The electrochemical reactivation test (ERT)

to detect the susceptibility to

intergranular corrosion
H.-E. B uuhler, L. Gerlach, O. Greven
*
, W. Bleck
Department of Ferrous Metallurgy, RWTH Aachen, Intzestrasse 1, Aachen 52072, Germany
Received 31 October 2002; accepted 25 February 2003
Abstract
A method was developed to measure the degree of sensitisation to intergranular corrosion.
This electrochemical reactivation test is fast, non-destructive and quanties the degree of
sensitisation. The test measures the current after reactivation associated with the corrosion of
chromium depleted regions. This test was carried out on a stabilised and on a not stabilised
steel grade in various heat treatment conditions. The test procedures and the results of the test,
which have been veried by a metallographical examination, are presented in this study in
comparison to results from conventional tests.
2003 Elsevier Ltd. All rights reserved.
Keywords: ERT; Reactivation; Sensitisation; Austenite; CrNi-steels; C. Intergranular corrosion; B.
Polarisation; Test method; EPR; Strauss test
1. Introduction
Corrosion resistant steels are used in many elds as for example in the food
industry, chemical industry, medical technology and household appliances. The
increasing importance of these chemical resistant steels is conrmed by the rise of their
production. Between 1950 and 2000 the amount of annually produced stainless steel
in the Western World rose from 973000 t up to about 19.5 million t [1].
*
Corresponding author. Tel.: +49-241-80-95842; fax: +49-241-80-92253.
E-mail address: oliver.greven@iehk.rwth-aachen.de (O. Greven).
0010-938X/03/$ - see front matter 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/S0010-938X(03)00062-3
www.elsevier.com/locate/corsci
Corrosion Science 45 (2003) 23252336
These chromium and nickel alloyed steels are available as ferritic, ferriticau-
stenitic, austenitic or martensitic steel grades depending on their alloying elements.
Austenitic chromiumnickel-steels with 18% chromium and 810% nickel, which
have been tested in the present study, oer a particularly favourable combination of
mechanical properties and corrosion resistance [2].
Chromium is responsible for the corrosion resistance because it permits the for-
mation of the passive layer on the steel surface, a dense and closed protective lm
based on chromium oxide. Owing to this potential-dependent passivation the steel
remains passive in contact with many aggressive media [3]. The condition required
for this passivation is that chromium remains unxed in the matrix and is not bound
as chromium carbide. The corrosion resistance of high alloyed chromiumnickel-
steels can deteriorate if, due to an improper heat treatment, the precipitation of
chromium carbides is induced and the content of dissolved chromium is reduced
locally.
High material-technological demands are made on the components, especially in
the chemical industry, in power plants and nuclear power, stations. Failure must be
prevented at any rate. The increasing demands on safety inevitably lead to the need
of testing methods, which can detect the susceptibility to corrosion accurately and
with a minimum of time need [4].
There are a number of standard methods, like the Strauss test, Huey test, or
Streicher test, which can be used to assess the susceptibility to intergranular corro-
sion, but none of them is quantitative and non-destructive. Moreover, the perfor-
mance of these tests is very time consuming. In the past thirty years, several authors
tried to innovate the test methods by developing the electrochemical potentiody-
namic reactivation test (EPR), a quantitative method which indicates increasing
sensitisation by increasing C-ratios. However, the results are inuenced by kinetic
eects due to the potentiodynamic character of this test. Thus, the interpretation is
dicult [5].
An innovative potentiostatic test method was developed at the Department of
Ferrous Metallurgy of Aachen University. This electrochemical reactivation test
(ERT) quanties the degree of sensitisation to intergranular corrosion in less time
compared to standard tests. Furthermore, the ERT is non-destructive and permits an
online measurement on the installed component. The ERT is carried out by po-
tentiostatic polarising in the passive and in the active region (Fig. 1), in contrast to
conventional tests which prove the susceptibility to intergranular corrosion by po-
larising the specimen in the passive or transpassive region of the current density
potential-curve.
The ERT is innovative so there are no regulations or standards which prescribe
the performance of the test. Therefore, a number of parameters have to be examined
and dened to allow a reproducible and interpretable test performance [59]. Results
of ERTs on the steel grades 1.4301 (X5CrNi18-10) and 1.4550 (X6CrNiNb18-10)
will be presented in this study and will be compared with results of a metallo-
graphical examination and with results received by the EPR method and the Strauss
test.
2326 H.-E. Buuhler et al. / Corrosion Science 45 (2003) 23252336
2. The development of the ERT
The ERT consists of three potentiostatic examination sections (activationpassi-
vationreactivation) with dened hold times (Fig. 2). First tests were carried out with
100 mV
SHE
activation potential and 500 mV
SHE
passivation potential. The polari-
sation time was 15 min each. While performing rst tests using these parameters, the
reactivation was inuenced by dynamic current density oscillations as shown in Figs.
3 and 4. To prevent dynamic eects which may have an inuence on the potentio-
static test, the electrochemical properties of the steels were tested extensively in a
number of potentiostatic examinations. It could be found out that the oscillations
occur in a potential range from about 80 to 130 mV
SHE
, in dependence on the tested
steel grade. Consequently an active polarisation at 70 mV
SHE
is convenient to per-
form the ERT without the described inuences.
The polarisation times were shortened successively to guarantee a minimum of
time need. All ERTs presented in this study were performed with 5 min potentio-
static polarisation time in the activation section (+70 mV
SHE
) and in the passivation
section (+500 mV
SHE
), as well. The reactivation (+70 mV
SHE
) lasted 100 s.
To assess the degree of sensitisation to intergranular corrosion, the ratio Q is
dened of i
R
, the reactivation current density after 100 s reactivation, and i
A
, the
activation current density at the end of the activation section (formula 1):
Q
i
R
i
A
100 formula 1:
-0.2 0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8
Potential ( V vs SHE )
10
-7
10
-6
10
-5
10
-4
10
-3
10
-2
10
-1
1
10
C
u
r
r
e
n
t
D
e
n
s
i
t
y
(
m
A
*
c
m

)
-
active
polarisation
ERT
passive
polarisation
ERT
Streicher
test
Huey
test
Strauss
test
Fig. 1. Schematic illustration of the polarisation sections of dierent IGC-testing methods within the
current densitypotential-curve of a chemical resistant steel.
H.-E. Buuhler et al. / Corrosion Science 45 (2003) 23252336 2327
A higher ratio Q, denoted in per cent, indicates an increasing degree of sensitisation
to intergranular corrosion.
0
10
20
30
40
50
60
70
80
0 500 1000 1500 2000 2500 3000
Time (s)
C
u
r
r
e
n
t
D
e
n
s
i
t
y
(
m
A
*
c
m
-

)
0
100
200
300
400
500
600
P
o
t
e
n
t
i
a
l
(
m
V
v
s
S
H
E
)
Current Density Potential
dynamic oscillations
Fig. 3. Dynamic current density oscillations in the reactivation section of an ERT, 1.4301.
0
10
20
30
40
50
60
70
80
0 100 200 300 400 500 600 700 800
Time (s)
C
u
r
r
e
n
t
D
e
n
s
i
t
y
(
m
A
*
c
m
-

)
0
100
200
300
400
500
600
P
o
t
e
n
t
i
a
l
(
m
V

v
s

S
H
E
)
Current Density Potential
activation passivation reactivation
i
A
i
R
Fig. 2. Example of an ERT curve, test on 1.4301 1300 C solution annealed, sensitised for 6000 min at
700 C.
2328 H.-E. Buuhler et al. / Corrosion Science 45 (2003) 23252336
The ERT is carried out according to the descriptions in the EPR test standards JIS
G 0508 [10] and ASTM 108-94 [11], as concerns to the specimen preparation and the
electrolyte composition. The electrolyte solution was a 30 1 C tempered 0.5 M
H
2
SO
4
+0.01 M KSCN, which was deaerated with nitrogen 5 min before and during
the test. This solution was renewed after every test.
The current density, which adjusts in the active condition, and the rate the current
rises with in the reactivation section, depend on the chemical composition of the
steel, on the present microstructure, and on the state of sensitisation. Due to chro-
mium depletion and martensite transformation on the grain boundaries, sensitised
steels show higher current densities than not sensitised steels in the activation section,
and a faster increase of the current density in the reactivation section. There are no
consolidated ndings which describe the inuence of grain size, ratio of delta ferrite,
martensite transformation and other precipitations, such as Laves-phases, on the
results of ERT. Therefore, those examinations are currently done at the Institute of
Ferrous Metallurgy, and rst results of a metallographical examination are pre-
sented in this study.
The ERT was carried out on the unstabilised steel grade 1.4301 (X5CrNi18-10)
and on the niobium stabilised steel grade 1.4550 (X6CrNiNb18-10). The chemical
composition is listed in Table 1. The steels were delivered as cold rolled sheets with 2
mm (1.4301) and 5 mm (1.4550) thickness, respectively. Specimens were prepared by
cutting and sawing. As shown in Table 2 these 10 10 mm
2
sized specimens were
heat treated to adjust dierent degrees of sensitisation. The average grain diameter
after heat treatment was 100 lm for the 1.4301 and 100200 lm for the 1.4550.
0
5
10
15
20
25
30
35
21 21.1 21.2 21.3 21.4 21.5 21.6 21.7 21.8 21.9 22
Time (h)
C
u
r
r
e
n
t
D
e
n
s
i
t
y
(
m
A
*
c
m
-

)
Fig. 4. Example of dynamic current density oscillations; 1.4301 1300 C solution annealed, sensitised for
1000 h at 700 C, polarised at 100 mV
SHE
.
H.-E. Buuhler et al. / Corrosion Science 45 (2003) 23252336 2329
To enable an electric contact, a copper wire was soldered to the back of each
specimen after descaling. The test pieces were mounted in epoxy resin and the sur-
faces were polished up to 1 lm. Then, they were covered with a chemical resistant
and punched foil to ensure, that only a strictly dened area is tested. A prepared
specimen is shown in Fig. 5.
Each sensitisation condition was tested three times. An average value Q
A
was
computed over these three single values.
Table 2
The dierent heat treatment conditions ( tested conditions)
Solution annealing
temperature/C
(water quenched)
Sensitisation
temperature/C
(air cooled)
Time/min 1.4301 1.4550
1300 700 0
1300 700 10
1300 700 60
1300 700 600
1300 700 6000
1300 650 0
1300 650 180
1300 650 1800
1300 650 6000
Table 1
Chemical composition of the tested alloys
Steel
grade
Chemical composition, mass contents in %
C Si Mn P Cr Mo Ni Nb
1.4301 0.05 0.54 1.27 0.024 18.00 8.86
1.4550 0.026 0.47 1.23 0.021 17.46 9.13 0.517
Fig. 5. A prepared ERT specimen.
2330 H.-E. Buuhler et al. / Corrosion Science 45 (2003) 23252336
3. Results
3.1. 1.4301
Fig. 2 shows a current densitypotentialtime-curve for steel 1.4301, which was
sensitised for 6000 min at 700 C. The current density rises up to 50 mAcm
2
in the
activation section and falls to 0.2 mAcm
2
after the potential is switched to passivate
the test piece. In the reactivation section, the current density rises up to 22.6
mAcm
2
. The ratio Q can be determined with 44.3%. Fig. 6 shows the run of the
computed average values Q
A
in dependence on the heat treatment time. The maxi-
mum and minimum single values Q are pictured, additionally. In some cases, the
deviation is so small that it cannot be visualised. All measured Q-values are listed in
Table 3.
Experiments with only solution annealed or short-time (10 min) heat treated
1.4301 show a comparatively low Q
A
of 1.7% and 3.0%, respectively. Extended heat
treatment times up to 60 and 600 min lead to a signicant increase of the Q
A
-values
up to 15.2% and 41.3%, respectively. The highest Q
A
-value of 46.6% can be measured
on 6000 min heat treated material.
Tests on only solution annealed 1.4301 show the highest deviation. The deviation
decreases with increasing heat treatment time. ERTs carried out on 600 and 6000
min sensitised material show very low deviations. The run of the Q
A
-values as given
in Fig. 4 shows that it is possible to distinguish between dierent degrees of sensi-
tisation. The increasing sensitisation can be stated by a metallographical examination
15.2
1.7
3.0
41.3
46.6
0.7
2.7
23.6
0
10
20
30
40
50
60
0 1 10 100 1000 10000
Sensitization Time (min)
R
a
t
i
o

(
%
)
Fig. 6. The trend of the ratios Q
A
and Q (black) for ERTs and the ratio C (grey) for EPR tests in de-
pendence on the sensitisation time for steel grade 1.4301.
H.-E. Buuhler et al. / Corrosion Science 45 (2003) 23252336 2331
of the specimen, which shows a increasing carbide precipitation on the grain
boundaries with increasing heat treatment time. Metallographical microstructures
are shown in Fig. 7 as examples.
The results of double loop EPR tests, which were performed with the same ma-
terial with 15 and 1200 min sensitisation time in a prior study [12], are printed in Fig.
6. Here, rising sensitisation is indicated by rising C-values. The lowest value C can be
measured on only solution annealed material with 0.7%. A heat treatment at 700 C
leads to increasing C-values with 2.7% (15 min) and 23.6% (1200 min).
A comparison of ERT and EPR results shows that up to a sensitisation time of 15
min the ERT as well as the EPR tests show similar values. However, at longer
sensitisation times ERT-values are always higher than EPR-values.
3.2. 1.4550
The mean values Q
A
, as well as the minimum and maximum values Q, are given in
Fig. 8. Q
A
increases from 1.7% for only solution annealed material up to 8.1% for
180 and 31.3% for 1800 min sensitised material, respectively. The highest Q
A
-value of
62.2% can be computed for 6000 min heat treated 1.4550. The single values Q are
given in Table 4.
Fig. 7. Left: 1.4301, 700 C 10 min, starting carbide precipitation; right: 1.4301, 700 C 600 min, grain
boundaries with carbide precipitations.
Table 3
The measured values Q and the average value Q
A
of ERTs on steel 1.4301
Sensitisation
time (min)
Q
1
(%) Q
2
(%) Q
3
(%) Q
A
(%)
0 2.7 0.9 1.4 1.7
10 2.5 3.2 3.4 3.0
60 13.8 16.9 16.9 15.2
600 41.3 39.7 42.9 41.3
6000 46.5 48.9 44.3 46.6
2332 H.-E. Buuhler et al. / Corrosion Science 45 (2003) 23252336
The tests show the highest deviation on 1800 min heat treated material. All the rest
of the tests show only low deviations. For steel grade 1.4301 as well as for steel grade
1.4550, an increasing sensitisation can be stated by a metallographical examination.
This examination shows increasing carbide precipitation with increasing sensitisation
time. Fig. 9 shows examples for this.
Fig. 8 shows results of double loop EPR tests which were performed on the
same material in a prior study [12]. Here, the specimens were sensitised for 180 and
1800 min at 650 C. Within the scope of measuring accuracy, the C-values for only
solution annealed and those for 180 min at 650 C sensitised 1.4550 are the same
with 1.5% and 1.4%, respectively. A heat treatment for 1800 min leads to a slight
increase of the ratio C up to 4.7%.
It can be stated that the dierence between ERT and EPR values rises with in-
creasing heat treatment time, whereby the ERT always shows higher values.
1.7
8.1
31.3
62.2
4.70
1.44 1.52
0
10
20
30
40
50
60
70
0 1 10 100 1000 10000
Sensitization Time (min)
R
a
t
i
o
(
%
)
Fig. 8. The trend of Q
A
and Q (black) for ERTs and the ratio C (grey, dotted) for EPR tests in dependence
on the sensitisation time for steel grade 1.4550.
Table 4
The measured values Q and the average value Q
A
of ERTs on steel 1.4550
Sensitisation
time (min)
Q
1
(%) Q
2
(%) Q
3
(%) Q
A
(%)
0 1.7 1.7 1.6 1.7
180 7.9 8.5 7.9 8.1
1800 25.7 38.9 29.2 31.3
6000 66.1 58.2 62.4 62.2
H.-E. Buuhler et al. / Corrosion Science 45 (2003) 23252336 2333
4. Discussion
4.1. 1.4301
High current densities, which can be measured in the activation section, can be
attributed to active anodic corrosion reactions without passive layer formation. If
the potential is switched to +500 mV
SHE
, a dense and closed passive layer, based on
chromium oxide, develops on the steel surface, due to the potential dependence of
the passivity. As a consequence, the iron solution is interfered and the measured
current density decreases to a minimum value. If the specimen is activated in the
reactivation section for the second time, the rise of the current density shows a time
and a sensitisation dependence. The time dependence can be explained by kinetic
eects during the dissolving of the passive layer. The sensitisation dependence can be
interpreted by a favoured anodic reaction due to carbide precipitation. Because of
the heat treatments after solution annealing, chromium carbides precipitate on the
grain boundaries. A rise of the amount of carbide precipitations was proven by the
metallographical examination. These precipitates initiate a local chromium depletion
and consequently a selective susceptibility to corrosion, i.e. intergranular corrosion.
The ratio of the chromium depleted grain boundary area increases with increasing
heat treatment time and thus, it takes less time to reactivate the specimen. Addi-
tionally a martensite transformation of unstable austenite is induced by chromium
depletion. A micrograph in Fig. 10 shows such a microstructure of a sensitised
1.4301 with martensite on the grain boundaries. The martensite is illustrated as
darker parts than the austenite sections due to less reectivity [1315].
The ERT results correspond to those of other studies [14], which state that the
Strauss test indicates a sensitisation of steel 1.4301 after about 15 min heat treatment
at 700 C. The ERT as well as the EPR method are able to detect the sensitisation of
steel grade 1.4301 and allow a dierentiation of dierent degrees of sensitisation.
However, the ERT seems to be more sensitive as far as sensitisation times of more
Fig. 9. Left: 1.4550, solution annealed, no carbide precipitations on grain boundaries; right: 1.4550, 650
C 1800 min, carbide precipitations on grain boundaries.
2334 H.-E. Buuhler et al. / Corrosion Science 45 (2003) 23252336
than 15 min are regarded. Furthermore there is a time advantage for the ERT, which
was performed within 16 min. The EPR test took 40 min.
4.2. 1.4550
The alloying element niobium has a higher anity to carbon and nitrogen than
chromium. As a consequence, carbon and nitrogen are bounded in the form of ni-
obium carbides and carbonitrides. The precipitation of chromium carbides is sup-
pressed, and the susceptibility to intergranular corrosion is reduced, due to the
formation of these stabilisation carbides. Yet, if stabilised steels are solution an-
nealed at temperatures of 1300 C, as done in this study, stabilisation carbides are
dissolved ass well and supplementary delta ferrite is formed on the grain boundaries
[16]. The solved carbon can be precipitated as M
23
C
6
, e.g. if the specimens were heat
treated. Then even stabilised steels can become susceptible to intergranular corro-
sion. Referring to data from other studies using the Strauss test, it is possible to
sensitise steel grade 1.4550 by 60 min heat treatment at 650 C [14]. Thus, the results
of the present ERT study correspond well to results from the literature. For the sake
of completeness, it must be mentioned that the results from the literature were de-
termined with steels of a higher carbon content. The general precipitation mecha-
nism is not inuenced by that, but the time to precipitate rst chromium carbides is
reduced. The EPR test did not indicate a sensitisation after 180 min heat treatment,
and even after 1800 min annealing, only a comparatively low sensitisation was
measured, which is in contrast to results from literature, to our metallographical
examinations and to results from ERT. Thus, the ERT is more sensitive than the
EPR test. It is well known from other studies [5] that the EPR test cannot detect the
susceptibility of niobium stabilised steel 1.4550 after solution annealing at 1100 C
and sensitising, although the Strauss test and the ERT can.
Chromium depletion and delta ferrite formation on the grain boundaries of the
niobium stabilised steel probably lead to higher reactivation current densities in
comparison to steel grade 1.4301, especially for longer heat treated specimens. The
Fig. 10. Martensite formation on grain boundaries (dark parts) due to chromium depletion.
H.-E. Buuhler et al. / Corrosion Science 45 (2003) 23252336 2335
reproducibility of the ERTs carried out on steel 1.4550 is good. A dierentiation of
dierent degrees of sensitisation is possible.
5. Summary
ERT were carried out on stabilised and unstabilised austenitic chromium nickel
steels in dierent heat treatment conditions. It was possible to dierentiate dierent
degrees of sensitisation for both tested steels which corresponds well to results from
another study using the standard Strauss test. A metallographic examination con-
rms the results of the ERT and indicates an increasing amount of chromium car-
bides on the grain boundaries with increasing heat treatment time.
A comparison with EPR test results of a prior study shows that the ERT is more
sensitive than the EPR. Moreover, the ERT needs less time.
References
[1] H. Pariser & Co Alloy Metals & Steel, Xanten, Germany, private information.
[2] Informationsstelle Edelstahl Rostfrei, Merkblatt 821 (2) (1997).
[3] H.D. Schulze, VDI-Nachrichten 47 (10) (1993) 28.
[4] A. Karas, V. Cihal, V. Vanek, J. Herzan, K. Protiva, Kovove Materialy 25 (5) (1987) 497508.
[5] L. Gerlach, Untersuchungen zur Eignung elektrochemischer Korrosionspr uufverfahren f uur die
Nachweisbarkeit einer interkristallinen Korrosionsanfaalligkeit unstabilisierter und stabilisierter,
chemisch bestaandiger Staahle nach sensibilisierender Waarmebehandlung, Dr.-Ing. thesis RWTH
Aachen, 2001.
[6] H.-E. B uuhler, L. Gerlach, Corrosion investigation on chemical resistant steels by means of steady state
electrochemical reactivation tests (change over tests), conference proceedings, Eurocorr 2000,
London, 2000.
[7] H.-E. B uuhler, L. Gerlach, H. Schlerkmann, W. Schwenk, M. Shoeib, Materials and Corrosion 52 (1)
(2001) 6570.
[8] H.-E. B uuhler, O. Greven, Corrosion investigations on chemical resistant steels by means of the
potentiostatic electrochemical reactivation test (ERT), conference proceedings, Eurocorr 2001, Riva
del Garda, 2001.
[9] H.-E. B uuhler, O. Greven, The potentiostatic electrochemical reactivation test (ERT)a new way to
quantify the degree of sensitization to intergranular corrosion, conference proceedings, Stainless Steel
2001, The Hague, 2001, pp. 399406.
[10] JIS G 0580, Method of Electrochemical Potentiokinetic Reactivation Ratio Measurement for
Stainless Steels, 1986.
[11] ASTM G 108-94, Standard Test Method for Electrochemical Reactivation (EPR) for Detecting
Sensitization of AISI Type 304 and 304L Stainless Steels, April 1994.
[12] O. Greven, Untersuchung des Einusses der Pr uufparameter auf die Nachweisbarkeit interkristalliner
Korrosionsanfaalligkeit stabilisierter und unstabilisierter Chrom-Nickel-Staahle im EPR-Test, diploma
thesis RWTH Aachen, 2000.
[13] A. Rahmel, W. Schwenk, Korrosion und Korrosionsschutz von Staahlen, Weinheim, New York, 1977.
[14] G. Hersleb, H.J. Sch uuller, P. Schwaab, Werkstoe und Korrosion 27 (1976) 560568.
[15] A. Baaumel, H.-E. B uuhler, H.-J. Sch uuller, P. Schwaab, W. Schwenk, H. Ternes, H. Zitter, Corrosion
Science 4 (1964) 89103.
[16] E. Folkhard, Metallurgie der Schweiung nichtrostender Staahle, rst ed., Springer-Verlag, Wien, New
York, 1984.
2336 H.-E. Buuhler et al. / Corrosion Science 45 (2003) 23252336