Corrosi on Science, 1963, Vol. 3, pp. 239 to 259. Pergamon Press Ltd. Printed in Gr eat Britain.

POTENTIOKINETIC AND CORROSIMETRIC

INVESTIGATIONS OF THE CORROSION BEHA'VIOUR
OF ALLOY STEELS*
M. POURBAaX, L. KLIMZACK-MATHIEIU, Ch . MERTENS, J . MEUNIEK, C1. VANLEUGEN-
HAGHE, L. DE MUNCK, J . LALrREYS, L. NEELEMANS a n d M. WARZEE
Centre Beige d' Et ude de la Corrosi on, 24, Rue des Chevaliers, Bruxeiles 5
Abst raet mThi s paper poi nt s out the importance, for a t hermodynami c i nt erpret at i on of polarization
curves, of a knowledge of the equi l i bri um t ensi onst H20/H2 and H20/ OI , and of the oxi dat i on tension
of HI O and the reduct i on tension of Oi. As an example of this a description is given of the evaluation,
for various safety margins, of the chloride concentrations capable of causing pitting corrosi on of
alloy steels AI SI 410, 304 and 316 in bicarbonate solutions, at temperatures of 20 , 40 and 80C.
A summary is then given of an investigation of the pitting corrosi on of alloy steels AI SI 410, 304
and 316 in chloride solutions, based on the concepts of "br eakdown t ensi on" and "prot ect i ve ten-
si on", whose values can be predetermined potentiokinetically, as well as by potentiostatic and chemical
methods. The value of the breakdown tension enables us to calculate the sensitivity of a steel to
pitting corrosi on; t he value of the protective tension enables us to determine the conditions for
cathodically protecting t he steel in t he presence of oxidizing agents.
Similarly, by studying t he behavi our of a given specimen of ahoy steel in solutions obtained by
adding chloride t o a given solution, we can define a chloride breakdown concent rat i on, above
which the steel undergoes pitting corrosi on in t he presence of oxidizing agents, and a chloride pro-
tective concentration, below which such corrosi on is impossible, even in the presence of . oxidizing
agents. The breakdown and protective tensions and concentrations depend on the nature of the steel
and its beat -t reat ment ; t he breakdown tensions and concentrations depend also on t he surface state
of t he steel.
The addi t i on of bi carbonat e to " pur e" water containing chloride can greatly i mprove t he corrosi on
resistance of an alloy steel in this solution. I n t he case of a specimen of 304 steel, t he value observed
f or the breakdown chloride concent rat i on was 9 mg/ l f or the " pur e" water, and 260 mg/ l for a solution
of 0"010M NaHCO, .
Finally the results are given of an investigation of the behavi our of alloy steels in the presence of
sulphuric solutions. The purpose of this investigation was to compare, f or AI SI 410, 304, 316 and 321
steels, heat-treated in various ways, the results of potentiokinetic experiments with those of vari ous
corrosimetric experiments. Some opinions are expressed concerning the influence of various oxidizing
and reducing agents, and also concerning pot ent i oki net i c criteria for controlling the efficiency of a
t reat ment f or immunizing AI SI 321 steel against intergranular corrosion.
Rq~amr---On signale d' i nt r r et que prrsente, pour l' interpr~tation t hermodynami que de courbes de
polarisation, la connaissance des tensions d' rqui l i bre HI O/ HI et HIO/O1, ainsi que l a tension d' oxy-
dat i on de HI O et la tension de r r duct i on de Oi. On en donne un exemple pour l ' rval nat i on, avec
diffrrentes marges de srcurite, des teneurs en chl orure susceptibles de pr ovoquer une corrosi on par
piqures d' aeiers allirs AI SI 410, 304 et 316 en pr~senee de solutions bi carboni ques, / t des temperatures
de 20 , 400 et 80C.
On rrsume ensuite une ~tude concernant la corrosi on par piqures d' aciers allies AI SI 410, 304 et
316 en prrsence de solutions chlornr~es, basres sur les not i ons de "t ensi on de r upt ur e" et de "t ensi on
de pr ot ect i on", dont les valeurs peuvent etre pr~d~terminc~e.s par vol e pot ent i oci nrt i que, ainsi que
par des mr t hodes potentinstatiques ou chimiques. La val eur de la tension de rupt ure permet de
chiffrer la sensibilit~ d' t m acier ~t la corrosi on par pi qure; l a val eur de la tension de prot ect i on permet
d' rt abl i r les condi t i ons de prot ect i on cat hodi que de l ' aci er en prrsence d' oxydant .
*Presented at t he 13th Meet i ng of t he Int ernat i onal Commi t t ee f or Electrochemical
Thermodyl l ami cs and Kinetics CI TCE (Rome, 23-30 September, 1962). Transl at i on of CEBELCOR
Technical Report , RT.120 (by J. A. Franklin).
t Th e t erm tension in this paper is used i n place o f pot ent i al .
239
240 M. PotmaAlX et al.
De m6me, si l ' on 6t udi e le compor t ement d' un6chant i l l on d6t ermi n6 d' aci er alli6 en pr6sence de
sol ut i ons obt enues par addi t i on de chl orure ~ une m6me sol ut i on de base, on peut d6finir une con-
cent r at i on de r upt ur e en chl orure au-dessus de laquelle r aci er subi t une cor r osi on pa r pi qur e en
pr6sence d' oxydant , et une concent r at i on de pr ot ect i on en chl or ur e en-dessous de laquelle une telle
cor r osi on est impossible, m6me en pr6sence d' oxydant . Les t ensi ons et concent r at i ons de r upt ur e et
de pr ot ect i on d6pendent de l a nat ur e de l ' aci er et de son t r ai t ement t her mi que; les t ensi ons et con-
cent r at i ons de r upt ur e d6pendent en out r e de l ' 6t at de surface de r aci er .
L' addi t i on de bi car bonat e/ ~ une eau pur e chl orur6e per met d' am61i orer f or t ement la r6sistance
d' un aci er alli6 en pr6sence de cet t e eau. Dans le cas d' un 6chant i l l on d' aci er 304 on a observ6, pour
l a concent r at i on de r upt ur e en chl orure, 9 mg/ l , darts le cas d' eau " pur e" , et 260 mg / l - dans le cas de
sol ut i ons de NaHCO3 0,010 Mol ai re.
Enfi n on expose les r6sul t at s d' une 6t ude rel at i ve au compor t ement d' aci ers alli6s en presence de
sol ut i ons sulfuriques, de nt r obj e t a 6t6 de compar er , pour des aciers AI SI 410, 304, 316 et 321 ayant
subi diff6rents t r ai t ement s t hermi ques, les r6sultats d' essai s pot ent i oci n6t i ques avec les r6sul t at s de
divers essais corrosi m6t ri ques.
On 6met quel ques opi ni ons au sujet de r i nf l uence de di vers oxydant e et r6duct eurs, ai nsi qu' au
sujet de crit6res pot ent i oci n6t i ques de contr61e de l' efficacit6 d' un t r ai t ement d' i mmuni s at i on d' aci er
AI SI 321 cent r e l a cor r osi on i nt ergranul ai re.
Zusammenf assung- - Es wird auf die Bedeut ung der Kermt ni sse der Gl ei chgewi cht sspar mungen
H20/H2 und H20/O2 f or die t her modynami sche Deut ung yon Pol ar i sat i onskur ven hingewiesen, sowie
auf die Bedeut ung der Oxydat i onsspannung des Wassers und der Redukt i onsspar mt mg des Sauerstoffs.
Al s Beispiel hi erfi i r wi rd die Chl or i d- Gr enzkonzent r at i on fiir die Er zeugung yon Lochfrass an den
Stfihlen AISI 410, 304, und 316 i n Bi kar bonat l f i sungen, bei Temper at ur en yon 20, 40 und 80C unt er
bes t i mmt en Vor ausset zungen abgeleitet. Es fol gt ei n Uher bl i ck fi ber Unt er suchungef i der Loch-
f r asskor r osi on der drei oben genannt en Stiihle i n Chl or i dl 6sungen unt er Zugr undel egung der Begriffe
Dur chbr uchpot ent i al und Schut zpot ent i al . Di e Wert e di eser Pot ent i al e k/Snnen pot ent i oki net i sch,
pot ent i ost at i sch oder mi t chemi schen Met hoden bes t i mmt werden. Das Dur chbr uchpot ent i al gi bt
ei n Mass ftir die Lochfrassernpfi ndl i chkei t des Stahles. Der Wer t des Schut zpot ent i al s l egt die
Bedi ngungen f'tir den kat hodi schen Schut z i n Gegenwar t yon Oxydat i onsmi t t el n lest. I n gl ei cher
Weise kann ei ne Chl or i d- Dur chbr uchs konzent r at i on angegeben werden, wenn Unt er s uchungen in
Lfi sungen ausgefi i hrt werden, denen steigende Chl or i dmengen zugesetzt werden. Ober hal b dieser
Konzent r at i on erl ei det der St ahl i n Gegenwar t yon Oxydat i onsmi t t el n Lochfrass. Fer ner liisst sich
ei ne unt er e Chl or i d- Gr enzkonzent r at i on angeben, unt er hal b derer Lochfrass unmfi gl i ch ist, auch
wenn Oxydat i onsmi t t el vor handen sind. Dur chbr uchs- und unt er e Gr enzkonzent r at i on hi i ngen von
der Zusammenset zung und War mbehandl ung des St ahl es ab. Di e Dur chbr uchpot ent i al e und -konzen-
t r at i onen hi i ngen auch yon der Ober f l / i chenvor behandl ung ab. Zusat z von Bi kar bonat zu r ei nem
Wasser er h6ht den Kor r osi onswi der st and der St/ihle erhebl i ch. FUr den St ahl Nr . 304 er gab sich
z.B. i n r ei nem Wasser ei ne Dur chbr uchkonzent r at i on yon 9 r ag/ l , i n ei ner 10 -8 mol ar en NaHCO2-
Lfi sung 260 mg pr o 1. schliesslich wer den Ergebni sse von Unt er s uchu~gen an l egi ert en St,~hlen i n
schwefel saurer Lfisung wiedergegeben. Der Zweck dieser Unt er s uchungen war ei n Vergl ei ch der
Ergebni sse pot ent i oki net i scher und kor r osi met r i scher Exper i ment e for die StLlale AI SI 410, 304, 316
und 321 bei unt erschi edl i cher Behandl ung. Einige Ans i cht en fiber den Einfluss verschi edener Oxyda-
t i ons- und Redukt i onsmi t t el und hi nsi cht l i ch der pot ent i oki net i sch er mi t t el t en Kr i t er i en f'tir ei ne
I mmuni si er ungsbehandl ung des St ahl es AI SI 321 gegen Kor nzer f al l werden zum Aus dr uck gebr acht .
I N T R O D U C T I O N
THIS article presents the contents of three lectures delivered at the 13th Meeting of
CITCE. Their titles were:
- - The use of potentiostats for studying corrosion phenomena.
--Pitting corrosion of alloy steels in chloride solutions.
- - The behaviour of alloy steels in sulphuric solutions.
Most of the experimental work mentioned here was carried out as part of the
Research and Development Program of the EURATOM/U. S. A. Co-operation
Agreement by a team of research-workers consisting of Mme L. K|imzack-Mathieu
Potentiokinetic and corrosimetric investigations of the corrosion behaviour of alloy steels 241
and Ch. Mert ens, J. Meuni er and C1. Vanl eugenhaghe (head of research), worki ng in
close consul t at i on with a t eam of research-workers of the Commi ssi on for Funda-
ment al Investigations and Appl i cat i ons CEFA, consisting of Mile N. de Zoubov and
C. Depommi er , R. Van Laer and J. Van Muyl der (heao of research). The pot ent i o-
static appar at us was due t o J. Laureys and L. Neelemans. The followfng technicians
assisted in the above-ment i oned wor k: L. Braekman, A. Pardaen, W. Peulders ahd
A. Regau. Mme M. Warzee and L. de Munck (Soci6t6 d' Et udes, de Recherches et
d' Appl i cat i ons pour l ' Indust ri e SERAI) carri ed out most of the pr epar at i on of alloy
steel specimens.
The wor k of CEFA is carri ed out with t he suppor t of t he Inst i t ut e f or t he Encourage-
ment of Scientific Research in I ndust r y and Agri cul t ure, IRSIA.
The principles of t he met hods used in this wor k have been described in ot her
papers, 1,~ and will be deal t with in Sect i on 2 of this article. Details of the experi ment al
results obt ai ned can be f ound in f our publ i cat i ons made j oi nt l y by EURATOM and
CEBELCOR. s-6
ON THE USE OF POTENTI OSTATS FOR STUDYI NG CORROSION
PHENOMENA
Met hods of cor r osi on research empl oyi ng pot ent i ost at s, which have been very
greatly devel oped duri ng t he last few years, are usually compl et el y satisfactory onl y
i f t he results t hey give are at t he same time reproduci bl e, capabl e of i nt erpret at i on and
selective.
These condi t i ons are oft en difficult t o realize simultaneously, mainly because t he
variables which can affect a t ensi on/ current curve obt ai ned in a pot ent i oki net i c* experi-
ment depend on t he nat ure of t he met al or alloy, and on the nat ure of t he solution.
In general, every new pot ent i oki net i c pr obl em raises new probl ems, in part i cul ar as
far as t he fol l owi ng f our fact ors are concer ned:
- - char act er i st i cs of t he pot ent i ost at used,
- - s ur f ace t r eat ment of t he met al or al l oy specimen,
---characteristics of t he electrolytic cell and accompanyi ng apparat us,
- - r a t e of vari at i on of the el ect rode t ensi on.
Consequent l y t he sat i sfact ory devel opment of a pot ent i oki net i c t echni que suitable
f or a part i cul ar case cannot result onl y f r om wor k of a general nat ure, but always
requires a detailed st udy of t he part i cul ar case. A t echni que can somet i mes be devel-
oped quickly (i ron, or di nar y steels and alloy steels in bi car bonat e solution, f or
example), and sometimes onl y aft er consi derabl e effort ; nevertheless, any i nf or mat i on
obt ai ned in a part i cul ar case may well be useful f or ot her cases.
Pot ent i oki net i c and pot ent i ost at i c met hods, greeted at first with some suspicion,
t hen with enthusiasm, now sometimes seem t o be disappointing, on account of t he
difficulties present ed by t hei r reproduci bi l i t y and i nt erpret at i on. One shoul d not t ake
an oversimplified view of these met hods, nor appl y t hem wi t hout careful study.
However, in all t he cases we know of in which t echni ques have been sufficiently
pat i ent l y and t hor oughl y devel oped bef or ehand, t he met hods have led t o an entirely
sat i sfact ory sol ut i on of t he pr obl em consi dered.
*In potentiokinetic experiments, the electrode tension (or potential) is changed at a given constant
rate, e.g. at 1500mV/hr, and the current measured.
D
242 M. PotmBArx e t al .
0
04
LM
I OF A/ c r n e
I o o o - ~ / . " , , , ' 3 ~ . A / c r n Z
aOO ~ a ; o *
600 -
p =l Ql m
- o o
400 - P %+ P
200 -
i i
0 - - BPI
t /
- 2 0 0 - - a 3 0 4
- 4 0 0 - -
-600 --
-800 - -
I I
20 30
p ,,.p - l al r c t
H 2 H20
~
I I I I I
4 0 50 60 70 80 90
T e mp e r o t u r e , C
PiG. 1. Influence of temperature on the characteristic electrode tensions A, B, B' and B"
for 0"10M NaHCO8 of pH = 8-6 (at 20C).
A HsO/Hs equilibrium
B H=O/O2 equilibrium
B' Oxidation of H~O
B u Reduction of O=
Experimental work carried out by L. Klimzack-Mathieu.
We shall not devel op here t he poi nt of view expressed above, but we shall emphasize
t he i mpor t ance of t he t her modynami c i nt er pr et at i on of t ensi on/ cur r ent curves, z
part i cul arl y with regard t o t he values, f or t he pH and t emper at ur e in quest i on, of t he
fol l owi ng f our el ect rode t ensi ons*:
- - t ens i on of t her modynami c equi l i bri um bet ween wat er and hydr ogen,
- - t ens i on of t her modynami c equi l i bri um bet ween wat er and oxygen,
---oxi dat i on t ensi on of wat er,
- - r educt i on t ensi on of oxygen.
Considering, by way of an example, t he behavi our of al l oy steels in bi car bonat e
solutions cont ai ni ng chloride, 6 we have represent ed in Fig. 1 t he influence of t em-
perat ure on t he f our el ect rode tensions given above, denot ed respectively by t he
symbols A, B, B' and B":
A. H~O/H~ equilibrium,
B. H20/O~ equilibrium,
B' . Oxi dat i on of H20 ( on AI SI 304 steel, f or t hree cur r ent densities, of 1, 3 and
10~tA. em -2 respectively),
B". Reduct i on of 03, on pl at i num and AI SI 304 steel respectively. I t is assumed here,
*Tensions were measured by means of saturated calomel electrode. (Esca denotes tension on
saturated scale.)
Po t e nt i o ki ne t i c a nd c or r os i me t r i c i nve s t i gat i ons o r t he c o r r o s i o n be ha v i o ur o f al l oy s t eel s 243
u~
I000
800
600
400
200
0
- 2 0 0
- 4 0 0
- 6 0 0
Log M
- 2 - i o
~ o ' ) 1 I I I I I I I I I I I I I I I I I I I a , ~ o l I I
- B ~ o
B~o . e. . , . ,
- ~....(8o -..0.(40 ~..zo
- " ' " - - - - . - . - . ~ . - - B,o L B 2 o
_ =-=.,. ~
I I I)1111 I I I I t l l ) l I I I I I I I I
0 . 4 0 ' 6 0 " 8 1 2 4 6 8 I0 20 40 60 80100 NoCL( g/ L)
I I I I I I I I I I ) I I I I I I I I I I I I I 1 1
0"2 0- 40. 60- 81 2 4 6 8 IO 20 40 60 CL-(g/L)
Breokdown tensions
Log M
- 2 -I 0
lO00 ' ( b ' ) ' ' ' - - ' [la'8o ' ' ' ~ ' I ' ' 4 o ' ' ' ' ' [ I ~ ~01 ' '
8 0 0 ~
L
/
i o '~ * *
2 0 ,
6 0 0 - - ~ / 8 0 ~ x / 4 0
4 0 0 - , so
200- .,, "-o- ~B~o
~51"-e.. R'4~
0 - - x 20"C t~ 80 ~ ' ~ . e . . . . o _ . ~.
- 2 0 0 - o 4 0 % . . . . . . ~ - ~ - - o - .
8 0 " C
- 4 0 0 - -
- 6 0 0 1 1 I I I I I I I I I I I I I I I I I I I I I I I
0"4 0' 60' 81 2 4 6 8 I0 20 40 6080100 NoCL( g/ L)
I t I I I I I t l l I I I l l l l l l I I I I I I I
0"2 0"4 0"60"8 I 2 4 6 8 I0 20 40 60 CL- ( g/ L)
Protecti ve tensions
FIG. 2. 316 st eel . Po t e nt i o ki ne t i c b r e a k d o wn and pr ot e c t i ve t e ns i o ns f o r AI SI 316 s t eel
( wi re) , i n 0"10M NaHCO8 sol ut i ons cont ai ni ng c hl or i de , at 20 , 40 and 80C (ori gi nal
he at t reat ment , l e c t r opol i s he d) . Expe r i me nt al wo r k carri ed o u t b y L. Kl i mzack-
Mat hi eu.
as a first a ppr o x i ma t i o n, t hat t he r e duc t i o n t e ns i ons * o f o x y g e n o n t hes e met al s
are pract i cal l y equal t o t he "free t e ns i o ns " o f t hes e met al s i n t he presence o f t he
s o l ut i o n sat urat ed i n oxyge n.
Fi gure 2 represents t he i nf l uence o f c hl or i de c o nc e nt r a t i o n o n br e a kdo wn t en-
s i ons ( Fi g. 2a) f or an el ect rol yt i cal l y pol i s he d AI SI 316 steel ( 16. 7/ 10. 6/ 2. 2 ni c ke l -
c h r o mi u m- mo l y b d e n u m steel ) at 20 , 40 and 80C. The prot ect i ve t e ns i ons ( Fi g. 2b)
o f t he st eel were det ermi ned pot e nt i oki ne t i c al l y by experi ment s i n whi c h t he el ec-
t rode t e ns i on was s ucces s i vel y i ncreas ed and decreased at a rate o f 2 5 mV rain -1
(i . e. 1. 5Vh-1).
Each o f t he curves i n Fi g. 2 s h o ws po i nt s marked wi t h t he l etters B, B' and B",
represent i ng respect i vel y c o ndi t i o ns c or r e s pondi ng t o t he three t e ns i ons gi ven previ -
o us l y ( t aki ng, f or t he r e duc t i on t e ns i o n o f o x y g e n B", t he val ue f or pl at i num) . The
*The r e duc t i o n t e ns i o ns , as def i ned b y P. v a n Rys s e l be r ghe , are t he t e ns i o ns b e l o w wh i c h t he
r e duc t i o n o f o x y g e n t ake s pl a c e at an appr e c i abl e rat e.
244 M. POURBAIX et al.
abscissae of these points represent respectively, for the t hree series of el ect rode ten-
sion values consi dered:
- - Fi g. 2a: the chloride breakdown concent rat i ons, above which localized
cor r osi on of t he electropolished steel occurs.
- - Fi g. 2b : the chl ori de prot ect i ve concent rat i ons, below which cor r osi on will not
occur, even i f t he surface is damaged.
The range of concent rat i ons lying between these t wo ext reme values is practically
t hat f or which steel remains uncor r oded i f its surface is perfect l y polished, but cor r odes
i f t he surface is damaged. Cor r osi on of a damaged surface will stop if the condi t i ons of
el ect rode tension and chl ori de concent r at i on are reduced below t hose represented in
Fig. 2b. Pr ot ect i on can thus be br ought about either by cat hodi c pol ari zat i on of t he
metal (cat hodi c prot ect i on), or by decreasing the chl ori de concent r at i on of t he solu-
tion.
In view of this, what are the el ect rode tensions and chl ori de concent rat i ons t hat are
significant f or practical cases of industrial structures ?
In t he case of structures immersed in a sol ut i on sat urat ed in oxygen, in t he absence
of any ot her oxidizing act i on, the maxi mum tension which t he metal can exert is the
tension B" (reduct i on tension of oxygen). The breakdown and prot ect i ve concent ra-
tions correspondi ng t o t he points B" will t herefore be evaluated without a saf et y margin.
The tensions B (tensions of t her modynami c equilibrium between H2 0 and 02)
cannot be attained by the act i on of the oxygen alone, on account of the great irre-
versibility of the react i on 2H20 = 02 + 4H + 4e-. The br eakdown and prot ect i ve
concent rat i ons for t he points B will t herefore be evaluated with a certain saf et y margin.
This margin will in general be sufficient for t he case of st ruct ures f or which t here is no
possibility of it being subjected to a more powerful oxidizing action t han t hat of oxygen.
The tensions B' (oxi dat i on tensions of water) are t he maxi mum tensions t o which
t he steel can be subjected wi t hout the decomposi t i on of wat er and f or mat i on of oxygen;
these tensions can be attained onl y by means of a particularly intense oxidizing act i on
(e.g. a " s t r a y" current ). The concent rat i ons referring t o the points B' will t herefore be
eval uat ed with a complete saf et y margin; under these condi t i ons, any possibility of
corrosi on is practically excluded, even in the presence of abnormal l y strong oxidizing
action.
Fi gure 3 represents the influence of t emper at ur e on t he chl ori de br eakdown ten-
sions thus det ermi ned, f or t hree el ect ropol i shed steel specimens (AISI 410, 304 and
316) in t he presence of 0.10 M NaHCO3 solutions cont ai ni ng chloride. I t is based on
a knowledge of the tensions B' (with a compl et e safety margin), B (with a cert ai n
safety margin), and B" (wi t hout a safety margin).
It can be seen, f or example, t hat in t he presence of such solutions, at 20C, t he
specimen of 410 steel examined will normal l y cor r ode onl y i f t he chl ori de concent ra-
t i on is as high as 2.1 g/l C1- (Fig. 3c). An absolute guarant ee in the case of an abnor m-
ally powerful oxidizing action, however, requires t hat t he chl ori de concent r at i on
should not reach 0.4 g/l C1- (Fig. 3a).
Fi gure 4 represents, f or the same t hree specimens, t he influence of t emper at ur e on
t he "br eakdown concent r at i ons" and "pr ot ect i ve concent r at i ons" calculated accordi ng
t o t he cri t eri on of the t ensi on B" (i.e. wi t hout safety margin). I t shows t hat , except
under abnormal requirements, the steel 410 (Fig. 4a) will cor r ode by pi t t i ng i f t he
Po t e nt i o ki ne t i c and c or r os i me t r i c i nve s t i gat i ons o f t he c o r r o s i o n be havi our o f al l oy st eel s 245
g
131
v
, j
t o o I - -
6O
0
2 0 - -
I 0 - -
8 - -
6 -
4 - -
- I
2 - -
t - -
0 " 8 - -
0 - 6
0 - 4 - -
- 2
( a )
- - %
- - I
_ _ l
- - ~ 3 1 6
%
3 0 4 " - ~
4 I 0 o. ___=. . ~ ?
F i I I I 1 I
2 0 4 0 6 0 8 0
I , C
. ( b )
\
_ _ " , , 316
%%
- \ , 3 o 4
- - \
- - . o
_ " ?..~.. . . . . ? - - ~
o
--o 410
- - "".o
I I I 1 I I
2 0 4 0 6 0 8 0
t , C
_(c) ",~ 316"*
I i ~ i I I
2 0 4 0 6 0 8 0
t , C
FIG. 3. Inf l uence o f t emperat ure o n t he c hl or i de br e akdown c onc e nt r at i ons f or AISI 410,
304 and 316 st eel s i n 0"IOM NaHCO3 s o l ut i o ns c o nt a i ni ng chl ori de. ( Spe c i me ns i n t he
f or m o f wi res, ori gi nal heat - t reat ment , e l e c t r o- pol i s he d) .
(a) wi t h a c o mpl e t e s af et y margi n ( e l e c t r ode t e ns i ons B' )
(b) wi t h an appreci abl e s af e t y margi n ( e l e c t r ode t e ns i ons B)
(c) wi t ho ut a ny s af et y margi n ( e l e c t r ode t e ns i ons B")
Expe r i me nt al wor k carri ed o ut by L. Kl i mz a c k- Ma t hi e u.
chl ori de c o nc e nt r a t i o n reaches 2.1 g/ l CI- , but will s t op c or r odi ng, even i f i ts surface
is damaged, i f t he c o nc e nt r a t i o n falls be l o w 0. 5 g/ l CI- .
P I T T I NG C OR R OS I ON OF AL L OY S T E E L S I N C HL OR I DE S OL UT I ONS *
Breakdown tensions and protective zensions. Cathodic protection of alloy steel s.
I f o n e carries o ut pot e nt i oki ne t i c experi ment s o n a s peci men o f "st ai nl ess" steel i n a
hi ghl y stirred chl ori de s ol ut i on, i n t he abs ence o f oxyge n, and at an el ect rode t e ns i on
successi vel y i ncreasi ng and decreasi ng at a gi ven rate (e. g. 25 mV mi n -1, i.e. 1.5 Vh- 1) ,
t he f e l l o wi ng is of t e n obs erved (Fi g. 5):
- - d u r i n g t he pol ar i z at i on at an i ncreasi ng t e ns i on, t he current densi t i es at t he
a no de remai n very smal l and rel ati vel y c ons t ant unt i l t he el ect rode t e ns i on
reaches a wel l -defi ned critical val ue ( t he "br e akdown t e ns i on" ER (Brennert))
at whi c h a s udde n and p r o n o u n c e d i ncrease in t he current dens i t y occurs . Thi s
t he n i ncreases i n an irregular f as hi on. The pas s i vat i on film whi c h nor mal l y
covers t he steel t hen ceases t o be prot ect i ve, and pi t t i ng c o r r o s i o n takes pl ace.
I f after pol ar i z i ng t he steel at an i ncreasi ng t e ns i on b e y o n d thi s br e akdown t e ns i on
it is t he n pol ari zed at a decreasi ng t e ns i on, a t e ns i on/ c ur r e nt curve is obt ai ned whi c h
doe s n o t c oi nc i de wi t h t he curve f or i ncreasi ng t ens i on, but lies cons i derabl y be l o w it.
The curve meet s t he ordi nat e axis ( wi t h a pract i cal l y zero current densi t y) at an el ec-
t rode t e ns i on represent i ng a s e c ond wel l - def i ned cri ti cal val ue, whi c h we have cal l ed
t he "prot ect i ve t e ns i on" Ee, be l ow whi c h t he steel s t ops corrodi ng.
A knowl e dge o f t he br e akdown t e ns i ons and prot ect i ve t e ns i ons f or a gi ven steel
* De t a i l e d de s c r i pt i ons o f t he s e i nve s t i gat i ons have be e n made i n publ i c at i ons 3, 4 and 5. The
e xpe r i me nt al wo r k o n t hi s s ubj ect wa s carri ed o u t by J. Meuni er, Ch. Me r t e ns and L. Kl i mzack-
Mat hi eu, unde r t he dai l y s upe r vi s i on o f Cl . Va nl e ug e nha g he .
2 4 6 M. POtntBAlX et al .
, o o
80
6 o
40~
2 0 m
, o -
6 - -
~. 4 - - ~
O~ __0 -I
u 2 ~
o . s ~ _
0 " 6 ~
0-4 -2
i ( a )
_
--B reo kdo y, , ~. . , ~. . . . - - - - - - e
i /
- - . ~ , 0 " . . . . . ?
- ' o - - - P r o t e c t i o n
~ [ I I I I I
20 40 "60 80
t, C
4 1 0 S t e e l
( _ b ) % -
- - 8 r e o k d o w n ' ~ o
Z,
i I I ~ I I I
20 40 60 80
t , C
5 0 4 S t e e l
~ c )
B r e o k d o w n ' ~ e
_ %x x
X x
- - P r o t e c t i o n \
t
__ t
t
- b
- I I I I I I I
2 0 4 0 6 0 8 0
t , " C
5 1 6 S t e e l
FIG. 4. I nf l uence o f t emperat ure o n t he c hl or i de b r e a k d o wn and pr o t e c t i o n c onc e nt r at i ons ,
f o r AI S I 410, 304 and 316 s t eel s i n 0"10M N a HC O. s o l u t i o n s c o nt a i ni ng chl ori de. ( The
val ue s ref er t o t he e l e c t r ode t e ns i o ns B n, wi t h o u t a ny s af e t y margi n) .
( a) 4 1 0 s t e e l
( b) 304 s t eel
( c) 316 st eel
Expe r i me nt al - wor k carri ed o u t by L. Kl i mz a c k- Ma t hi e u.
EP308 EP202 EPI60 EP320
wl p:l~
P . , I - - E , - ]
0 I0 20 I0 20 0 I0 20 I0 20
C u r r e n t d e n s i t y , /J-A/cm z
O.O05MNoCL(O.29gNoCL/L) O.O09MNoCL(O.55gNoCL/L] O.050MNoCL(2-92gNoCL/L) O.IOMNoCL(5"85gNoCL/L)
FIO. 5. I nf l ue nc e o f Na CI o n t he po t e nt i o ki ne t i c t e ns i o n- c ur r e nt curves at 20 C o f AI S I
AI S I 4 1 0 s t eel i n t he f o r m o f a r od, pol i s he d wi t h N o . 1F emery. Expe r i me nt al wo r k
carri ed o u t b y J. Me uni e r a nd L. Kl i mz a c k - Ma t h i e u .
I1 0 0
i , : 0 o
O 0
O0
1 ~ o o
1 3 0 0 3 <
1 2 o o
1 :
Potentiokinetic and corrosimetric investigations of the corrosion behaviour of alloy steels 247
specimen in a given sol ut i on thus enables us t o predi ct t hat t he behavi our of this steel
specimen will depend as follows on its el ect rode t ensi on:
---if the el ect rode t ensi on remains steadily bel ow the br eakdown tension, t he steel
will not be corroded,
----if t he el ect rode t ensi on reaches t he br eakdown tension, even f or a short time,
pitting cor r osi on will occur, and this will cont i nue so l ong as the el ect rode
t ensi on remai ns above t he prot ect i ve t ensi on,
- - t he devel opment of such cor r osi on can be st opped by lowering the el ect rode
t ensi on bel ow t he prot ect i ve br eakdown t ensi on; cat hodi c pr ot ect i on of t he
stainless steel can t hus be br ought about . *
We were able t o confi rm t he validity of these predi ct i ons in t wo series of pot ent i o-
static experiments (Fig. 6) on t he behavi our of el ect ropol i shed wires of stainless steel
AI SI 410, in bi car bonat e sol ut i on cont ai ni ng chl ori de (0.10M NaHCO8 and 0.040M
NaCI, at 20C) f or which t he br eakdown and prot ect i ve tensions were:
Br eakdown t ensi on ER = q- 280 mV/ SCE
Prot ect i ve t ensi on Ee = - - 80 mV/ SCE.
In t he first series of experiments, specimens were mai nt ai ned f or a fairly l ong peri od
(1-15 hr accordi ng t o the case), and wi t hout prepol ari zat i on, at vari ous el ect rode
tensions lying respectively above t he br eakdown t ensi on and bel ow it. As shown in
Fig. 6a, t he cur r ent density f or t he experi ment s carri ed out above t he br eakdown
t ensi on (4- 400, q- 350 and 4- 300 mV), undergoes sharp and i rregul ar vari at i ons,
and presents relatively high values, t Pi t t i ng cor r osi on of the el ect rode was observed
aft er t he experi ment .
For t he experi ment s carri ed out bel ow t he br eakdown t ensi on (-+- 200, 4- 100,
0, - - 100, - - 200 and - - 400 mV), t he cur r ent density does not undergo any sharp
var i at i on; it remai ns l ow and relatively const ant , and, i f it varies, t hen it is a decrease
t hat occurs. Curves of this t ype cor r espond t o absence of corrosi on.
In agreement wi t h the predictions, t he met al either cor r odes or does not cor r ode
accordi ng t o whet her its t ensi on lies above or bel ow its br eakdown t ensi on (-k 280 mV
v. SCE).
I n t he second series of experiments, t he pr ocedur e was t he same as f or t he first,
except f or t he fact t hat before carryi ng out t he pot ent i ost at i c par t of t he experi ment ,
t he specimen was prepol ari zed f or 3 mi n at -k 450 mV, i.e. at a t ensi on above t he
br eakdown t ensi on (q- 280 mV), t hus damagi ng t he met al surface, which had been
electropolished. The results of the experi ment s varied as follows accordi ng t o t he
val ue present ed by t he el ect rode t ensi on with respect t o t he br eakdown t ensi on
(-k 280 mV (v. SCE)) and t he pr ot ect i on t ensi on ( - - 80 mV (v. SCE)).
As shown in Fig. 6b, t he cur r ent density f or t he experi ment carri ed out above t he
br eakdown t ensi on (q- 300 mV) is relatively high, and undergoes sharp and i rregul ar
vari at i ons; intense pi t t i ng cor r osi on t hen occurs.
For t he experi ment s carri ed out bet ween t he br eakdown t ensi on and t he prot ect i ve
t ensi on (4- 200, q- 100 and 0 mV), t he cur r ent density, al t hough much l ower t han in
*After drawing up this report, we learned that May and Humble, using a different method of
investigation, showed in 1952 that austenitic steels AIS1302 and 316 can be protected against corrosion
in sea-water by means of cathodic polarization, x2
t For the experiment at 4- 350 mV, however, these relatively high values appear only during the
first 2 min.
248 M. POORBAIX et al.
E
u
::L
6 0 0
500
4 0 0
3 0 0
200
(o)
o N O c o r r o s i o n
+4OOmV
/ J~3oomv
, o o L - , o o m v
~ . . . . . . . ~ ~* 2oomv
I ~ " ~ ' ~ " ~ 1oo=v
0 l ~ - 200mV
I I I I I : ~ o o ~ v
(b)
300mVa
Loc ol i s ed c o r r o s i o n ( pi l t i ncj )
- - 2OOmV 20OmV
/;,oomv ,oo:v
~ - ~ - " ~. t - 2OOmV
\ OmV ~ 3 0 0 mV
I ] I I I -4oo~,v
0 10 20 50 4 0 50 ' 6 0 0 I 0 20 30 4 0 50 6 0
Ti me, mi n Ti me , rai n
Ser i es I e x p e r i me n l s Ser i es 2 experiments
( no p r e p o l o r i s o t i o n ) ( o f f e r prepolorisotion ot + 4 5 0 mV )
FIG. 6. Pot ent i ost at i c exper i ment s (series 1 and 2). Stai nl ess steel t ype A I S I 410 ( wi r e) ,
in solutions of 0"10M NaHCO8 + 0"040M NaCI, at 20C (Gas-N~; original heat-
treatment; electro-polished by the Jacquet method). Experimental work carried our by
J. Meunier and L. Klimzack-Mathieu.
the previ ous case, remai ns appr eci abl e and vari es shar pl y and irregularly, i ndi cat i ng a
cert ai n cont i nuat i on of t he pi t t i ng cor r osi on initiated duri ng t he pr epol ar i zat i on at
+ 450 mV.
For the experi ment s carri ed out bel ow t he pr ot ect i ve t ensi on ( - - 100, - - 200, - - 300
and - - 400 mV), the current density remai ns pract i cal l y zero, i mpl yi ng t hat t he cor-
rosi on initiated duri ng pr epol ar i zat i on is no l onger proceedi ng.
Finally, t o t hr ow mor e light ont o t he possibility of cat hodi cal l y pr ot ect i ng a
stainless steel by t r eat ment at a t ensi on l ower t han the pr ot ect i ve t ensi on, pot ent i o-
static experi ment s were carri ed out on pl at es of AI SI 410 steel, dry-pol i shed wi t h
car bor undum, in a bi car bonat e sol ut i on cont ai ni ng a large concent r at i on of chl ori de
(0.10M NaHCO3 and 3. 43M NaC1, i.e. 200 g NaCI/1) at 20C, sat ur at ed wi t h oxygen at
at mospher i c pressure, f or whi ch t he t ensi on charact eri st i cs are:
Br eakdown t ensi on ER = - - 150 mV (v. SCE)
Prot ect i ve t ensi on Ee = - - 300 mV (v. SCE)
I n t he presence of this sol ut i on, t he unpol ar i zed steel under goes pi t t i ng cor r osi on,
and its t ensi on shows varyi ng values lying bet ween - - 150 and + 300 mV (v. SCE).
Aft er 1 mi n wi t hout pol ari zat i on, it was mai nt ai ned f or 15 hr at vari ous tensions.
As in t he t wo precedi ng series of experi ment s, t he cur r ent densi t y val ues were r ecor ded
(Fig. 7) and t he appear ance of t he speci mens was not ed vi sual l y (Fig. 8).
The current -densi t y is hi gh and fl uct uat i on above t he br eakdown t ensi on (0, and
- - 100 mV) and increases wi t h t i me; under these condi t i ons t here is intense pi t t i ng
of t he met al .
At t ensi ons bet ween t he br eakdown t ensi on and t he pr ot ect i ve t ensi on ( - - 200
Potentiokinetic and corrosimetric investigations of the corrosion behaviour of alloy steels 249
f
450 0 mV/scs ~ ,,j~i~' ~ . , ~
400 IOOmV J ~ -
"E 300 - ' 2 5 mV~
..~ e 5 o
<~
::L 200
, . 150 / J 0 NO Corrosion
I00 / / Locolized corrosion(pilting) it -=
l J j ' r 4 9 9 m v o i ~
o 5,/ o o v o
-50 ~ 1 I I I
0 I 2 3 4 5 6
Time, hr
FIG. 7. Potentiostatic experiments (series 3). Stainless steel type AI SI 410 (plate), in
solutions of O' IOMNaHCOa + 3"42M NaCI, at 20C (gas--O2; ori gi nal heat-treatment;
polished wi t h 180A carborundum; after being kept f or I rain at a " f r ee" tension).
Experimental wor k carried out by J. Meunier and L. K]i mzack-Mathi eu.
and - - 250 mV) t he cur r ent density, al t hough much less t han in the previ ous' case, still
increases wi t h t i me and is i rregul ar; pi t t i ng remai ns very consi derabl e.
At t ensi ons bel ow the prot ect i ve t ensi on ( - - 300, - - 400 and - - 500 mV), t he cur r ent
density is regul ar and cor r osi on is no l onger observed.
I n Fig. 8 it is of interest t o not e the very pr onounced cor r osi on of the speci mens
t reat ed at 0 and - - 100 mV, t he pr onounced cor r osi on of the speci mens t reat ed at
- - 200 and - - 250 mV, and t he absence of cor r osi on of t he cat hodi cal l y pr ot ect ed
speci men t reat ed at - - 300 mV.
All this is in compl et e agr eement wi t h t he predi ct i ons made.
I t shoul d be poi nt ed out , wi t h regard t o this r epor t , t hat , in general, resi st ance t o
pi t t i ng cor r osi on will be great er t he hi gher the br eakdown t ensi on and t he prot ect i ve
t ensi on; this cor r osi on resistance will be pract i cal l y perfect when no br eakdown
t ensi on exists, i.e. when a pot ent i oki net i c exper i ment at i ncreasi ng t ensi on shows no
sudden and i rregul ar i ncrease of the cur r ent density.
I nf l uence o f t he nat ur e o f t he st eel , i t s h e a t - t r e a t me n t a n d i t s s ur f ace s t at e . The val ue
of t he br eakdown t ensi on of an al l oy steel in a chl ori de sol ut i on, and consequent l y
t he resi st ance of this steel t o the cor r osi ve act i on of the sol ut i on, depend on t he nat ure
of t he steel, its heat - t r eat ment and its surface state.
For t hree steels of t ypes AI SI 410 ( chr omi um) , 304 (chromi um-ni ckel ) and 316
( chr omi um- ni ckel - mol ybdenum) , we have observed t hat t he br eakdown t ensi ons
decrease in t he or der 316> 304> 410 in a sol ut i on of 0. 10M Na HCO a (8.3 g Na HCOa /
1) and in 0. 600M NaCI (35.0 g NaC1/ 1, i.e. 21.3 g C1-/1) at 20C. Thi s or der is t he
or der of decreasi ng resi st ance t o pi t t i ng cor r osi on 3 in t he presence of chloride.
250 M. POtrRSAIX et al.
In general, t he br eakdown t ensi on (and t he resistance t o pitting corrosi on) are
highor t he mor e perfect the polishing. For an el ect ropol i shed quenched specimen of
316 steel, no br eakdown tension has been observed in the presence of the chloride
sol ut i on indicated above, despite its very high chl ori de concent rat i on.
I n general, heat -t reat ment of t he steel affects t he values of the br eakdown tensions.
Influence of the chloride concentration and the presence of oxidizing agents. I f t he
behavi our of a steel is exami ned in t he presence of vari ous solutions obt ai ned by adding
different quantities of NaCI t o t he same sol ut i on (pure water, solutions of NaHCOs
of vari ous concent rat i ons), it is seen t hat an increase in the chl ori de concent r at i on
causes a large decrease in the br eakdown and prot ect i ve tensions (Fig. 9).
For each t ype of sol ut i on and f or each steel specimen, t here exists a cert ai n
critical value of the chl ori de concent r at i on, bel ow which a pot ent i oki net i c experi ment
I 000
800
600
400(
200
d o
:200
- 400
- 6 0 0
I
(o)
B ~ I o %~ ~Ori gi nol heot - l r eot men! B
B r e o k d o wn - - - ~ - ~ e ~ o , , ~ ~ ^ ~ J Heot ed f or 2 hr o! 675 C
, en, , oos
Pr ol ecf i ve . J - " " . ~ . ' ~ ( - ~ / ~ ) /
, e n , i o n , \ o " ~ . ~ / - " y - - - - - - - - - , - - , ~ - - - ' ~ " "
" . . . . " ~ - - , . . . . . . Z _ - o . . . . . . . . . . . o - - ' : ~ . . _ ,
- - - - - - - - - 0 . . . . . .
I I I ] I I i I I I I i I
6 a io-Z 2 4 6 e I 0" a ~ 6 s I MNoCL/ L
I I I I f I I I I I I I I
0-4 0, 60, 8 I 2 4 6 8 tO 20 4 0 60 gNoCL/ L
AISI 3 0 4 S t e e l
( b )
~ooo - ~ , ~ \
800 " ~ ~ . Or i gi nol , heat - t r eol ment
600 -- ~ ' k ~ ' He a t e d . f or 2 hr at 675 C
200 - " x"~x__ x
,,, 0 Prot:CJinVse" ~ / / - " "~.,.,~x . . . . . x
-200 Br eo:?thr oucjh / - "-..~ "~r: : -
-400 tensions
- 6 0 0 I I I I I I I I I I I I I
6 s io-Z z 4 6 8 iO-i 2 4 6 e I MNoCL/ L
I I I I I I I I I I I I
I 014 0. 60. 81 2 4 6 8 I0 20 40 60 gNoCL/ L
Al Sl 316 St eel
FIG. 9. Influence of a heat-treatment (304 and 316 steels). Potentiokinetic breakdown
and prot ect i ve t ens i ons o f AI SI 304 and 316 steel s (rods), i n s ol ut i ons o f 0 . 1 0 M NaI-ICOs
cont ai ni ng chl ori de, at 20C ( pol i s hed wi t h 1F emery) . Experi ment al wor k carried out
by I. Meuni er and L. Kl i mz ac k- Mat hi e u.
i
l Y 'i
[ ,
~. 0 ~ -~
.E ~ ~. . ~
.~ ~._~
, ~' ~
,-, .~- ,,., ~
~Oo.E
._~= ~ ~
~ Z
O 0
~ - ~
u 0
~.o~
"= =' 6 o
~ "~~
Potentiokinetic and corrosimetric investigations of the corrosion behaviour of alloy steels 251
shows no r upt ur e of t he passi vat i ng film. Consequent l y, in the presence of such solu-
t i ons, cor r osi on of t he steel by pi t t i ng is i mpossi bl e, whet her the sol ut i on cont ai ns an
oxidizing agent or not .
Gi ven below, f or ' t he t hree steel speci mens exami ned, are t he val ues f ound f or these
critical chl ori de concent r at i ons, whi ch var y accor di ng t o the heat - t r eat ment and t he
surface st at e of t he met al :
410 steel: 0.24 t o 0.54 g C1-/I
304 steel: 0.53 t o 1.04 g CI-/1
316 steel: 0.62 t o 24.3 g C1-/1
When t he chl ori de concent r at i on is above this critical concent r at i on t here is a
risk of localized cor r osi on. Such cor r osi on cannot however occur in the absence of
oxidizing act i on: it can onl y t ake pl ace in the presence of an oxidizing agent or anodi c
pol ar i zat i on capabl e of raising the el ect rode t ensi on of t he steel, even t empor ar i l y,
above t he br eakdown t ensi on.
I t was possi bl e t o veri fy this fact easily by experi ment s in whi ch an oxidizing agent
(KMnO4, NaC10) was added gradual l y to a bi car bonat e sol ut i on cont ai ni ng chl ori de
(0.10M Na HCOa and 0-05M NaCI , f or i nst ance) (Fig. 10). I f t he t ensi on of the steel
is measur ed while t he oxi di zi ng agent is bei ng added, it is seen t hat , dependi ng on the
case (Fig. 10a), ei t her this t ensi on rises regularly, r emai ni ng const ant l y bel ow t he
br eakdown t ensi on det ermi ned pot ent i oki net i cal l y, t he met al r emai ni ng unat t acked,
or t he t ensi on, aft er a sl ow and regul ar increase, undergoes a rapi d fall and cont i nues
in an i rregul ar manner , t he met al under goi ng pi t t i ng cor r osi on. We have observed t hat
t he t ensi on at whi ch this pi t t i ng occurs (det ermi ned here chemically by addi t i on of
oxidizing agent ) is exact l y t he same as t he br eakdown t ensi on ER (which had been
2 " 6
2 . 4
2 ' 2
2
I - 8
<
E 1"6
I-4
0 I ' Z
1. 0
0 . 8
0 . 6
0 " 4
0 - 2
0
ECL53
400 \ ~ / - - - (0) [ t (b)
Electrode tension Electrode tension
300 / //./---- . . . . . . . .
E
/ / . -
200 / , / / / / , , " ~ KMn04 concent re t i o n
ioo f /
f f
J
o / / '
/
/
- I 0 0 / . . . . . . . . . . . . . . . . . . . . . .
/
/ / / ' ~ K MnO 4 concentration
- 2 o o /
/ i I I I 1 I I I I i I f I I I I I I I i
0 4 6 8 I0 12 14 16 ' 8 0 :~ 4 6 8 I 0 12 14 ' 6 IO
T i m e , ml n T i me , mi n
0 . 0 2 M N o C L / L , 1.169g N o C L / L 0 ' 0 5 M N o C L / L , 2 . 9 2 g N o C L / L
FIG. 10. Chemical experiments. Tension-time curves with gradual addition of KMnO=.
Stainless steel type AISI 410 (wire), in solutions of 0"IOM NaHCO3 + NaCI, at 20C
(gas--N0. Experimental work carried out by J. Meunier and L. Klimzack-Mathieu.
ECL30
252 M. POURBAIX e t al .
det ermi ned potentiokinetically by electrolytically raising t he el ect rode tension).
This is clearly seen in Fig. 11 f or an AI SI 410 steel (having an unt reat ed surface in
chl ori de-cont ai ni ng solutions of NaHCOa at 20C. This shows a line representing t he
br eakdown tensions det ermi ned potentiokinetically, and some points representing the
br eakdown tensions det ermi ned chemically (by addi ng vari ous oxidizing agents:
KMnO4, NaCIO, H202, 02); it can be seen t hat the points cor r espondi ng t o the
chemical br eakdown tensions agree very satisfactorily with the line showing t he
pot ent i oki net i c br eakdown tensions.
The concept of br eakdown tension of a steel specimen in a sol ut i on is t herefore of a
fundament al nat ure: t he value of this t ensi on is t he same f or a chemical oxi dat i on as
f or an electrolytic oxi dat i on, and this value is i ndependent of t he nat ure of the oxi-
dizing agent.
Practical importance of the breakdown tension and the protective tension. It follows
f r om t he above t hat a det ermi nat i on of the br eakdown t ensi on can enable us quickly
to select alloy steels which will satisfactorily resist pitting cor r osi on in a given solution.
This conclusion, obt ai ned f r om research on chl ori de-cont ai ni ng bi car bonat e solutions,
can be ext ended quite generally t o any solution. Measurement s of br eakdown tensions
can t herefore greatly help in determining, f or a given steel alloy specimen, heat -t reat -
ments and surface t reat ment s which will confer on this steel a bet t er resistance t o
pitting in any given sol ut i on; these measurements can also help in devel opi ng ot her
steels and alloys which will resist such corrosi on.
Also, a knowl edge of the prot ect i ve t ensi on of an alloy steel in a given aqueous
solution c a n help in developing devices for cat hodi cal l y prot ect i ng t he steel in t hat
solution. It is well known t hat alloy steels can be prot ect ed by anodi c pol ari zat i on in
sulphuric solutions: t he investigations described here (see also reference 2) show t hat
these steels can a so sometimes be usefully prot ect ed by cat hodi c pol ari zat i on.
Finally, it is probabl e t hat t he principles discussed above, concerni ng t he influence
of chl ori de and oxidizing agents on t he cor r osi on behavi our of alloy steels in bicar-
K M n 0 4 +
I 0 0 0 ~ Break-through tensions !iCLO o
d e t e r m i n e d c h e m i c o l l y O z x
8 0 O
6 0 0
>E 4 0 0 i o-~+, B i
~, ZOO
o + " - ' + ' ' - ' + + " ' + ~ . o - . _ . ~ . +
- 2 0 0 B r e o k - f h r o u g h t e n s i o n s d e t e r m i n e d
- 4 0 0 p o f e n f i o k i n e t i c o l l y
- 6 0 0 I [ I I I I I I I I I I I
e 10-2 a 4 6 a iO-J z 4 6 a I M N o C L / L
I I I I I I [ I I I I 0 / g N e C L I / L
0 " 4 0 ' 6 0 - 8 I 2 4 6 8 10 2 0 4 0 6
F i G . 1 1 . B r e a k d o w n t e n s i o n s d e t e r m i n e d c h e m i c a l l y a n d p o t e n t i o k i n e t i e a l l y f o r A I S [
410 steel (wire), in solutions of 0"10M NaHCO8 containing chloride, at 20C (original
heat-treatment; original surface state). Experimental work carried out by J. Meunier
and L. Klimzack-Mathieu.
Potenttokinetic and corrosimetric investigations of the corrosion behaviour of alloy steels 253
bona t e sol ut i ons, ar e qual i t at i vel y t r ue f or all met al s and al l oys whi ch can be passi -
vat ed i n aqueous sol ut i ons. Knowl e dge o f t hi s f act ma y c ont r i but e t o t he s ol ut i on o f
t he pr obl ems still r ai sed by t he sear ch f or t he cause o f t he act i vat i ng act i on o f chl or i des
on t he c or r os i on o f met al s and al l oys.
Influence of chloride on the behaviour of an alloy steel hz "pure" water and in bicar-
bonate solutions.* Si nce i ndust r i al pr act i ce has s hown t hat c or r os i on o f al l oy steels
can oc c ur in rel at i vel y pur e wat ers, at muc h l ower chl or i de c onc e nt r a t i ons t ha n t hose
quot e d a bove f or 0. 10M bi c a r bona t e sol ut i ons (e.g. 0.53 t o 1.04 g/1 f or an AI SI 304
steel), we have car r i ed out exper i ment s t o det er mi ne t he cri t i cal chl or i de c onc e nt r a t i on,
a bove whi ch l ocal i zed c or r os i on o f a gi ven al l oy steel can oc c ur in such wat ers, on t he
basi s o f t he c onc e pt o f b r e a k d o wn t ensi on.
Fo r t hese i nvest i gat i ons we e mpl oye d a speci men o f AI SI 304 steel, in t he f or m o f
a r od, whi ch had been heat - t r eat ed i ndust r i al l y and pol i shed wi t h 1F emer y.
Fo r exper i ment al conveni ence we pr oceeded, not pot ent i oki net i cal l y as bef or e
(i.e. i ncr easi ng t he el ect r ode t ensi on o f t he steel r egul ar l y in a gi ven sol ut i on) , b u t
pot ent i os t at i cal l y (i.e. i ncr easi ng r egul ar l y t he chl or i de c onc e nt r a t i on o f t he s ol ut i on
in c ont a c t wi t h t he steel mai nt ai ned at a gi ven el ect r ode t ensi on).
Fi gur e 12 s hows a c ur r e nt / t i me cur ve obt ai ned i n such an exper i ment , in whi ch
Na CI was added gr adual l y t o doubl e- di st i l l ed wat er in c ont a c t wi t h 304 steel mai n-
t ai ned at + 600 mV (v. SCE) at 20C. I t is seen t ha t t he b r e a k d o wn o f t he pr ot ect i ve
film, r eveal ed by a s har p i ncr ease in t he cur r ent , occur s at a chl or i de c onc e nt r a t i on o f
0 026 g/1.
*Details of this work are to be found in reference 4.
250
N 200
E
~t 150
~7 I00
50
- 4 O
- <
~ ' 3 0
I0
0
Breokdown of f
-- protective f i l m . /
-- CL- br eokdown I / . ~ " I J
co nce nt rot i on~. ~. . . _ _ / . . . . . . . . . . . . .
C o n c e C L : a t i o n _ . . " ' ' ' " / / ~ ' E l e c l r o l y s i s
/ f c u r r e n t
j JS
/
- - s s S
Y l ~ L I I i I 1 I I I I I
I0 20
Time, rain
FIG. 12. Potentiostatic determination of the NaCI breakdown concentration.
Steel: type AISI 304 (rod); original heat-treatment; polished with 1F emery.
Basic solution: double-distilled water
Electrode tension: + 600 mV (v. SCE)
Temperature: 20 -- IC
Gas: N~
Experimental work carried out by J. Meunier.
254 M. Potn~ArX et al.
1000900 H E ~ f 0 N o H C O 3 & O ' O I O M N o l i C O 3 B O , I O M
8 0 0 x B ~
7oo \
, o o , o , . , ,
5 0 0 ,' ' ~ . B ~ b , , , , , Q , ~ ~ I
u ~ 4 0 0 I
2 0 0 ~ x "
I O 0 B ; ~ x ~ ,
0 I I I
- ' - 3 - 2 - I L o g M
I I I I I I I I I I I [ I I I I
1 0 - 4 z 4 e l O - 3 z 4 6 e l o - z z 4 ~ e l O - t z M / L
I I I I I I I I I I I I I I i l l
o - o o 4 0 " 0 1 o . o z 0 . 0 6 0 . I o . z o - 4 o . s I z 4 e l O C L - g / L
F~o. 13. Rel at i on bet ween t he el ect rode t ensi on and t he NaCI br eakdown concent r at i on
det er mi ned pot ent i ost at i cal l y.
St eel : type AISI 304 (rod); original heat-treatment; polished with 1F emery.
Base solutions: double-distilled water and 0"IOM NaHCO3
Temperature: 20 IC
Experimental work carried out by .1. Meunier.
Figure 13 shows, for three series of solutions made up by the addition of NaC1
respectively to double-distilled water and to 0.010M and 0.10M solutions of NaHCOa,
the relationship found in such potentiostatic experiments between the electrode tension
and the chloride breakdown concentration. It can be seen from this figure that, at the
tension B' (oxidation of water) for which the conditions of protection against corrosion
can be calculated with a complete safety margin (see above), the chloride breakdown
concentrations have the following values for the three solutions considered:
--double-distilled water 9 mg C1-/I.
--0.84 g NaHCOa/1 (0.010M) 260 . . . . . .
--8.4 g NaHCOs/1 (0.10M) 1260 . . . . . .
The addition of NaHCO8 to double-distilled water thus considerably reduces the
risk of pitting corrosion which would result from the presence of chloride.
On the other hand, for the different tensions B', B and B" dealt with previously,
which enable us to estimate the danger of pitting corrosion with d'd]'erent safety margins,
the chloride breakdown concentrations have the following values (for distilled water):
--tension B' (oxidation of H20) 9 mg CI-/1 (complete safety margin)
--tension B (H20/O~ equilibrium) 32 . . . . . . (considerable safety margin)
--tension B" (reduction of 02) 516 . . . . . . (no safety margin)
Finally, the chloride breakdown tensions determined potentiostatically are, as
shown in Fig. 14, higher than those obtained potentiokinetically. This means that the
quality of the passivating film on the 304 steel considered was improved by the anodic
prepolarization in a non corrosive medium.
Potentiokinetic and corroslmetric investigations of the corrosion behaviour of alloy steels 255
E
I 0 0 0 ~ N o H C 0 3 O . I O M
oo:i'li
5 0 0 1 _ k . _ P o t e n t i o s t a t i c
B ~ . B ~ / m e t h o d
,o o 1 - \ . , , .
3 0 0 F ~ + / P o t e n t l o s k i n e t i c
z o o 1 - % - + met hod
0 - - [ B " ~ ' + ~ ' +
~ , , , , - I , , I o L o ~ M
i O - Z a 4 s a l O - t 2 4 e M / L
| 1 I I I I I I I I I I
0 . 4 o.a I z 4 s alO 2 o C L - g / L
FIG. 14. Relations between the electrode tension and the NaCI breakdown concentration,
determined potentiostatically and potentiokinetically.
Steel: type AISI 304 (rod); original heat-treatment; polished with 1F emery
Basic solution: 0"10M NaHCOa
Temperature: 20 + 1C
Experimental work carded out by J. Meunier.
THE BEHAVI OUR OF ALLOY STEELS I N SULPHURI C SOLUTI ONS*
As a cont r i but i on t o t he i nvest i gat i on of t he cor r osi on behavi our of alroy steels
in sul phuri c sol ut i ons, pot ent i oki net i c det er mi nat i ons were made of t ensi on/ cur r ent
curves f or t hree aust eni t i c chr omi um- ni ckel steels (t ypes AI SI 304, 316 and 321) and
one ferritic chr omi um steel (t ype AI SI 410) in 1M sul phuri c aci d sol ut i on at 25C,
under a ni t rogen at mospher e. The austenitic steels were exami ned aft er bei ng subjected
t o var i ous t her mal t r eat ment s, in par t i cul ar sensi t i zat i on t o i nt er gr anul ar cor r osi on
(heat i ng f or 2 hr at 675C) and in addi t i on, f or steel 321, a t r eat ment of i mmuni zat i on
agai nst i nt er gr anul ar cor r osi on (heat i ng f or 2 hr at 870C). The ferritic steel 410 was
exami ned af t er bei ng subj ect ed t o a sensi t i zat i on t r eat ment (heat i ng f or 10 mi n at
1000c).
These steels were also subj ect ed t o var i ous cor r osi met r i c t est s: in par t i cul ar t he
Strauss t est wi t h copper sul phat e, t he Huey t est wi t h nitric acid, i mmer si on t est s
in sul phuri c sol ut i ons t o whi ch vari ous oxidizing subst ances ( HNOs, Fe2(SO4)a,
CuSO0 or reduci ng subst ances (As2Oa, Na~SO.~) had been added, and pot ent i ost at i c
t r eat ment s at var i ous el ect rode t ensi ons in sul phuri c sol ut i ons.
A compar i s on was made bet ween t he results of t he cor r osi met r i c tests and t hose o f
t he pot ent i oki net i c experi ment s.
I t shoul d be poi nt ed out t hat this was onl y a r ough i nvest i gat i on, but cer t ai n
i nt erest i ng results were obt ai ned.
Potentiokinetic experiments. I n general t he t ensi on/ cur r ent curves obt ai ned f or an
*Details of this work can be found in reference 6. A bibliographic study of this subject is given in
7. The experimental work on this problem was carried out by Ch. Mertens and L. Klimzack-Mathieu,
under the daily supervision of CI. Vanleugenhaghe.
256 M. Potmn~aX et al.
LtJ
Log I I I , m A / c m z
- 2 - 2 . 6 - 2 -= o =
I I 2ooo1 _ I I I I I I I I I I I I I I I I I I I I "']/
2200 - -
2 0 0 0 - - 1 8 0 0 - -
1800 - - 1600
14oo - - ~ ~ = ~ = ~ = ~ B~ 16oo - -
1200
1400 - -
J200- I 0 0 0 ~ - 8
I 0 0 0 - - 8 0 0 / , -
; 6 0 0 - - /i
800--,600_ 400 -- I ( I { / No' loborotory ,reotmen,
oo- oo-
_ o _ . . . . .
o- -2oo ;~ . . . . . . . . . 2~-.'~ A
-200 -- ---400-
I I I I I I I I I I I I I I I L I I I I I I I t l
s 4 *-2'5 4 6 S IO-Z 2 4 6 8 iO-I 2 4 s 8 I 2 4 6 e I 0 ~ 4 s e tO z
JI r e d l , r n A/ c m 2 I o x , mA / c r n 2
F I o . 15. S t a i n l e s s s t e e l t y p e A I S I 3 0 4 . W i r e s . P o t e n t i o k i n e t i c e x p e r i m e n t s . L a b o r a t o r y
h e a t - t r e a t m e n t s : - - n i l , - . . . . 2 h r a t 6 7 5 C , c o o l e d i n s t i l l a i r . S o l u t i o n : I M
H = S O 4 ; G a s : N . ; T e m p e r a t u r e : 2 5 C ; P o l i s h i n g : d r y 6 0 0 A c a r b o r u n d u m . E x p e r i m e n t a l
w o r k c a r r i e d o u t b y C h . M e r t e n s a n d L . K l i m z a c k - M a t h i e u .
inereashag t ensi on (pl ot t ed at a rat e of increase of 100 mV/ mi n -1) showed t he classical
f or m represent ed by Fig. 15. In agreement with the observat i ons made by Edel eanu s
and Berge and Jacquet, 9 we not ed t hat t he sensitization t r eat ment causes an increase
in t he cur r ent densities in t he passi vat i on regi on (tensions above about - - 300 mV
(v. SCE)); however we did not observe t he results obt ai ned by Clerbois et al. ~ who
r ecor d t he appear ance of a second cur r ent densi t y maxi mum, aft er such a t reat ment ,
at an el ect rode t ensi on of about - - 100 inV.
As shown in Fig. 16, t he "i mmuni zat i on" t r eat ment of t he 321 steel caused t he
di sappearance of t he cur r ent density maxi mum due t o t he phenomenon of secondar y
passivity; in this case we not i ced onl y an inflexion of t he curve, wi t hout any maxi mum
or minimum.
I f t ensi on/ l og current curves are pl ot t ed f or cat hodi c pol ari zat i on, on t he ot her
hand, it seems t hat these curves result in general f r om t he superposi t i on of two Tafel
straight lines in t he case of steels which are not sensitive t o i nt ergranul ar cor r osi on,
and three Tafel st l ai ght lines f or t hose whi ch are sensitive t o such corrosi on.
Comparison of results of corrosimetric and potentiokinetic experiments. Fi gur e 17
which refers t o an AIS1304 steel in t he f or m of a quenched plate, shows f our pot ent i o-
kinetic curves pl ot t ed f or different rat es of increase of t ensi on (respectively 450, 900,
6000 and 24000 mV/ h -~) in 1M HzSO4 solution. I t also shows t he results of vari ous
corrosi met ri c tests (i mmersi on tests in solutions of sul phuri c acid t o whi ch vari ous
oxidizing and reduci ng substances had been added) and vari ous pot ent i ost at i c experi-
ment s in sulphuric solutions.
i
Lo
E
Potentiokinetic a n d corrosimetric investigations of the corrosion behaviour of alloy steels 257
8 0 0
7 0 0
6 0 0
5 0 0
4 0 0
3 0 0
2 0 0
moo
0
- I 0 0
- 2 0 0
- 3 0 0
- 4 0 0
~, - 5 0 0
L o g T , m A / c m 2
" 2 - 2 ' 6 - 2 - I 0
, , , o o r >_ ~ i i i L - - ~ - I
, o o o L - , 8 o o i - . , ~ c - ' \ / - I
I . . ~ ~ o o I - . , . f / : O m ~ n . _ , o ~ ' ~ I
c o o l - - " ' " ' " I ! | ; . . . . . 2hr. 870- C I
~ I - L L I ",I~ 'i I
e e l - ' 1 - " , . X I I
2oo I o I - " ' - _ ' ~ , . _ k . /
- 2 0 0 ~ ~ 1
8 6 4 . 2 5 4 S alO-Z Z 4 s 8 1 0 - 1 Z 6 8 I Z 4 6 I 0 Z 4 I 0 2
I r e d , m A / c m - 2 I o x , m A / c m 2
FIG. 16. S t a i n l e s s s t e e l 32]. Plates. P o t e n t i o k i n e t i c experiments . L a b o r a t o r y h e a t t r e a t -
merits: 10 min at 1 0 5 0 C; . . . . 2 h r at 8 7 0 C ; - - - - - 2 h r a t 6 7 5 C, c o o l e d i n s t i l l
air. Solution: IM H2SO4; Gas: N. ; Temperature: 2 5 C ; P o l i s h i n g : diamond, 7 F.
Experimental work carried out by Ch. Mertens and L. Klimzack-Mathieu.
L o g I, m A / c m 2
- 2 -I O |
_
I 0 0 0 bB O 0 0 m V / h r " B
- - 9 0 0 ~ HNO ( 3 0 ( l y s ) m v / h r [ ~ ~ / J a a s
, , , o t . . o $ , o . c . ~ , o . . r o , . c o . . , o < , ~ m / = , o
- - ^ ^ - Fe2(S04}3 I / P o t e n t i o s t o t i c e x p t s generalised corroslon>lp.m/month I
u u u i ' ( 3 0 d o y s ) I I o Corros m e t r i c e x p t S , g e n e r o l i s e d corrosion<l/.~m/momhl
- - 7 0 0 " ! - I I Corrosimetr|c explS, generolised corroslon~.lp.m/monthJ
- - I ( ' S h r ) I ~ - - ~ " ~
s ooj - I " ~ ~' ~ \ ~ -~
- 2 . . / . , =.=_ = o ~ \ ~ ~ . . . .
~ O 0 ( ( 1 5 h r ~ : 6 - 0 : 6 ~ " ~ - o - - o o ~ ' N - -
- ~ C u S O 4 , "~~ ~o" ~ ~
- - I 0 0 s 2 0 ~ ( 5 O d o y s ) 15h O 0 0 m V / h r
- \ 4 5 ; m V / ~ 9 0 0 m V / h r
-ZOO r
- -~oo ! I I I I I I I I I I I ! ! I I ! ! !
4 6 e i O - 2 2 4 s a I 0 - 1 z 4 1 z I 0
, ' ! I I I I , o ! J i ~ = ~ , o o m " / c ? ' j I
6 2 6 e 2 I 0 0 0
M e a n p e n e t r a t i o n r o t e , / z m / m o n t h ( C o l c u l o t e d )
F I G . 1 7 . S t a i n l e s s s t e e l t y p e A I S I 3 0 4 . P l a t e s . Q u e n c h . T e m p e r a t u r e : 2 5 C . Compari son
between the potentiokinetic, potentiostatic and corrosimetric experiments. Experimental
work carded out by Ch. Mertens and L. KlLmzack-Mathieu.
258 M. POURBAIX et al.
Thi s figure s ho ws t hat , i n general , t he be havi our o f t he st eel f rom t he po i nt o f vi ew
o f c o r r o s i o n i n sul phuri c aci d s ol ut i on, whe t he r t hi s c ont ai ns an oxi di z i ng s ubs t ance
or not , depends essent i al l y o n t he el ect rode t e ns i o n o f t he steel , i rrespecti ve o f t he
me t ho d o f obt ai ni ng a parti cul ar t e ns i on.
I n general , t he st eel wi l l remai n pract i cal l y unc o r r o de d i f its t e ns i on lies bet ween
- - 250 mV and q- 750 mV (v. SCE) .
On t he ot her hand, t he st eel wi l l c or r ode i f i t s t e ns i o n is be l o w - - 250 mV or
above -q- 750 mV. It is t o be expect ed nevert hel es s t hat t he st eel wi l l n o t c or r ode i f a
very l o w t e ns i o n ( whi c h we have n o t det ermi ned) is i mpos e d o n i t, as t hi s t e ns i o n wi l l
be abl e t o prot ect it cat hodi cal l y, wi t h, o f cours e, a cons i derabl e e v o l ut i o n o f hydr oge n.
I n vi e w o f t hi s, t he c o r r o s i o n o f 304 steel i n s ul phuri c aci d c an be prevent ed by
anodi c pol ar i z at i on bet ween - - 250 and q- 750 mV, or by addi ng t o t he s o l ut i o n
oxi di z i ng agent s s uch as HNOa ( q- 650 mV) , Fez(SO4)a (-q- 600 mV) and CuSO4( 0mV) .
On t he ot her ha nd c o r r o s i o n is s t i mul at ed by t he addi t i on o f Na~SO3. I n agreement
wi t h predi ct i ons made o n t he basi s o f t e n s i o n - p H equi l i bri um di agrams f or t he syst ems
Fe - HaO and As - H~O, 11 c o r r o s i o n o f t he st eel is prevent ed by t he addi t i on o f As~Oa
t o t he s ul phuri c s ol ut i on, o n a c c o unt o f t he r e duc t i on o f arseni t es t o el ement ary
arseni c, whi c h deposi ts' i t sel f o n t he st eel t o f or m a film whi c h i s t o al l i nt ent s and
purpos es prot ect i ve.
REFERENCES
1. M. POURBAtX, Sur l' interprdtation thermodynamique de courbes de polarisation. CEBELCOR
Technical Report RT.1 (1952). See also The Utility o f Thermodynamic Interpretation o f Polariza-
tion Curves. J. Electrochem. Soc. 101, 217-221C (1934).
2. M. POURaAtX and F. VANDERVELDEN, Les mdthodes intensiostatiques et potentiostatiques. Utilisa-
tion pour la prdddtermination des circonstances de corrosion et de non corrosion de m~t aux et
d'alliages. CEBELCOR Technical Report TR. 89 (1961).
3. L. KLIMZACK-MATHIEU, J. MEUNIER, M. POURBAIX and CI. VANLEUGENX-IAGHE, Sur le comporte-
ment d' aciers alli~s en solution chlorur~e. L Influence d' oxydant s en solution bicarbonique. CEBEL-
COR Technical Report RT.103 (Euratom Report 3413 (1962).
4. L. KLnVtZACK-MATmEU, J. MEUNIER, M. POURBALX and CI. VANLEUGENHAGHE, Sur le comporte-
ment d' aciers allies en solution chlorur~e. I L Influence de bicarbonate et de sulfate, t] 20C. CEBEL-
COR Technical Report RT.104 (EURATOM Report 3513 (1962).
5. L. KLIMZACK-MATHIEU, Ch. MERTENS, J. MEUNIER, M. POURBAIX and CI. VANLEUGENHAGHE,
Sur le comportement d' aciers allids en solution chlorurde. I I L Influence de la temperature sur les
tensions de rupture et de protection d'aciers, et sur les concentrations de rupture et de protection en
chlorure (solutions bicarboniques). CEBELCOR Technical Report RT.105 (EURATOM Report
360 (1962).
6. L. DE MUNCK, L. KLIMZACK-MATH/EU) Ch. MERTENS, J. MEUNIER, M. POURBAIX, CI. VANLEUGEN-
HAGHE and M. WARZEE, Sur le comporlement d' aciers inoxydables en solution sulfurique. I.
Recherches expdrimentales. CEBELCOR Technical Report RT.106 (EURATOM Report 37t")
(1962).
7. Ch. M~RTENS, Sur le comportement d' aciers inoxydables en solution sulfurique. I L Et ude biblio-
graphique. CEBELCOR Technical Report RT.107 (EURATOM Report 38t3 (1962).
8. C. EDELEANU, The potentiostat as a metallographic tool. J. Iron St eel Inst. (London) 185, 482--488
(1957).
9. Ph. BERGE and P. A. JAcQtrET, Quelques exemples d' application du pot ent i ost at aux ~tudes sur le
comportement des m~t aux en milieu aqueux. Proceedings of the 3rd Metallurgy Colloquium--
Saelay (June 1959).
10. L. CL~a3om, F. CLEReOm and J. MASSART, Corrosion intercristalline des aeiers inoxydables
austdnitiques. Electroehim. Act a 1, 70-82 (1959).
Pot ent i oki nvt i c and cor r osi met r i c i nvest i gat i ons of t he cor r os i on behavi our of al l oy steels 259
11. J. VAN MUgLDER and M. POURnALX, Comportement dlectrochimique de l'arsenic. Diagramme ten-
si on-pH du syst~me As-H. O, tt 25C. CEBELCOR Techni cal Repor t RT. 46 ( Febr uar y 1957).
See al so Atlas d'Equilibres Electrochimique, CEBELCOR, 523.
12. T. P. MAY and H. A. HUMBLE, Effectiveness of cat hodi c current s i n reduci ng crevice cor r osi on and
pi t t i ng of several mat eri al s i n sea water. Corrosion 8, 50-56 (1952).