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Corrosion behavior analysis of an austenitic

stainless steel exposed to fire

Article in Engineering Failure Analysis July 2013

DOI: 10.1016/j.engfailanal.2013.01.044

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 Engineering Failure Analysis 31 (2013) 4047

Contents lists available at SciVerse ScienceDirect

Engineering Failure Analysis

journal homepage: www.elsevier.com/locate/engfailanal

Corrosion behavior analysis of an austenitic stainless steel

exposed to re
C.A. Della Rovere a,, M. Castro-Rebello b, S.E. Kuri a
a
DEMa/UFSCar, Department of Materials Engineering, Federal University of So Carlos, Rodovia Washington Luis, Km 235, 13565-905 So Carlos, SP, Brazil
b
FESP, Engineering Faculty of So Paulo, Av. Nove de Julho, 5520, Jardim Europa, 01406-200 So Paulo, SP, Brazil

a r t i c l e i n f o a b s t r a c t

Article history: In December 2008, a re broke out in a brewery in southeastern Brazil, burning seven fer-
Received 22 September 2012 mentation tanks during their initial installation. The tanks were built entirely from austen-
Received in revised form 13 December 2012 itic stainless steel type 304 (SS 304) and were subjected to high temperatures during their
Accepted 15 January 2013
approximately 90 min of exposure to the re. The intensity of the re and the length of
Available online 9 February 2013
time during which the tanks and components were exposed to its heat raised concerns
about the possible metallurgical damage sustained by the SS 304 used in the construction
Keywords:
of the tanks and components. This study investigates the corrosion performance of stain-
Austenitic stainless steel
Fire
less steels after exposure to re, and in particular discusses the approach adopted to eval-
Sensitization uate the possible damage to the corrosion resistance of SS 304 caused by re. The ndings
Intergranular corrosion of this investigation indicate that, during their exposure to re, the tanks underwent tem-
Electrochemical techniques perature excursions within the sensitization range, which changed the microstructure and
corrosion properties of the SS 304 plates.
2013 Elsevier Ltd. All rights reserved.

1. Introduction

In December 2008, the thermal insulation of expanded polyurethane of seven fermentation tanks that were under con-
struction at a brewery caught re. The re, whose origin is unknown and still under investigation, burned for approximately
90 min and the intense heat to which the fermentation tanks were subjected affected a large part of their austenitic stainless
steel structure, as illustrated in Fig. 1.
Austenitic stainless steels (which contain 18% Cr8% Ni) are engineering materials widely used in many branches of
industry, especially in the food and beverage manufacturing and processing sector, due to their attractive combination of
good mechanical properties, formability, and corrosion resistance. Their corrosion resistance is afforded by a thin Cr2O3 sur-
face lm (typically 13 nm thick), known as passive lm, which has self-healing capability in a wide variety of environments
[1,2]. However, when austenitic stainless steels are exposed to the critical temperature range of 425870 C for a given per-
iod of time, chromium (Cr) carbides are formed at the grain boundaries and Cr depletion occurs adjacent to these carbides,
affecting their corrosion resistance [1,35]. According to the literature [1,4], even a brief exposure (approximately 10 min) in
the critical temperature range sufces to render an austenitic stainless steel type 304 containing more than 0.05 wt% C sus-
ceptible to intergranular attack. This phenomenon, known as sensitization [1,37], renders stainless steel more susceptible
to localized corrosion attack because the passive lms formed on Cr depleted areas are unstable in the presence of certain
specic corrosive agents. The literature [1,8] also reports that the sensitization phenomenon may drastically increase the
corrosion rate of stainless steels due to intergranular corrosion attack (IGC), which may eventually lead to complete grain

Corresponding author. Tel.: +55 16 33518507; fax: +55 16 33518258.

E-mail address: carlosdrovere@hotmail.com (C.A. Della Rovere).

1350-6307/$ - see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.engfailanal.2013.01.044
 C.A. Della Rovere et al. / Engineering Failure Analysis 31 (2013) 4047 41

Fig. 1. External surface appearance of the tanks after exposure to re.

detachment. In addition, it has been shown [915] that sensitized stainless steel is prone to intergranular stress corrosion
cracking (IGSCC) in response to the combination of an applied tensile stress, even if residual, plus a specic corrodent.
The intensity of the re and the fairly long time the tanks and components were exposed to its heat raised concerns about
the possible metallurgical damage the tanks stainless steel may have sustained, which would directly affect its properties
and could lead to the premature failure of the tanks and components.
This situation led to a dispute between the brewery and the insurance company. The latter proposed the possibility of
replacing only those parts of the tanks that were rendered unusable due to excessive deformation, and of making dimen-
sional repairs by simple straightening methods on the parts were only slightly distorted to render them reusable. In addition,
the insurer wanted to know if these measures would allow the stainless steel structure to be used with the full expectation of
it performing with its specied corrosion properties. Therefore, a technical report was required to assess the possible met-
allurgical damage which the tanks had sustained.
In view of the above, this study concerns the corrosion behavior of an austenitic stainless steel after direct exposure to re
and, in particular, discusses the approach adopted to evaluate the possible impairment of the corrosion resistance of a stain-
less steel structure due to re.

2. Chemical analysis

As a rst step, it was necessary to identify the type of austenitic stainless steel used in the construction of the tanks. Table
1 describes the chemical composition of the stainless steel, which was determined by spark optical emission spectrometry (
S-OES). Note that the material in question is an austenitic stainless steel type 304 (SS 304) with a substantial carbon content
(about 0.06 wt%). Since the key alloying element responsible for sensitization is carbon [1,3,4], stainless steels with high car-
bon content are more prone to Cr carbide precipitation at the grain boundaries. Therefore, it is highly probable that sensi-
tization occurred in the parts of the tanks that were subjected to the critical temperature range even for a short period of
time [1,3,4].

3. Visual inspection

A visit to the area of the brewery where the re occurred was also required for a visual inspection. Fig. 1 depicts a pho-
tograph of one of the tanks involved in the re, whose surface shows numerous areas darkened by the combustion of poly-
urethane insulation. In addition, note that the tanks and components show areas with different levels of oxidation, indicating
that the SS 304 plates were exposed to different temperatures (temperature gradients) for different lengths of time during
the re. After a careful visual inspection to identify the areas where the re had wrought the greatest damage, ten specimens
of SS 304 were carefully extracted from different points of the fermentation tanks for laboratory testing. Specimens of SS 304
plates that were not exposed to re were also extracted for use as references. In addition, one specimen was furnace sensi-
tized at 600 C for 1 h in the laboratory for comparison of results.

Table 1
Chemical composition (wt%) of the austenitic stainless steel type 304 (SS 304).

Element Cr Ni C Mn Si P S Mo Ti Cu Co Na
Content (%) 18.21 8.07 0.062 1.16 0.39 0.03 0.001 0.09 0.005 0.09 0.14 434
a
Units in parts per million (ppm).
42 C.A. Della Rovere et al. / Engineering Failure Analysis 31 (2013) 4047

4. Metallography

Metallographic specimens were cut and prepared after removal of the oxidation products on the surface of the SS 304
plates. To obtain clear and detailed images, the specimens were polished mechanically with alumina of up to 1.0 lm (mirror
nish) before etching. The specimens were then etched electrolytically in 10% (w/v) oxalic acid solution, using a stainless
steel beaker as cathode and a current density of 1 A/cm2 for 90 s, according to the ASTM A262 standard, practice A [16].
The etched structures were classied as step (free of Cr carbides), dual (no single grain completely surrounded by Cr car-
bides) and ditch (one or more grains completely surrounded by Cr carbides).
Table 2 summarizes the results obtained by electrolytic etching, while Fig. 2 depicts OM images of typical structures ob-
tained from the specimens exposed and not exposed to re. Note that the non-re-exposed specimen has a step structure,
while the furnace-sensitized specimen and half of those exposed to re have a ditch structure. In addition, note that ve
re-exposed specimens have dual and step structures, as indicated in Table 2.
According to practice A of the ASTM A262 standard [16], only the ditch structure is unacceptable for SS 304. This kind of
structure indicates that the sensitization phenomenon has occurred because it reveals the presence of a continuous chro-
mium-depleted area around the grain boundaries of the material, thus requiring a second test in a specic hot acid solution,
which, in the present case, is the ferric sulfate/sulfuric acid immersion test.

5. Immersion tests

Immersion tests were carried out in a boiling solution of 50%H2SO4 + 2.5%Fe2(SO4)3 for 120 h, according to practice B of
the ASTM A262 standard [16]. Before immersion, the specimens were wet ground with #600-grit silicon carbide paper,

Table 2
Classication of the structures etched electrolytically with oxalic acid 10% (w/v) solution.

Specimen Condition Etched structures Corrosion ratea (mils/month)

NEF Non-re-exposed Step 2
FS1b Furnace-sensitized Ditch 55
1 Fire-exposed Dual n.d.c
2 Ditch 22
3 Step n.d.
4 Step n.d.
5 Ditch 38
6 Ditch 46
7 Ditch 33
8 Dual n.d.
9 Dual n.d.
10 Ditch 64
a
In the 120-h boiling ferric sulfate-50% sulfuric acid test;
b
1 h at 600 C.
c
Not determined.

Fig. 2. OM micrographs of the typical structures after 10% oxalic acid etching: (a) FS1; (b) NEF; re-exposed specimens Nos. (c) 8, (d) 10, (e) 6, and (f), 5.
 C.A. Della Rovere et al. / Engineering Failure Analysis 31 (2013) 4047 43

washed in distilled water, cleaned with acetone, dried with hot air and weighed on an analytical balance. After the test, the
specimens weight loss was determined and the corrosion rate in mils per month penetration was calculated. Scanning elec-
tron microscopy (SEM) images were then recorded.
Table 2 also describes the corrosion rate obtained from the ferric sulfatesulfuric acid immersion test. Note that the cor-
rosion rate of the re-exposed specimens (2264 mils/month) is much higher than that of a non-re-exposed specimen
(2 mils/month), suggesting that the corrosion resistance of SS 304 plates was seriously impaired by the re. In addition, it
can also be seen that one of the re-exposed specimens presented a higher corrosion rate (64 mils/month) than the fur-
nace-sensitized specimen (55 mils/month), indicating that, due to the re, the corrosion resistance of some parts of the fer-
mentation tanks was more degraded than the specimen furnace sensitized at 600 C for 1 h.
Fig. 3 shows SEM micrographs of typical surface morphologies of the specimens exposed and not exposed to re after the
ferric sulfatesulfuric acid immersion test. The non-re-exposed specimen Fig. 3a shows a smooth surface which sustained a
weak general corrosion attack. On the other hand, as depicted in Fig. 3b, the re-exposed specimens exhibited a much more
pronounced corrosion attack that clearly occurred preferentially at the grain boundaries, probably due to the preferential
precipitation of Cr carbides at these sites during the re. This gure Fig. 3b also suggests that the high corrosion rates ob-
served in the re-exposed specimens results from a severe intergranular corrosion attack, which likely promoted the com-
plete detachment of surface grains from the material.
It should be emphasized that practice B of the ASTM A262 standard [16] species only testing details, but makes no men-
tion of acceptable intergranular corrosion rates. Therefore, it is common to use the acceptance criteria specied by Du Pont
for services where susceptible material might undergo intergranular attack [1,4]. The maximum corrosion rate reportedly
allowable by Du Pont for SS 304 in practice B of the ASTM A262 standard is 4 mils/month, which indicates that at least ve
re-exposed specimens should be rejected.

Fig. 3. SEM micrographs of the typical surface morphologies of specimens after 120 h of immersion in boiling 50%H2SO4 + 2.5%Fe2(SO4)3 solution: (a) NEF
(b) re-exposed specimen No. 10.
44 C.A. Della Rovere et al. / Engineering Failure Analysis 31 (2013) 4047

At this point, since the dual structure is an acceptable structure according to practice A of the ASTM A262 standard, but
implies that some Cr carbide precipitation occurred in the stainless steel, questions were raised about the extent of the sen-
sitization phenomenon. Therefore, to measure the degree of sensitization of the re-exposed specimens, electrochemical
tests were undertaken.

6. Double loop electrochemical potentiokinetic reactivation (DL-EPR) test

The extent of the sensitization phenomenon in SS 304 has already been measured effectively through the double loop
electrochemical potentiokinetic reactivation (DL-EPR) test [1,57,10,17,18]. In this work, specimens with a circular surface
area of 1 cm2 were cut from SS 304 plates, embedded in polyester resin after inserting the electric contact, and subjected to
DL-EPR tests to quantify the degree of sensitization (DOS). The DL-EPR tests were carried out in a 0.5 M H2SO4 + 0.01 M KSCN
solution at 30 C. A conventional electrochemical cell was used, consisting of a platinum counter electrode and a saturated
calomel reference electrode (SCE) connected to a potentiostat (Solartron 1287A). Before the DL-EPR tests, the specimens
were wet-sanded with #600-grit silicon carbide (SiC) paper, washed in distilled water, and immersed in the electrochemical
cell. The polarization scan was started 2 min after immersion of the specimens. The potential was scanned in the anodic
direction up to +300 mVSCE, after which the polarization scan was reversed in the cathodic direction up to 400 mVSCE. A
sweep rate of 1.67 mV/s was used. The DL-EPR test results are expressed in terms of the current density ratio, Ir/Ia, which
was used to measure the DOS in the specimens. The Ir term is the reactivation peak current density (maximum current den-
sity in the cathodic scan), and the Ia term is the activation peak current density (maximum current density in the anodic
scan). Optical microscopy (OM) images were recorded after taking the DL-EPR measurements.
Fig. 4 shows the typical DL-EPR curves of the re-exposed and non-exposed specimens. Note that all the specimens pres-
ent a wide range of passivity from 50 mVSCE to +300 mVSCE, with a magnitude of anodic current density in the order of
10 5 A/cm2. In addition, it can also be noted that the non-re-exposed specimen showed no maximum current density in

Fig. 4. DL-EPR curves plotted for specimens: (a) FS1; (b) NEF; re-exposed specimens Nos. (c) 10 and (d) 8.
 C.A. Della Rovere et al. / Engineering Failure Analysis 31 (2013) 4047 45

Fig. 5. Degree of sensitization (DOS) of the specimens, obtained from the DL-EPR curves.

the cathodic scan and therefore did not present intergranular sensitization, as indicated in Fig. 4b. In this condition, the spec-
imen did not present Cr-rich intergranular precipitates or consequent Cr-depleted zones, which was conrmed by the mor-
phologies after the DL-EPR test (Fig. 6a and b). On the other hand, the behavior of most of the re-exposed specimens was
similar to that of the furnace-sensitized specimen, and the reactivation peak current density indicated the presence of inter-
granular sensitization.
Fig. 5 shows the values of DOS obtained from the DL-EPR curves. Note that most of the re-exposed specimens showed
signicantly higher values of DOS than the non-re-exposed specimen. Moreover, in some cases, the DOS reached values as
high as that of the furnace-sensitized specimen, indicating the great severity of the sensitization phenomenon that took
place during the re. In this gure (Fig. 5), it can also be noted that even the specimens presenting a dual structure show
a considerable DOS.
Fig. 6 exhibits the OM images of typical morphologies after the DL-EPR test. Note that all the morphologies are very
strongly correlated with the DOS plotted in Fig. 5 and in previous tests. The non-re-exposed specimen showed no signs
of intergranular attack, as indicated in Fig. 6b. Fig. 6a indicates that the specimen furnace-sensitized at 600 C for 1 h under-
went considerable intergranular corrosion attack that affected most of its grain boundaries. Severe intergranular corrosion
occurred on the surface of some of the re-exposed specimens and all the grain boundaries were strongly attacked, as de-
picted in Fig. 6c. A less pronounced intergranular corrosion attack was observed in the re-exposed specimens that pre-
sented step and dual structures (Fig. 6d). In addition, spots of localized corrosion were also found in all the surface
morphologies after the DL-EPR test, but their incidence was much higher in the re-exposed specimens, which also indicates
that these specimens were more prone to localized attack [19,20].

7. Discussion

The sensitization phenomenon occurs when stainless steel is cooled slowly from high temperatures or reheated to the
critical temperature range of 425870 C. Therefore, at some point in the re (during the heating and cooling cycle), some
parts of the tanks underwent temperature excursions within the sensitization range. In this condition, the carbon content
exceeded the solubility limit of austenite phase, causing carbon atoms to migrate toward sinks for point defects, such as
grain boundaries, and bond with the Cr atoms, forming a continuous network of Cr carbides along the grain boundaries. Since
carbon atoms diffuse faster than chromium atoms, a Cr-depleted region develops in the austenite matrix adjacent to these
Cr-rich precipitates, providing a continuous path of lower corrosion resistance along the grain boundaries for the propaga-
tion of IGC or IGSCC [1,3,4,915].
A high carbon content is a critical point for the occurrence of sensitization. As can be seen in Table 1, the SS 304 plates
used in the construction of the tanks have a carbon content of 0.06%, which is twofold higher than the maximum allowable
limit of 0.03% for a weldable grade. This high carbon content increases the possibility that sensitization occurred in the parts
of the tanks that were subjected to the critical temperature range even for short periods of time during the re. In fact, it is
well known that limiting the carbon content of stainless steel to a maximum of 0.03% is one of the best measures to prevent
sensitization during manufacturing and welding processes [1,3,4].
The electrolytic etching of the re-exposed specimens in 10% (w/v) oxalic acid solution showed that ve specimens pre-
sented an unacceptable structure (ditch), indicating that one or more grains were completely surrounded by Cr carbide
precipitation. Therefore, when the grain boundaries underwent sufcient Cr carbide precipitation to completely envelop
at least one grain, it was to be expected that the grains in the boiling acid test would be undermined, resulting in the high
corrosion rate described in Table 2, indicating that the material is susceptible to IGC and IGSCC. On the other hand, the other
ve re-exposed specimens showed acceptable structures (dual and step), and were therefore not subjected to the boil-
46 C.A. Della Rovere et al. / Engineering Failure Analysis 31 (2013) 4047

Fig. 6. OM micrographs of the typical morphologies after the DL-EPR test: (a) FS1; (b) NEF; re-exposed specimens Nos. (c) 10 and (d) 8.

Table 3
Comparison of the DOS of specimens exposed and non-exposed
to re.

Specimen Etch Comparison with the DOS of

structures the non-re-exposed specimen
10 Ditch 279 times greater
FS1 Ditch 229 times greater
6 Ditch 183 times greater
5 Ditch 171 times greater
7 Ditch 97 times greater
8 Dual 75 times greater
2 Ditch 72 times greater
1 Dual 31 times greater
9 Dual 22 times greater

ing acid test. However, as the dual structure implies that some Cr carbide precipitation occurred in the SS 304, it was nec-
essary to measure the DOS to evaluate the extent of this metallurgical damage. This evaluation was done based on the DL-
EPR curves (Figs. 46).
Table 3 presents a comparison of the DOS of re-exposed and non-re-exposed specimens. Note that the DOS of eight
re-exposed specimens is much higher than that of the one not exposed to re, indicating that the corrosion resistance of
SS 304 plates was seriously impaired by their exposure to re. In addition, also note that even the three specimens present-
ing a dual structure show a DOS that is not negligible and should not be disregarded, since the Cr depleted regions adjacent
to some Cr carbide may have already become active initiation sites for other forms of corrosion, such as pitting corrosion in
chloride solutions [19,20].
The above facts make it clearly evident that their exposure to re changed the microstructure of the 304 SS plates, and
that consequently, their corrosion performance would be adversely affected. Therefore, unlike carbon steel structures, which
can generally be put into use after exposure to re without affecting the stability of the whole structure, a stainless steel
structure exposed to re requires a more careful post-re incident analysis because the microstructure even of members
or parts that did not undergo signicant dimensional distortion may be modied, which can seriously impair their corrosion
performance, leading to their premature failure.

8. Conclusions

The following conclusions can be drawn from the results of the corrosion analysis of SS 304 plates exposed to re that
were obtained in the present study:
 C.A. Della Rovere et al. / Engineering Failure Analysis 31 (2013) 4047 47

1. Exposure to re changed the microstructures and corrosion properties of SS 304 plates in several areas of the fermenta-
tion tanks.
2. Many areas showed a high degree of sensitization, leaving the SS 304 plates susceptible to intergranular corrosion and
intergranular stress corrosion cracking.
3. A considerable degree of sensitization was identied in the DL-EPR tests, even in the specimens that were considered
acceptable according to practice A of the ASTM A262 standard.

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