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Report
EUR 10607 EN
Blow-up from microfiche original
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
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
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
- 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
elektrochemische
Aspekt,
Spannungsrikorrosion,
werden
dargelegt.
Lochfra,
Wasserstoffvereprdung,
interkri-
praktische
spielen
scher
Anwendung
aufgezeigt:
aus
leitungen
Dampfgeneratoren
nichtrostendem
aus
dieser
Stahl,
Kupferlegierungen
von
Kernkraftwerken,
Wrmeaustau-
meerwassergekhlten
Kondensatoren,
Zur
Bekmpfung
senden
Aktionsprogramms
auf
Rahmen
Laborforschungen
(vor
Korrosionseiemente),
Gemein3chaftsebene
allem
Forschungen
vorgeschlagen, in dessen
Schlsselwrter
rtliche
Korrosion
Lochfrakorrosion
- Spaltkorrosion - Spannungsri-
Entlegierung
Kupfersthle.
Kernreaktoren
nichtrostende
Sthle
- Kupfer -
CONTENTS
ES
12
13
1.2.2. Metallurgy
14
15
16
16
17
18
21
22
23
24
25
26
26
28
28
29
The
29
The second
31
33
35
36
36
43
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
5C
53
58
61
63
66
76
76
79
80
S3
84
86
87
87
89
90
93
4. RESEARCH REQUIRED
95
95
96
96
4.1.3. Study of
97
98
100
100
100
101
102
102
Recommendations. Publications
ACKNOWLED GEMENT S
102
INDEX OF TABLES
103
INDEX OF FIGURES
105
BIBLIOGRAPHY
109
FIGURES
123
AUTHOR INDEX
149
characteristics, their
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
Materials
(1 to 2mm sheets)
Ecus
(June 1985)
Carbon steel
Price as compared
0.2
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
6 820
2.6
AustenofertitiC
steel
6 360
2.3
3 600
1.3
Copper
stainless
1.4
10.2
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
nonferreux
Minerais in Brussels).
Materials, country, year
Apparent consumption
per year
special types
252 110
783 700
156 900
250 000
1 442 700
10 000
hot-rolled,
15 700
25 700
20 0G0
Table II (cont'd)
23 000
- copper
FRG + GB + F + + NL + I + D + G, 1984
2 197 709
12-
inexis-
localized
corrosion.
despite a l l
forecasting
and
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
be t r e a t e d
called
in
the
section
"maritime
transportation
and
of l o c a l i z e d c o r r o s i o n i n atmospheric
corrosion
13
-14
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
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
crevices,
: tanks, pipes,
cracks
separators,
crevice
15 -
environment
the
since
: equipment
16
boiling tanks,
filling
a u t o c l a v e s consume
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,
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
plant
shut-down.
This
corrosion
titanium)
was a t t r i b u t e d
to
the
17
18
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
19
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 -
make i t
specifications
possible
for t h e i r
metallurgie
to o b t a i n both t h e
mechanical
this
application.
- The d e s a l i n a t i o n
of
sea water
decarbonated
by
acidification
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
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 -
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
23 -
- 24
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
25 -
additional
26
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
it,
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
alkaline solu-
for zinc in s l i g h t l y
alkaline
are
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
28
The
study
of
corrosion
entails
a group
of
disciplines
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
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
there
for a reaction :
+ ne
= 0
(i.e. Fe = Fe++ + 2e )
aq
free electrons,
and
(i.e.
- 23060 nEo = 0
(1)
where
" 23060
u ++ - Mu
*Te
Fe
aq
Eo =
46120
30 -
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
'
sh
- 31
and
the
(2)
|(E - Eo) x i
(T|
32
> 0
for oxidations
for reductions
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
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
successively
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
the
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
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
is
34
is uncorrodible.
35
d i a g r a m s which make i t
possible to specify
the
theoretical
- 36
t h e i r v a l i d i t y and t h e i r
experimentally,
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,
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,
(fi-
stirred
37
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
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
e q u i v a l e n t s mg per hour,
38
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.,
against
perfect
atom.grams
^ e in the
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
potential
39
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
existing
oxygen-free
'_ o
M in
40 -
having an
remains more or l e s s c o n s t a n t u n t i l
the
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
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
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
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
potential
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.
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
42
as i n d i c a t e d
above,
that
the
saturated
solution
in
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
gne.
nonsaturated,
ferrous
Fe20 between t h e
used
the
SATHLER
experimental
results
to
plot
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
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
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
cathodic
polarization
which d e c r e a s e s
the
e l i m i n a t e i r o n c o r r o s i o n and
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
AISI 410,
chromiumnickelmolybdenum
chromiumnickel
steel
steel
AISI 304,
AISI 316 r e s p e c t i v e l y ;
and
their
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,
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.
46 -
A.cm
-0.29 volt u
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
the
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
in a c o r r o s i o n
pit
(as compared t o a
is
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
is
against
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
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
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
50 -
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
corrosion r a t e s of 10
and 10
A.cm
d i a g r a m shows t h e
and
sophisticated
outside
localized
methods of
surface
corrosion
analysis
crevices.
do e x i s t ;
Certain
they
are
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.
ESCA
XPS
UPS
AES
ELS
SIMS
ISS
LAMMA
EDAX
Ellipsometry
Microdiffraction of Xrays
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
Elements or
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
chemical composition
valence
(sometimes difficult)
(sometimes difficult)
lpm
10 to 30 A
10 A
elements based
on Na
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
rapid method
long method
semi-quantitative
using standards
rapid method
53 -
the r e s u l t s of
54 -
in t h e
therefore
systems
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
55
Determining
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
t y p i c a l of titanium a l l o y s (A)
loading,
by a g i v e n
as t h e
initial
ma
rec u:
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
l a b o r a t o r i e s . The v a l u e s
of
Kjscc
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
recently,
phenomena
of
fatigue
corrosion
under
low
steel, sensitized
austenitic
stainless steels
(pipes
the constraint.
da diagrams as a function
Results are usually expressed on log dN
of the log
of
the
constraint
max
. , for
min
the stress
applied
*v
and
of
. .
D
= m m = lmm
K.
max
lmax
57 -
observe
the
and K.
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
particular
placed
in
an
electrolytic
cell having
two
compartments
58 -
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
initiation
of stress corrosion
cracking
is related
to the
deformation
can either
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
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
a new explanation
localized
of
propagation
of
corrosion".
This
protection
potential
was defined
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
corrosion" is undeniable;
its value is not exactly the same as the potential at zero current
determined
by
the
polarization
curves at
decreasing
potentials
presented
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
triangle. The
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
61
iodides, SO,
chloride, CIO,
consists
..
under specific
and the
62
pitting in iron : some suggest that the Cl
vating film penetrate this film and create weak spots. But no evidence
of incorporation of the CI
ions accumulate
defects). Even
ions
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
fairly
recent
presentation
of initiation of pitting
phenomena
r
of pits are not necessarily rigourous values but are statistical measurements, that should be treated as such (70,71). The physical interpretation
that would
then
be neutralized
or maintained
depending
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
various tentatives
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
by smell
(56).
oxygen
(78).
- intergranular cracking corrosion of sensitized
steel, in a humid environment
austenitic stainless
(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
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"
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
"
ref (77)
'
ref (77)
"
H 2 0 pure
lead contaminated solutions
"
C 2 H 5 C1
CaCl 2 , MgCl 2 , LiCl, MnCl2, ZnCl2
- boiling
"
"
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
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
also has
This very
short phenomenology
- 70
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 -
environment
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
contributions
were
(88) were assessed in the bottom of pits, and crack growth rates of
the order of mm.h
embrittlement
is
preponderant.
The mechanism
of
propagation
by dissolution
described
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
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
potentional/pH
curve obtained
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 ,
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
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
This
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
the occluded
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
the
diffusion
electrode
potentials
rising
76
Below
77
understood
by comparing
the
78 -
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
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
B e c a u s e of t h e d e v e l o p m e n t
of
Essentially
non-
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
the
the interface,
f o r each of
(alloy,matrix,
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?
mention
only
briefly
the
de-alloying
phenomena
which
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
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
80
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
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
hydroxides
and/or
place, although
because
salt, under
more
slowly
because
they
and
the
passive
exterior
surfaces, and
some
research
to 8.0 A.cm
the
hydrodynamic
conditions
- 81 -
phenomena
because of
of
or of
localized
determining
electrolyte
corrosion
and
the velocity
the dissolved
oxygen content,
of penetration of localized
elaborate
models
effectively
take
into
account
diffusion
species
bottom
of
the crevice
and
even
the
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 -
- 83
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
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
long
potentiostatic
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
publications
industrial
these
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
it
- 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 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
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.
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
Austenitic
stainless
steels
and
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.
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
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
of d i s s o l v e d
species,
creating agressive
the
conditions.
result
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
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
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.
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
the
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
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 -
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
value :
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
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
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
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 -
relationship
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
convinced
power p l a n t
operators.
Measuring
electrode
thermal treatment
for
stress
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
derivative
limit,
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,
which i n t u r n i s i n f l u e n c e d
by
by
s t r e s s e s . The approach t h a t
is
93-
94-
these
sulfuric
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
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
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,
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.
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
and imperfect
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
during
laboratory
- 97
The e x p e r i m e n t a l
is desirable
to have
the
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
(aeration,
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
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
electrodes
identical
p l a c e d between t h e e x t e r n a l and
internal
(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
of p r o t e c t i o n a g a i n s t
the
for
99 -
these
studies,
one should
notably
try to specify
the
100 -
lead to
in
possible
t o study c o n c e n t r a t e d
aqueous
much
hope
to
be
able
to
precautions
gather
precise
data
on
measure
101 -
inhibitors,
also
inhi-
v a l i d i t y of t h i s p r o g r e s s on a semi-
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
-102
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.
sessions. After
installations
and discussed
in
and
ACKNOWLEDGEMENTS
-103
INDEX OF TABLES
Table I
Table II
52
66
105-
INDEX OF FIGURES
Figure 1
123
Figure 2
124
125
Figure 3
Figure 4
Figure 5
126
Figure 6
126
Figure 7
127
Figure 8
Experimental areas
corrosion, perfect
iron and steels, in
(3.5 g Cl/1. at 25
128
Figure 9
(diagram)
129
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(
13'
13'
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
134
135
107 -
' ->'
138
139
140
141
141
142
142
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
144
108
144
Figure
31 : Electrochemical behaviour of a 12 % Cr steel in a
.
.
.
.
10
molar CI solution. Polarization in oxygen
rree solutions (provisional schemes)
145
146
146
147
148
148
109-
BIBLIOGRAPIIY
1.
A report
Special
3.
septembre 1980.
4.
D.C. BENNETT.
Corrosion 85 - NACE,
3.
Corrosion 85
-110-
Material Performance
NP-2879-SR
March 1985.
18. R.N. PARKINS, R.D. TEMS.
Material Performance
111 -
Infiuence de
Caractristiques lectro-
RT.127, 1965.
21. J. VAN MUYLDER, M. POURBAIX.
durch
Ueberlagerung von elektrochemischen Teilvorgngen und ber die Potentialbildung an Mischelektroden, Z. Elektrochemie, 44, pp 391-402, 1938.
26. M. POURBAIX. a) Leons en corrosion lectrochimique, 2 dition, CEBELCOR,
1975. b) Lectures on electrochemical corrosion, Plenum Press and CEBELCOR,
1973.
27. H. KAESCHE. Die Korrosion der Metalle.
Physikalisch-chemische Prinzipien
- 112
Impedance,
a) J. Electrochem. S o c , 123,
23c-36c, 1976.
33. M. POURBAIX.
113
39. . POURBAIX.
de
l'acier en solutions
Caractristiques lectro
42. L. SATHLER.
46. A. TURNBULL.
Caractrisation
- 114 -
pp 603-635, 1981.
b) Rapports Techniques CEBELCOR, 141, RT.262, 1981.
Cathodic protection of
Corrosion behaviour,
Comportement lectrochimique du
54. H.L. CRAIG, D.O. SPROWLS, D.E. PIPER, Stress Corrosion Cracking,
in "Handbook on Corrosion Testing and Evaluation", Ed. AILOR, Wiley,
1971.
55. R.N. PARKINS.
56. B.F. BROWN, Stress Corrosion Cracking in High Strength Steels and in
Titanium and Aluminum Alloys, Naval Research Laboratory, 1972.
57. D.R. TICE.
Corrosion Science,
115
59. M. POURBAIX.
Caractrisation
63. M. JANIKCZACHOR.
67. A. DESESTRET.
68. G. WRANGLEN.
116 -
A statistical Approach to
Embrittlement of Iron Base Alloys, Firminy, 1973, Paper E-3, NACE 1977.
76. H.L. LOGAN. Stress Corrosion Cracking of Metals, John Wiley, 1966.
77. R.M. LATANISION, R.W. STAEHLE.
Cracking, Ed. R.W. STAEHLE, A.J. FORTY, D. VAN ROOYER, NACE, Houston,
1969, p. 214.
78. H. CORIOU, L. GRALL, P. OLIVIER, H. WILLERMOZ.
Influence of carbon
Int. Conf. on
117 -
Corrosion,
21, n 1, 1965.
82. R.N. PARKINS.
An
Proc
- 118
B.F. BROWN.
Electrochimie et Corrosion.
stress corrosion cracking of carbon steels in nitrate and alkaline solutions , Corrosion, 28, pp. 427..., 1972.
- 119
cracking of 63-37 brass in ammoniacal and tartrate solutions, J. Electrochem. S o c , 122. p. 343, 1975.
100. D. HIKSON, H.H. UHLIG.
102. H.H. UHLIG. Applying critical potential data to avoid stress corrosion
cracking of metals, J. Applied Electrochem.,
103. R.W. STAEHLE.
Environments, Proc
Houston, Texas, March 22-26, 1976, pp. 66-72, Pubi. NACE, 1977.
106. G.J. THEUS, J.R. CELS.
caustic SCC studies, Proc. ASTM Symposium on SCC "The constant strain
rate technique", Toronto, May, 2-5, 1977, pp. 76-31, pubi. RDTPA (Babcock &
Wilcox).
-120
RT.66/3, 1958.
110. L. CLERBOIS, F. CLERBOIS, J. MASSART.
Rapports Technique:
121
seurs en alliage cuivreux par addition de sels ferreux dans l'eau de mer
en circulation,
120. J. LEGRAND.
Rapports
ou
Rapports
161.
125. J.R. WEEKS, B. VYAS, H.S. ISAACS. Environmental factors influencing
stress corrosion cracking in boiling water reactors,
Corrosion Science,
122
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.
******
-123
", Mih al
Figure 1
124-
VWA
C orrosion by dissolution
Corrosion Dy osi/icotion
NWWW^N
1 /.//,' 1
jj
Immunity
;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
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
127 -
oiC-W
-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
-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
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
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
-131
/
/
partie a c t i v e /
chantillon d'acier
partie
passive
'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 '
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
'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)
-134-
" (Ci :
(maUnf'j
cg ,'CC (lolMif !
og : rt', crebri fy
2
a.
iH
steels
135
3;
d _
--
o _.
I
_0
-<o
o -,
KK.
-WUB'B
*
'
'
-
-T
':0
-o
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tn
rI
CT
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en
rt
4-1
rt 3
u
cu m
4-1
1
O
CO
1-1
4-1
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t n ^o
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m ,
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nj
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14-1
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fi
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a
3
60
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r-<
r-1
H
4-1
3 C
cr O
CU
o
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X l
eu
x:
4-1
C
c
3 C
o
e
a.
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en
cu
CNCX.
>
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en
4-1
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CO
CU
>>
cNrt
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C
-(
en ex
as
CN
I
rOO
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r-t
Q.
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E
I
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en .
.
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CO
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rt
a.
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c
14-1
^
4-1
tn
M-4
00
(-
LO
CN
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4-1
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oo o
R
a,
cu o ,
CO
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u-i
en
C
co
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M
M
O
O
00
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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
-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)
138
'3'
; cr?
TO,?
".
TiOi
:'.5 .
PM
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^
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1~
IO
12
pH
IH
141 -
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
142
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
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
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
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-
v.
io*
b.
io;
10
io*
C'JSRtNT CcNSIT'
C U R R N T oeNsiTr (mi/cm)
&
EsAc
(vol b i
(.volts)
,,Q.
-o/I .
-0.3-
^o.3
-0.2-0.1 .
= o.\
o_
-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
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
70-55 '
u
n
l=
li*
s u m gouNOAR-r
-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
-148 -
s CUSTOMARY START-UP
i - - *
ro O-
5
4h
3L
Undesirable Region
o
c_;
>c 0.3 h
o
0.2 h
0.1 r
50
100
150
200
250
| 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
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 .
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.
GILMAN J.
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
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
HUA H..
CELS J.R.
CHILDS W.
HUEY
113
78, 146
HURST P.
122
ISAACS H.S.
121
CIHAL W.
93, 122
FICK
CLARKE W.L.
93 , 112
FISHER L.
CLERBOIS F.
93, 120
CLERBOIS L.
COLLINS J.A.
116
49, 114
CARIUS C.
35
118
110, 7 , 121
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.
110 RAMAN
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.
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.
SATHLER L.
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.
LEGRAND J.
LENNOX T.J.
114
SERRE
SHIBATA T.
116
SHOJI T.
122
STLVERMANN D.
110
SINGBEIL D.L.
109
109
LIANG W.
119
LOGAN H.L.
116 PASSAGLIA E.
LUGGIN
72, 117
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.
115
STEFEC R.
MANSFELD F.
112
STERN
MAREK M.
114 POURBAIX M.
MASSART J.
93, 120
MAZILLE H.
118
MEUNIER J.
120
102, 118
114
Mac BEE C L .
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 .
116
TEMS R.D.
110 WINAND R.
114
TAFEL
TAKEYAMA T.
1 16
107
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.
UGIANSKY G.M.
UHLIG H.H.
ZOUBOV N.
VAN DROFFELAAR H.
VAN LAER P.
VANLEUGENHAGHE C.
VAN MUYLDER J.
120
WAGNER C.
121
WAGNER G.H.
1 22
WALKER W.L.
122
WANKLYN J.N.
121
WATSON T.R.B.
109
109
111, 114
CDNA10607ENC