Protection of Metals, Vol. 39, No. 6, 2003, pp. 595–596. From Zashchita Metallov, Vol. 39, No.

6, 2003, pp. 660–661.

Original English Text Copyright © 2003 by Zhao, Li, Jiang.

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COMMUNICATIONS

Failure Analysis of an Oxidative Chlorination Reactor Clad

with AISI 304L Stainless Steel1
M. Zhao, J. C. Li, and Q. Jiang
Key Laboratory of Automobile Materials of Ministry of Education and Department
of Materials Science and Engineering, Jilin University, Changchun, 130025 P. R. China
e-mail: jiangq@jlu.edu.cn
Received October 21, 2002

Abstract—Failure analysis of the hermetical AISI 304L stainless steel cladding in oxidative chlorination reac-
tor shows that its pitting and stress corrosion arose due to the presence of chlorine ion in the working environ-
ment. In order to improve its corrosion resistance, AISI 316L stainless steel should be utilized.

Stainless steels have become well known for their
passivity and, hence, resistance to corrosion and high-
temperature oxidation. Thus, they were the material of
choice for offshore industries, petrochemical plants,
and naval constructions. AISI 304 stainless steel offers
good mechanical properties and corrosion, as well as
oxidation, resistance. Nevertheless, its use is limited
due to its susceptibility to some types of local corrosion
attack, such as pitting and stress corrosion in the pres-
ence of Cl– ions [1–4]. In our case, the inside cladding
of an oxidative chlorination reactor made from
AISI 304 stainless steel at a chloroethylene workshop
of a chlorine and alkali factory showed a service life of
incomplete two years, which was much shorter than
expected [5, 6]. The working medium of the parts con-
sists of ethene (C2H4) and dichloroethane (EDC). The
working temperature of the reactor is 503 K while the
working temperature of the cladding is 513–523 K
under a pressure of 0.20–0.24 MPa. The diameter and
the thickness of the cladding are 5100 and 16 mm,
respectively. In this report, the failure analysis of the
parts under this special working conditions is made to
find a way to extend the working life of the equipment.
Based on the analysis, the material substitution for the
alloy and welding technique are suggested.
To identify the cause of the corrosion, the corroded
surface of the parts was cleaned in turn with a 10-%
HCl solution, water, and alcohol and then was dried.
The samples were cut along vertical direction. The
microstructure of a crack in the part was observed by
optical microscope. The crack’s source and crack
expansion zone were analyzed by a scanning electronic
microscope (SEM), the surface composition at the
source and the tip of the crack, as well as the propaga-
tion range were determined by energetic dispersive
X-ray spectrum (EDS).
Figure 1 shows the source of the crack of the surface
of the cladding. The results evidence the crack propa-
gates with branching, and the ruptures are intracrystal-
line. Figure 2 shows that the sample exhibits pitting
corrosion initiated by nonmetallic inclusions. The
crack forms and first propagates from pits or nonmetal-

(a) 200 µm (b) 200 µm

Fig. 1. Optical micrograph of crack: (a) crack source and (b) crack’s propagation zone.

1 This article was submitted by the authors in English.

0033-1732/03/3906-0595$25.00 © 2003 MAIK “Nauka /Interperiodica”

596 ZHAO et al.

304L 304L

(a) 8419 25 KV ¥ 70 100 µm WD37 (b) 8400 25 KV ¥ 200 100 µm WD38

304L 304L

(c) 8402 25 KV ¥ 1.000 10 µm WD39 (d) 8401 25 KV ¥ 500 10 µm WD38

Fig. 2. SEM micrograph of the failed part: (a) crack’s source at the outer surface, (b) crack’s origin, (c) tip of the crack, and (d) far
propagation zone.

lic inclusions themselves, where the accumulation of
Cl– ions makes stress corrosion proceed further. As a
result, the equipment fails. The above consideration is
supported by an elemental analysis of different zones
listed in table. In the crack’s, Cr and Ni contents are
lower than around it. By contrast, Cl, S, and Si contents
are higher just here; specifically, Cl and S contents are
almost forty times in the tip of the crack.
According to the above analysis, the parts can reli-
ably withstand corrosion for an allowable working life
only when the alloy is pitting-resistant. Thus, in our
Composition analysis in different corrosion zones, wt %
Position Cr Ni Si Ca Cl
Crack’s source 10.36 2.56 28.32 2.61 4.72 4.96
The tip of the crack 19.88 7.99 1.19 – 0.41 0.09
The propagation zone 21.84 9.72 0.69 – 0.05 0.03
operating conditions, an AISI 304L stainless steel
should be replaced by AISI 316L stainless steel, which
exhibits better pitting resistance due to the presence of
molibdenum.
REFERENCES
1. Scdkris, A.J., Corrosion of Stainless Steel, New York:
Wiley, 1979, pp. 63–87.
2. Tanno, K. and Yashiro, H., Corros. Eng., 1988, vol. 37,
p. 65.
3. Chen, T.H. and Yang, J.R., Mater. Sci. Eng. A, 2001,
vol. 311, p. 28.
4. Li, J.C., Zhao, M., and Jiang, Q., Mater. Corros., 2002,
S vol. 45, p. 269.
5. Li, J.C., Zhao, M., and Jiang, Q., Mater. Performance,
2002, vol. 41, p. 50.
6. Nan, S.H., Lü, X.X., and Jiang, Q., J. Jilin Univ. Tech.,
1995, vol. 25, p. 75.

PROTECTION OF METALS Vol. 39 No. 6 2003