a l l i c i r o n Fe i s s t a b l e ) , nor t h e " p a s s i v a t i o n p o t e n t i a l " EL
(above which a p a s s i v a t i n g f e r r i c oxide film appears). But, above the
"rupture p o t e n t i a l " E r (which depends on the value of pH), the f e r r i c
oxide f i l m l o c a l l y s t o p s being p r o t e c t i v e , and p i t t i n g c o r r o s i o n
appears. The e l e c t r o d e p o t e n t i a l E

where, on the back-bending part

of t h e p o l a r i z a t i o n c u r v e , t h e e l e c t r o l y s i s c u r r e n t r e a c h e s z e r o
value (in a s o l u t i o n free of oxygen or other oxidizers) i s , as s t a t e d
previously in section 2.2.1.4.,

the " p o t e n t i a l of protection

against

p r o p a g a t i o n of l o c a l i z e d c o r r o s i o n " , above which e x i s t i n g p i t t i n g

c o n t i n u e s t o spread and below which p i t t i n g does not s p r e a d . The
p o l a r i z a t i o n c u r v e s drawn i n f i g u r e 7a make i t p o s s i b l e t o p l o t
figure 7b which shows, in addition to c o r r o s i o n and immunity a r e a s ,
an area of p i t t i n g , and an area of imperfect p a s s i v i t y (in which new
p i t s cannot be formed, but where e x i s t i n g p i t s may s p r e a d ) and an
a r e a of p e r f e c t p a s s i v i t y ( i n which new p i t s cannot be formed and
where e x i s t i n g p i t s cannot s p r e a d ) . The immunity and t h e

perfect

p a s s i v i t y areas are the only two areas where no danger of corrosion

exists.
F i g u r e 8a which i s s i m i l a r t o f i g u r e 7b i n d i c a t e s the experimental
c o n d i t i o n s of e l e c t r o d e p o t e n t i a l and pH under which, for i r o n and
non-alloy s t e e l s , immunity, generalized corrosion, p i t t i n g corrosion,
perfect p a s s i v i t y and imperfect p a s s i v i t y take place, in addition to
the extreme v a l u e s of p o s s i b l e e l e c t r o d e p o t e n t i a l on iron surfaces
in the presence of water having a pH 8 and containing 10

atom.grams

of c h l o r i d e per l i t r e (3.5 gr C l / 1 ) : about -0.5 v o l t

^ e in the

oxygen-free areas and about -0.1 voltg^g in areas containing oxygen.

As U.R. EVANS showed i n 1923 (24), t h e c o u p l i n g of i r o n

surfaces

which a r e l o c a l l y a e r a t e d and l o c a l l y n o n - a e r a t e d t r i g g e r s

off

corrosion by d i f f e r e n t i a l aeration r e s u l t i n g from the coexistence of

aerated and more or l e s s passive surfaces at r e l a t i v e l y high e l e c t r o d e p o t e n t i a l ( c a t h o d e s ) where oxygen i s reduced, and of nonaerated and a c t i v e surfaces at r e l a t i v e l y low e l e c t r o d e

potential

(anodes) where iron corrodes. This low corrosion p o t e n t i a l leads to

the formation of c a v i t i e s for which Floyd BROWN has proposed the name

39

"occluded c o r r o s i o n c e l l s ( o . c . c . ) " (33, 34), in which, as a number

of r e s e a r c h s c i e n t i s t s have shown (among them J.R. BAYLIS (35), T.P.
HOAR (36), C. EDELEANU

and U.R. EVANS (37)), t h e s o l u t i o n becomes

a c i d i c due to h y d r o l y s i s phenomena.

As i n d i c a t e d i n f i g u r e 8a by a

b l a c k dot , t h e pH in t h e s e o.c.c. s t a b i l i z e s a t 3.9, and e l e c t r o d e

p o t e n t i a l s t a b i l i z e s a t -325 mV g h e . F i g u r e 8a a l s o shows t h a t t h e
" p o t e n t i a l of protection against l o c a l i z e d corrosion" (about -260 to
-300 mV t ) which s e p a r a t e d " p e r f e c t " and " i m p e r f e c t " p a s s i v a t i o n
a r e a s , i s s l i g h t l y h i g h e r than t h e e l e c t r o d e p o t e n t i a l

existing

inside an "occluded corrosion c e l l " (-325 mV^g).

b) a r t i f i c i a l l y produced "occluded corrosion c e l l s "
F i g u r e 9 shows a d e v i c e for s t u d y i n g d i f f e r e n t i a l a e r a t i o n which
makes i t p o s s i b l e to produce a c o r r o s i o n c r e v i c e by p a s s i n g oxygen
and nitrogen r e s p e c t i v e l y on the outer and inner, p a r t s of a sample of
duplex iron and to c o n t i n u a l l y measure the pH and e l e c t r o d e p o t e n t i a l
i n t h e " c a t h o d e " zone exposed t o oxygen and i n t h e

oxygen-free

"anode" zone ( t h i s i s an " o c c l u d e d c o r r o s i o n c e l l " o.c.c.) and t h e

diffusion p o t e n t i a l between these two zones.
J . VAN MUYLDER o b s e r v e d i n 1969 (38) t h a t t h e pH and the e l e c t r o d e
potential,

which i n i t i a l l y are r e s p e c t i v e l y 8.0 and 0 niVg^g i n the

_ o

presence of oxygen (in a 10

'_ o

M solution in NaCl and 10

M in

NaOH), stabilize in the absence of oxygen respectively at 3.8 and

about -0.33 Vshe If oxygen has access to the crevice formed in this
way, the pH decreases from 3.8 to 0.6 and the electrode potential
rises from -0.33 to -0.15 Vshe*
The two series of points marked 0 to 9 in figure 10 show the
influence of slow cathodic polarization of the outside surface on pH
and electrode potential inside the crevice. One can see that this
cathodic polarization causes a progressive increase in the pH inside
the crevice and that, when the electrode potential of the outside
surface has reached the "potential of protection against localized
corrosion" (about -0.4 V s h e ), the solution inside the crevice has

40 -

stopped being a c i d i c and t h e i r o n has reached a s t a t e of immunity:

However, hydrogen evolution s u b s i s t s inside the c r e v i c e ,

having an

a f f i n i t y which i s measured by the v e r t i c a l distance between the l i n e

r e l a t i n g t o t h e c r e v i c e and t h e "hydrogen l i n e " a_ (about 200 mV per
faraday). This a f f i n i t y

remains more or l e s s c o n s t a n t u n t i l

the

s o l u t i o n becomes n e u t r a l , and i n c r e a s e s s h a r p l y when t h e s o l u t i o n

becomes notably a l k a l i n e (about 400 mV per faraday a t pH 11).
In

1971, Antoine

P0URBAIX m o d i f i e d t h e e x p e r i m e n t a l

device

r e p r e s e n t e d i n f i g u r e 9 by i s o l a t i n g t h e i n t e r n a l p a r t of t h e i r o n
sample from t h e e x t e r n a l p a r t ,

which he connected by p l a c i n g a

microampermetre (figure 11) (39) between them. Using t h i s device, he

studied the influence of rapid e x t e r n a l cathodic p o l a r i z a t i o n (having
l i t t l e effect

on pH i n s i d e t h e c r e v i c e ) on t h e d e n s i t y of

the

e l e c t r i c current c i r c u l a t i n g between the exposed e x t e r n a l surface (pH

9.5) and the unexposed i n t e r n a l surface (pH5.5) of a c r e v i c e in mild
steel.

A.

P0URBAIX has o b t a i n e d

the

two p o l a r i z a t i o n

curves

represented in figure 12, r e l a t e d r e s p e c t i v e l y to the l a r g e e x t e r n a l

s u r f a c e ( p a s s i v e ) and t h e s m a l l i n t e r n a l s u r f a c e ( a c t i v e ) . One can
see in t h i s figure t h a t when the e l e c t r o d e p o t e n t i a l of the outside
surface decreases,

the w a l l inside the c r e v i c e p r o g r e s s i v e l y stops

acting as an anode, reaches the s t a t e of zero current at -0.43 V g n e ,

(points 4) and then behaves l i k e a cathode . When " the p o t e n t i a l of
protection against l o c a l i z e d c o r r o s i o n " i s reached (-0.38 V .

between

p o i n t s 5 and 6) on t h e e x t e r n a l s u r f a c e , t h e e l e c t r o d e p o t e n t i a l
i n s i d e t h e c r e v i c e r e a c h e s -0.44 V s h e The w a l l of t h e c r e v i c e has
then reached a s t a t e of immunity and t h e d e n s i t y of t h e c a t h o d i c
current (about 2uA.cm

) corresponds e n t i r e l y to hydrogen e v o l u t i o n

(0.07 pg H2 per cm .hour). When t h e e x t e r n a l e l e c t r o d e

potential

f a l l s below the " p o t e n t i a l of protection against l o c a l i z e d corrosion"

( p o i n t s 6 and 7), a r e d e p o s i t of a l l or p a r t of t h e i r o n t h a t has
p r e v i o u s l y been dissolved in the o.c.c. appears i n s i d e the c r e v i c e ,
along with hydrogen evolution.

41 -

c) Evolution of "occluded corrosion c e l l s " and study of 'the e l e c t r o chemical behaviour in these c e l l s
Since 1963, Jean VAN MUYLDER e t a l . have been using methods s i m i l a r
to those described a propos of figure 9 for preparing s o l u t i o n s l i k e
those

existing

in

the

corrosion

crevices

of

copper and

iron.

Experiments l i k e these g e n e r a l l y need long term work and only give

r e l a t i v e l y small q u a n t i t i e s of s o l u t i o n s (a few cm ). However, in the
case of l o c a l i z e d corrosion of a metal (copper of iron) by a s o l u t i o n
containing

chloride,

t h e s o l u t i o n s i n t h e o.c.c. a r e ,

in

fact,

c h l o r i d e s o l u t i o n s of t h i s metal, which e v o l v e up to s a t u r a t i o n in
the l e a s t s o l u b l e c h l o r i d e (CuCl for copper, or FeClo.AH^O for iron)
In t h e c a s e of a l o c a l i z e d c o r r o s i o n of pure m e t a l (copper or i r o n
for example) the s o l u t i o n s can therefore be prepared s y n t h e t i c a l l y by
simply adding increasing q u a n t i t i e s of c h l o r i d e , up to s a t u r a t i o n , to
oxygen-free pure water, preferably in the presence of the powder of
the metal under consideration (33). One can thus e a s i l y and r a p i d l y
o b t a i n a s o l u t i o n s i m i l a r t o t h e s o l u t i o n t h a t e x i s t s i n s i d e an
o . c . c , i n any q u a n t i t y (100 cm , 1000 cm , or more)which can be used
for any chemical a n a l y s i s or any electrochemical experiment. This has
been done f o r copper i n 1962 by J VAN MUYLDER ( 4 0 ) , and f o r i r o n i n
1973 by C.T. FUJII (41) and i n 1974 by L. SATHLER ( 4 2 , 4 3 ) . In t h e
case of c o p p e r , J . VAN MUYLDER has t h u s o b t a i n e d a s o l u t i o n 0.0037
molar i n Cu and 0.076 molar i n C I , with a pH of 3.5 i n which t h e
e l e c t r o d e p o t e n t i a l of copper +270 V g h e ( a t 25C). I n t h e c a s e of
iron, J. VAN MUYLDER and L. SATHLER obtained a s o l u t i o n of 4.6 molar
i n FeCl2 w i t h a

pH of 3.8 i n which t h e e l e c t r o d e p o t e n t i a l of i r o n

a t z e r o c u r r e n t i s -325 mV s h e ( 4 3 , 32). And, f o r each of t h e s e two

metals, electrochemical experiments, including p l o t t i n g p o l a r i z a t i o n
c u r v e s i n t h e p r e s e n c e of t h e s e s o l u t i o n s , have made i t p o s s i b l e t o
completely c l a r i f y the conditions under which the corrosion c r e v i c e s
are formed, develop, or do not develop.

42

F i g u r e 13a shows t h e changes in pH and c o n c e n t r a t i o n of d i s s o l v e d

i r o n o b s e r v e d by L. SATHLER when adding i n c r e a s i n g q u a n t i t i e s of
FeCl 24^0 to pure oxygenfree water, in the presence of iron powder
(42, 43). Figure 13b shows the e v o l u t i o n of pH and e l e c t r o d e poten
t i a l of i r o n o b s e r v e d d u r i n g t h i s o p e r a t i o n . One can see i n t h e s e
figures,

as i n d i c a t e d

above,

that

the

saturated

solution

in

FeCl2.4H20 has a pH e q u a l t o 3.8 and i s 4.6 molar i n FeCl2 ( i . e . 9.2

molar of CI). The p o t e n t i a l of iron a t zero current in t h i s s o l u t i o n
i s 0.33 Vg'he 0 n e

can

a l s o see t h a t t h e i n t r o d u c t i o n of oxygen i n

t h i s s o l u t i o n d e c r e a s e s t h e pH from 3.8 t o 0.3 and r a i s e s t h e e l e c

trode p o t e n t i a l of iron from 0.33 to about 0.15 to 0.07 V

gne.

L. SATHLER used ferrous c h l o r i d e s o l u t i o n s thus obtained to study, by

means of p o t e n t i o k i n e t i c and p o t e n t i o s t a t i c p o l a r i z a t i o n experiments,
the k i n e t i c behaviour of iron in "occluded corrosion c e l l s " which can
form during l o c a l i z e d corrosion of iron in the presence of s o l u t i o n s
containing c h l o r i d e . SATHLER observed t h a t , in the presence of con
centrated,

nonsaturated,

s o l u t i o n (3.0 and 4.1 molar of

ferrous

c h l o r i d e , pH 4.8 and 4.2), anodic p o l a r i z a t i o n of the metal increases

the v e l o c i t y of corrosion and p a s s i v a t i o n does not occur. But, i f the
s o l u t i o n i s saturated in ferrous c h l o r i d e (4.6 molar a t pH 3.8), when
the e l e c t r o d e p o t e n t i a l reaches 0.18 voltg^g a c e r t a i n passivation
a p p e a r s due t o t h e f o r m a t i o n of an o x i d e f i l m

Fe20 between t h e

metal and the ferrous c h l o r i d e c r i s t a i s (figure 14).

We h a v e

used

the

SATHLER

experimental

figures 15a and 15b which notably r e p r e s e n t ,

results

to

plot

for occluded corrosion

c e l l s of pH 8.0 t o 3.8 (0.001 t o 4.6 molar i n f e r r o u s c h l o r i d e ) the

e q u i l i b r i u m c o n d i t i o n s , t h e v e l o c i t i e s of r e a c t i o n s , the condition
for immunity, general corrosion, p a s s i v a t i o n and p i t t i n g corrosion of
iron r e s p e c t i v e l y .
The immunity and general corrosion conditions are separated by a bold
c o n t i n u o u s l i n e i n t h e s e f i g u r e s . In f i g u r e 15a, t h e s e t of l i n e s a
i n d i c a t e s t h e e q u i l i b r i u m p r e s s u r e s i n hydrogen and t h e s e t of
l i n e s c_ i n d i c a t e s ( a p p r o x i m a t e l y ) t h e e q u i l i b r i u m a c t i v i t i e s

in

43

dissolved
velocities

iron.
of

In f i g u r e 15b,

iron

corrosion,

the
the

lines

vc>QX
v

c^Te

lines

indicate

the

indicate

the

v e l o c i t i e s of e l e c t r o d e p o s i t of iron and the l i n e s v a ^ r e ( j indicate

the v e l o c i t i e s of hydrogen e v o l u t i o n .
In figure 15b, the bold dotted l i n e i n d i c a t e s the conditions existing
at zero current in the case of any anodic and cathodic p o l a r i z a t i o n .
For example, a t pH 3.8, t h e r e a c t i o n F e + + + 2H+ * F e + + +H2 t a k e s
place at a v e l o c i t y of 10

A.cm

with an e l e c t r o d e p o t e n t i a l
3

0.34 v o l t

shg.

An anodic p o l a r i z a t i o n of 10

of

A.cm

w i l l r a i s e the

e l e c t r o d e p o t e n t i a l of iron up to 0.22 V ^ g , increase the speed of

corrosion to 0.001 A.cm
to 10

and reduce the speed of hydrogen evolution

A.cm . Moreover, a t pH 8 (for a s o l u t i o n about 0.001 molar

of f e r r o u s c h l o r i d e ) an a n o d i c p o l a r i z a t i o n c u r r e n t of 10

A.cm

w i l l r a i s e the e l e c t r o d e p o t e n t i a l above the passivation p o t e n t i a l

(0.30 v o l t g^g) and w i l l therefore cause p a s s i v a t i o n of the metal.
On t h e o t h e r hand,

cathodic

polarization

which d e c r e a s e s

the

e l e c t r o d e p o t e n t i a l below the immunity p o t e n t i a l (0.36 V g n e a t pH

3.8 or 0.58 V g ^ a t pH 8 ) , w i l l

e l i m i n a t e i r o n c o r r o s i o n and

conversely w i l l cause an e l e c t r o d e p o s i t on the metal with an increase

in the v e l o c i t y of hydrogen e v o l u t i o n .
2 . 2 . 1 . 6 . 2 . Alloy s t e e l s
a) Experimental potential/pH diagrams
F i g u r e s 8a t o 8d, which s h o u l d be c o n s i d e r e d as p r o v i s i o n a l and
subject

to

more or

less

major

modifications,

show

immunity,

g e n e r a l i z e d c o r r o s i o n , p i t t i n g c o r r o s i o n , i m p e r f e c t p a s s i v i t y and
perfect p a s s i v i t y areas in the presence of r e l a t i v e l y

concentrated

c h l o r i d e s o l u t i o n s ( 1 0 1 molar, i.e. 3.5 g of CI per l i t r e ) for iron,

chromium s t e e l

AISI 410,

chromiumnickelmolybdenum

chromiumnickel
steel

steel

AISI 304,

AISI 316 r e s p e c t i v e l y ;

and
their

surfaces are polished with emery paper and e l e c t r o l y t i c a l l y polished.

44

The narrow vertical band drawn in the middle of these figures indi
cates conditions which can exist when the metal is in contact with a
pH 8.0 solution at zero current (i.e. when it is not subjected to any
exterior electric current). The upper part of these vertical bands
indicates the behaviour of the metal in the presence of oxygen; the
lower part of these bands corresponds to the behaviour of the metal
in the absence of oxygen, which can be the case when access to oxygen
is impeded by the particular shape of the structure (under a screw,
or because of the deposit of a solid corrosion product (rust). As
said at the end of section 2.2.1.6.1.a, this can lead to localized
corrosion, with the formation of occluded corrosion cells o.c.c, in
which the solution becomes acidic due to hydrolysis phenomena : as we
mentioned above, the pH drops to 3.8 for iron and for non-alloy
steels. It may drop still further on alloy steels (YANG WU et al
(44,45), . TURNBULL (46)*) : about 3 to 2 for chromium steels, to
about zero for chromium-nickel and chromium-nickel-molybdenum steels.
The conditions at which the electrode potential and the pH in the
o.c.c. stabilize are indicated in figures 8 by a black dot .
We can see from these figures that for non-alloy steel and for chro
mium steel (figures 8a and8b\ the black dots t are located below the
line a, which means that hydrogen evolution is possible in the o.c.c.
Conversely, in the case of chromium nickel steels and chromiumnickel-molybdenum steels considered in figures 8c and 8d , the dots
are located above the line a_, which means that hydrogen evolution is
impossible. If this is the case (we want to recall that the diagrams
in figure 8 should be considered provisional and be improved with
further research), this would mean that, unlike non-alloy steels and
chromium steels, chromium-nickel steels and chromium-nickel-molybde
num steels are normally not susceptible to hydrogen embrittlement.
Due to the major scientific and technical importance of this conclu
sion, research into the subject is of the utmost urgency.
* In this publication, A. TURNBULL did an in-depth examination of the
literature on the chemistry and electrochemistry of occluded corro
sion cells in alloy steels and titanium, aluminium and copper alloys.

45

One can also see in figures 8 that, if iron is alloyed with chromium
nickel, molybdenum,

the resistance of the metal to pitting corrosion

which could result from the presence of air increases significantly this pushes the electrode potential towards the "oxygen line" b_; this
improvement in resistance to pitting corrosion is particularly
pronounced if the metal is polished electrolytically.
We should also point out that in several studies related to crevice
corrosion, several authors have spoken of the notion of a
"depassivation pH (47) under which, in a non-oxidizing solution, the
metal stops being passive and corrodes. This "depassivation pH" is,
after all, the pH which, on figures 8b to 8d, is located at the
extremity of the triangular generalized corrosion area, i.e., in the
case of the steels, pH 9.5 for AISI 410 steel, 7.0 for AISI 304 steel
and pH 6.0 for AISI 316 steel.
We should also recall that the potentials of protection against localized corrosion shown in figure 7b and figures 8a and 8d are slightly
higher than the zero current potentials inside the o.c.c. These
potentials of protection are in fact, electrode potentials (measured
on the passive external surfaces) under which the electrode potentials inside the o.c.c.(measured compared to a reference electrode
placed inside the o.c.c.) drop below their value at zero current, so
that the metal inside the crevice reaches a state of immunity due to
some kind of cathodic protection.
b) Occluded corrosion cells of a chromium steel
Figure 16b reproduces a previous published diagram (48, figure 16)
which gives a schematic indication* of the conditions for immunity,
corrosion and passivation of a 12% Cr steel in the presence of
* We are not aware of in-depth studies on the subject of the composition of solutions existing in "occluded corrosion cells" in chromium
steels. Figure 16b, which was drawn up as indicated above (48) should
be considered as provisional. The numerical values
as an example to put ideas on the right track.

below are given

46 -

chloride solutions, of the velocities of corrosion of steel and of

the velocities of hydrogen evolution on the steel. In figure 16a, for
comparison and for the same values on the horizontal and vertical
axes, we have reproduced figure 15b related to a non-alloy carbon
steel.
In these two figures, the bold continuous line shows the immunity
potentials on the steel and separates the immunity regions from the
general corrosion regions. The bold dotted line shows the potentials
at zero current. The set of thin continuous lines gives the corrosion
or electrodeposition velocities of the steel. The set of thin dotted
lines indicates the velocities of hydrogen evolution on the steel.
9

These velocities are calculated in Amps per cm .

A comparison between figures 16a and 16b shows that adding chromium
to the steel raises its immunity potential and drops its passivation
potential. This addition of chromium reduces the extent of the
general corrosion area and greatly increases the passivation area
which, for the values of electrode potential under consideration in
these figures (less than zero volt^g), already appears, at pH values
around 2, without any pitting corrosion.
In the presence of the solution saturated with ferrous chloride (pH
3.8) which was already considered in section 2.2.1.6.c pertaining to
a non-alloy steel, the corrosion of the steel with hydrogen evolution
J,J
5 3

will take place, at zero current, at a velocity of 10

A.cm

(instead of 10~ 6,0 ) with an electrode potential of -0.30 v o l t s h e

(instead of -0.34). An anodic polarization current of around 10
A.cm

(which would take the electrode potential of carbon steel to

-0.29 volt u

and would significantly increase the corrosion velocity)

will raise the electrode potential of chromium steel above its passivation potential (-0.09 voltg^g) and thus cause passivation.
It is currently admitted that localized corrosion phenomena which
affect alloy steels can disappear, either due to "repassivation" or

47

to " d e a c t i v a t i o n " . I t i s p r o b a b l e t h a t t h e s e two phenomena r e s u l t

from a change i n the e l e c t r o d e p o t e n t i a l (and p o s s i b l y pH) of t h e
occluded c o r r o s i o n c e l l s in diagrams l i k e t h a t of f i g u r e 16b : t h e
repassivation probably comes from an increase in the e l e c t r o d e potent i a l in the o.c.c. above the passivation p o t e n t i a l (-0.09 v o l t ^ g in
the case of figure 16 pertaining to a 12% Cr s t e e l ) . Deactivation i s
probably due to a drop in t h i s p o t e n t i a l below the immunity p o t e n t i a l
(about -0.33 v o l t ^ g ) .
We w i l l have the occasion to come back to the s c i e n t i f i c and t e c h n i c a l i n t e r e s t t h a t in-depth studies on the chemistry and e l e c t r o c h e mistry of occluded corrosion c e l l s can provide.
2 . 2 . 1 . 6 . 3 . Copper and copper a l l o y s
Here we w i l l t a l k o n l y very b r i e f l y about l o c a l i z e d c o r r o s i o n of
copper due to cold water d i s t r i b u t e d in urban areas, the causes and
remedies of which already have been the subject of numerous p u b l i c a t i o n s (see f . e . 32). Here we w i l l be c o n t e n t to r e c a l l t h a t , i n t h e
p r e s e n c e of w a t e r c o n t a i n i n g c h l o r i d e s and b i c a r b o n a t e s , o c c l u d e d
corrosion c e l l s can be formed on the copper, containing red cuprous
oxide CU2O , white cuprous c h l o r i d e CuCl, p l u s a s o l u t i o n about 0.01
molar of c h l o r i d e and copper, obturated by a green deposit of basic
copper c a r b o n a t e CCOg.CuOH^ ( m a l a c h i t e ) . F i g u r e 17a i s

the

equilibrium diagram of the Cu-Cl-H^O system a t 25C for s o l u t i o n s

_9

of 10 ~ molar in d i s s o l v e d CI. The s t a t e of equilibrium of a copper

p i t , in which the three s o l i d s coexist, Cu, C^O and CuCl, i s r e p r e sented in t h i s figure 17a by the i n t e r s e c t i o n of the s t a b i l i t y areas
of these three s o l i d s ,

i . e . pH = 3.5 and E = +270 n V g ^ . Given t h a t ,

under t h e s e c i r c u m s t a n c e s , t h e c o r r o s i o n r e a c t i o n of t h e copper i s
r e v e r s i b l e , a p i t l i k e t h i s could develop by corrosion or, conversely
be s t i f l e d by a r e d e p o s i t i o n of copper, depending on whether t h e
e l e c t r o d e p o t e n t i a l of the metal in the c r e v i c e s i s g r e a t e r than or
l e s s than 270 mV ^ . And t h i s i s a very simple and formal
for understanding and mastering t h i s corrosion phenomenon.

criterion

-48

But where i t i s g e n e r a l l y d i f f i c u l t ,
the e l e c t r o d e

potential

or even impossible, to measure

in a c o r r o s i o n

pit

(as compared t o a

r e f e r e n c e e l e c t r o d e i n s i d e the p i t ) , i t i s u s u a l l y very easy to

measure the e l e c t r o d e p o t e n t i a l of the external surface of the metal.
And, in a case l i k e t h e one r e p r e s e n t e d in f i g u r e 18, t h e e x t e r n a l
electrode p o t e n t i a l i s equal to the i n t e r n a l e l e c t r o d e p o t e n t i a l p l u s
the difference in p o t e n t i a l between the two reference e l e c t r o d e s , a
difference which, i f the two reference e l e c t r o d e s are i d e n t i c a l ,

is

more or l e s s equal to the diffusion p o t e n t i a l between the i n t e r n a l

solution (generally concentrated)

and

the e x t e r n a l

solution

(generally d i l u t e d ) .
In t h e case of p i t t i n g c o r r o s i o n of copper in t h e p r e s e n c e of water
d i s t r i b u t e d in the Brussels area, which contains 22ppm of CI, 229 ppm
of CO2 and 46 ppm

of SOg ( v a l u e s f o r which the potential/pH

equilibrium diagram i s represented in figure 17b), t h i s difference in

p o t e n t i a l between the two reference e l e c t r o d e s i s c l o s e to 80 to 150
mV. The " p o t e n t i a l of p r o t e c t i o n a g a i n s t p r o p a g a t i o n of l o c a l i z e d
corrosion", which i s +270 niV^g i f i t i s measured inside the c a v i t y ,
w i l l t h e r e f o r e be 270 + (80 t o 150) = +330 t o 420 m V s h e i f i t

is

measured on the e x t e r n a l surface of the metal. Figure 17c shows the

experimental corrosion, immunity or p a s s i v a t i o n a r e a s of copper i n
t h e p r e s e n c e of s o l u t i o n s t h e composition of which i s i n d i c a t e d i n
f i g u r e 17b; we have a l s o reproduced i n f i g u r e 17c t h e e q u i l i b r i u m
conditions of a copper p i t , formed in the presence of Brussels water;
as w e l l as t h e v a l u e s of t h e " p o t e n t i a l of p r o t e c t i o n

against

l o c a l i z e d corrosion" which we have j u s t discussed.

According to figure 17c, the cuprous oxide CU2O i s p r o t e c t i v e , and the
m a l a c h i t e CuCOg.CuiOH^ (or t h e t e n o r i t e CuO) are not p r o t e c t i v e or
h a r d l y so and p e r m i t , i n an environment of about

pH 8,

general

corrosion of the copper above about 300 mV^g (49). Let us point out
t h a t t h e " p o t e n t i a l of g e n e r a l i z e d c o r r o s i o n " has about t h e same
v a l u e as t h e " p o t e n t i a l of p r o t e c t i o n a g a i n s t -the p r o p a g a t i o n of
localized

corrosion".

49 -

2.2.1.6.4. Aluminium
Figures 19a and 19b show the potential/pH equilibrium diagram for
aluminium and the theoretical conditions for corrosion, immunity and
passivation, with an indication of the electrode potential of the
metal corroding in a solution of pH 3.5, as well as the rupture
potentials of the alumina protective film in the presence of 10
molar chloride solutions.
According to the works published in 1969 by R.E. GROOVER et al,
aluminium alloys which have an electrode potential in the presence of
sea water which is higher than the equilibrium potential of hydrogen
(line a_ of figure 19b) undergo pitting corrosion (50) and aluminium
alloys having a potential under this

value, corrode without forming

pits. This is in conformity with figure 19.

2.2.1.6.5. Titanium

F i g u r e s 20a and20b show t h e p o t e n t i a l / p H e q u i l i b r i u m diagram for

titanium

and t h e t h e o r e t i c a l

passivation,

conditions

of c o r r o s i o n

and

w i t h an i n d i c a t i o n of t h e e l e c t r o d e p o t e n t i a l

of

the metal corroding in a hydrochloric acid s o l u t i o n of pH 2, and the

probable values of the protection p o t e n t i a l against t h i s c o r r o s i o n .
The corrosion area t h a t t h i s figure shows agrees with the r e s u l t s of
an e x p e r i m e n t a l

study c a r r i e d out by A.POURBAIX e t a l (51). By

c a t h o d i c a l l y p o l a r i z i n g titanium passivated i n the a i r (and having

T1O2 f i l m ) ,

t h e a u t h o r s have s u c c e s s i v e l y

o b s e r v e d an a b r u p t

a c t i v a t i o n of t h e m e t a l w i t h g e n e r a l i z e d c o r r o s i o n , and i m p e r f e c t
p a s s i v a t i o n (with formation of the titanium hydride).
2 . 2 . 1 . 6 . 6 . Tungsten
Figure 21a is the electrochemical equilibria diagram of the W-H 2 0
system at 25C. Figure 21b shows the theoretical conditions of
corrosion-immunity-passivation

which correspond to figure 21a.

50 -

Figure 21c shows the experimental conditions of

corrosion-immunity-

p a s s i v i t y in c h l o r i d e - f r e e s o l u t i o n s , as determined by A. POURBAIX et
a l (52), where t h e two l i n e s l a b e l l e d - 5 and - 4 c o r r e s p o n d t i v e l y t o c o r r o s i o n r a t e s of 10
r a t e s of 0.052 and 0.52 mm.yr

-1

and 10

A.cm-

(i.e. penetration

).

Diagram 21c confirms that the oxide WO3 has a good p a s s i v a t i n g action
i n an a c i d environment (pH l e s s than 4), and t h a t t u n g s t e n and i t s
oxides are highly s o l u b l e in an a l k a l i n e environment.
2 . 2 . 1 . 6 . 7 . Molybdenum
Figure 22a i s the electrochemical equilibrium diagram of the Mo-R^O
system a t 25C. F i g u r e 22b shows t h e t h e o r e t i c a l

conditions

of

c o r r o s i o n - i m m u n i t y - p a s s i v a t i o n of molybdenum which corresponds to

figure 22a. Figure 22c shows t h e e x p e r i m e n t a l c o n d i t i o n s of c o r r o
s i o n - i m m u n i t y - p a s s i v i t y i n c h l o r i d e s o l u t i o n s , as published along
with those which we j u s t mentioned concerning tungsten, and where the

corrosion r a t e s of 10

and 10

A.cm

correspond, as for tungsten,

to penetration v e l o c i t i e s of 0.052 and 0.52 mm.yr

According t o diagram 22c, p a s s i v a t i o n of molybdenum i n a s l i g h t l y

o x i d i z i n g environment i s shown t h r o u g h o u t t h e pH s c a l e , i n c l u d i n g
a c i d e n v i r o n m e n t s , where t h e t h e o r e t i c a l

d i a g r a m shows t h e

p o s s i b i l i t y of corrosion. This p a s s i v a t i o n seems to be e s s e n t i a l l y

due to the formation of film of M0O2.
2 . 2 . 2 . Methods of Analysis
The r o l e of surface a n a l y s i s in the study of l o c a l i z e d corrosion i s
an important one. One would l i k e to be a b l e to i d e n t i f y the nature of
s u r f a c e s , of s u r f a c e f i l m s or of c o r r o s i o n p r o d u c t s , v e r y l o c a l l y
inside

and

sophisticated

outside

localized

methods of

surface

corrosion
analysis

crevices.
do e x i s t ;

Certain
they

are

mentioned and described very b r i e f l y below. Using them has enabled

n o t i c e a b l e progress in the a n a l y s i s of l o c a l i z e d corrosion phenomenon

51

to be made, although one would still like to have more local methods,
which perturb the environment less, and give indication of overall
chemical values or compositions.

Among the methods of surface analysis, we can mention :

ESCA

Electro Spectroscopy for Chemical Analysis

XPS

Xray Photoelectron Spectroscopy

UPS

Ultraviolet Photoelectron Spectroscopy

AES

Auger Electron Spectroscopy

ELS

Energy Loss Spectroscopy

SIMS

Secondary Ion Mass Spectroscopy

ISS

Ion Surface Scattering

LAMMA

Lazer Microprobe Mass Analysis

EDAX

Energy Dispersive Analysis Xray

Electron Probe Micro analysis

Ellipsometry
Microdiffraction of Xrays

To choose a method of a n a l y s i s , i t i s important to know what i t

e n a b l e s one t o a n a l y s e (the element, the chemical compound . . . ) , on
which s u r f a c e or over what volume, whether i t i s q u a n t i t a t i v e or
q u a l i t a t i v e , whether i t permits an a n a l y s i s at v a r i o u s depths
s t a r t i n g from the s u r f a c e , whether i t d e t e r i o r a t e s the sample,
whether i t can be a p p l i e d in s i t u or whether i t r e q u i r e s a vacuum,

Table I I I shows a few aspects of the answer to these questions for the
SIMS, AES, ESCAXPS and EDAX methods.
E l l i p s o m e t r y makes i t p o s s i b l e to determine the t h i c k n e s s of a
s u r f a c e l a y e r d i r e c t l y with a s e n s i t i v i t y of 2.5 t o 10.0 . I t i s
also used to determine the absorption of ions in the solution on the
surface of an electrode.
Making t h e s e few remarks, we would a l s o l i k e to i n d i c a t e t h a t , for

Table III : A FEW CHARATERISTICS OF SOME METHODS OF ANALYSIS

SIMS

Elements or

all light ions

substances anlysed

Surface analysed
depth, possibility

SURFACES

AES

elements based

ESCA-XPS

heavy elements

on Li
less sensitive for

heavy ions

light elements

detects H

does not detect H

chemical composition

valence

(sometimes difficult)

(sometimes difficult)
lpm

10 to 30 A

10 A

elements based
on Na

less sensitive for

about 8000 pm 2

ECDAX

about 8000 p m 2
15 A

of erosion

en
1 to 2 m
1 pm
no erosion possible

vacuum mm Hg

10

Quantitative

no

to 10

10-7to IO" 10

-7
10

-4
10

yes, more or
less

yes, less than AES

rapid method

long method

semi-quantitative
using standards
rapid method

53 -

the s t u d i e s of l o c a l i z e d corrosion, we would l i k e to have methods for

analysing ions in s o l u t i o n a t our d i s p o s a l , which refer to extremely
small volumes, would not d i s t u r b the s o l u t i o n s being analyzed, and
would i n d i c a t e the nature and the valency of the ions being analyzed.
An approach to t h i s problem which in p r i n c i p l e i s p o s s i b l e , would be
to use methods of bombarding deep-frozen s o l u t i o n s in r e l a t i v e vacuum
brought down t o very low t e m p e r a t u r e s . For t h e time being, such
methods for analyzing ions in s o l u t i o n l o c a l l y are severely lacking.
2 . 2 . 3 . Study of corrosion phenomena due to mechanical deformation
Among t h e methods of t e s t i n g s t r e s s c o r r o s i o n , s e v e r a l methods of
applying s t r e s s can be distinguished : methods using constant load
where the load per u n i t of surface increases during the propagation
of cracking and methods using a constant deformation where the load
d e c r e a s e s as t h e c r a c k i n g p r o g r e s s e s . V a r i o u s a s s e m b l i e s a r e d e s cribed in the l i t e r a t u r e (53,54).
These methods can only provide an i n i t i a l approach,

the r e s u l t s of

which can under no c i r c u m s t a n c e s g i v e a c o r r e c t i d e a of t h e s t r e s s

corrosion behaviour of the m a t e r i a l being studied.
A method d e v e l o p e d by PARKINS, u s i n g a c o n s t a n t speed (slow) of
deformation (Constant Extension Rate Testing CERT, with p o t e n t i o s t a t i c c o n t r o l ) has made i t p o s s i b l e to b e t t e r understand and quantify
the influence of a l a r g e number of parameters which affect the s u s c e p t i b i l i t y of a m a t e r i a l to s t r e s s corrosion. In t h i s method (55), a
sample (smooth or notched) i s s u b m i t t e d , a t a c o n s t a n t e l e c t r o d e
p o t e n t i a l , to deformation a t a constant speed, g e n e r a l l y between 10
3
1
J
and 10
cm.s , and t h e r e s u l t s a r e e x p r e s s e d , for example, by
c o n s t r i c t i o n or elongation to rupture point or by the time of rupture
as compared t o r u p t u r e in dry a i r . One of t h e major a d v a n t a g e s of
t h i s method i s to h i g h l i g h t speeds of deformation which, for a given
system, l e a d t o t h e g r e a t e s t s e n s i t i v i t y to s t r e s s c o r r o s i o n . This
u n d e n i a b l y c o n s t i t u t e s an i m p o r t a n t f a c t o r i n t h e study of the mechanisms of t h i s phenomenon.

54 -

Applying notions of rupture mechanics has brought an i n t e r e s t i n g tool

to s t u d i e s of s t r e s s c o r r o s i o n . These n o t i o n s make i t p o s s i b l e to
e v a l u a t e t h e s t a t e s of c o n s t r a i n t around the c r a c k - t i p ,

in t h e

m a t e r i a l s which obey l i n e a r e l a s t i c phenomena. We already know that

s t r e s s corrosion cracks contain a very p a r t i c u l a r environment which
i s very d i f f e r e n t from the ambient environment, and i t i s

therefore

imperative to work on the t r i g g e r i n g off of cracks which e f f e c t i v e l y

make i t p o s s i b l e t o c o n s t i t u t e t h i s p a r t i c u l a r environment. The
r e s t r i c t i o n of t h e t h e o r y to t h e e l a s t i c l i n e a r f i e l d i s not too
c o n s t r i c t i v e in s t r e s s corrosion, because i n most p r a t i c a i

systems

where s t r e s s corrosion occurs, the c o n s t r a i n t s are considerably lower

than the e l a s t i c l i m i t .
Simplifying a great d e a l , l o c a l c o n s t r a i n t s that e x i s t a t the edge of
a d e f e c t , a notch or t h e end of a c r a c k a r e not simply e q u a l t o t h e
load a p p l i e d d i v i d e d by t h e remaining s e c t i o n of t h e m a t e r i a l . To
c a l c u l a t e the s t a t e of the s t r e s s a t these places, rupture mechanics
use a s t r e s s i n t e n s i t y factor K, (expressed for example as N.mm ' ),
which depends on t h e l o a d a p p l i e d , on t h e form of t h e p a r t and t h e
shape of t h e d e f e c t . And, i n t h e absence of a corroded e n v i r o n m e n t ,
there i s a c r i t i c a l value for t h i s f a c t o r , c a l l e d tenacity , above
which cracking progresses r a p i d l y and leads to an abrupt rupture. The
values of Ki

are c h a r a c t e r i s t i c of a m a t e r i a l , within a given s t a t e

of s t r u c t u r e , for a given heat treatment, a t given temperature .

In t h e p r e s e n c e of a c o r r o d i n g e n v i r o n m e n t , r a p i d r u p t u r e can t a k e
p l a c e for v a l u e s of Ki which a r e much lower than Ki . And in many
cases, there i s a value of K^ under which the cracks do not progress
in

t h e p r e s e n c e of a c o r r o d i n g e n v i r o n m e n t , t h i s v a l u e i s c a l l e d

^ l s c c o r ^ s c c ' ^*n t n e c a s e f aluminium a l l o y s , i t seems t h a t no

value e x i s t s for K i s c c (the r a t e of propagation w i l l never be zero),
but in most other cases, v a l u e s of
, possibly with an indication
of the duration of the t e s t or of the l i m i t of detection of the speed
of p r o p a g a t i o n , e x i s t and a r e c h a r a c t e r i s t i c s of t h e m a t e r i a l
( i n c l u d i n g t h e s t r u c t u r e , h e a t t r e a t m e n t , o r i e n t a t i o n ) and of t h e
environment, as w e l l as the e l e c t r o d e p o t e n t i a l .

55

Determining

and expressing the r e s u l t s can be done in s e v e r a l

ways depending on, as i n d i c a t e d , whether t h e r e i s a n e t v a l u e of

,

under which p r o p a g a t i o n of s t r e s s c o r r o s i o n c r a c k i n g i s not

o b s e r v e d , or whether t h e r e i s no n e t v a l u e of K^ under which t h e

speed of propagation i s n i l .
In t h e f i r s t

c a s e , t h e r e s u l t s can be expressed by t h e r e l a t i o n

between i n i t i a l K,, K i i and the logarithm of rupture time (figure

23) (56). Several samples are required to p l o t the curves. The curves
represented in figure 23 are f a i r l y

t y p i c a l of titanium a l l o y s (A)

and s t e e l s of the Maraging type. In the second case, the c o r r e l a t i o n

between t h e i n t e n s i t y f a c t o r of c o n s t r a i n t Ki and t h e l o g a r i t h m of
the speed of propagation of the crack i s expressed. To do t h i s , only
one sample i s used; i t has a shape such t h a t K^ decreases
crack p r o p a g a t e s .

The system for

loading,

by a g i v e n

as t h e
initial

d i s p l a c e m e n t , i s very s i m p l e and t h e s e t e s t s a r e w i d e l y used t o

determine K2 SCC .
A t y p i c a l curve drawn up in t h i s way i s shown in figure 24 (56), but,
with c e r t a i n m a t e r i a l / e n v i r o n m e n t c o m b i n a t i o n s , t h e form of t h i s
c u r v e i s q u i t e d i f f e r e n t : zone I I I does not e x i s t i n c e r t a i n c a s e s
for aluminium and t h e r e may be two p l a t e a u x i n r e g i o n I I I . The
r e l a t i v e p o s i t i o n s and s l o p e s of zones I and I I , for titanium a l l o y s ,
a r e i n f l u e n c e d c o n s i d e r a b l y by h e a t t r e a t m e n t . The e x p r e s s i o n of
^lscc

ma

rec u:

l ' - r e s p e c i f i c a t i o n of an a r b i t r a r y value of propagation

of cracks t h a t one has s e t for supervising the t e s t s .

Despite these r e s t r i c t i o n s and p a r t i c u l a r i t i e s , the expression of the
r e s u l t s of s t r e s s c o r r o s i o n t e s t s using K i s

and t h e n o t i o n s of

r u p t u r e mechanics make i t p o s s i b l e to g e n e r a l i z e t h e r e s u l t s of
s i t u a t i o n s where t h e geometry of t h e p a r t s and t h e d e f e c t s
different,

are

and to v a l i d l y compare the r e s u l t s obtained in d i f f e r e n t

l a b o r a t o r i e s . The v a l u e s

of

Kjscc

i n s t a l l a t i o n s and for forecasting

are useful

for

designing

the r e s i d u a l l i f e expenctancy of

s t r u c t u r e s exposed to s t r e s s corrosion.

56

We should recall that the correct expression of a value of K,

lscc
for a material/environment combination must necessarily specify
the structural state, the heat treatment of the material and the
electrochemical conditions, i.e. the electrode potential of the
sample being tested.
Relatively

recently,

phenomena

of

fatigue

corrosion

under

low

stress conditions of slow frequency have appeared to be more preoc

cupying than phenomena of stress corrosion at a static or monotonie
load. Phenomena-of fatigue corrosion with slow cycles create prac
tical problems in the case of steel having an average resistance
(the cladded
resistance

steel of reactors in nuclear power plants), high

steel, sensitized

austenitic

stainless steels

(pipes

for boiling water in nuclear reactors) and aluminium alloys with

high mechanical characteristics.
Fatigue corrosion involves cases where the limit of fatigue (or
endurance), as defined on the curves (maximum constraint-minimum
constraint) as a function of log (number of cycles) is lower
in the presence of a corroding environment (solution or humid
atmosphere) than in the presence of a inert environment, such
as dry argon (figure 25). In certain cases, a fatigue corrosion
limit does not really exist and results must therefore be expressed
as a relation between

the speed of propagation of cracks and

the constraint.
da diagrams as a function
Results are usually expressed on log dN
of the log

, where a is the length of the crack, is the

number of cycles and is the difference between intensity fac

tors

of

the

constraint

max

. , for
min

the stress

applied
*v

and

Figure 26 gives a schematic representation

of

the expression of the results of a fatigue test, where the entire

curve is obtained from one test-piece. The frequency of cycles,
the form of the stress cycles and the relationship

. .
D
= m m = lmm

K.

max

lmax

57 -

should be mentioned in presenting the results.

The Paris law states that there is a linear relationship
da
log = m log Co + m log
dN
where m and Co are constants which are linked by a relationship,
in the case of a certain group of materials. This relation is
valid

in a certain area of flat deformation, elastic behaviour

and slow propagation of fatigue corrosion cracks. This is characte

rized by
one can

as a threshold of non-propagation in fatigue, and

observe

the

influence of the corroding environment by

the position of the curve shown in presence of the environment

as compared to the curve in the presence of an anion of dry argon.
The fatigue corrosion curves are often presented for two values
of R (figure 27) (57).
It should be noted that the fatigue or fatigue corrosion tests
can provide values of K1

and K.

: in the absence of a corroding

environment, rapid
rupture
occurs for ..
= . , or
=
r
r
lmax
lc'
max
(1-R) K1 and in presence of a corroding environment, abrupt rup
ture occurs for ,
= K.
lmax
lscc
Fatigue corrosion tests expressed in this way present a certain
number of interesting characteristics, among which is the possibi
lity to forecast the residual life expectancy of structure having
known dimensions and containing cracks which are subject to fati
gue corrosion.
To end this glimpse of methods of the study of corrosion phenomena
induced by mechanical deformation, it should be recalled that elec
trochemical reactions which take place at the end of the cracks
(anodic

dissolution, hydrogen

evolution...) are very

particular

because they take place in a very particular environment. It is

therefore important to conduct these tests, either on pre-cracked
test-pieces, (where the local conditions have been able to form,
and, in this case, it would be absolutely necessary to know the
natural evolution of these local conditions), or on smooth testpieces

placed

in

an

electrolytic

cell having

two

compartments

58 -

(where the deformed surface is immersed in a solution which simulates

the

solutions

existing

in the

occluded

corrosion cells,

and where the passive surfaces which are joined to them are in
the presence of the solution under study, with control or measurement of electrode potentials.)
2.3. INITIATION ANU PROPAGATION OF LOCALIZED CORROSION
To understand why all at once corrosion occurs locally and often
rapidly, one must try to understand the stages of localized corrosion initiation and propagation.
These two phases are important and the initiation stage is certainly the hardest to study, because it relates to what happened
before there were any observable phenomena.
The initiation mechanisms show particularities for each type of
local

corrosion

(pitting,

crevices, cracking

...) and

we will

come back to this in more detail in the following paragraphs.

Simplifying a great deal, it is easy to conceive that the initiation of corrosion crevices is due to a local lack of oxidizer
or to the weakening, followed by the destruction of a passivating
film which needs those oxidizers to form or to be reconstituted.
The

initiation

of stress corrosion

cracking

is related

to the

local rupture of a passivating film by a mechanical deformation.

This mechanical

deformation

can either

cause the rupture of a

film that is less ductile than the base metal, or more often,
by slip steps or dislocations. A number of questions are still
to be asked about the initiation mechanism of stress corrosion,
for example concerning the specificity of metal/environment combinations that may lead to this type of corrosion, or the intergranular or transgranular properties of these types of corrosion.
Understanding stress corrosion remains one of the most current,
difficult and important problems in corrosion. This type of corrosion affects expensive materials and equipment, it is still insufficiently understood, and it is in part uncontrolled and gives
rise

to

unforeseeable

accidents. This

major economic importance.

naturally

explains

its

- 59
The initiation of pitting corrosion is related to the action of specific agressive ions (mainly CI

chlorides, F

fluorides, Br~bromides,

but also sulfates and sulfur derivatives, nitrates ...) High concentrations of these ions and high electrode potentials increase the risk
and the velocity of this phenomenon. There are still debates about
the reasons for the specificity of the action of certain ions on certain metals, and the mechanisms which, at a given time and at certain
places, results in pitting whereas earlier or elsewhere, nothing apparently is happening.
These questions on the initiation of localized corrosion are extremely
important to forecast under what conditions it may appear and what
are the risks involved. The replies to these questions require advanced
laboratory methods of study which are still to be developed.
One pertinent point of view is as follows : the initiation of localized
corrosion is related to a series of local or temporary defects or
accidents that are difficult, or even impossible, to avoid under real
operating conditions

: these for example might be blows, scratches

start-ups or shut-downs, deposits, local stress .. For this reason,

being able to limit the propagation of localized corrosion often appears more important than understanding the conditions of its initiation in detail.
Over the last ten years, we have seen remarkable progress in the knowledge of electrochemical aspects of propagation of localized corrosions
:

the notion of "occluded corrosion cells" and local modifications

of the environment in the corroded

crevices are now generally well

described, acknowledged and used in most specialized studies.

These phenomena are set down in detail in paragraph 2.2.1. They have
brought

a new explanation
localized

of

the "potential of protection against

propagation

of

corrosion".

This

protection

potential

was defined

in 1962 as a potential under which localized corrosion

that had already been triggered off no longer progresses;at that time,
the potential was determined by potentiokinetic tests at successively
increasing or decreasing potentials, or

by potentiostatic

techniques

60
applied

to

samples

where

localized

corrosion

had

begun, where

the protection potential corresponds to a total reaction current

that is nil or decreasing over time (58). More recently, it was
shown there are electrode potential conditions on exterior surfaces
of a crevice for which corrosion stops in a crevice having a given
pH and concentration, a given form and which has given exchanges
with the exterior (59,60). The reality of a "potential of protection against propagation of localized

corrosion" is undeniable;

its value is not exactly the same as the potential at zero current
determined

by

the

polarization

curves at

decreasing

potentials

: the composition of a corrosion crevice changes and its activity

decreases, and the result is that the protection potential also
varies somewhat with the concentration, the pH .. of the crevices.
One may consider that there is no longer any controversy on the
foundation and the principle of these notions. One must be careful
however, not to oversimplify or to create confusion on the subject.
For example, a series of propagation models for localized corrosion
are being

presented

based on Fick's equations for the diffusion

phenomena and on the mass and load balance sheets for convection
and migration phenomena (61). These models, which are often very
elaborate, generally do not take into account phase changes due
to precipitation which, somewhere between the bottom of the crevice
and the exterior environment, occur for very specific values of
concentrations, pH, aeration or the value of the electrode potential. Another example concerns the use of the "depassivation pH"
to compare the resitance of alloys to the progression of localized
corrosion

(62). This depassivation

pH, in the case of steels,

corresponds to the extremity of the corrosion triangle represented,

in figure 8 for example. In the case of localized corrosion, the
electrochemical conditions existing in the crevice are necessarily
in the corrosion

triangle. The

area of the corrosion triangle

and the "depassivation pH" therefore are not, a priori, an indication of the velocities of propagation of corrosion. To compare
the resistance of alloys to the propagation of localized corrosion, it is better

to follow the spontaneous evolution of the

electrochemical conditions in a natural crevice or in a simulated

crevice and to study the kinetics of the corrosion reactions under
these conditions.

61

2.4. PITTING CORROSION

Pitting corrosion affects passivable metals and alloys under condi
tions of pH, potential, concentrations... where they are passive and
in the presence of specific aggressive ions like the CI
Perchlorates, Br~ bromides, I

iodides, SO,

chloride, CIO,

sulfates and other ions

derived from sulfur, like sulfite, thiosulfates, sulfides and, in certain

systems, silicates and nitrates.
It is recognized that pitting is triggered off more easily and ra
pidly at electrode potentials equal to or greater than the "rupture poten
tial" or "pitting potential" , and that they are not triggered off
or with difficulty at potentials lower than E . It should be noted that
it is not easy to determine this potential E

experimentally and this

constitutes an element of debate among research scientists. Experimental

values of E

are influenced by the sweeping speed of the potential, for

potentiokinetic methods, and by the duration of the potential landings

for potentiostatic methods. A correct method for determining E

consists

in doing long-term potentiostatic tests, using a different sample for

each level of potential (58). For certain research specialists, the li
miting value of rupture potential E , for tests of a longer and longer
duration approaches the value of the potential of protection E

..

depends to a great extent on the state of the surface of the samples.

Because of the influence of these experimental parameters, a cata
logue of values of E

for various materials in different environments

would not mean a lot. Determining the rupture potential E

experimental

under specific

conditions is however interesting in helping to evaluate

the risk of pitting corrosion, and also in comparing the performances

of alloys or surface treatments or water treatments...
The theories proposed for initiation of pitting all take into account
the existence of a rupture potential or a pitting potential E

and the

harmful role of high concentrations of chloride or specific ions.

JANIK-CZACHOR (63) has reviewed some of the initiation mechanisms for

62
pitting in iron : some suggest that the Cl

ions absorbed by the passi-

vating film penetrate this film and create weak spots. But no evidence
of incorporation of the CI

in the passivating film has been observed

by measuring conductivity of the film or by Auger electron spectroscopy,

and conversely, there is direct evidence that the CI

ions accumulate

in solution at the film/solution interface, and in certain spots. This

accumulation occurs preferentially at irregularities or at local defects
of the film itself or of the underlying metal (inclusions, grain boundaries, other macroscopic

defects). Even

any irregularity of the surface, the CI

in the apparent absence of

in solution seems to agglomerate

in "islands" rather than uniformly. This covering of a film by CI

ions

is clearly related to electrode potential. Opinions agree that the CI

ions do not penetrate through the film, but they do not all agree on
the effect of the CI

on the thickness and quality of the passivating

film : for some, the agglomeration of CI

has an effect that thickens

the oxide film (64); for others, on the contrary, the oxide film thins
out (65, 66).
The role of inclusions on the initiation of pitting has been shown
by several research scientists, with interesting remarks : for DESESTRET
(67), certain inclusions are simply more reactive and constitute preferential dissolution sites; this is the case for inclusions of MnS in steels,
as shown by WRANGLEN (68). Other inert inclusions, such as alumina or
magnesia, serve as a polar attraction for sulfides which also favour
localized dissolutions. And these inert inclusions can also, by a slight
differential

dilatation or dissolution, form microcrevices which give

rise to concentration and local acidification phenomena.

In pure water at high temperature (175-260C), it was clearly observed that pitting of slightly alloyed carbon steel is triggered off at
MnS inclusions when the dissolved oxygen content is O.lppm and that
this particular localization of the pits is no longer observed for higher
dissolved oxygen contents (69).
A

fairly

recent

presentation

of initiation of pitting

phenomena

consists in considering that the values of E and the incubation time

r
of pits are not necessarily rigourous values but are statistical measurements, that should be treated as such (70,71). The physical interpretation

- 63 of this way of seeing things is based on the constant competition between

the rupture process and the repair process in passivating films (72).
For E

in particular, one can imagine a gradient of potential through

a film presenting irregular rugosity which would constantly cause local

acidification

that would

then

be neutralized

or maintained

depending

on the combination of rugosity, thickness or hydrodynamic conditions.

The difficulty

in defining the laws that govern the results of these

combinations has encouraged treating them in a stochastic manner. Formation of pitting would then be stable when the velocity of rupture phenomena exceeds the velocity of repassivation. Statistical analysis makes
it possible to study the influence of potential on the velocity of these
two contradictory phenomena separately (70).
It should be noted that, whether the approach used is stochastic or deterministic, and whatever the mechanism proposed for chloride action, all
the propositions of mechanisms recognize the role of the parameters which
have long been considered capital for pitting corrosion : the electrode
potential, and in particular a rupture potential and a protection potential, the concentration of chloride or other specific ions, the state
of the surface, local irregularities, hydrodynamic conditions.
2.5. CREVICE CORROSION
Crevice corrosion is the form of localized corrosion where initiation
is the easiest to understand. For this reason, scientific and technical
progress related to this type of localized corrosion is more advanced
than for other forms like pitting corrosion or stress cracking corrosion.
There are various devices for example for detecting the appearance of
crevice corrosion or, more precisely for making it possible to determine
the risk of crevice corrosion in a given environment, and for a given
geometric disposition which is reproduced by an instrument assembly arid
constitutes the detection cell. Devices of this type are described in
the literature (73). In certain units of production, they trigger off
an alarm when operating conditions are favourable to propagation of crevice corrosion (74). Progress has been made with regard to some of the
detection cells described, which consists in connecting the cell which
contains the simulated crevice, not to a simulated cathode on a well
polished and prepared surface, but rather to the industrial structure
itself, to monitor a more realistic situation.

64

In addition

to these detection systems, currently

various tentatives

are being made to produce mathematic models of crevice corrosion (61).

These models take into account exchanges between the interior of the
corrosion crevice and the external environment by diffusion, migration
and convection, and they try to determine the critical geometries for
triggering off crevice corrosion in a given solution, the max.imum velocities of propagation, the maximum depths of penetration. We will come
back in more detail to these models in paragaph 2.10, but here we can
already mention that few, if any, among them has yet been able to correctly take into account all of the chemical and electrochemical reactions
that take place between the bottom of a crevice and the external environment, and for the moment the conclusions suggested by these models should
be considered with circumspection.
2.6. STRESS CORROSION
The mechanisms of initiation and propagation of stress corrosion cracking
are still a real challenge for research scientists. Many studies have
supplied useful results to the present and have made possible technical
progress in elaborating alloys which perform better in hostile environments, for example, but the problem as a whole is not yet under control:
accidents and unforeseeable problems still occur, and today no satisfactory model of the mechanism exists to explain and to forecast stress
corrosion phenomena and other cracking corrosion phenomena induced by
mechanical deformation.
It is true that the elements required for understanding these phenomena
must come from various disciplines (chemistry, electrochemistry, metallurgy, solid state physics, rupture mechanics...) and it is probable
that a unique model for the mechanisms of all cracking corrosion phenomena induced by deformation, for all material/environment systems, will
not be produced in one stage.
As of the middle of the 19th century when the first phenomena of this
type were identified

(seasonal cracking of brass cartridges, then, at

the end of the 19th century caustic cracking of riveted boilers in mild
steel), the constant growth of the number of material/environment combinations where stress corrosion has been observed has surprised everyone:

65

between 1900 and 1920, aluminium alloys and high resistance steels in
a chloride environment, in 1930 austenitic stainless steels and magnesium
alloys,between 1950 and 1960 titanium alloys in organic and chloro-organic
environments, in the 1970's zirconium and its alloys.
In table IV (75, 76, 77, 56) a list is given, and it is certainly incomplete, of material/environment

combinations in which

stress corrosion

has been observed. A few situations are mentioned which, at first sight
and at the time of occurrence, perhaps did not raise a suspicion of stress
corrosion:
- cracking of brasses in atmospheres which contain small amounts of ammonia

at concentrations much lower than those which can be detected

by smell

(56).

- intergranular stress corrosion cracking of Inconel 600 after two years

in very pure water, at 300-350C, with or without dissolved

oxygen

(78).
- intergranular cracking corrosion of sensitized
steel, in a humid environment

austenitic stainless

(workshop atmosphere), in the presence

of very small amounts of S0 (79).

- cracking corrosion of T-6A1-4V alloys in pure and dry methanol (56).
- cracking of steel with very average mechanical characteristics (635
MPa as

elastic limit at 25C) after degreasing with trichlorethane

(79).
- stress cracking of austenitic stainless steel AISI 302 in boric acid
+ thiosulfate, at ordinary temperature;
A particular aspect of stress corrosion that is not easy to explain is
the type of intergranular or transgranular cracking, which is very specific for very precise conditions
steels crack transgranularly

: for example, austenitic stainless

in the presence of chloride and also at

66
Table IV : Some combinations of materials and environments in which stress
corrosion was observed
Mild steel_in_the_presence_of :
NH,NO, with evaporation

ref (75)

N0 3
OH"

NH_ + C0 + HS + HCN (washing coal gas)

NH anhydrous
H O + CO + C0 2
C O " + HC0 3 HCN + SnCl2 + AsCl2 + CHC13
Na 3 F0 4
HN03
HCN
ethanolamine + H0 + C0
Fe(A10)3 + AL 2 0 3 + CaO
HS0,

fuming

"

FeCl3
NaOH + Na2Si03

ref (76)

HN03 + H 2 S0 4
H2S
CH3CH2C1 + H20

"

(NH 4 ) 2 C0 3
It

polythionic acids

- 67

Table IV (cont'd)
Ferritic stainless steels containing a certain quantity of Ni, Cu, Co,
in the presence of MgCl, CaCl9.
brasses in the presence of :
ammonia

ref (56)

amines

"

so 2
Hg
Certain organic compounds

"

austenitic stainless_steels_ and_Fe-Ni-Cr alloys in the presence of :

chlorides (including CaCl2, CuCl 2> HgCl2> NI^Cl, NiCl2)

ref (77)

(FeCl- : intergranular cracking)

H2'S04

'

ref (77)

OH - (even without 0_. Trans- or intergranular

cracking)

"

H 2 0 pure
lead contaminated solutions

"

C 2 H 5 C1
CaCl 2 , MgCl 2 , LiCl, MnCl2, ZnCl2

- boiling

"

HCi (intergranular cracking)

"

HF + fluosilicic acid

"

CI" + NO"
CI" + P O "
Cl" + N0 2
Cl" + HS0~
Cl + COI"

- 68

Table IV (cont'd)

I:HE!_E2IS_in_!}e presence of :
N0,
2 4

liquid

ref (56

pure and dry methanol

cci 4
methanolic solutions

+ H.SO. or HCl
2 4

chlorinated hydrocarbons
H

"

ci 2 . HCl
Cd

gaseous

solid or liquid

Alumini^_all^ys_iji_the_presence f
sea water or chloride
distilled water
humid air
NaoCr0,
2
4
Na 2 S0 4 + H 2 0 2

"

 69

a free potential in boiling NaOH 60%, but crack intergranularly at higher

potential in the same 60% boiling solution (80). Another example is Inco
nel 600 which cracks intergranularly in pure water at 300C, but whose
crack becomes transgranular if the water is contaminated with lead (81).

It seems that the velocity of deformation at the crack tip

also has

some influence on the type of cracking and, in certain systems, on the

propagation or the stoppage of cracking.

This very

short phenomenology

on certain aspects of stress corrosion

can be accompanied by a comment which may give an idea for simplifiying

the synthesis : stress corrosion, as is the case for pitting corrosion
and crevice corrosion, is a "disease of the passive state". It therefore
can occur only under conditions where the metal is passive, and where
their passivity presents local defects due to the formation of pits or
further to a mechanical deformation. For each material/environment combi
nation, there are therefore conditions of electrode potential, pH, concen
tration, circulation...where

the metal is partially passive and where

there may be risks of stress corrosion, and conditions where, in the

same environment, the metal is either entirely active, or marvelously
passive and the risk of stress corrosion does not exist.

In the case of austenitic stainless steels, stress corrosion in a chloride

environment can be stopped by decreasing the electrode potential : decrea
sing the potential eliminates the risk of stress corrosion and stops
propagation of cracks that have begun. The potential to be reached for
this is indeed the "potential of protection against propagation of loca
lized corrosion" which we mentioned in sections 2.2.1.4. and 2.3. of
this report. Protection against stress corrosion can be obtained simi
larly for slightly alloyed steels in nuclear reactor tanks and for sensi
tized 304 steel in pure water at 280300C. In the latter case, the cri
tical potential to be reached should be 300 mV , , which can be reached
when the dissolved oxygen contents are much lower than 50 ppb. High resis
tance carbon

steels behave differently

: their sensitivity to stress

corrosion increase both by an increase in electrode potential and by

a decrease in that potential. In both cases, the morphology of the cracked

- 70

surfaces is exactly the same and, in both cases, the electrochemical

conditions at the end of the crevice are such that hydrogen evolution
is possible there.
Susceptibility to stress corrosion therefore definitely depends on the
electrode potential but also depends on the nature of the cations present,
and the effects of the additive elements of an alloy are not necessarily
the same in the presence of all solutions. With the relatively rapid
and convenient CERT (Constant Extension Rate Testing) method, PARKINS
shows that the cations associated to nitrates have a significant effect
on susceptibility

of stress corrosion, and that the elements used in

steel alloys do not have the same effects in solutions that are as similar
as NaOH and Na2C0 (82).
To present all of the stress corrosion mechanisms mentioned so far, a
very large number of different metal/solution combinations would have
to be considered successively, which is not practicable in this presentation. As an illustration we will mention the cases of stress corrosion
in mild steel, high resistance steel and iron-chromium-nickel alloys.
In the case of mild steels, which undergo stress corrosion by intergranular cracking in solutions of ammonium nitrate, ammonium carbonate or
caustic soda, the mechanism proposed by PARKINS principally implies an
anodic dissolution of the locally active surfaces generated by the deformation (83). The active surfaces are usually located at grain boundaries.
In the case of high resistance steels which was mentioned above, BROWN
suggests that cracks are initated at the pits and underlines that the
closed medium in the crack is acidic and that the electrode potential
in the bottom of the cracks is low (84). Under these conditions, and
whatever the potentials measured outside of the cracks, the conditions
inside the cracks permit hydrogen evolution, and the cracking mechanism
proposed is based on hydrogen embrittlement.
For iron-chromium-nickel alloys, several mechanisms have been proposed
(80):

71 -

- One of these mechanisms suggests that hydrogen formed at the bottom

of the pit favours the transformation of unstable austenite into fragile
martensite. Indeed, the formation
if the external

environment

of hydrogen can be observed even

is oxidizing, and hydrogen does favour

the transformation of unstable austenite into martensite. But, to argue

against this theory is the fact that a decrease in potential stops
propagation

of stress corrosion and

the fact that stress corrosion

also affects very stable austenites, like those in AISI 310 steels,
and stable ferrites as is the case for chromium steels which contain
a bit of copper, cobalt or nickel.
Another mechanism proposes a cleavage induced by selective absorption
of certain ions, which would decrease the energy of the atomic bonds
which are already subject to mechanical forces.
Another explanation entails the formation of long and narrow tunnels
by dissolution starting at pits which were triggered off at slip lines
and the wedge effect produced by the expansion of the corrosion products.
Another mechanism, based on physical metallurgy supposes that the fact
that slip lines are on the same plane favours stress corrosion, either
by rupturing the passivating film, or by concentrating the deformation
energy, which would accelerate the chemical reactions.
Finally one model which proposes selective dissolution at spots where
the passivating film has been broken or weakened by mechanical stress
or by the emergence of dislocations, has been developed more largely
(80). A,number of research projects and publications have contributed
to the various features of this model. The local dissolution current
from the small surfaces thus bared is initially large; it can decrease
in the case of repassivation under appropriate conditions of potential,
pH, agressivity and velocities of deformation, remain stable or rise,
for example under more severe local electrochemical conditions, or
for more important local velocities of deformation. This model includes
local formation of particular electrochemical conditions (such as acid
pH, high chloride concentration, possibility of hydrogen evolution...)
described

in

section

2.2.1. Moreover, important

contributions

were

made by GALVELE and his collaborators which have shown, theoretically

- 72 and experimentally, that it is possible to conceive of local current

densities sufficient to explain the velocities of propagation of stress
-2
corrosion cracks (85,86).The local current densities of 0.3A.cm
2
2
for aluminium (87), 2 A.cm

for iron and 8 A.cm

for stainless steels

(88) were assessed in the bottom of pits, and crack growth rates of
the order of mm.h

are classic for austenitic stainless steels. SCULLY

has presented interesting discussions on what can occur at the bottom

of the crack depending on the speed of deformation , or repassivation r" and of the quantity of electric charge required to extend
the crack (89a).
In certain systems (high resistance steels, titanium alloys and zirconium
alloys), stress corrosion cracking comes closer to fragile rupture, where
hydrogen

embrittlement

is

preponderant.

The mechanism

of

propagation

of fragile ruptures by cleavage is different from the mechanism of propa

gation

by dissolution

described

above. The cracking conditions depend

on the quantity of hydrogen absorbed and its localization in the cristal

line network.
Of the recent progress made concerning the struggles against corrosion
in the case of extreme stress, we would like to point out the developments
by M.O. SPEIDEL et al of strongly

alloyed

manganese-chromium-nitrogen

steels (19% Mn, 19% Cr, 0.03% C, 0.74% ) which show excellent resistance
to stress corrosion cracking, to hydrogen embrittlement and to fatigue
corrosion (89b, 89c). These steels are particularly suitable for rotor
rings of electric power generators.
In this summary devoted to stress corrosion, we will note that, although
it would be satisfying from an intellectual standpoint to have one and
only one model to explain all of these types of corrosion, it must be
admitted that we are currently a long way from this stage. However, un
deniable progress has been made since the mid 60's. One

particularly

decisive point is the already quite precise description of the very parti
cular chemical and electrochemical conditions which exist at the bottom
of cracks : these are active conditions generally acidic, low in oxygen,
rich in anions and cations with oxide, hydroxide and salt deposits, where
the kinetics

of

the

corrosion, repassivation

and

eventually

hydrogen

evolution reactions are also very particular. This description represents

remarkable progress because it is valid for all cases of stress corrosion

73

and even for other localized corrosion phenomena. This is a major step
towards a general synthesis of these problems.
This strong point in the knowledge of localized corrosion must still
be put to use. In analysing the literature, one definitely realises that
experiments done in different laboratories on different systems using
different methods often are not easy to interpret or compare because
the many experimental parameters (potential, pH, composition of the solution at the bottom of the crack, velocity of deformation at the bottom
of the crack, local current density, surface analysis, hydrogen evolution,
fractography) are not always described or are not measured in a comparable
manner.
Without wanting to hamper the freedom and imagination of research scientists, it would certainly be useful to agree on and to carry out a certain
series of identical tests on identical materials under very specific
conditions

in different

laboratories

to determine the reliability of

various experimental methods.

At the current stage and despite considerable progress, we are still
unable to forecast all of the practical cases of stress corrosion behaviour on many materials. Too many accidents still occur in aviation,
in the navy, in bridges, in chemical industries, in petrochemical industries or in energy generation. And this corrosion causes accidents because we are partially unable to predict it.

On finishing this expos on stress corrosion cracking, we would like

to draw attention to the usefulness of electrochemical methods mentioned
in section 2.2.2. of this report for studying this kind of localized
corrosion.
The principles set out above with regard the "occluded corrosion cells"
are valid for all cells, whatever their nature and origin.
Concerning stress corrosion cracking, B.F. BROWN has confirmed this similarity in a number of his well-known works on cathodic polarisation of
cracked steels using his "freezing method" (90, 91). One can see that
the electrode

potentional/pH

curve obtained

by B.F. BROWN for cracks

in chromium steels (figure 28) is very similar to the one obtained by

74J. VAN MUYLDER for a crevice in mild steel (figure 10). These results
lead B.F. BROWN to the very important conclusion that, for the steels
he examined, the electrode potential inside the crack is always lower
than the potential of the "hydrogen line" a_, even if the external solution
is alkaline, and that, consequently, there is always hydrogen evolution
in the crack. During cathodic polarization experiments, the results of
which are shown in figure 28, the velocity of propagation of cracks ("dial
deflection rate") observed above about -0.7 V , is due to both corrosion
she
and hydrogen embrittlement, and the velocity of propagation of the crack
observed below about - 0.7 V ,

is due to hydrogen embrittlement, without

corrosion.
During two meetings held respectively in 1978 in Rio de Janeiro (92,
93) and in Calcatoggio (48), an electrochemical method of studying stress
corrosion cracking was proposed, based notably

on J. VAN MUYLDERS's,

B.F. BROWN's and SATHLER's experiments, which are mentioned above and
for which we will recall the essential points below.
Thanks to

the works done by H.H. UHLIG (94 to 102), R.W. STAEHLE (103),

R.N. PARKINS (104, 116), P.E. MORRIS (105) and G.J. THEUS (106), it is
well known that, when stress corrosion cracking appears, it manifests
itself in a certain range of electrode potentials (measured on the external surface of the metal), near the limit between passivity and general
corrosion. This means that in this range, in R.W. STAEHLE's words, "the
passivating film presents kinetic instability". This range of electrode
potential can be determined by using PARKINS' "slow traction method".
It seems very probable that this range of dangerous electrode potential,
the precise significance of which does not seem to be currently known,
must correspond to circumtances in which corrosion occurs in the "occluded cells" which the cracks in the metal constitute. If this is indeed
the case, the dangerous range of electrode potential (measured on the
outside surface of the metal) might be predetermined quantitatively by
simply superimposing the polarization curves determined in the presence
of the solution in which metal is immersed (which notably show the conditions for generalized corrosion of the external surface), and the polarization curves determined in the occluded solution (which show the conditions for corrosion, immunity and passivity on the internal surfaces,

- 75

i . e . t h e i n s i d e of t h e occluded c o r r o s i o n c e l l s Os.cc), and which

a l s o show the conditions under which hydrogen can e v o l v e . I t should
be u n d e r s t o o d t h a t t h i s superimposing must be done t a k i n g
account,

as mentioned in s e c t i o n 2.2.1.6.3. of t h i s r e p o r t ,

into
the

e x i s t e n c e of a d i f f u s i o n p o t e n t i a l (and an e v e n t u a l "ohmic drop")

between t h e i n t e r n a l c a v i t i e s and t h e e x t e r n a l s t r u c t u r e .
diffusion

This

p o t e n t i a l i s equal to the difference in p o t e n t i a l between

two i d e n t i c a l r e v e r s i b l e reference e l e c t r o d e s p l a c e d

respectively

i n s i d e and o u t s i d e t h e o.c.c. (figure 18).

Figures

31 a.b.c which reproduce f i g u r e s p r e s e n t e d p r e v i o u s l y (48,

f i g u r e 17), d e t e r m i n e t h i s dangerous zone of e l e c t r o d e p o t e n t i a l s .

These f i g u r e s g i v e a p r o v i s i o n a l s c h e m a t i c r e p r e s e n t a t i o n of t h e
study of s t r e s s corrosion cracking of chromium s t e e l ,

the occluded

c o r r o s i o n c e l l s of which were p r e s e n t e d i n f i g u r e 16b of s e c t i o n

2.2.1.6.b. Figure 31a shows the p o l a r i z a t i o n curves determined on the
e x t e r n a l s u r f a c e of t h e m e t a l i n t h e p r e s e n c e of pH 7.0, 0.1 molar
chloride solution.

One can see notably the " p a s s i v i t y p o t e n t i a l P"

and t h e " p o t e n t i a l of p r o t e c t i o n a g a i n s t p r o p a g a t i o n of l o c a l i z e d
corrosion,

"prot".

Figure

31b shows t h e p o l a r i z a t i o n

curves

determined i n the presence of ferrous c h l o r i d e s o l u t i o n s e x i s t i n g in

t h e o c c l u d e d c o r r o s i o n c e l l s (pH 7.0 t o 3.8 and 0.1 t o 9.2 molar i n
chloride).

For four v a l u e s of pH (7.0 t o 3.8) one can see

the

v e l o c i t i e s of corrosion of the metal and the v e l o c i t i e s of hydrogen

e v o l u t i o n , a l o n g w i t h t h e p a s s i v i t y p o t e n t i a l s a l r e a d y shown i n
f i g u r e 16b (-0.31 v l l i g a t pH 7.0, -0.26 v o l t s h e a t pH 6.3, -0.16
v o l t s h e a t pH 4.9, and -0.09 v o l t s h e a t pH 3.8). I n f i g u r e 31c,
figures 31a and 31b have been superimposed by s h i f t i n g the l i n e s in
f i g u r e s 31b towards t h e top of a v a l u e e q u a l t o t h e

diffusion

p o t e n t i a l ( t h a t we have assessed r e s p e c t i v e l y a t 0, 59, 100 and 115

mV for the four s o l u t i o n s under consideration). According to figure
31c, c o r r o s i o n i n t h e o.c.c. would s t a r t above e x t e r n a l

electrode

p o t e n t i a l s r i s i n g from -0.35 t o -0.15 v o l t g ^ g a s pH d e c r e a s e s from

6.3 t o 3.8. And t h i s c o r r o s i o n would s t o p by " r e p a s s i v a t i o n " above
external

potentials

rising

from -0.21 t o +0.30 v o l t ^g a s pH

decreases. According to t h i s expos, the range of e x t e r n a l p o t e n t i a l s

76

in which 12% Cr steel is sensitive to stress corrosion runs from

about -0.21 to +0.30 v o l t s h e

(i.e. -0.46 and +0.05 v o l t g c e ) .

Below

-0.21 Vste any possible cracks are in a state of immunity; above

+0.30 voltg^g they are passivated.
We recall that figure 16b is an approximate provisional diagram.
Complementary research which would make it possible to adjust this
diagram, obtaining precise results for the approximation given in
figures 31, would be helpful.
2.7. HYDROGEN EMBRITTLEMENT
We will only speak very briefly here about hydrogen embrittlement,
which was already described

in the part of section 2.2.1.6.

concerning occluded corrosion cells in steels, and in section 2.6. on

stress corrosion cracking.
We will simply point out that hydrogen is not the only gas which can
be formed in occluded corrosion cells and which can therefore cause
mechanical embrittlement of the metal. Methane CH 4 can also be
formed, and perhaps other hydrocarbons, and, in the presence of
nitrate, nitrogen N 2 and nitrogen oxides N2O and NO, which also can
have an embrittlement effect.
On the other hand, we think that, despite the lack of success that
has been met with up to date, it is probably possible to perfect
devices which would eliminate all or part of the hydrogen formed on
industrial structures, gradually as it is formed. Devices like these
would be of a major practical interest.
2.8. INTERGRANULAR CORROSION
As indicated in section 1 of this report, intergranular corrosion of
sensitized stainless steels is one of the most common forms of
localized corrosion in the chemical industry. The term "sensitized"
means that the stainless steels have been brought to and kept for a

77

certain time at a temperature range where the chromium diffuses

toward the grain boundaries and precipitates there as chromium
carbide. The chromium, added as an alloying element, has two effects
on the behaviour of steel in an acid environment :
1) it decreases the range of generalized corrosion area at low
potentials,
2) it gives rise to a transpassive corrosion area at high potentials,
with formation of hexavalent dissolved chromium.
These effects are illustrated by the polarization curves for iron,
for poor and for rich chromium alloys in sulfuric acid, shown in
figure 32. It can be observed that 10% chromium is not enough to
allow for the formation of a high quality passive layer.
In sensitizing treatments or conditions for stainless steels, for a
temperature range from 550 to 850C for austenitic steels and for
nickel-rich chromium alloys, and from 925 to 1150C for ferritic
steels, the mobility of chromium and its affinity for carbon is so
great that the chromium carbides are formed preferentially at grain
boundaries, to the detriment of the chromium which was in uniform
solid solution in the matrix of the grains. The result is that, near
the grain boundaries, the percentage of chromium in the matrix can
fall below 8 to 10%, and it can attain 70 to 95% at the grain
boundaries. This intergranular corrosion mechanism, presented by BAIN
(108) as chromium depletion near grain boundaries, is illustrated in
figure 33 (107).
These mechanisms can be readily

understood

by comparing

the

polarization curves of different zones of the metal. Figure 32 traces

the three curves relating respectively to the non-affected matrix of
a stainless steel 18 Cr 10 Ni (18% Cr), to zones near the grain
boundaries of sensitized steels rich in carbon (C > 0.03%), where the
concentration of chromium can fall below 10% Cr (the grain boundaries
themselves then consist of chromium carbide inclusions which are very
rich in chromium), and to a carbon steel without chromium (0 % Cr).

78 -

Comparing these curves notably shows t h a t , in a range of a r e l a t i v e l y

low p o t e n t i a l s (between +0.05 Vg^g and +0.25 V g n e according to figure
32), zones h a v i n g l e s s than 10% chromium a r e c o r r o d e d , whereas t h e
matrix with 18% chromium remains p a s s i v e . In an acid environment at
v e r y high p o t e n t i a l s (above + 1.20 V g ^ e ) , c o n v e r s e l y , t h e chromium
r i c h zones, t h e s e being t h e s e n s i t i z e d g r a i n b o u n d a r i e s and t h e
sigma phase (which c o n t a i n s n e a r l y 50% chromium), c o r r o d e more
rapidly.
Empiric t e s t s on s u s c e p t i b i l i t y to i n t e r g r a n u l a r corrosion have been
used for quite some time : for example, the Huey t e s t in concentrated
b o i l i n g n i t r i c a c i d i s commonly used i n t h e United S t a t e s ,

the

S t r e i c h e r t e s t i n s u l f u r i c a c i d - f e r r o u s s u l f a t e t h e c o n d i t i o n s of
which are s l i g h t l y l e s s oxidizing t h a t the Huey t e s t , and the Strauss
t e s t i n s u l f u r i c a c i d - c o p p e r s u l f a t e i n t h e p r e s e n c e of m e t a l l i c
copper i s used, p a r t i c u l a r l y in Europe and in the Soviet Union. Since
t h e works of CARIUS (109) i n 1958 and CLERB0IS e t a l (110) i n 1959,
major

progress

has been made i n

understanding

and

monitoring

i n t e r g r a n u l a r c o r r o s i o n t e s t s . Each of them c o r r e s p o n d s t o a v e r y
well-defined range of p o t e n t i a l s represented in figure 32 and shows
the p a r t i c u l a r e f f e c t s of the i r r e g u l a r d i s t r i b u t i o n of chromium in
sensitized

steel

: the b o i l i n g n i t r i c acid t e s t d i s s o l v e s

the

chromium carbides accumulated in the grain boundaries and the sigma

phase. The f e r r o u s s u l f a t e a c i d does not d i s s o l v e t h e chromium
carbides,

i t d i s s o l v e s the chromium depleted zones s l i g h t l y and i t

d i s s o l v e s the sigma phase. The Strauss t e s t d i s s o l v e s the chromium

d e p l e t e d zones e x c l u s i v e l y .
electrochemical methods of study,

B e c a u s e of t h e d e v e l o p m e n t

of

these more or l e s s empiric t e s t s

can and should be much b e t t e r c o n t r o l l e d , which means t h a t they might

be more r e a d i l y reproduced and have more significance.

Essentially

electrochemical t e s t s could r e p l a c e them, and a q u a n t i t a t i v e ,

non-

d e s t r u c t i v e electrochemical method does c u r r e n t l y e x i s t to assess the

degree of s e n s i t i v i t y of s t a i n l e s s s t e e l s to i n t e r g r a n u l a r corrosion.
This method EPR (for Electrochemical P o t e n t i o k i n e t i c Reactivation) i s
described in Chapter 3 .

79

F u r t h e r m o r e , t h e c r a c k s i n which t h e i n t e r g r a n u l a r c o r r o s i o n p r o
g r e s s e s a r e i n f a c t o c c l u d e d c o r r o s i o n c e l l s a s they a r e d e s c r i b e d i n
s e c t i o n 2,2.1.6.
the chemical
electrode

I t i s c u r r e n t l y possible to accurately

predetermine

c o m p o s i t i o n of s o l u t i o n s i n s i d e t h e o . c . c

potentials

t h a t may be p r e s e n t on t h e c o r r o d i n g

and

the

surfaces.

I t i s a l s o p o s s i b l e t o e x p e r i m e n t a l l y d e t e r m i n e t h e i n f l u e n c e of t h e
e l e c t r o d e p o t e n t i a l and pH on t h e n a t u r e and v e l o c i t y of a l l

the

r e a c t i o n s which may be produced a t

the

the interface,

f o r each of

substances that e x i s t along the grain boundaries

(alloy,matrix,

c a r b i d e s and o t h e r composites d e p o s i t e d a l o n g t h e b o u n d a r i e s ) and f o r

t h e d e p l e t e d zones i n t h e a l l o y . Those r e a c t i o n s may be :

corrosion

and d e p o s i t i o n of m e t a l s , p a s s i v a t i o n , o x i d a t i o n of c a r b i d e s and
o t h e r c o m p o u n d s , f o r m a t i o n of h y d r o g e n and o t h e r g a s e o u s e l e m e n t s
( m e t h a n e ? n i t r o g e n and n i t r o g e n o x i d e s ? ammonia?
hydrogen s u l f i d e ? ) .

carbon dioxide?

S i n c e 1970, e x c e l l e n t r e s e a r c h has been done i n

t h i s d i r e c t i o n by R.W. STAEHLE ( 1 1 1 ) , J . KRUGER and G. UGIANSKY ( 1 1 2 ,

113) and i t seems v e r y d e s i r a b l e t h a t t h e p r o j e c t s s h o u l d c o n t i n u e .
T h i s would make a l a r g e c o n t r i b u t i o n t o c l e a r i n g up problems which
c u r r e n t l y s u b s i s t c o n c e r n i n g t h e i n f l u e n c e of a d d i n g e l e m e n t s t o
a l l o y s on i n t e r g r a n u l a r c o r r o s i o n (and s t r e s s c o r r o s i o n c r a c k i n g ) on
t h o s e a l l o y s . F o r e x a m p l e Cu, N i , , S and Sn f o r s t e e l s and As, B i ,
F e , Sb, Sn f o r n o n - f e r r o u s a l l o y s .
2 . 9 . CORROSION BY DE-ALLOYING
We w i l l

mention

only

briefly

the

de-alloying

phenomena

which

sometimes a f f e c t c e r t a i n a l l o y s , such a s b r a s s e s . There i s not

total

a g r e e m e n t on t h i s m e c h a n i s m ( 1 1 4 , p g . 2 3 9 ) . Some a u t h o r s m a i n t a i n
t h a t d e - a l l o y i n g c o n s i s t s i n a p r e f e r e n t i a l d i s s o l u t i o n of z i n c which
leaves residual

copper. Other a u t h o r s c o n s i d e r t h a t both copper and

z i n c a r e d i s s o l v e d , w i t h a s u b s e q u e n t r e d e p o s i t i o n of c o p p e r .
Our p r e f e r e n c e t e n d s towards t h e second mechanism. At any r a t e ,
d e - a l l o y i n g would c r e a t e o c c l u d e d c o r r o s i o n c e l l s i n both

this
cases

which, i f c h l o r i d e i s p r e s e n t , would probably c o n t a i n m e t a l l i c copperj

80

Cu09 and copper chloride CuCl in addition to more or less modified

brass. The electrochemical conditions existing in such cells would
therefore be very similar to those in copper pits which have been
described in section 2.2.1.6.3. This would mean that the criteria
for developing and stopping this de-alloying phenomenon are similar
to those which have been cited above for copper corrosion pits.
2.10. LOCALIZED CORROSION MODELS
We know

that conditions which

exist

in the occluded

corrosion

cells are very different from those which exist in the external
environment. There are diffusion exchanges (due to the differences
in

concentration

of

the

same

dissolved

substances),

migration

exchanges (due to the existence of an electric field and the passage of an electric

current) and

convection exchanges

(due to

stirring and to pumping) between the bottom of the occluded corrosion cells and the outside.
These exchanges do indeed take place : in the corrosion pits of
pure

iron, local chloride concentrations

have been observed up

to 9.2 molar (327 g/1 of CI ) , which corresponds to saturation

_3
of FeCl~.4H.-0, starting with a 10

molar exterior chloride solu-

tion. This represents a concentration

of almost

10 000 times.

Chlorides are particularly mobile and soluble and they are easily
carried by diffusion. Diffusion of metallic cations in the other
direction
are

also

takes

less mobile and

hydroxides

and/or

place, although
because

salt, under

more

slowly

because

they

of their precipitation as oxides,

particular

pH, concentration and

aeration conditions for each system. The migration phenomena are

real also

: different electrode potentials of several hundreds

of millivolts or of more than one volt (in the case of titanium

and aluminium alloys), exist between the active surfaces of the
crevices

and

the

passive

exterior

surfaces, and

some

research

scientists have assessed the loca'1 current densities in the acid

cavities at 0.5

to 8.0 A.cm

( , 86, 87, 88). The convection

phenomena are partly associated wit

the

hydrodynamic

conditions

- 81 -

of the fluid but they have a particular aspect in the fatigue-corrosion

phenomena

because of

the pumping effect of cracks which

are opened and closed alternatively.

Mathematical models of occluded corrosion in cells are being set

up with the objective, for example, of correlating the velocity
of propagation of crevice corrosion and the density of the current
coming from the crevice, or of correlating the velocity of propagation

of

or of

localized

determining

electrolyte

corrosion

and

the velocity

the dissolved

oxygen content,

of circulation of the exterior

for which the velocity

of penetration of localized

corrosion is the strongest, or helping to elaborate and measure

localized corrosion mechanisms.
Some

elaborate

models

effectively

take

into

account

diffusion

according to Fick's laws,transport of mass, records of charge and

electric field, given temperature and reactions inside the crevice
which produce or consume a chemical

species

(61). But, as far

as we know, no model proposed has been able to explain or to take

into account all of the reactions which may take place between
the

bottom

of

the crevice

and

the external environment. These

must include reactions that dissolve the matrix, grain boundaries

or inclusions, and

even

the

reduction of water with formation

of H, recombining 2H into H, with formation of gas bubbles, formation of simple ions or complex ions depending on the total concentration in the crevice, changes in conductivity between the bottom
and the outside of the crevice, precipitation reactions to form
oxide and/or hydroxide or basic salt, eventual repassivation reaction on portions of the surface, either by saturation in a salt
dissolved in the bottom of the crevice or by an oxide which is
likely to be found more to the opening of the crevice.
A lot of work remains to be done to create exhaustive mathematical
models of localized corrosion. Until that time, conclusions

which

82 -

may seem clear must be considered with circumspection - they may

be too hasty. In reference 61, descriptions are given of the current state of a few tentatives of models of localized corrosion.

- 83

3. APPLICATIONS OF CURRENT KNOWLEDGE OF LOCALIZED CORROSION

A f i r s t r e s u l t of t h e k n o w l e d g e r e c e n t l y a c q u i r e d a b o u t
c o r r o s i o n has been immediate and s i g n i f i c a n t
t h e m s e l v e s : study methods, u n d e r s t a n d i n g ,

localized

progress in the
interpretation

studies

of

mecha-

nisms.
For example,

recognizing that

l o c a l i z e d c o r r o s i o n i s accompanied by

major, w e l l - d e f i n e d m o d i f i c a t i o n s in the s o l u t i o n s p r e s e n t in the

cavities

o r c r a c k s h a s g i v e n much more u n d e r s t a n d i n g of t h e me-

chanisms of a c t i v e d i s s o l u t i o n ,

p a s s i v a t i o n , hydrogen e m b r i t t l e m e n t ,

... T h i s h a s a l s o made i t p o s s i b l e t o d e s i g n s i m u l a t i o n t e s t s
localized

corrosion

founded

are comparable to r e a l

on a s e r i o u s ,

quantitative

basis,

of
that

situations.

Recognizing t h e r o l e of t h e e l e c t r o d e p o t e n t i a l on s t r e s s

corrosion

c r a c k i n g phenomena has a l l o w e d comparison of r e s u l t s which p r e v i o u s l y

seemed c o n t r a d i c t o r y and i m p o s s i b l e t o reproduce. Not too v e r y
a g o , many s t r e s s c o r r o s i o n t e s t s were done w i t h o u t

long

potentiostatic

m o n i t o r i n g and g a v e a l m o s t u s e l e s s r e s u l t s . Since about 1971, thanks

t o exchanges between a c e r t a i n number of r e s e a r c h teams i n many p a r t s
of t h e w o r l d , t e s t s a r e b e i n g c a r r i e d o u t u n d e r b e t t e r

controlled

c o n d i t i o n s , n o t a b l y i n c l u d i n g measurement of e l e c t r o d e p o t e n t i a l , and
interpretation

has t h u s become p o s s i b l e . Analysing of t h e way t h e s e

exchanges took p l a c e and t h e r o u t e they f o l l o w e d i s a l s o w o r t h w h i l e :

t h e y d i d n o t o r i g i n a t e i n c o n g r e s s e s and s c i e n t i f i c

publications

a l o n e . C o o r d i n a t e d r e s e a r c h programmes d e a l i n g with major

industrial

p r o b l e m s w h i c h i n c l u d e d c o o r d i n a t i n g meetings, programmes for comp a r i s o n and exchange among s e v e r a l r e s e a r c h teams have c r e a t e d

these

exchange c h a n n e l s which h a v e sometimes proved very r a p i d and b e n e f i c i a l . A t h i r d example d e a l s w i t h t h e f a c t t h a t t h e e l e c t r o d e

tial

measured or monitored o u t s i d e corrosion c a v i t i e s i s

from t h e p o t e n t i a l

poten-

different

i n s i d e t h e s e c a v i t i e s and t h i s d i f f e r e n c e

can be

measured. W e l l informed teams today a r e aware of t h i s n o t i o n , but

it

i s n o t a s i m p l e o n e , and much r e m a i n s t o be done t o g i v e us a c l e a r

u n d e r s t a n d i n g and a p r e c i s e d e s c r i p t i o n of the r e l a t i o n s between t h e

- 84

interior and the exterior of the cavities. The road, however, has
been paved and much effort is being exercised in the right direction.
In addition to this general progress which results from new knowledge
acquired about the electrochemistry of localized corrosion and its
application to new research projects, we can cite a few praticai
problems as examples to show the progress which has been made by
applying recently acquired notions. The examples given below by no
means represent a comprehensive review of the question.
3.1 ELECTROCHEMICAL PROTECTION AGAINST LOCALIZED CORROSION
This means of protection is a direct result of the notion of the
"potential of protection against propagation of localized corrosion"
Ep (see section 2.2.1.4.). This potential is defined as an electrode
potential under which localized corrosion does not make headway, even
if it is present. This effect was observed and noted in 1962 for
pitting corrosion (115) and in 1968 for stress corrosion cracking
(23). In 1970, Du Pont de Nemours reported a case of protection
against stress corrosion cracking in stainless steel heat exchangers
in the presence of sea water : stress corossion was held in check by
metallising the stainless stell tubes with lead. The lead coating,
which does not necessarily have to be continuous or protective, by
slowly corroding in the sea water, kept the electrode potential of
the tubes at about -0.5 V

this being a value less than the value

see

of the "potential of protection against localized corrosion" of

stainless steel.
A method of protection was proposed, and in fact required by the
American Navy for any stainless steel structure

used in sea water.

This protection, by connecting with zinc or carbon steel, was intended to lower the potential of the stainless steel, although, at
the time, the notion or the precise value of a potential of protection was not clearly understood by the persons initiating this proposition.

85 -

There are other practical applications of this process against localized corrosion : aluminium alloy reactive anodes were used to lower
the electrode potential of surfaces of tubular sheets on stainless
steel heat exchangers, near the tightness joints on the covers of the
water boxes (117). These exchangers were seriously corroded under the
joints when the commissioning tests were carried out in a unit cooled
by sea water.
Another stainless steel condenser with chucked tubes was protected
against crevice corrosion at the chucked tubes/tubular sheet joints,
which also occurred during tests before commissioning of the equipment. A protection system using impressed current was chosen for this
case because of the resistivity of the water in the cooling circuit
supplied by river water (117).
Crevice corrosion in the chucked tube/tubular sheet joints of stainless steel concentrators, used for concentrating slightly acidic and
chlorinated juices was stopped

by simple partial cathodic protection

by connecting sheets of Armco steel. The potential of stainless steel

was thus lowered from 0 V g c e to -0.4 V g roughly, and the number of
incidents dropped from 4 in six months to 0 in one year (117).
For quite some time, copper alloy tubes of condensers cooled by sea
water have been protected against localized corrosion by regular
injections of ferrous iron above the condensor. For a long time, the
question of determining the distance from the tubes, the frequency
and the concentration of these injections was debated (118). This
protective procedure is still important today for protecting aluminium brass and

cupro-nickel tubes from pitting corrosion and from

stress corrossion in clean or polluted sea water. Regulating this

method of protection is said to be very delicate, and the results are
not always convincing.
In light of the concepts of 1 calized corrosion in occluded cells, it
has been shown that putting

ron in a solution of water distributed

in urban areas lowers the lectrode potential of copper up to about

86 -

+20 and +50 mV^g (+270 to +300 mV ghe y which considerably limits the
effects of pitting corrosion and generalized corrosion (49). Based on
the same reasoning, works done by Electricit de France (EDF) concerning the protection of copper alloy condensers by addition of
ferrous salts to the sea water in circulation (119,120) showed that
this drop in potential is caused by the oxidation reaction of ferrous
ions in ferric oxide on copper surfaces outside of the pits. One
important result of this study is to demonstrate that the protective
ferrous sulfate process which was reputed to be difficult to control,
can be easily controlled and commanded by simply measuring electrode
potential.

3.2 SPECIFICATIONS FOR CRITICAL CHLORIDE CONTENT IN SECONDARY

CIRCUITS OF NUCLEAR REACTORS
Before 1972, Westinghouse and Combustion Engineering specifications
required maximum chloride content of 75ppm for the water of steam
generators treated using the congruent phosphate process. In 1974,
the manufacturers recommended abandoning this treatment in favour of
an "all volatile" phosphate-free treatment, with maximum chloride
content of 150 ppb. Several months later, a very serious corrosion
problem called "denting" occurred in the carbon steel support plates,
at the passage holes for the Inconel 600 tubes, with deformation and
possible cracking of the tubes. It rapidly became obvious that this
was an occluded cell corrosion problem, where the oxidiser (present
in the form of copper,

nickel and iron oxides formed in the

reheaters) and the chloride came from small condenser leaks. Because
of newly acquired knowledge of the mechanism of this type of corrosion, it was recognized that acidification and local concentration
can take place even when the external solutions contain very little
chloride. An implacable hunt for chloride was launched, mainly by
improved design, supervision and management of the condensers : the
specifications requiring 150 ppb chloride (1975) became 15 ppb for
serious operators (1978) and since 1978 one school of thought maintains that the chloride content should be rigorously zero; the 15 ppb

- 87

dissolved chloride are considered excessive in 1985; the "bar" was

set at 5ppb dissolved Cl~, which is the praticai equivalent of the
theoretical zero recommended.

3.3 USE OF FERRITIC STAINLESS STEEL AGAINST CORROSION OF SUPPORT

PLATES OF STEAM GENERATORS IN NUCLEAR REACTORS
The "denting" phenomenon mentioned in the paragraph above is the
result of corrosion of the carbon steel support plates with formation
of magnetite which causes a deformation of the Inconel 600 tubes. In
1978, during a large American-Japanese conference on these problems
(121), alternative solutions were proposed for the support plate
material.

Austenitic

stainless

steels

and

Inconel 600 were not

retained, because of the risk of stress corrosion for the former,

and fretting from contact with tubes in the same material for the
latter.

Westinghouse

and Combustion

Engineering

decided

on AISI

405 (13% Cr) and AISI 409 (11% Cr) ferritic stainless steels.
Yet by applying the localized corrosion mechanisms to the "denting"
problem it was possible to foresee that ferritic steels were not
appropriate for this application (122), and the projected manufacture
of support plates in chromium stainless steel was not followed up, as
far as we know.

Since that time, one year tests on a miniature steam

generator operating with contaminated water (3ppm chloride on the

average) have shown that, indeed, AISI 405 and 409 steels cause the
same denting phenomenon.
This example is an illustration of a correct forecast made by
applying knowledge acquired about localized corrosion theory.
3.4 INHIBITORS OF LOCALIZED CORROSION
The localized corrosion process naturally suggests a certain number
of preventive methods, and notably the use of inhibitors. Three
groups of inhibitors can be envisaged in this case :

88

- oxidizing i n h i b i t o r s which would c o n s t a n t l y c r e a t e a perfect pass i v a t i o n of the metal surface and thus e l i m i n a t e t r i g g e r i n g off of
l o c a l i z e d corrosion (at l e a s t in the absence of mechanical degradation) (for example, for

s t e e l s , phosphochromic coatings and pastes

with an oxidizing phosphatation a c t i o n ) .

- consumable reducing i n h i b i t o r s which, by means of a c a r e f u l l y monit o r e d a p p l i c a t i o n , would m a i n t a i n t h e p o t e n t i a l of t h e e x t e r n a l
s u r f a c e of t h e metal below t h e " p o t e n t i a l of p r o t e c t i o n a g a i n s t
propagation of l o c a l i z e d corrosion". We are not aware of the use of
t h i s type of i n h i b i t o r .
- i n h i b i t o r s s p e c i f i c t o l o c a l i z e d c o r r o s i o n which would d i f f u s e
towards t h e c o r r o d i n g c a v i t i e s , which by and l a r g e a r e a c i d i c ,
reducing, r i c h in m e t a l l i c ions, and most often in c h l o r i d e .
The r o l e of t h e s e i n h i b i t o r s would be e i t h e r t o d e l a y or p r e v e n t
local acidification,

or to promote r e p a s s i v a t i o n of the metal in

t h e ' c a v i t y , or to d e c r e a s e t h e a f f i n i t y or t h e k i n e t i c s of t h e
corrosion reactions in the c a v i t y .
This t h i r d group of i n h i b i t o r s a r e s t i l l being s t u d i e d , and i n t h e
most developed cases they have reached the development stage (117) :
t h e main q u e s t i o n i s i d e n t i f y i n g

and o p t i m i z i n g t h e

inhibiting

s u b s t a n c e s t h a t a r e c a p a b l e of d i f f u s i n g p r e f e r e n t i a l l y from t h e
e x t e r n a l s o l u t i o n towards the i n t e r i o r of corrosion p i t s , c r e v i c e s or
c r a c k s , and which f u l f i l l

one or s e v e r a l of t h e r o l e s mentioned

above.
There a r e numerous a p p l i c a t i o n s of t h i s p r i n c i p l e . This i s a f i e l d
where current research i s developing p a t e n t a b l e products, and one can
predict t h a t new ideas for a p p l i c a t i o n s may give the s i m i l a r r e s u l t s
in a l a r g e r number of cases.
Another example concerns a serious i n d u s t r i a l problem which affected
s t e e l pipes carrying pressurized gas. This i s a l s o a case of s t r e s s

89

c o r r o s i o n c r a c k i n g : i n t e r g r a n u l a r c r a c k s o c c u r r e d s t a r t i n g below t h e
compression s t a t i o n s of t h e o u t s i d e s u r f a c e

of b u r i e d p i p e s covered

with c o a l - t a r or a s p h a l t and p r o t e c t e d c a t h o d i c a l l y . The compression

of t h e g a s c a u s e s h e a t up t o 35 t o 60C w h i c h s e e m i n g l y f a v o u r s
cconcentration

of d i s s o l v e d

species,

creating agressive

the

conditions.

The e l e m e n t s c o l l e c t e d near t h e c r a c k s under t h e c o v e r i n g a r e F e 3 0 4 ,

FeC0, NaC0 and NaHC0; t h e c a r b o n a c e o u s e l e m e n t s no doubt

result

from t h e d e g r a d a t i o n of t h e c o a l - t a r . Very e x t e n s i v e t e s t i n g has show

that,

f o r e n v i r o n m e n t s of t h i s t y p e ,

potential

values,

intergranular

cracking

reproduced (57). Although i t i s s t i l l

values

of

the p o t e n t i a l

at

and f o r s p e c i f i c
of

difficult

the crack-tips

electrode

steels

could

be

to determine the

and u n d e r

the

loose

c o v e r i n g , and what they become c o n s i d e r i n g t h e e f f e c t of t h e c a t h o d i c

p r o t e c t i o n , i t may be e a s i e r t o d e v e l o p s p e c i f i c i n h i b i t o r s t o be
incorporated

i n or under t h e c o v e r i n g which would impose v a l u e s of

p o t e n t i a l on t h i s m e t a l a t w h i c h c r a c k i n g c a n n o t o c c u r . T h i s i s a
l o n g - a w a i t e d a p p l i c a t i o n of t h e n o t i o n of a s p e c i f i c i n h i b i t o r t o
combat p r e c i s e s t r e s s c o r r o s i o n

phenomena.

3 . 5 STEELS RESISTING LOCALIZED CORROSION

S t a i n l e s s s t e e l s c o n t a i n i n g molybdenum have l o n g been r e c o g n i z e d
more r e s i s t a n t

as

t o l o c a l i z e d c o r r o s i o n . The e x a c t r o l e of molybdenum

i s s t i l l open t o some d e b a t e , b u t i t seems more and more c l e a r

the

t h e molybdenum forms a p r o t e c t i v e f i l m of M0O2 under p o t e n t i a l and pH

c o n d i t i o n s which e x i s t s p e c i f i c a l l y

in localized corrosion

crevices

on s t a i n l e s s s t e e l s (44, 123). I n t h e p r e s e n c e of d i s s o l v e d i r o n ,

as

i s t h e c a s e i n a c t i v e c o r r o s i o n c r e v i c e s , molybdenum, i r o n and oxygen

form an i r o n m o l y b d a t e w h i c h h a s a p a s s i v a t i n g r o l e u n d e r a wide
range of p o t e n t i a l and pH c o n d i t i o n s (124, 44). T h i s well-known

role

of molybdenum i s now b e t t e r u n d e r s t o o d , g i v e n t h e k n o w l e d g e of i t s
b e h a v i o u r i n t h e s p e c i f i c e l e c t r o c h e m i c a l c o n d i t i o n s of c r e v i c e s , and
one c a n

easily

s e e how i t

has a

very

favourable

role

against

p r o p a g a t i o n of l o c a l i z e d c o r r o s i o n . S i m i l a r r e a s o n i n g , a l s o based on
t h e a n a l y s i s of b e h a v i o u r s i n a c i d and r e d u c i n g s o l u t i o n s ,
exist

in the "occluded

corrosion

c e l l s " in s t e e l s ,

which

forecast

or

90 -

explain similar effects

of c o p p e r ,

t u n g s t e n and s i l i c i u m a l l o y e d

to

s t a i n l e s s s t e e l s , and some r e s e a r c h i s now t a k i n g p l a c e t o i l l u s t r a t e

t h e s e d e m o n s t r a t i o n s . T h i s r e s e a r c h has i m p o r t a n t i n d u s t r i a l

value :

i n t h e p r e s e n t and t h e f u t u r e i t h a s d e v e l o p e d s t a i n l e s s s t e e l compos i t i o n s with c h a r a c t e r i t i c performances and a d v a n t a g e s .

A good e x a m p l e of t h e i n d u s t r i a l d e v e l o p m e n t of s t a i n l e s s

steels

based p a r t l y on e l e c t r o c h e m i c a l l o c a l i z e d c o r r o s i o n s t u d i e s and t e s t s
h a s come from t h e C r e u s o t - L o i r e r e s e a r c h l a b o r a t o r i e s

(currently

Unirec) : a s e r i e s of a u s t e n i t i c and a u s t e n o - f e r r i t i c s t e e l s

alloyed

w i t h molybdenum and copper h a v e been d e v e l o p e d (not j u s t by C r e u s o t L o i r e , i n Sweden and i n West Germany a l s o ) and, t h e i m p o r t a n t a s p e c t
is

that

their

behaviour

electrochemical

tests

has

(67),

been

clearly

which w i l l

help

illustrated

by

t h e u s e r s make an

informed c h o i c e among v a r i o u s s t e e l s . F i g u r e 34 shows an e x t r e m e l y

s i m p l e t e s t t h a t , h o w e v e r , h a s m a j o r s i g n i f i c a n c e f o r a s e r i e s of
f e r r i t i c , a u s t e n i t i c and a u s t e n o - f e r r i t i c s t a i n l e s s s t e e l s i n n a t u r a l
sea water

the

steels

which r e s i s t

t h e a p p e a r a n c e of

pitting

c o r r o s i o n b e s t a r e t h o s e f o r which t h e p o t e n t i a l c u r v e a s a

function

of exposure time does not show a s h a r p d e c l i n e .

3.6 DEFORMATION INDUCED CRACKING CORROSION IN NUCLEAR REACTORS
One v e r y s e r i o u s c r a c k i n g c o r r o s i o n problem appeared i n t h e w e l d s i n
304 s t a i n l e s s
cracks,

steel

pipes in b o i l i n g

i n 1974, a f f e c t e d

water r e a c t o r s .

The

first

s e r v i c e of b y - p a s s p i p e s , b u t l a t e r on

c r a c k s a l s o appeared i n t h e main r e t u r n p i p e s f o r cooled w a t e r , which

c o u l d c r e a t e a LOCA t y p e ( l o s s of c o o l a n t ) a c c i d e n t s . The c r a c k i n g s
were i n t e r g r a n u l a r and s t a r t e d off a t t h e i n s i d e s u r f a c e ,
which was a f f e c t e d

i n a zone

t h e r m a l l y by w e l d s . F o r e c o n o m i c r e a s o n s ,

s t e e l s used f o r t h e s e p i p e s d i d n o t h a v e a p a r t i c u l a r l y
c o n t e n t and they had been s e n s i t i z e d a g r e a t d e a l ,
s t r e s s e s t h a t were sometimes above t h e e l a s t i c

low carbon

and s u b m i t t e d

limit.

the

This

to

problem

was a t t h e o r i g i n of a m a j o r r e s e a r c h e f f o r t on t h e i n s t i g a t i o n of
t h e E l e c t r i c Power R e s e a r c h I n s t i t u t e

EPRI i n t h e U n i t e d S t a t e s .

R e s e a r c h showed t h a t t h e r e i s a r e l a t i o n s h i p b e t w e e n t h e oxygen

91 -

c o n t e n t i n t h e r e l a t i v e l y pure r e a c t o r water ( C I - <200 ppb), t h e

t e m p e r a t u r e and t h e a p p e a r a n c e of i n t e r g r a n u l a r s t r e s s c o r r o s i o n
c r a c k s . In r e a l i t y , under t h e c l a s s i c c o n d i t i o n s for s t a r t i n g BWR
r e a c t o r s , t h e r e a r e dangerous combinations of oxygen c o n t e n t and
t e m p e r a t u r e which a r e r e p r e s e n t e d i n f i g u r e 35. The

relationship

between d i s s o l v e d oxygen and the e l e c t r o d e p o t e n t i a l of 304 s t a i n l e s s

s t e e l has been shown, and the influence of p o t e n t i a l on the r i s k of
c r a c k i n g a p p e a r s once a g a i n

t o comply with t h e mechanisms of

l o c a l i z e d c o r r o s i o n w i t h a m o d i f i c a t i o n i n t h e environment of t h e
c r a c k s . I t c u r r e n t l y seems t h a t t h e r e i s a c r i t i c a l p o t e n t i a l for
i n t e r g r a n u l a r s t r e s s corrosion of s e n s i t i z e d s t a i n l e s s s t e e l s in the
water of t h e BWR r e a c t o r s and t h a t t h e v a l u e of t h i s

critical

p o t e n t i a l i s located around -0.35 Vg^g (125).

As a r e s u l t of these s t u d i e s , since 1978 the s t a r t i n g - u p procedures
in BWR have changed; a degassing stage has been added at the time of
s t a r t - o f f t o a v o i d t h e dangerous zone shown i n f i g u r e 35. P r o g r e s s
was put i n t o p r a c t i c e h e r e t h a n k s t o s t u d i e s of t h e phenomena, and
the c l e a r and obvious r o l e of the electrochemical parameters which
rapidly

convinced

power p l a n t

operators.

Measuring

electrode

p o t e n t i a l once again appeared here as a precise and r e l i a b l e means of

supervising the r i s k of s t r e s s corrosion.
Other measures were t a k e n t o minimize t h e problem on IGSCC i n 304
s t e e l i n the BWR r e a c t o r s : use of other m a t e r i a l s (AISI 304L, 316L,
347, 347L or 316LN or 347LN s t a i n l e s s s t e e l s where L means "low
carbon c o n t e n t " and N "with n i t r o g e n " ) ,

thermal treatment

for

s o l u t i o n annealing a f t e r welding when p o s s i b l e ( t h i s must be done in

the workshop), the l a s t stage of e x t e r i o r welding on the pipe cooled
from t h e i n s i d e with i c e w a t e r ("heat s i n k w e l d i n g " ) , or s t r e s s
r e l i e f by i n d u c t i v e heating of the e x t e r n a l surface while the inside
i s being cooled ("induction heat s t r e s s improvement").
A second s e r i o u s problem i s t h e c r a c k i n g of low a l l o y s t e e l under
dynamic s t r e s s i n pure w a t e r a t high t e m p e r a t u r e . These
corrosion and fatigue corrosion phenomena affect

stress

reactor tanks with

92

d e f e c t s i n t h e s t a i n l e s s s t e e l c l a d d i n g , make-up water i n j e c t i o n
pipes and t u r b i n e d i s c s .

An i n t e r n a t i o n a l group

(International

Cyclic Crack Growth Rate) was developed to conduct fatigue corrosion

t e s t s and t e s t s on corrosion by slow and constant deformation (CERT)
in various l a b o r a t o r i e s and to compare the r e s u l t s (126). These t e s t s
show the influence of a c e r t a i n number of v a r i a b l e s on the phenomenon
: the s u l f u r content of the s t e e l , the oxygen and sulfur

derivative

content of the water, the v e l o c i t y of c i r c u l a t i o n of the water. There

is also a c r i t i c a l

p o t e n t i a l under which cracking i s not observed,

and i t s v a l u e i s l o c a t e d around - 0.25 V 3 ^ (127, 128). These

cracking phenomena in slow c y c l i c a l deformation conditions are cur
r e n t l y preoccupying because the dynamic deformations in the bottom of
the cracks may create l o c a l s t r e s s e s that exceed the e l a s t i c

limit,

and d e f o r m a t i o n s and v e l o c i t i e s of deformation t h a t exceed t h o s e

e n v i s a g e d a t t h e d e s i g n s t a g e . For t h i s r e a s o n , t h e slow dynamic
s t r e s s e s associated with s t a r t - o f f and shut-down periods must be very
c a r e f u l l y attended.
Remarkable p r o g r e s s i s c u r r e n t l y t a k i n g p l a c e , on t h e one hand i n
rupture mechanics and p a r t i c u l a r l y in the c a l c u l a t i o n of s t r e s s e s and
l o c a l deformations,

and on t h e o t h e r hand i n t h e measurement i f

p o s s i b l e i n s i t u of t h e e l e c t r o c h e m i c a l c o n d i t i o n s in t h e c r a c k s
(129) : t e s t s a r e being done t o measure e l e c t r o d e p o t e n t i a l i n s i d e
the cracks and a t various p l a c e s along the cracks in the laboratory,
and to t r y to measure t h e m i c r o c h e m i s t r y a t t h e bottom of t h e c r a c k
by means of Raman s c a t t e r i n g s p e c t r o s c o p y u s i n g o p t i c f i b e r s i n a
heat and pressure r e s i s t a n t c a p i l l a r y (130). As indicated in Chapter
2.6, the cracking mechanisms by anodic d i s s o l u t i o n and/or by hydrogen
embrittlement seemingly a c t with r e s p e c t i v e weights, which are

af

f e c t e d by t h e s t r e s s e s n e a r t h e c r a c k - t i p , by t h e v e l o c i t i e s of
baring new surfaces,

by the eventual v e l o c i t y of repassivation,

the chemistry in the c r a c k - t i p ,

which i n t u r n i s i n f l u e n c e d

by
by

diffusion phenomena, by an eventual formation of hydrogen bubbles and

by a "pumping action" exercised at the opening of the cracks subject
to c y c l i c a l s t r e s s . A l l of these aspects play a part in the cracking
induced by dynamic and c y c l i c a l

s t r e s s e s . The approach t h a t

is

93-

currently the most often used, both in rupture mechanics and in

electrochemistry, was inspired by the method used in monotonic stress
corrosion; this approach may well continue to shed new light on these
new problems.
3.7 EVALUATION OF SENSITIZATION TO INTERGRANULAR CORROSION
In Chapter 2.8 we saw how the mechanisms and empiric tests of intergranular corrosion on Fe-Cr and sensitized FeCr-Ni alloys could be
understood using electrochemical studies. As a logical consequence,
electrochemical methods of appreciation of the degree of sensitization to this intergranual corrosion have been developed. This electrochemical approach to intergranular corrosion was initiated by
CARIUS and EDELEANU (109), by CLERBOIS, CLERBOIS and MASSART in 1959
(110), and was then considerably developed by CIHAL in 1973 (131),
during works done in collaboration with DESESTRET in the CreusotLoire laboratories, and with NOVAK (132). Shortly thereafter, the
General Electric company saw the major intrest of this approach for
studying intergranular stress corrosion of sensitized stainless steel
pipes and the method called "EPR" (Electrochemical Potentiokinetic
Reactivation) was described by CLARKE et al in 1977 (133). The method
works as follows : the stainless steel surface to be tested is put
into contact with a solution of 0.5 M H 2 S0 4 + 0.01 M KNCS (thiocyanate) at 30C in a nitrogen atmosphere. If the free potential is
not lower than the equilibrium potential ffVlLj, the stainless steel
should be reactivated. Afterwards, the surface is passivated at + 200
mVgtg for two minutes, and then polarized at decreasing potentials at
a speed of 6 V/H. Charge Q, i.e. the integral of the current from +
200 niVghe to the potential at which the current changes direction is
measured near the initial free potential (figure 36). The maximum
current at the peak of reactivation i m a x (or pH on figure 36) and the
Flade potential (Eg on figure 36), at which reactivation on the
passive surface appears, are measured. The result is given by the
charge expressed as a ratio of the surface of the grain boundaries,
Pa in Cb/cm . The test should be completed with a metal lographic
photography enlarged 100 times.

94-

By comparing t h e p o s s i b i l i t i e s of t h i s EPR t e s t method to t h o s e of

the empiric methods described in the ASTM H A262 - p r a c t i c e 1), both
are s e n s i t i v e and more or l e s s q u a n t i t a t i v e in the case of l i t t l e or
medium sensitized s t e e l s . In the case of l a r g e s e n s i t i z a t i o n ,
methods " s a t u r a t e " , and t h e method u s i n g copper s u l f a t e -

these

sulfuric

acid - m e t a l l i c copper (ASTM A262 - p r a c t i c e 2) i s more s u i t a b l e .

For major i n d u s t r i a l problems which have a r i s e n due to i n t e r g r a n u l a r
c o r r o s i o n of s e n s i t i z e d 304 s t e e l ,

t h e EPR method i s t h e most

s e n s i t i v e and has the a d d i t i o n a l advantage of being q u a n t i t a t i v e and

not d e s t r u c t i v e .

I t i s a p p l i c a b l e on i n s t a l l e d

pipes,

using a

removable p o l a r i z a t i o n c e l l . Current developments of t h i s method tend

t o m i n i a t u r i z e t h e c e l l , t o be a b l e t o s e p a r a t e l y i n v e s t i g a t e t h e
various p a r t s of the zone thermally affected by welding.
This represents a good example of the d i r e c t use of electrochemistry
for s t u d y i n g , d e t e c t i n g and a s s e s s i n g phenomena of an u n d e n i a b l e
electrochemical nature.

95

4 . RESEARCH REQUIRED
As Roberto PIONTELLI s a i d d u r i n g t h e t h i r d " S t e e l Congress" h e l d
Luxembourg

in

1968 u n d e r

corrosion

phenomena

are

the auspices

of

essentially

the

in

ECSC ( 1 3 4 ) ,

"the

electrochemical,

and

e l e c t r o c h e m i s t r y must p r o v i d e t h e l i g h t by which we seek",

needless

t o s a y , w i t h t h e a i d of o t h e r d i s c i p l i n e s , among w h i c h i s p h y s i c a l
m e t a l l u r g y . D e s p i t e t h e p r o g r e s s made t h a n k s t o p i o n e e r works done by
U l i c k R. EVANS and C a r l WAGNER, t h e r e s t i l l

remains a g r e a t d e a l

be done t o d e v e l o p t h e s c i e n c e of c o r r o s i o n t o t h e f u l l

to

and so t h a t

i t s r e s u l t s a r e f u l l y a p p l i e d i n i n d u s t r i a l p r a c t i c e . This i m p l i e s a
p e r f e c t k n o w l e d g e of t h e m a g n i f i c e n t t o o l w h i c h i s t h e " e l e c t r o d e
p o t e n t i a l " in

the four

s t a g e s of f u n d a m e n t a l

and

techniques.

With

research,

regard

to

applied

research,

education

localized

corrosion,

t h i s means a p e r f e c t knowledge of t h e phenomena t h a t t a k e

p l a c e i n t h e "occluded c o r r o s i o n c e l l s " .
We f e e l t h a t d e v e l o p i n g r e s e a r c h a l o n g t h e s e l i n e s , and implementing
c u r r e n t and f u t u r e r e s u l t s i n i n d u s t r y s h o u l d be a p r i o r i t y ,
completely

master

corrosion,

and

intergranular

the

b a n e of

particularly

the

various

stress

forms

corrosion

of

so a s t o
localized

cracking

and

corrosion.

Proposed actions are :

- laboratory research,
- research in pilot installations,
- research on industrial structures,
- seminary sessions during which all of the results obtained will be
discussed.
4.1 LABORATORY RESEARCH
We suggest that this research' be particularly

devoted to the

following points which we feel are of obvious interest, and for which
success can be considered highly probably. It is of course understood
that the recommendations which follow, which stem from the neces-

96

sarily incomplete information we possess, can in no way be considered

as a hindrance to the imagination and creativity of research scientists. We also recommend that coordinated experimental campaigns with
comparison of results (sort of "round robin tests"), be organized on
specific subjects using specific methods, particularly in order to
promote progress where the validity of the methods and the ability of
reproducing the results might still be doubtful.
4.1.1. Determination of general conditions of immunity, generalized
corrosion, pitting corrosion, perfect passivity

and imperfect

passivity of alloy steels and their mainconstituants

With the help of potentiokinetic and potentiostatic polarization
experiments similar to those the results of which are presented in
figures 5a and 5b, one can go on

to determine experimental poten-

tial/pH diagrams in order to improve the approximate schemas presented in figures 8a, b, c, d concerning the real conditions of corrosion and non-corrosion of metals (including the potentials of
immunity, passivity, pitting and protection against propagation of
localized corrosion).
New diagrams will

be drawn up for other steels for which the

behaviour in industrial practice has proven to be particularly good

or particularly bad.
One could proceed in the same way for the main constituants of these
steels : chromium, nickel, molybdenum, niobium ...
4.1.2. Study of natural "occluded corrosion cells"
One should try to obtain as much information as possible on the
chemical and electrochemical characteristics of natural localized
corrosion cavities ('pits, crevices, cracks ...) which are formed and
developed
structures.

during

laboratory

experiments and/or on industrial

- 97

The e x p e r i m e n t a l

methods which c o u l d be c o n s i d e r e d a r e : deep

f r e e z i n g the s o l u t i o n s and doing l o c a l a n a l y s i s w h i l e u n f r e e z i n g ,

m i c r o e l e c t r o d e s , s p e c i f i c i n d i c a t o r s , Raman spectroscopy... Any new
v a l i d , v e r i f i a b l e method would be welcome.
We want to draw a t t e n t i o n to t h e danger t h e r e might be in modifying
the c h a r a c t e r i s t i c s of corrosion c a v i t i e s by trying to measure them
( c o n t a m i n a t i o n by e l e c t r o d e s i p h o n s , a c c e s s of a i r to the c a v i t i e s
. . . ) . Great c a r e must be taken and i t

is desirable

to have

the

p o s s i b i l i t i e s of verifying the r e s u l t s by cross-checking. This kind

of experiment must r e l a t e to a l l material/environment couples where
l o c a l i z e d c o r r o s i o n o c c u r s . However, one should g i v e p r i o r i t y to
s t a i n l e s s s t e e l s ( c o n t a i n i n g Cu, Cr, Mo, N, Ni, S i , W...), t i t a n i u m
a l l o y s , aluminium a l l o y s and some metals with amphoterous hydroxide
(Al,

Zn, Z r . . . ) , t o l o o k f o r

the

local

alkaline

hydrolysis

conditions.
We recommend

gathering,

as much i n f o r m a t i o n

as p o s s i b l e

from

experiments on n a t u r a l l o c a l i z e d corrosion (formed in the laboratory,

and even more on the production l i n e ) which would make i t p o s s i b l e to
e s t a b l i s h a r e l a t i o n s h i p between e x t e r i o r c o n d i t i o n s

(aeration,

hydrodynamics, composition, conductivity, e l e c t r o d e potential...) and

characteristics

i n s i d e the l o c a l corrosion c a v i t i e s . Various shapes

and m a t e r i a l / e n v i r o n m e n t c o u p l e s s h o u l d be c o n s i d e r e d for t h e s e
cavities

(pits,

crevices,

cracks...).

Given t h e d i f f i c u l t y

in

c a r r y i n g out e x p e r i m e n t s , i t would be j u d i c i o u s to o r g a n i z e c r o s s checking t e s t s or a "round robin" system between various teams, using
the systems and the methods agreed upon.
4.1.3. Study of simulated "occluded corrosion c e l l s "
As we a r e c o n s c i o u s of t h e d i f f i c u l t i e s

i n v o l v e d in t h e s t u d i e s

mentioned in point 4.1.2., we suggest pursuing the same objectives by

using simulated l o c a l i z e d corrosion c e l l s as they are represented in
figures 9 and 11 (section 2.2.1.6.) i n c l u d i n g two compartments (with

98

very v a r i a b l e shapes) in d i f f e r e n t i a t e d

s o l u t i o n s (highly

variable

composition, a e r a t i o n , c o n d u c t i v i t y ) . A l l i n t e r i o r s u r f a c e s of the
r e a c t i o n s c a v i t i e s (bottom, s i d e , opening...) should be s t u d i e d on
the simulation assemblies.
The i n f l u e n c e

of a n o d i c or c a t h o d i c e x t e r n a l

polarisation

on

e l e c t r o d e p o t e n t i a l s of the e x t e r n a l and i n t e r n a l surfaces and on the

d e n s i t i e s of a n o d i c and c a t h o d i c c u r r e n t c i r c u l a t i n g between these
two s u r f a c e s , on t h e d i f f e r e n c e in p o t e n t i a l between
reference

electrodes

identical

p l a c e d between t h e e x t e r n a l and

internal

s o l u t i o n s ( d i f f u s i o n p o t e n t i a l and ohmic drop) and on pH and the

chemical c o m p o s i t i o n of t h e s o l u t i o n c o n t a i n e d i n t h e s i m u l a t e d
o.c.c

(see

figures

10 and

12) s h o u l d

be s t u d i e d .

One

p a r t i c u l a r l y n o t e t h e v a l u e s of e x t e r n a l and i n t e r n a l

should

electrode

p o t e n t i a l s corresponding to a zero value for the current c i r c u l a t i n g

between t h e two s u r f a c e s , and to t h e s t a t e of immunity of t h e m e t a l
or a l l o y i n t h e o . c . c . ( p o t e n t i a l

of p r o t e c t i o n a g a i n s t

the

propagation of l o c a l i z e d corrosion). The conditions in which hydrogen

e v o l u t i o n and corrosion occurs (or does not occur) in the o.c.c. and
at what speeds should be i d e n t i f i e d .
To g i v e a q u a n t i t a t i v e e s t i m a t e of the chances of s u c c e s s
forecasts based on these kinds of experiments,

for

the studies proposed

h e r e w i l l be c a r r i e d out on samples of m e t a l s and a l l o y s behaving

d i f f e r e n t l y , and notably on m e t a l l u r g i c a l l y very clean metals, and on
metals known for t h e i r r e s i s t a n c e to l o c a l i z e d corrosion.
In order to explain the mechanism of l o c a l i z e d corrosion t e s t s based
on n i t r a t e s o l u t i o n s , t e s t s should take place using n i t r a t e s o l u t i o n s
as an e x t e r n a l s o l u t i o n ,

and then examine notably whether nitrogen

and/or nitrogen oxide gasses are given off in the i n t e r n a l s o l u t i o n .

4.1.4 Study of a r t i f i c i a l "occluded corrosion c e l l s "
Given the time required to develop the simulated o.c.c. mentioned in
section 3.1.3. and the small q u a n t i t i e s of s o l u t i o n s formed in these

99 -

cells, one should try to create similar solutions artificially by

simple dissolution of chemical products in pure water (or in other
aqueous solutions of practical interest, like sea water), in the
presence of powder or shavings of the metal or alloy under study,
using the method indicated in section 2.2.1.6.I.e. We should recall
that this method makes it possible to obtain these solutions very
rapidly in whatever quantity desired, which makes all chemical and
electrochemical studies relating to these solutions much easier.
In the case of localized corrosion in the presence of chloride, these
chemical products will be ferrous chloride FeCl2.4H20 in the case of
iron, and copper chloride CuCl in the case of copper. In the case of
steels alloyed to Cr, to Cr-Ni or to Cr-Ni-Mo these chemical products
will be mixtures of Fe, Cr, Ni and Mo chlorides (or basic
chlorides) in which the proportions of the various metals will be the
same as those existing in the steel.
By carrying out chemical and electrochemical analyses similar to
those done by L. SATHLER with regard to iron one could establish, for
iron and for alloy steels, precise diagrams analogous to the
provisional schematic representations given for iron and for 12% Cr
steel in figures 16a and 16b.
These diagrams would relate to all substances existing in the metal
or alloy (particularly including those existing in grain boundaries).
If they are drawn up as a complement to other electrochemical and
chemical examinations, they should give total understanding of all
phenomena linked to all forms of localized corrosion.
During

these

studies,

one should

notably

try to specify

the

particular behaviour of components or classical inclusions in

materials: carbides, nitrides, sulfides, intermetallic compounds. One
will see if the transformations in methane CH 4 , hydrogen sulphide
H 2 S, nitrogen N'2 and nitrogen oxides NoO and NO are possible under
the conditions of localized corrosion cavities. The role of nitrogen
in stainless steel will be studied.

100 -

Particularly with regard to stress corrosion cracking, one could make

wider use of the PARKINS method which proceeds by slow deformation
under controlled' external potential, and it should be verified
whether the results of this method are compatible with the results of
these diagrams, and with diagrams drawn up using the method proposed
in figure 31. Of course, any conclusions which could

lead to

industrial progress, should be emphasized. In this case as well,

which is extremely important, it would be prudent to consider some
very different systems at low and high temperatures, and to study
them in a coordinated

fashion within several research teams.

4.1.5. Diffusion phenomena in occluded corrosion cells o.c.c.

One would try to give a quantitative value to the intensity of the
exchanges (current, charge, mass...) which occur between the interior
and the exterior of localized corrosion cavities. It would be
interesting to know how the diffusion of ions, which may be complex
and have known mobility, takes place towards the interior and the
exterior. Ions which could have an inhibiting effect on localized
corrosion should be Included.
4.1.6. Thermodynamic data
Thermodynamic and physical chemical data regarding complex ions

in

s o l u t i o n must be more numerous and r e l i a b l e , p a r t i c u l a r l y a t high

temperature; there i s a great need for these. T h e o r e t i c a l t o o l s must
a l s o be found making i t

possible

t o study c o n c e n t r a t e d

aqueous

s o l u t i o n s and mixed s a l t s of one or s e v e r a l metals.

4.1.7. I n d u s t r i a l information and experimental
We v e r y

much

hope

to

be

able

to

precautions

gather

precise

data

on

e l e c t r o c h e m i c a l behaviour of i n d u s t r i a l s t r u c t u r e s : heat exchangers

in operation and a t r e s t , b o i l e r s , concentrators, pumps, d e s a l i n a t i o n
i n s t a l l a t i o n s . We would a l s o l i k e to be a b l e to c a r e f u l l y

measure

101 -

e l e c t r o d e p o t e n t i a l s , pH and chloride contents on p i l o t i n s t a l l a t i o n s

equipped with c e l l s , for simulation of l o c a l i z e d corrosion and having
i n s t r u m e n t s to f o l l o w the i n i t i a t i o n and development of n a t u r a l
localized corrosion.
We i n s i s t once again on the fact that " l o c a l i z e d corrosion" implies a
" l o c a l modification of the milieu". Any study of a l l o y s ,

inhibitors,

c o v e r i n g s , . . . m u s t a l s o and above a l l be done under t h e s e modified

conditions, once l o c a l i z e d corrosion i s suspected. One should

also

notably study changes in the conditions modified by the a l l o y ,

inhi-

b i t o r , p i g m e n t , . . . and t h e k i n e t i c s of t h e r e a c t i o n s i n t h e s e modified conditions should be q u a n t i t a t i v e l y assessed.

4.2. WORKS IN PILOT INSTALLATIONSA few r e s u l t s l i k e l y to lead to important t e c h n i c a l progress should
be chosen among t h e r e s u l t s of l a b o r a t o r y r e s e a r c h , mentioned in
s e c t i o n 4 . 1 . , and p i l o t i n s t a l l a t i o n s s h o u l d be s e t up i n o r d e r to
experiment the p r a c t i c a l

v a l i d i t y of t h i s p r o g r e s s on a semi-

i n d u s t r i a l s c a l e . These p i l o t i n s t a l l a t i o n s w i l l be equipped in such

a way as to enable measurement and recording of v a l u e s of e l e c t r o d e
p o t e n t i a l s and other useful numerical data. These i n s t a l l a t i o n s would
be c a l l e d upon to r e a l i s e , ad libitum, favourable and defavourable
v a l u e s of t h i s p o t e n t i a l , and t h u s t o v e r i f y t h e v a l i d i t y of t h e
criteria

for good or bad behaviour e s t a b l i s h e d in the

P a r t i c u l a r a t t e n t i o n should be paid to v e r i f y i n g

the

laboratory.
practical

v a l i d i t y of t h e " p o t e n t i a l of p r o t e c t i o n a g a i n s t p r o p a g a t i o n of
l o c a l i z e d c o r r o s i o n " concept

and to t h e p o s s i b i l i t y of measuring

this potential industrially.

Also care should be taken to e s t a b l i s h the influence of shut-down or
s t a r t - u p periods of the i n s t a l l a t i o n s , as w e l l as of the operating
i n c i d e n t s on t h e b e h a v i o u r of t h e s e i n s t a l l a t i o n s with r e g a r d to
corrosion.

-102

4.3. WORKS ON INDUSTRIAL STRUCTURES

Technical procedures which have been judged valid would then be

implemented on industrial installations, which have been equipped
with regulation and control devices with recording, which would be
useful to properly carry out the procedure.

One should also verify the conditions of good and bad behaviour of
the installation, by paying particular attention to the influence of
shut-down periods and start-up periods, and to operating incidents.

4.4. SEMINARY SESSIONS, RECOMMENDATIONS, PUBLICATIONS

The result of research done in laboratories, on pilot

and industrial structures should be disclosed
seminary

sessions. After

installations

and discussed

these seminaries, recommendations

in
and

publications should be brought out which w i l l propagate correct

industrial implementation of the results of all of the research.

ACKNOWLEDGEMENTS

Mr. Antoine POURBAIX has made a very large contribution to setting up

this entire report, and particularly with regard to the economic and
technical parts (sections 1, 2.2.2 to 2.10 and section 3).

We want to thank Mr. E. GALVELE, Mr. E. HEINTZ

and Mr. M.O. SPEIDEL

who transmitted recent and very useful scientific information to us,

and Mrs. R. SCHERER and Miss M.F. TONDREAU who have taken care of the
presentation and the composition of the french report.

This study has been made pursuant to contract n ECI-1273-B-7240-84B

of the Commission of the European Communities (Directorate General of
Science, Research and Development, DG XII B 2 ) .

-103

INDEX OF TABLES

Table I

: Indicative and comparative prices (June 1985) of some

materials used for their resistance to corrosion

Table II

: Apparent annual consumption in the EEC of materials

used for their resistance to corrosion

Table III : A few characteristics of some methods of analysis

surfaces
Table IV

52

: Some combinations of materials and environments in

which stress corrosion was observed

66

105-

INDEX OF FIGURES
Figure 1

Measurement of electrode potential

123

Figure 2

Metals ranked in order of their thermodynamic nobility,

with indication of the areas of corrosion, immunity and
passivation.

124
125

Figure 3

Types of polarization curves

Figure 4

Theoretical conditions of corrosion, immunity and passivation of iron at 25 C

a) assuming that Fe 0. and Fe 0, are both protective
b) assuming that Fe0 is protective and Fe 0, is not
protective

Figure 5

126

Behaviour of iron in the presence of chloride-free aqueous

solutions at 25 C.
,
a) polarization curves
b) experimental diagram of corrosion, immunity and passivation

Figure 6

126

Electrocheminal behaviour of iron in the presence of water

at 25 C.
a) reduction velocities of water into hydrogen and
oxidation velocities of water into oxygen on an
iron surface
b) corrosion velocities of iron
c) corrosion cf iron with hydrogen evolution

Figure 7

127

Behaviour of iron in the presence of aqueous solutions

10 -2 molar in chloride i.e. 0.35 g Cl/1. at 25 C
a) polarization curves
b) experimental diagram of general corrosion, immunity,
pitting corrosion, imperfect passivity and perfect
passivity

Figure 8

Experimental areas
corrosion, perfect
iron and steels, in
(3.5 g Cl/1. at 25

128

of general corrosion, immunity, pitting

passivity and imperfect passivity of
the presenceof a10 - 1molar chloride solution
C)

a) iron and non alloyed steels

b) chromium steel AISI 410 (diagram)
c) chromium-nickel steel AISI 304

Figure 9

(diagram)

d) chromium-nickel-molybdenum steel AISI 316 (diagram)

129

Device for the study of crevice corrosion

(j. Van Muy 1 der (40, 41)).

130

106

Figure 10 : Influence of
slow external cathodic polarization on the pH
and electrode potential conditions inside a corrosion
crevice (mild steel in an aerated solution 0.001 M NaOH
and 0.001 M NaCl), (J. Van Muylder).

1 3(

Figure 11 : Device for the study of localized corrosion (Antoine

Pourbaix (39)).

13'

Figure 12 : Influence of a rapid external cathodic polarization on the

electrochemical behaviour of mild steel outside and inside
a corrosion crevice (external pH = 9.5, internal pH = 5.5)
(Antoine Pourbaix (39))

13'

Figure 13 : variations in solutions obtained by adding increasing

quantities of iron chloride to pure, free water
in the presence of iron powder
a) relation between the pH and the concentration of
dissolved iron
b) relation between the pH and the electrode potential
of iron
Figure 14 : Polarization curves for iron in the presence of a stirred
solution saturated with iron chloride (pH = 3.8, 25 C)
( by L. Sathler (42, 43))

13

13:

Figure 15 : Experimental potential-pH diagrams relating to the electrochemical behaviour of iron in the presence of iron chloride
at 25 C (schemas)
a) Areas of immunity, general corrosion, pitting corrosion
and passivation. Equilibrium conditions of the reactions
of iron corrosion and hydrogen
b) velocities of the reactions of iron corrosion and electrodeposition, and of hydrogen evolution

13

Figure 16 : Experimental potential-pH diagrams relating to the behaviour of

steels in occluded corrosion cells
a) iron and unalloyed steels
- b) 12 % Cr steel

134

Figure 17 : Potential-pH diagrams for copper at 25C

a) equilibrium of the Cu-Cl-H0 system for solutions containing
10" 2 atom.gram CI /l. (0.35 ppm Cl)
b) equilibrium of the Cu-Cl-C0 -SO -H 0 system for solutions
containing 22 ppm Cl, 229 ppm CO and 46 ppm SO .
c) experimental conditions of immunity, passivity, general
corrosion and pitting corrosion in the presence of Brussels
tap water

135

Figure 18 : Measurement of electrode potential in the interior and exterior

of a corrosion pit
136

107 -

Figure 19 : Potential-pH diagrams for aluminium at 25C

a) equilibrium of the Al-H 0 system
b) theoretical and experimental conditions for corrosion,
immunity and passivation of aluminium

' ->'

Figure 20 : Potential-pH diagrams for titanium at 25C

a) equilibrium of the Ti-H0 system
b) theoretical and experimental conditions for corrosion
and passivation of titanium

138

Figure 21 : Potential-pH diagrams for tungsten

a) equilibrium of the W-H0 system
b) theoretical conditions for corrosion, immunity and
passivation of tungsten
c) experimental conditions for corrosion, immunity and
passivation of tungsten

139

Figure 22 : Potential-pH diagrams for molybdenum

a) equilibrium of the Mo-H0 system
b) theoretical conditions for corrosion, immunity and
passivation of molybdenum
c) experimental conditions for corrosion, immunity
and passivation of molybdenum

140

Figure 23 : Results of stress corrosion tests expressed by the

correlation between the intensity of the initial
stress
K.
and the logarithm of rupture time (56)

141

Figure 24 : Schematic representation of the experimental relation

between the logarithm of the speed of propagation of a
stress corrosion crack and the intensity factor of the
stress (56)

141

Figure 25 : Schematic representation of results of fatigue tests and

fatigue-corrosion tests (Whler curve)

142

Figure 26 : Schematic representation of results of fatigue-corrosion

tests, logarithm of the speed of propagation of cracking as a
function of the logarithm of the difference between the
intensity factors of the cyclical stress (128)

142

Figure 27 : Reference fatigue and fatigue-corrosion curves, using the

ASME XI A code (57)

143

figure 28 : Influence of
cathodic polarization on the electrochemical
characteristics and the speed of propagation of
stress sorrosion cracking
(chromium steels in the presence of
a 3 % NaCl solution) (B.F. Brown (90, 91))
143
r

igure 29 : Potentiokinetic polarization curve and electrode potential

values at which stress corrosion cracking appears (schema)
(accordong to R.W. Staehle (103))

144

108

Figure 30 : Potentiokinetic polarization curves and electrode

potential values at which intergranular and trans
granular stress corrosion cracking appears, in a
10 % NaOH solution at 288C
a) 600 alloy (Inconel)
b) 800 alloy (Incoloy)
c) AISI 304 alloyed steel (G.J. Theus (106))

144

Figure
31 : Electrochemical behaviour of a 12 % Cr steel in a

.
.
.
.
10
molar CI solution. Polarization in oxygen
rree solutions (provisional schemes)

a) external surface in the presence of the external

solution (0.1 M Cl, pH 7.0)
b) internal cavities in the presence of iron chloride
solutions 0.1 to 9.2 M Cl (pH 7.0 to 3.8)
c) external and internal surfaces, and conditions of
stress corrosion (as function of the electrode
potential of the external surface)

145

Figure 32 : Schematic polarization curves for iron and austenitic

stainless steels with 10 % Cr and 18 % Cr in hot H SO
(107)

146

Figure 33 : Schematic representation of chromium depletion

around grain boundaries and enrichment of grain boundaries
in sensitized stainless steels (107)

146

Figure 34 : Variations in the zero current electrode potential as a

function of time for stainless steels immersed in natural
sea water (67) . Characterization of their resistance
to pitting corrosion.

147

Figure 35 : Variations in dissolved oxygen content and temperature

when starting up a nuclear BWR without degassing, and
indication of the dangerous zone for intergranular stress
corrosion of welded AISI 304 steel

148

Figure 36 : Schematic representation of the EPR intergranular corrosion

test, with indication of the characteristic test parameters
(133)

148

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Corrosion Science, 25, 8/9, pp. 583-606, 1985.

122

127. J. CONGLETON, T. SHOJI, R.N. PARKINS.

The stress corrosion cracking of

reactor pressure vessel steel in high temperature water, Corrosion

Science, 25, 8/9, pp. 633650, 1985.

128. P. HURST, D.A. APPLETON, P. BANKS, A.S. RAFFEL.

Slow strain rate stress

corrosion tests on a A508III and A533B steel in deionized and PVR water
at 563 K, Corrosion Science, 25_, 8/9, pp. 651671, 1985.
129. G. GABETTA, R. RIZZI.

Electrochemical potentials measured at the tip

of a growing fatigue crack in demineralized water 93 C : the effect

of frequency, wave form and oxygen content, Corrosion Science, 2_3, n 6,
pp. 613620, 1983.
130. W. CHILDS, D. CUBICCIOTTI, M. FOX, A. GIANNUZZI, J. GILMAN, R. JONES.
EPRI Plant Material Program : Progress June 1981 to May 1982. NP2879
SR, pp. 417, 1983. Reporting work at Westinghouse and Framatome.

131. V. CIHAL, A. DESESTRET, M. FROMENT, G.H. WAGNER.

Tests d'tude et d'va

luation de la sensibilit des aciers inoxydables la corrosion nter

granulaire. Proc 5 Congrs Europen de la Corrosion, Paris, p. 249,
1973.
132. P. NOVAK, R. STEFEC, F. FRANZ.

Testing the susceptibility of stainless

steel to intergranular corrosion by a reactivation method, Corrosion, 31,

n 10, pp. 344347, 1975.

133. W.L. CLARKE, R.L. COWAN, W.L. WALKER.

Comparative methods for measuring

degree of sensitization in stainless steels.

Proc of ASTM Symposium

(1977) in ASTM STP 656 (1978).

134. R. PIONTELLI.

C R . Congrs Acier 1965, Luxembourg, CECA, p. 978.

******

-123

", Mih al

Figure 1

EUcirodt c/z rtfrznce

: Measurement of electrode potential

124-

VWA

C orrosion by dissolution
Corrosion Dy osi/icotion

NWWW^N

Possivo'ion by oxide or nyorcxiae loyer

1 /.//,' 1

PassivoHon oy nydrauae layer

jj

Immunity

Figure 2 : Metals ranked in order of t

thermodynamic nobility, wit
indication of the areas of corrosion,
immunity and passivation.

;riP2o3 !o5i2e3 27

-125

E \

| - = t : .cr.:2fcj

Figure 3

Types of p o l a r i z a t i o n curves

2716

-126
+2

{vaiti-

'.

--(21

corTOS/on

: 2o31CI5i233r17 S 7

Figure 4

: Theoretical conditions of corrosion, immunity and passi

vation of iron at 25 C
a) assuming that Fe 0

and Fe 0, are both protective

b) assuming that Fe 0
protective

is protective and Fe

is not

0 i

10

12

14.

C
voll
vh..

3<>

30

80

80

~"^
3Q

b.

Figure 5

Behaviour of iron in the presence of chloridefree aqueous

solutions at 25 C
a) polarization curves
b) experimental diagram of corrosion, immunity and passi
vation

127 -

oiC-W

Figure 6 : Electrochemical behaviour of iron in the presence of water

at 25C
a) reduction velocities of water into hydrogen and
oxidation velocities of water into oxygen on an
iron surface
b) corrosion velocities of iron
c) corrosion of iron with hydrogen evolution

-128

30
SO

30

8< Sr-7-L

- ^

I H P M O J 1 o S i i n -2,7-ia

Figure 7

/ 9

^ ^ | , , . !'
Y / <^/t? l , , l n 9^^TT- , r i i 'd

/ - U . . c o f f o i i o n * - / ^ - . ^ W i r n o i r i ^ c i

: I

: Behaviour of iron in the presence of aqueous solutions

102molar in chloride i.e. 0.35 g Cl/1. at 25 C
a) polarization curves
b) experimental diagram of general corrosion, immunity,
pitting corrosion, imperfect passivity and perfect
passivity

-129

H
- I

IO

12

12

'

'

!M
1 ,-

ikcrzpaJishesI jhd,
e/nen pa//s/i:d '
imperfect
= proti Cd en

-O

perfeilr , .
pdXJ/Viy

immunity
T

Figure 8

<s

r-

io

12

Experimental areas
corrosion, perfect
iron and s t e e l s , in
(3.5 g C l / 1 . at 25

IH

io

12

12

IH

of general corrosion, immunity, p i t t i n g

p a s s i v i t y and imperfect p a s s i v i t y of
the presenceof a10~1molar chloride s o l u t i o n
C)

a) iron and non alloyed s t e e l s

b) chromium s t e e l AISI 410 (diagram)
c) chromiumnickel s t e e l AISI 304 (diahram)
d) chromiumnickelmolybdenum s t e e l AISI 316 (diagram)

130-

c3lomel
electrode

calomel
electrode

glass
electrode

>j3 W

0,or

i
pH

metal

11 925J

solution
Plexiglas

KXVI
7(

*> asbcste

fS3
rubber w a s h e r

>&'

.lacquer

stirrer

Figure 9 : Device for the study of crevice corrosion

(J. Van Muylder 40, 41))

E 5he (v)

12

'

li

11

_-1

Q_ ^

JC/j/iO

or crtri c

**.rMtd
*Ktern*l
sur act

_0

arre/con
non
atrt
i td
et/ or crtncc.

-1 _

pH

Figure 10 : Influence of slow external cathodic polarization on the pH and

electrode potential conditions inside a corrosion crevice (mild
steel in an aerated solution 0.001 M NaOH and 0.001 M NaCl),
(J. Van Muylder)

-131

/
/
partie a c t i v e /
chantillon d'acier

partie

passive

Figure 11 : Device for the study of l o c a l i z e d corrosion (Antoine

Pourbaix ( 3 9 ) ) .

'V)

tei

*. sans

pol'ar i s a t i o n

-03
-0.1

cu
02
-OS

(pH .5.SJ

-05
5 t l * l O pTOtLKt*

-0A

-07

05

surface

Interne
1 active )

cs
-0E
0.1

. tm '

Figure 12 : Influence of a rapid external cathodic polarization on the

electrochemical behaviour of mild steel outside and inside
a corrosion crevice (external pH = 9.5, internal pH = 5.5)
(Antoine Fourbaix (39))

132
J

r>

she
0.1

-o.

0.2

--0,2

0,3

0,3

0.4

-0.4

0,5

0,5

Figure 13 : V a r i a t i o n s in s o l u t i o n s
obtained by adding
increasing q u a n t i t i e s of i r o n
0,6 jOxygsnated solution Solution without oxygen
0,6
chloride to p u r e , free w a t e r
1
I
I
1
I
I

1
1
in the p r e s e n c e o f iron p o w d e r
8
10
2
4
6
0
a) relation between the pH and
PH
the concentration of dissolved
iron
_J

b) relation between the pH and

the electrode potential of
iron
_

.Saturation en FcCI2 H20

'0

. 10

CU

10

10'

10-

io-

10-*

. io-

IO" 3 .

- 10"

1/1

D
O
i/i
ui

c
c

io-

io-

Solution oxygne.
io-

io-

-133

-a

-7

-H

-2
foc L OVCT.*1)

Figure 14 : Polarization curves for iron in the presence of a stirred

solution saturated with iron chloride (pH = 3.8, 25 C)
( by L. Sathler (42, 43))

-134-

" (Ci :

(maUnf'j

cg ,'CC (lolMif !
og : rt', crebri fy

Figure 15 : Experimental potentialpH diagrams relating to the electro

chemical behaviour of iron in the presence of iron chloride
at 25 C (schemas)
a) Areas of immunity, general corrosion, pitting corrosion
and passivation. Equilibrium conditions of the reactions
of iron corrosion and hydrogen
b) velocities of the reactions of iron corrosion and electro
deposition, and of hydrogen evolution

2
a.

iH

Figure 16 : Experimental potentialpH diagrams relating to the behaviour of

steels in occluded corrosion cells
a) iron and unalloyed
b) 12 % Cr steel

steels

135

3;
d _

--

o _.

I
_0

-<o

o -,

KK.

-WUB'B
*

'

'

-
-T

':0

-o

""'

tn
rI

CT

OJ

en

rt

4-1

rt 3
u
cu m

4-1

1
O

CO

1-1

4-1

14-4

t n ^o
>.<r

S -^
m ,

4J

u
nj

M
Ol
U.

,
o

14-1

en
b

cd

ou

rt

rt

4-1

4-1

o
P H

3
00

Pu

3 n i hf
,

d
()3

o -:

as m

fi

1
1 C N

r-4

O)

4J

IM

tfl
M
00

XI

4J

rt

HCN

3 I
ero
* /-N

rt

CN

1
3

u
tl)

r-4
O

CT\

x
4J

f*

u
F.
a.
o.

14-1
O CN
CN

a
3

60
C

r-<

r-1
H

4-1

3 C
cr O
CU
o

/~\
X l

eu

x:
4-1
C

c
3 C
o
e

a.

U
I

en
cu

CNCX.

>
r4
en

4-1
H

CO

CU

>>

cNrt

o
C

-(

en ex

as
CN
I
rOO
O u

r-t

Q.

CNO

E
I

>* s

en .
.

U.

IC

CO

Qj

rt
a.

-a
c

14-1

^
4-1

tn

M-4

00

(-

LO
CN

.m

4-1

CU

oo o

R
a,
cu o ,

CO

CO

r-4

u-i

en
C

co
O
M
M
O

O
00
C
4->
i - I 4-1
T S 4-1
3

o
o
r-l

a.
a
CS

rt

4-1

e c u

cu
o C U

4J
H
en rt

cu
.
><!
m

CJ

o 3

o.
o rt
u u

136

REF.EXT

REF.

INT

Figure 18 : Measurement of electrode potential in the interior and exterior

of a corrosion pit

-137
. - l

-I

>-

<t

IO

IO

11

11

IJ

IJ

13

13

!.

IS

16,

15
pH

she

tm
passivity

o_ : < ^ : : : : :
* :

-1 _

(or pitting)

passirity
Cor genero I
f^ corrosion)

Figure 19 : Potential-pH diagrams for aluminium at 25C

a) equilibrium of the Al-H 0 system
b) theoretical and experimental conditions for corrosion,
immunity and passivation of aluminium

138

'3'

; cr?
TO,?

".

TiOi

:'.5 .

PM

Figure 20 : Potential-pH diagrams for titanium at 25C

a) equilibrium of the Ti-H 0 system
b) theoretical and exDerimental rnnHirinn; fn

rnrrncinn

139

-o
S

rt
>.

rt
>>

4-1
r4

4_l
r4

es

C
O
r-1
tn
O
M

cu

4-1

tn

CS
Ti

CU
tn

^to
O

u
o

as
I

tn

4-1

<4-l

tn

M-4

14-4

CN

tn

C
O

CU

4-1

cu

4-1

r-l

-a

4-1

4-1

00

14-4

14-1

rt
H
TI

as

r4

il
01
H

4J

0)

cr
cu

&
I

CS

4-1

P^

ai

03

4-1

,-

cu

rt

4-1

c
o

to
CU

rt

CO

4-1

rt
>

r-l
tn
tn

rt
CX

4-1
H

V.
CU
iJ
CO

O)

c
3

4-1

o
u

U-4

r-l

rt

H
4-1

4-1

CU

td

H
l-i

CU

rt
>

r-l
tn

a.

CO

CU

rt
a.

/N

(J

<S:

_o_
4>

1^
O

Figure 22 : PotentialpH diagrams for molybdenum

a) equilibrium of the M o H O system
b) theoretical conditions for corrosion, immunity and
passivation of molybdenum
c) experimental conditions for corrosion, immunity
and passivation of molybdenum

1~

IO

12

pH

IH

141 -

LOGARITHM OF TIME TO FAILURE

Figure 23 : Results of stress corrosion tests expressed by the

correlation between the intensity of the initial
stress
K.
and the logarithm of rupture time (56)

REGION III
CRACK GROWTH
RATE STRONGLY DEPENDENT ON
STRESS INTENSITY
REGION
CRACK GROWTH
RATE INDEPENDENT OF
STRESS INTENSITY

LOGARITHM OF
CRACK GROWTH
RATE

REGION 1
CRACK GROWTH
RATE STRONGLY DEPENOENT ON
STRESS INTENSITY
DESIGNATED
K,._
STRESS INTENSITY

Figure 24 : Schematic representation of the experimental relation

between the logarithm of the speed of propagation of a
stress corrosion crack and the intensity factor of the
stress (56)

142

,en argon sec

en milieu corrodant
limite d'endurance
en fatigue
limite d'endurance
en fatiguecorrosion
*. pas de limite d'endurance apparente
log
Figure 25 : Schematic representation of results of fatigue tests and
fatiguecorrosion tests (Whler curve)
= max m.m
= nombre de c y c l e s
log = A B log

CORROSION FATIGUE
CRACK G R O W TH v
P L A T E A U DUE TO
STRESS CORROSION-

SR
FATIGUE

CRACK

GROWTH

IN

AN

INERT

ENVIRONMENT

LOG

Figure 26 : Schematic representation of results of fatiguecorrosion

tests, logarithm of the speed of propagation of cracking a
function of the logarithm of the difference between the
intensity factors of the cyclical stress (128)

143
1000
700
500

200
AIR ENVIRONMENT
d* = (0026710" 3 ), 3,!6

100

70
50

WATER ENVIRONMENT
|/<025
K

MIN/KMAX>065

'
50 70 100

20

10

STRESS INTENSITY FAC TOR RANGE, (KSI Via)

Figure 27 : Reference fatigue and fatiguecorrosion curves, using the

ASME XI A code (57)

e/v

10

11

12

13

'4

-.

Dial deflexion r a t e
O

C 2 0 4 Q6 0 8

EH/V

""-

17-JpH
,'2Ni.SCr.3Mo
..'.x3Ni.4Cr.0 2C
/s'
^ ' A I S I 4340

-1

.1

-1

O
J

1 2

-IO

02

Q<1 c e

o.e

'

7
pH-

10

11

12

13

14

119271
Figure 28

Influence of
cathodic polarization on the electrochemical
characteristics and the speed of propagation of
stress sorrosion cracking
(chromium steels in the presence o:
a 3 % NaCl solution) (B.F. Brown (90, 91))

144

log

Figure 29 : Potentiokinetic polarization curve and electrode potentia

values at which stress corrosion cracking appears (schema
(accordong to R.W. Staehle (103))

i.a

1.3

iHTEaCRA-iULAfl SCC
3 I

CI

>

0 s

3.1

11

<

<

^ ^ ^ ^ ^ ^ N

0.1

INTESCRA

NULA* SCC

^^gj

3.

Ui

S 9

T^ANSGRANULAR

SCC

TAj,ni.[T*TtH -Ce;
" A V A N> y

:^>\

<T~
10-

CTJRRtNT DENSITY l i N / t m ' l

v.

io*

b.

io;

10

io*

C'JSRtNT CcNSIT'

C U R R N T oeNsiTr (mi/cm)

Figure 30 : Potentiokinetic polarization curves and electrode

potential values at which intergranular and trans
granular stress corrosion cracking appears, in a
10 % NaOH solution at 288C
a) 600 alloy (Inconel)
b) 800 alloy (Incoloy)

&

EsAc
(vol b i

(.volts)
,,Q.

-o/I .
-0.3-

^o.3

-0.2-0.1 .

= o.\

o_

corro j/' velocity inside the ac.c. s

-o.1_
velocity 1 hijdrQcn
oluti on n staicene
ces

-0.2 _
-o.3_

-0.5

IO

6.3

O. /

7. O

Z.-O.0
7.

-
(oef . (A.cm

_-o.2

= o.M

-o.
-0.7

corrosion o. 1
cricking
^o.3

C.2/-1 pHO.
so
y. 9

-o.M _

, O

~\~
-5

-
(cf.i (A.cni2)

12679

Figure 31 : Electrochemical behaviour of a 12 Cr steel in a

10
molar CI solution. Polarization in oxygen
rree solutions (provisional schemes)
a) external surface in the presence of the external
solution (0.1 M Cl, pH 7.0)
b) internal cavities in the presence of iron chloride
solutions 0.1 to 9.2 M Cl (pH 7.0 to 3.8)
c) external and internal surfaces, and conditions of
stress corrosion (as function of the electrode
potential of the external surface)

bo.
= o.7

en

146

IO C f - I O N . - Boi Ft
IS C r - IO h. - Bal Ft

Fe

Huey Test
Streicher Test
Strauss Test

CumtexT oeMSITT (pa/cm 2 )

Figure 32 : Schematic polarization curves for iron and austenitic

stainless steels with 10 % Cr and 18 % Cr in hot H SO
(107)
2 L

70-55 '

u
n
l=

li*

s u m gouNOAR-r

Figure 33 : Schematic representation of chromium depletion

around grain boundaries and enrichment of grain boundaries
in sensitized stainless steels (107)

-147

I URANUS 6 3 I

'ja^Nus jT)
l URANUS 2 j I

0 5 t) 153 5 M S SO a3

TO

50

3 13

7C

130

0 Su :60

TO ISO SO

Figure 34 : Variations in the zero current electrode potential as a

function of time for stainless steels immersed in natural
sea water (67) . Characterization of their resistance
to pitting corrosion.

-148 -

s CUSTOMARY START-UP

i - - *

DEGAS METHOD START-UP

ro O-

5
4h

3L

Undesirable Region

o
c_;

0.5 rC3 0.4

>c 0.3 h
o
0.2 h

0.1 r

50

100

150

200

250

REACTOR WATER TEMPERATURE C

Figure 35 : Variations in dissolved oxygen content and temperature

when starting up a nuclear BWR without degassing, and
indication of the dangerous zone for intergranular stress
corrosion of welded AISI 304 steel

| ACTIVE

I
PASSIVE

-'. ' ' \

(<0\
, " < - ' . :

' ri Q :;.

LJL-

1
1
1

LU |

?
Q CHAP.GE I N T E C H A L IC .cn
Ph M A X I M U M P E A K WEIGHT ( m A / c m

I
o

I
;oo

,
' So,,

FL-*DE POTENTIAL ( n w |
C C AflOSION P O T E N T I A L !

v|

1
TIV

POTENTIAL

Figure 36 : Schematic representation of the EPR intergranular corrosion

test, with indication of the characteristic test parameters

149

AUTHOR INDEX

ABORN

120

R.H.

AGARWALA V.S.

CONWAY .E.

1 10 COPSON H.R.

112

FROMENT M.

122

117

FUJI I C T .

41, 113, 118

118

CONGLETON J.

122

AL ZANRI I.A.

112

CORIOU H.

116

AMBROSE J.R.

121

COWAN R.L.

120, 122

APPLETON D..

122

CRAIG H.L.

114

ASPHAHANI .

119

CROLET J.L.

ALBRECHT

J.

CUBICCIOTTI D.

113, 115
110, 116, 122

GABETTA G.
GALVELE J.R.
GARNER A.
GEARY

77;, 120

BAIN E.C.

122

BANKS P.

39, 112

BAYLIS J.R.

109

5ENNETT D.C.

109

BENNETT L.F..

GIANUZZI A.

110, 116, 122

GILMAN J.

110, 116, 122

GILL J.S.

1 12

DAWSON J.L.

112

GLINEUR W.

114

DEAN S.W.

117

GRALL L.

32

DE DONDER Th.

113, 115

BERMAN D.A.

110

, 93, 115, 122

DESESTRET A. 62,

BERMAN E.B.

109

DE WEXLER S.B.

117

BOCKRIS J.O.M.

112

DIEGLE R.B.

116

BOSTWICK T.W.

121

DEFRANOUX J.M.

BRENNEST
38, 70, 73, 74,

GROOVER R.E.
GUPTA K.

119

HABER F.

29

HEITZ E.

102, 112

HEUSLER K.E.

115

EDELEANU E.

HIKSON D.

119

EPELBOIN I.

35

HOAR T.?.

39, 112

m,

HOCHMAN R.H.

114

112, 120

HOTALING A.C

109

EVANS U.R.28, 38, 39, 95,

HUA H..

CELS J.R.
CHILDS W.

HUEY

78, 93, 120

1 19

113
78, 146

HURST P.

122

ISAACS H.S.

121

110, 116, 122

CIHAL W.

93, 122

FICK

CLARKE W.L.

93 , 112

FISHER L.

CLERBOIS F.

93, 120

CLERBOIS L.

33, 78, 93, 120

COLLINS J.A.

116
49, 114

39, 93, 112

107, 112, 114,

CARIUS C.

35

118

110, 7 , 121

117, 118, 143

109

DAHLBERG E.P.

BERGE J.Ph.

BROWN B.F.

122
71,, 102,117

no

FLEISCHMANN M.
FOX M.
FRANZ F.

60 , 81
115
116
110, 116, 122
122

150

JANIK-CZACKOR M.
JONES R.

109 RAFFEL A.S.

61, 115 MIURA M.

110 RAMAN

110, 116, 122 MONAK M.L.

27, 111

MONTUELLE

m,

KAESCHE H.
KANE R.D.

122
92, 96
109

REIMANN C.

MOROISHI T.

109 RIZZI R.

1 22

MORRIS P.E.

74, 119 ROWLANDS J.C.

RUFF A.W.

112
109
120

RUTERFORD J.B.

117
109

KETCHAM S.
NAGAYAMA T

117

120 NEWBERG R.
121 NI R.C.

118, 119

KISSEL J.
KLIMZACK-MATHIEU L.
KUDAMA T.

110 NOVAK P.
109, 117

KOHLAAS G.
KUDO T.
KRUGER J.

117

113 SAKASHITA M.
93, 122

117

SATO N.

41, 42, 74, 99,

SATHLER L.

106, 113, 132, 133

79, 109, 115, 116

120
OKADA H.

121
116

OLIVIER P.

SAWARAGI Y.
SCARLIN R.B.

109

SCHARFSTEIN L.R.

109

SCHERER R.

102

118

121

SCOTT P.M.
LATANISION R.M.

116

SCULLY J.

LAUWERS J.

113, 115

SERAPHIN L.

LECOINTRE G.

121

LEE H.

118 PARKER R.L.

LEGRAND J.

121 PARKINS R.L.

LENNOX T.J.

114

SERRE
SHIBATA T.

116

SHOJI T.

122

74, 100, 110, 114,

STLVERMANN D.

110

116, 117, 119, 122

SINGBEIL D.L.

109

109

LIANG W.

119

LOGAN H.L.

116 PASSAGLIA E.

LUGGIN

72, 117

23, 53, 70,

109

29 PETERSON L.M.H.
PIONTELLI R.

113
29, 95, 122

SKLARSKA-SMIALOWSKA S.

115

SPAEHN H.

110

SPEIDEL M.O.

PIPER D.E.

114

SROWLS D.O.

PLICHON V.

121

STAEHLE R.W.

POURBAIX A.

40, 49, 50, 102,

115

106, 109, 111, 113

STEFEC R.

MANSFELD F.

112

114. 115, 121, 131

STERN

MAREK M.

114 POURBAIX M.

MASSART J.

93, 120

MAZILLE H.

118

MEUNIER J.

120

114, 115, 118, 120

102, 118
114

74, 7 9 , 107, 116,

117, 119, 12C, 144

Mac BEE C L .

111, 112, 113,

72,

STRAUSS
STREICHER

122

35
78,146
78, 146

-151

121

TARUTANI Y.

32 WEEKS J.R.
1 16 WESTCOTT C
109 WILLERMOZ H.

116

TEDMON C S .

120 WILLIAMS D.E.

116

TEMS R.D.

110 WINAND R.

114

TAFEL
TAKEYAMA T.

1 16

107

THEUS G.I. 74, 108, 119, 144 WOEHLER

114 WOOLAM R.C
TICE D.R.

112

TONDREAU M.F.

102 WRANGLEN G.

62, 114

TRAUD W.

1 11 WRITE M.E.
113, 115 WU Y.

TRICOT R.

1 12
113

109
44, 113, 115

TSUGE H.
TURNBULL

109

TUTTLE R.N.

YANG W.

109
44

YEAGER E.

112

YAKOWITZ H.

79, 120 YARUTANI, Y

74, 118, 119

UGIANSKY G.M.
UHLIG H.H.

ZOUBOV N.
VAN DROFFELAAR H.
VAN LAER P.

VANLEUGENHAGHE C.
VAN MUYLDER J.

120

111, 113, 114

120
39, 41

74, 105, 106, 111,

112, 113, 114, 130
VYAS B.

WAGNER C.

121

28, 95, 111

WAGNER G.H.

1 22

WALKER W.L.

122

WANKLYN J.N.

121

WATSON T.R.B.

109

109

111, 114

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