J OURNAL OF MATERI ALS SCI ENCE LETTERS 2 ( 1983) 304- - 306

Potential-dependence of oxide film composition on Fe- Cr - Ni

alloys in elevated temperature solutions
W. BOGAERTS, A. VAN HAUTE
University of Leuven (KU Leuven), Electrochemistry and Corrosion Laboratory, de Croylaan 2,
B-3030 Heverlee, Belgium
The understanding of the passivity and corrosion
behaviour of metals at elevated temperatures be-
comes more and more important since operation
temperatures have been raised in many industrial
processes. Especially in the chemical industries and
power generating plants many attempts have been
made to understand and solve corrosion problems
encountered in high temperature and high pressure
aqueous environments.
Unfortunately, numerous experimental diffi-
culties have impeded a detailed study of the mech-
anisms and electrochemical reactions controlling
the composition and structure of anodic passive
films under these circumstances.
Some previous investigations concerning the
electrochemical behaviour of different Fe - Cr - Ni
alloys indicated the probable important extent of
selective dissolution and enrichment phenomena
of individual alloying elements at various electrode
potentials in high temperature aqueous solutions
[ 1, 2] . No studies seem, however, to have been
undertaken to assess the influence of the applied
potential on the properties and composition of
oxide films formed at different temperatures. Only
sporadic information is available in the literature.
Some results of Scanning Auger Microprobe in-
vestigations have, for instance, been published by
the present authors for stainless steel AISI 304 at
a fixed potential and at different temperatures
ranging from 65 to 275 C [3].
These results revealed, for instance, Cr-depletion
processes in the passive film and possible Ni-
enrichment phenomena in the deeper oxide layers
or at the oxi de- met al interface.
In this work we report more details about the
influence of the electrode potential and tempera-
ture on the passive film composition for F e - Cr -
Ni alloys, such as Type 304 (18Cr-8Ni ) stainless
steel, Incoloy 800 (20Cr-30Ni ) and Inconel 600
(16Cr-75Ni ) in alkafine chloride-containing solu-
tions.
Samples have been treated at different con-
trolled anodic potentials in an autoclave system at
temperatures ranging from 65 to 275 C. Deoxy-
genated test solutions, containing various amounts
of C1- (475 to 3550ppm) together with HCO~
and/or OH- (0.1 M) were used. After exposure,
the samples were transferred to a Scanning Auger
Microprobe (SAM) with sub-micron spatial reso-
hitiono Depth profiles or surface distributions of
different alloying or environmental species in the
surface oxide layer were determined. More details
about the measuring instrumentation and the
adopted experimental procedure have been des-
cribed elsewhere [ 1, 3] .
At lower temperatures only minor relative
enrichment phenomena of different alloying
constituents have been found in the passive poten-
tial range. Typical results show rather small oxide
thicknesses and an initial passive film composition
which is greatly influenced by previous surface
treatment procedures and the bulk composition of
the alloy.
At somewhat more elevated temperatures (e.g.
150 C) increasing enrichments of chromium and
nickel, due to a selective dissolution of iron, occur
at electrode potentials in the primary passive
electrode-potential range. Strong transpassive dis-
solution behaviour of chromium causes, however,
a sharp decrease of the chromium content and a
corresponding relative nickel enrichment at higher
potential values. Secondary passivation phen-
omena may be observed in some of the test solu-
tions (rather low C1- concentrations and/or
higher pH) and may be primarily ascribed to a
favourable anodic behaviour of nickel under these
experimental conditions.
With increasing temperature, the transpassive
304 0261- 8028/ 83 $03.00 +. 12 ] 983 Chapman and Hail Ltd.
1
, n m * - ' ] ~ O . O nrn min "1
~ J
a i
i
t : i
_ /
C~
<{
u, 6 U 70
0
I--
<{
ilj
06. '= v ' : t
| \
%
30
S P U T T E R T I ME ( m i n )
di ssol ut i on r eact i on of chr omi um al r eady st ar t s at
l ower el ect r ode pot ent i al s and becomes i ncreas-
i ngl y si gni f i cant . Transpassi ve and s econdar y
passi vat i on pr ocesses ma y al most c ompl e t e l y
det er mi ne t he oxi de fi l m compos i t i on o f t he
di f f er ent al l oys in t he hi gh t e mpe r a t ur e range. Thi s
S a mp l e : 3 0 4
2 2 5 C
+ 1 5 0 mV
4 5
Figure I AES composition pro-
files of surface film on Type
304 stainless steel sample after
anodic treatment during 1000
min at + 150mV vs Ag/AgC1
(solution: 1000 ppm KC1 + 0.1/d
KHCO 3; 225 C).
is cl ear l y i l l ust r at ed by means o f t he AES de pt h
pr of i l e i n Fi g. 1 ( Type 304 st ai nl ess st eel ; 225 C;
1 0 0 0 p p m KC1 + 0.1 M KHCO3, pH 8. 4; + 1 5 0 mV
vs Ag/AgC1). Cor r espondi ng anodi c pol ari sa-
t i on curves at 225 C and pH 8. 4 sol ut i ons are
shown in Fi g. 2 for st ai nl ess st eel 304, i nc ol oy
] i i i i 1 . 1 T i i i i r r l l l i 1 1 1 y r . I i I l l , l , I ~ 1 i i i 1 ~ 1 I i 1 1 m ,
2 2 5 0 0
1 0 0 0 p p m. ,
-
4-150 ~ k , ~ . o . 1 M I
" + 100
t , o
- 1 OO ~ ~f~"~.~...~," . . . . ~
.. ....... ] ~.
~ t . . . , . i j - - 5 o o
( i
. . . . . . . . . . . . . " - - - 1 0 0 0
[ i J t [ l l . I ; L I I I L = ~ ] ~ i i i i l u ] t i I I I I L I [ i I * L l m l J J L l m
10- 4 10"3 10-2 10-1 10 101 1 0 2
I a ( m A )
( a) I c
E
O~
5 0 0
i i i l l i l ~ I F i i 1 1 ~ ] i I l l l ~ ~ 1 1 1 1 1 1 1 r I r I 1 ~ 1 I l l l l ~
2 2 5 C 0.1 M KCI
a d d i t i o n
+100
- - 1 0 0 m, - m~
- - 3 0 0
i ncOl o._8_O_ 0
j J
i t ~ * l l l n ] i i J l , l . I I I H . n d i ; l l l . d i i i . l u l ~ l l i l
0 - 4 1 0 - 3 1 0 - 2 1 0 - 1 1 0 101
(b)
1 0 2
/ m ( m A )
/ c
Figure 2 Anodic polarisation curves of Type 304 stainless steel, incoloy 800, inconel 600, iron and nickel in xKC1 +
0.1 M KHCO 3 at 225 C (x = 1000 ppm or 0.1 M; see figure).
305
800, inconel 600 and pure iron and nickel. The
different potentials at which passivation treat-
ments and subsequent AES analyses have been car-
ried out, are indicated at the left.
In the lower potential range ( e. g. - - 300mV) ,
strong enrichments of chromium and nickel are
found. This is in agreement with the high anodic
dissolution current of iron under the present
experimental conditions (cf. Fig. 2: pure iron). At
electrode potentials higher than about - 1 0 0 mV
transpassivity of chromium and a corresponding
depletion of this element occurs. This possibly
results in a generalized passivity breakdown i f
experimental conditions are unfavourable for
establishing secondary passivity. Secondary pass-
ivity is mainly governed by the behaviour of nickel
and is favoured by lower Cl--concentrations and
higher values of solution pH (e.g. 10.5).
The situation might, however, become more
complicated because of the additional selective
dissolution processes of nickel (e.g. about - - 200
mV), resulting in an increased anodic reactivity.
This is particularly apparent for inconel 600 (Fig.
2) and of course for pure Ni-samples. The combi-
nation of these processes might provide an expla-
nation for many aspects of the corrosion behaviour
of Fe - Cr - Ni alloys in the present type of solu-
tions.
References
1. W. BOGAERTS, A. VANHAUTE, M. J. BRABERS
and P. VANSLEMBROUCK, Research Symposi um
Corrosion '82, Houston (1982) p.81.
2. D. D. MACDONALD, B. C. SYRETT and S. S. WING,
Corrosion 35 (1979) 1.
3. W. BOGAERTS, A. VAN HAUTE and M.J.
BRABERS, Proceedings of the 8th International
Congress on Metallic Corrosion, Mainz (1981) p.31.
Received 29 December 1982
and accepted 6 January 1983
306