Engineering Failure Analysis 14 (2007) 36–40

www.elsevier.com/locate/engfailanal

Chloride-induced stress corrosion cracking of furnace

burner tubes
R.C. Yin *, A.H. Al-Shawaf, W. Al-Harbi
Materials and Corrosion Section, Sabic Technology Center, P.O. Box # 11669 Jubail Industrial City 31961, Saudi Arabia

Received 9 January 2006; accepted 10 January 2006

Available online 27 March 2006

Abstract

The burner tubes (316SS) of an ethylene cracking furnace in a Saudi petrochemical plant experienced repeated prema-
ture failures. One failed sample was investigated by chemical and microstructural analytical techniques to find out the fail-
ure cause and provide preventive measures. The results indicate that the burner tube failed due to chloride-induced stress
corrosion cracking (SCC). Chloride could be due to the contamination coming from the ambient industrial environment.
The forming process (bending and drawing) of the tubes prior to installation introduced residual tensile stresses necessary
for SCC. It is recommended to stress relieve (or shot peen) the tubes following the forming process, or alternatively apply
protective coatings (chloride-free) to prevent contamination. Periodic cleaning of the tube exterior is necessary.
 2006 Elsevier Ltd. All rights reserved.

Keywords: Burner tube; 316SS; Chloride-induced SCC; Residual tensile stress

1. Introduction

The burner tubes of an ethylene cracking furnace in a Saudi petrochemical plant experienced repeated
premature failures. The burner tubes connect the main header of the mixed fuel gas with the furnace burn-
ers to supply the fuel. This facility has been in service for 7 years since commissioning. For the past 2
months, two failures in those tubes were encountered. For the first failure, the tube was replaced with a
new one. The second failure indicated it was a common problem existing in the burner tubes of the ethylene
cracking furnace. The tube measures approximately 12.43 mm in outer diameter (OD) and 0.8 mm in thick-
ness, and is constructed of 316 stainless steel (Table 1). The tube contains the mixed flowing fuel gas inside,
and exposes to the ambient air outside. The process parameters are the temperature 45 C, the pressure
230 kPa, and the flow of a single burner 0.349 MT/D. One failed burner tube, the oily liquid sample drained
from inside the tube, and the surface deposit on the failed tube were analyzed in order to elucidate the fail-
ure cause.

*
Corresponding author. Tel.: +966 3 3599133; fax: 966 3 3599112/3599292.
E-mail addresses: ruchuany@sabic.com, yinruchuan@yahoo.com (R.C. Yin).

1350-6307/$ - see front matter  2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.engfailanal.2006.01.002
 R.C. Yin et al. / Engineering Failure Analysis 14 (2007) 36–40 37

Table 1
Nominal composition of 316 stainless steel
Elements Ni Cr Mo Fe Mn Si C Other
Wt% 10–14 16–18 2–3 Bal 2.0 1.0 0.08 P < 0.045; S < 0.03

2. Experimental

Visual and stereoscopic inspections were carried out on the failed burner tube. Then, the tube was sectioned
and prepared for microstructural evaluation. The etchant used was glyceregia (10 ml HNO3, 20–50 ml HCl,
and 30 ml glycerol). Optical microscopy of as-polished and as-etched samples on transverse cross-section
was conducted. The oily liquid sample was studied by liquid chromatography (LC). The tube surface deposit
was analyzed by energy dispersive spectroscopy (EDS), X-ray fluorescence (XRF), and X-ray diffraction
(XRD) techniques, respectively.

3. Results

The failed burner tube cracked almost transversely near one of the elbows (Fig. 1), which obviously had
suffered substantial plastic deformation of bending and drawing during the forming process. Prior to being
taken out, the tube was covered with thick deposit on its outer surface.
Stereoscopic examination indicates that the major crack has another smaller branched crack (Fig. 2), and
additionally several tight and apparent branched cracks are also present in an adjacent area on the same side.
Optical microscopy conducted on the transverse cross-section of the cracked portion (Figs. 3a and 3b) shows
that the cracks are apparently branched, both intergranular and transgranular. It appears that the cracks were
initiated at the outer surface of the tube, and subsequently propagated inwardly. No sensitization has been
observed in the microstructural examination.
Fig. 4 shows the surface EDS spectrum inside the crack and on the tube surface deposit. Appreciable
amount of chloride and sulfur were detected, and high peaks of oxygen, carbon, and calcium, etc. were also
found. It is noticed that moderate amount of zinc is present in the surface deposit as well.
Chemical analysis by LC (Table 2) indicates that the liquid sample is mildly acid (pH 3.9), chloride and
sulfur contents (sulfate) are in the level of 91 and 11 ppm, respectively, and it consists primarily of various

Fig. 1. Close-up of the failed tube after cleaning surface deposit.

38 R.C. Yin et al. / Engineering Failure Analysis 14 (2007) 36–40

Fig. 2. The major crack and a branched crack (3·).

Fig. 3a. The transverse cross-section morphology of the cracked portion (50·, as-polished).

types of organic compounds. XRF (Table 3) done on the surface deposit confirms the presence of chloride,
sulfur, and zinc, etc.

4. Discussion

Obviously, stress corrosion cracking is responsible for the failure. The cracks are apparently branched, con-
forming to the typical SCC features, and likely propagated inwardly from the OD. Chloride and sulfur are the
two aggressive species for stress corrosion cracking of austenitic stainless steels, such as 316SS. The absence of
sensitization in the microstructures indicates the failure is not attributed to polythionic acid stress corrosion
cracking due to sulfur. The substantial plastic deformation resulting from the forming process of bending and
 R.C. Yin et al. / Engineering Failure Analysis 14 (2007) 36–40 39

Fig. 3b. The cross-section morphology showing branching of typical SCC (200·, etched by glyceregia).

Fig. 4. EDS spectrum of the deposit on the tube surface.

Table 2
Chemical analysis of the liquid sample (detecting limit: 0.1 ppm)
pH Chloride Sulfate Styrene Indene Octadecane Eicosane
3.9 91 ppm 11 ppm 20 wt% 15 wt% 10 wt% 10 wt%
Heptadecane Hexadecane Ethyl benzene P-xylene Propyl benzene Other alkyl substituted
decane and decene
10 wt% 5 wt% <1 wt% <1 wt% <0.5 wt% 25 wt%
40 R.C. Yin et al. / Engineering Failure Analysis 14 (2007) 36–40

Table 3
XRF analysis of the surface deposit (wt%)
Mg Al Si Cl S K Ca Ti
1.03 2.34 8.01 6.67 6.97 1.57 26.89 0.769
Cr Mn Fe Ni Zn Cu P
0.528 0.239 22.46 0.387 21.74 0.017 0.38

drawing created residual tensile stresses on the tube surface, which must have reached maximum at the outer
side of the tubes. Moisture could have been readily acquired in the ambient industrial environment, which pro-
duced an aqueous environment. The temperature (45 C) and mildly acid environment (pH 3.9) also favored
the chloride-induced SCC. Chloride has been found in both the outer surface deposit and the oily liquid inside
the tube. However, the chloride on the tube surface might be responsible for the failure since the tube cracks
were initiated on the OD side. In short, this failure possesses all favorable conditions necessary for SCC to
occur, and chloride-induced stress corrosion cracking was the culprit of the failure. It has to be mentioned
that zinc could come from the nearby furnace exterior and other equipment with Zn hot sprayed or dipped
(galvanized) coatings for atmospheric corrosion protection.
In general, the corrosion resistance of austenitic stainless steels to SCC depends on the following [1]: (1)
Alloy composition. Increasing Ni and Mo content of austenitic stainless steels enhances resistance to SCC;
(2) Tensile stresses. Lowering stresses (residual or applied) increases time to failure. Stress relieving or shot
peening is usually utilized to release tensile stresses or introduce compressive stresses; (3) Microstructures.
Delta ferrite in austenitic stainless steels generally improves resistance to chloride SCC. Sensitization can pro-
mote SCC; (4) Environmental factors. Higher temperature, higher concentration of chloride, presence of oxy-
gen, and lower pH promote the occurrence of SCC. Taking all the pros and cons into consideration, the most
feasible and cost-effective approach is to stress relieve or shot peen the tube prior to installation. Caution
should be exercised to avoid sensitization during the heat treatment process. Alternatively, protective coating
(chloride-free) can be applied to the tube external surface to prevent contamination. No material change is
required. Periodic cleaning of the tube surface deposit is necessary.

5. Conclusion

 The burner tube failed by chloride-induced stress corrosion cracking.

6. Recommendations

 Stress relieving (or shot peening) should be done following the forming process of the tubes.
 Alternatively, protective coating (chloride-free) can be applied to the tube external surface to prevent
contamination.
 Periodic cleaning of the tube surface deposit is necessary.

Reference

[1] John Sedriks A. Corrosion of stainless steels. New York: John Wiley & Sons, Inc.; 1996.