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Sensitization evaluation of the austenitic stainless steel AISI 304L, 316L, 321
and 347

Article in Journal of Materials Science · January 2005

DOI: 10.1007/s10853-005-5699-9

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J O U R N A L O F M A T E R I A L S S C I E N C E 4 0 (2 0 0 5 ) 139 – 144

Sensitization evaluation of the austenitic

stainless steel AISI 304L, 316L, 321 and 347
A. S. LIMA, A. M. NASCIMENTO
Departamento de Engenharia Mecânica, Universidade Federal do Ceará, Campus do Pici,
Bl. 714, 60455-900 Fortaleza, Ce, Brazil; Departamento de Quı́mica Analı́tica e
Fı́sico-Quı́mica, Universidade Federal do Ceará, C.P. 6035, 60455-970 Fortaleza, Ce, Brazil
H. F. G. ABREU
Departamento de Engenharia Mecânica, Universidade Federal do Ceará, Campus do Pici,
Bl. 714, 60455-900 Fortaleza, Ce, Brazil
P. DE LIMA-NETO ∗
Departamento de Quı́mica Analı́tica e Fı́sico-Quı́mica, Universidade Federal do Ceará,
C. P. 6035, 60455-970 Fortaleza, Ce, Brazil
E-mail: [email protected]

This work presents a systematic investigation of the influence of time and temperature in
the sensitization of stainless steel AISI 304L, AISI 316L, AISI 321 and AISI 347 pipes used in
petroleum refining plants. The sensitization was assessed by Scanning Electron
Microscopy (SEM) according to ASTM A-262 and by the Double Loop Electrochemical
Potentiokinetic Reactivation test (DLEPR). The results showed that all steels did not present
sensitization at operating temperature (380◦ C) in the desulfurizers process, but the
temperature of 500◦ C was critical to the appearing of sensitization for the both low carbon
stainless steels and AISI 321 SS, while for the AISI 347 the critical temperature was 550◦ C.
The stabilized steels confirmed to be more resistant to sensitization than the low carbon
stainless steels, and niobium showed to be more efficient stabilizing agent than titanium.
C 2005 Springer Science + Business Media, Inc.

1. Introduction is in accordance with Padilha et al. [4], which showed

Sensitization is a deleterious phenomenon that occurs that at temperatures around 600◦ C chromium carbide
in austenitic stainless steel (SS) when it is submitted to formation was more favorable than titanium carbides.
an inappropriate increase in temperature such as what Additionally, it is shown in the literature [5–7] that it
happens during welding or operating in the temperature is possible to nucleate carbides on grain boundaries by
range between 400◦ C and 800◦ C. This is a well-known brief exposure of the SS at temperatures in the normal
phenomenon and consists of carbide precipitation at sensitization range without observation of a detrimen-
grain boundaries and chromium depletion in adjacent tal degree of chromium depletion. However, sensitiza-
regions, making the material susceptible to intergranu- tion can develop during subsequent heat treatment at
lar corrosion [1]. Recently, a previous study from our low temperature which is not expected to cause sen-
laboratory showed that sensitization at 650◦ C also pro- sitization. This phenomenon has been termed as low-
motes the embrittlement of the AISI 304 steel [2]. temperature sensitization (LTS). Thus, this practical ob-
The AISI 321 SS has been used in the desulfuriz- servation of the AISI 321 SS tubes can be explained by
ing process in the petroleum refining plants because of the temperature excursions to 600◦ C resulting in the
its good corrosion resistance and mechanical proper- formation of the carbide nuclei that were then stable
ties at the operating temperature of 380◦ C. However, enough to grow at very low temperature (380◦ C).
despite the fact that this steel contains titanium in or- Since the studied case showed that sensitization was
der to combine with carbon to avoid chromium car- not avoided even using a titanium stabilized AISI 321
bide precipitation, a practical case previously studied SS [3], it is suitable to study alternatives SS to be used
[3] showed that AISI 321 SS tubes were unsuitable after in a petroleum refining plant. Thus, this work carried
one year of operation due to severe sensitization. This out a systematic investigation of the influence of time
occurrence was related to the increase of the temper- on the intergranular corrosion of the AISI 304L, AISI
ature, which reaches around 600◦ C during shutdown 316L and AISI 347 steels with the temperature range
for maintenance or power failure. This practical case varying from the operational temperature of 380◦ C

∗Author to whom all correspondence should be addressed.

0022–2461 
C 2005 Springer Science + Business Media, Inc. 139
T A B L E I Chemical compositions of austenitic stainless tubes in wt%

Steel/elements Cr (%) Mn (%) P (%) Si (%) Ni (%) Mo (%) Ti (%) Nb (%) C (%)

AISI 304L 17.2 1.68 0.012 0.245 10.8 – – – 0.03

AISI 316L 18.3 1.54 0.012 0.622 9.8 0.423 – – 0.03
AISI 321 14.1 2.81 0.037 0.957 15.2 – 0.818 – 0.08
AISI 347 18.9 1.37 0.017 0.308 9.79 – – 0.841 0.08

up to 600◦ C. The AISI 321 tubes were also studied at the new period of time has being reached. This opera-
the same conditions for comparison. The AISI 304L and tion was systematically repeated until 96 h. A total of
AISI 316L were chosen because they are less expen- 424 samples, 105 of each steel and four in the condi-
sive than AISI 321 and contain low carbon percentage tion as received, were prepared. The objective of this
(≤0.3 wt%) to minimize the sensitization when operat- sequence was to simulate a long period of operation
ing in this temperature range, while AISI 347 was cho- with many shutdowns.
sen to be another stabilized steel containing niobium to
combine with carbon to avoid sensitization. The eval-
uation of the sensitization at the different heat treat- 2.2. Metallographic etchings
ment conditions was assessed by optical microscopy Metallographic etching according to ASTM A-262 was
and scanning electron microscopy techniques and dou- performed. Photomicrographs were acquired using a
ble loop electrochemical potentiokinectic reactivation Zeiss optical microscope and a Philips XL-30 scanning
test (DLEPR), proposed by Akashi et al. [8]. electron microscope (SEM). The microstructures ob-
tained were classified into three types: “step” structure
2. Experimental with no ditches at grain boundaries; “dual” structure,
2.1. Materials and samples preparation with some ditches at grain boundaries; and, “ditch”
Four austenitic stainless types ASTM A 312, 2.5 in structure, with one or more grains completely sur-
diameter tube, with the chemical composition shown rounded by ditches. Fig. 2 presents the microstructures
in Table I, were used in this investigation. Samples classified according ASTM A-262.
with approximately 1 cm2 of quadrangular geometric
face were obtained from each tube, as shown in Fig. 1.
The samples were heat treated at different tempera- 2.3. DLEPR tests
tures and different periods of time as shown in Fig. 3. The DLEPR tests were conducted in a conventional
All the samples were put at the same time in a pre- three-electrode cell using a Pt foil as the auxiliary elec-
heated air furnace atmosphere, at the desired tempera- trode and a saturated calomel electrode (SCE) as the
ture, and after each period of time they were cooled in reference one. The working electrode was constructed
water. One of them was picked up for metallographic using SS samples embedded in epoxy resin. The ex-
preparation and two other for electrochemical test. The periments were initiated after nearly steady-state open
others returned to the furnace and stayed there until circuit potential (E oc ) had developed (about 30 min)

Figure 1 Geometry of samples obtained from the tubes.

Figure 2 Classification of sensitized microstructure according to ASTM A-262: (a) step, (b) dual, and (c) ditch.

140
Figure 3 Classification of the microstructures observed on samples of AISI 304L and AISI 316L (a), AISI 321 (b) and AISI 347 (c) for different time
of exposition to temperature range from 380 to 600◦ C according ASTM A-262.

141
followed by the potential sweep in the anodic direc- the peak current of the anodic scan and Ir is the peak
tion at 1 mV s−1 until the potential of 0.3 V (vs. SCE) current in the reversed scan [1, 8].
was reached, then the scan was reversed in the cathodic
direction until the E oc . Prior to each experiment, the
working electrodes were polished with 400 grit emery 3. Results and discussion
paper, degreased with alcohol and cleaning in water. The plots shown in Fig. 3 present the classification
The working solution was 0.5 M H2 SO4 + 0.01 M of microstructure of the SS samples after exposure
KSCN (potassium thiocyanate). The sensitization in- to temperature from 380 to 600◦ C and periods of
tensity was evaluated from the ratio Ir /Ia , where Ia is time from 0 to 96 h. The microstructures were

Figure 4 Microstructures of AISI 304L SS (a), AISI 316L SS (b), AISI 321 SS (c) and AISI 347 SS (d) samples exposed 96 h at 380◦ C.

Figure 5 Microstructures of AISI 304L SS (a), AISI 316L SS (b), AISI 321 SS (c) and AISI 347 SS (d) exposed 24 h at 500◦ C.

142
Figure 6 Microstructures of AISI 304L SS (a), AISI 316L SS (b), AISI 321 SS (c) and AISI 347 SS (d) exposed 24 h at 600◦ C.

classified according to ASTM A-262 standard, as

shown in Fig. 1.
A very important practical result is revealed by these
plots. All the four steels did not show a sign of sen-
sitization at 380◦ C, the operational temperature in the
desulfurizers process in petroleum refining plants, sug-
gesting that all are suitable to be used for this applica-
tion if the temperature is maintained under control at
380◦ C. Fig. 4 shows the microstructures for samples of
the four steels which were exposed to 380◦ C for 96 h.
These plots also reveal that at 450◦ C the dual mi-
crostructure is only observed in samples of AISI 304L,
AISI 316L and AISI 321 heat treated for 96 h. Addition-
ally, it can also be observed in Fig. 3 that at 500◦ C the
sensitization process is evident, even in short exposure Figure 7 The sensitivity intensity evaluated from the ratio of Ir /Ia for
time, and the microstructure of the samples exposed at AISI 304L at 500◦ C.
500◦ C during 24 h is shown in Fig. 5. The micrographs
of AISI 304L (Fig. 5a) and AISI 316L (Fig. 5b) sam-
ples show microstructure classified as ditch, indicating
that these materials were sensitized. The micrograph of
AISI 321 (Fig. 5c) sample presents some chromium car-
bides around grains characterizing a dual microstruc-
ture, while the micrograph of AISI 347 (Fig. 5d) sample
presents a chromium carbide free structure character-
izing a step structure. On the other hand, all the steel
samples presented ditch structures when heat treated at
600◦ C after 24 h in the furnace, as can be observed in
Fig. 6. According to these analyses, the stabilized steels
are more resistant to sensitization than the low carbon
steels. Additionally, these results also suggest that nio-
bium is more efficient than titanium to avoid sensitiza-
tion, since ditch structure was observed for AISI 347
SS samples only when this material was heat treated at Figure 8 The sensitivity intensity evaluated from the ratio of Ir /Ia for
550◦ C after 48 h (see Fig. 3c). AISI 321 at 550◦ C.

143
T A B L E I I Time of heat treatment to reach the maximum of Ir /Ia • The addition of niobium and titanium to steel com-
Steel/T (◦ C) 380◦ 450◦ 500◦ 550◦ 600◦
position is more efficient to reduce the sensitiza-
tion than the decrease of the carbon content in steel
AISI 304L 96 h 96 h 84 h 24 h 84 h composition.
AISI 316L 96 h 96 h 36 h 84 h 84 h • Niobium is a more efficient stabilizing agent than
AISI 321 36 h 48 h 84 h 36 h 24 h titanium for this study conditions.
AISI 347 130 h

Acknowledgments
Figs 7 and 8 show the sensitization intensity evalu- The authors thank to CNPq (Proc. 460033/01-
ated from the electrochemical tests through the ratio of 8), PIBIC-CNPQ-UFC, ANP and FINEP (Proc.
Ir /Ia , where Ia is the peak current of the anodic scan 22.01.0762.00), Brazil, for financial assistance.
and Ir is the peak current in the reverse scan, for a
AISI 304L sample at 500◦ C and a AISI 321 sample at
550◦ C, respectively. For each temperature and steel a References
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(J. Wiley & Sons, 1996).
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• All the studied steel did not present sensitization 7. M . C . J U H A S and B . E . W I L D E , Corros. 46 (1990)
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AISI 347 the critical temperature is 550◦ C. and accepted 12 August 2004

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