Engineering Failure Analysis 90 (2018) 14–22

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Engineering Failure Analysis

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

Short communication

Stress corrosion cracking failure of a SS 316L high pressure heater

T
tube
⁎
M. Ananda Raoa, , R. Sekhar Babub, M.V. Pavan Kumarc
a
CSIR, National Metallurgical Laboratory Madras Center, Chennai, India
b
Paradeep Phosphates Limited, Paradeep, India
c
Department of Chemical Engineering, National Institute of Technology, Calicut, Kerala, India

A R T IC LE I N F O ABS TRA CT

Keywords: A service failure by environmentally induced cracking in austenitic stainless steel 316 L is pre-
Stress corrosion cracking sented in this work. Extensive research has been carried out on stress corrosion cracking of
Caustic corrosion different materials and environment combinations by various established experimental proce-
Chlorine attack dures. The list of alloy/environment combination that causes stress corrosion cracking is con-
HP heater tube
tinuously increasing. Stress corrosion cracking is a great concern in corrosion resistant alloys
Thermal power plant
exposed to aggressive environments. Stainless steel 316 L material used as high pressure water
heater tube failed by stress corrosion cracking was evaluated by various metallurgical char-
acterisation techniques. Results and apparent causes leading to failure were explained in detail.

1. Introduction

Almost all process equipment in thermal power plants are prone to corrosion due to high interconnectedness of the hardware
elements with potential corrosive nature of the process streams. For the successful avoidance of operation failures caused by the
corrosion of the equipment, it is vital that the root cause of the corrosion and its progression are investigated and understood
thoroughly. As any thermal power plant is an extremely important generator of electrical energy, many case studies pertaining to the
failures in boilers due to corrosion phenomena were reported earlier [1–3]. In a comprehensive study on the failure of feed water tube
of a boiler by Hales et al. [1], the failure was attributed to a specific phenomenon called “flow assisted chelant corrosion”. Some
useful recommendations were enlisted for the safe operation of boilers. Ranjbar [4] highlighted the aspect of the control of feed water
chemistry to prevent corrosion of the cold and hot reheater tubes in the boilers. Nevertheless, the makeup feed water undergoes a
series of physical/chemical treatments for to be compatible in the boiler operation. Hence, the contact/accumulation of the chemical
agents inside the equipment with or without chemical transformation at the prevailing operation conditions thus becomes an im-
portant and crucial aspect in the sustainability of the whole operation.
Caustic soda is a widely used as water softening agent to control feed water pH in the operation of boilers. However, if present
above the critical levels, it can lead to caustic gouging [5] [6]. The corrosion of steels due to caustic soda was discussed by Fontana
[7] and Rondelli et al. [8]. It is also reported that low alloy steels of 300 series are more prone to caustic corrosion above 366 K [9]
[10]. The mechanism of corrosion inside boiler pipes due to caustic and phosphates was presented by Khajavi et al. [11]. Pritchard
et al [12] studied the deposition of NaCl, NaBr and NaOH on the surface of AISI Type 316 stainless steel tube. Their study revealed
that the deposition is possible even with low concentrations of the salts at high pressures and low to moderate temperatures. Poulson
[13] systematically investigated the stress corrosion cracking of stainless steel 316 in caustic solutions. A relation between crack

⁎
Corresponding author at: National Metallurgical Laboratory, Madras Centre, Taramani, Chennai, India.
E-mail address: anandm04@gmail.com (M. Ananda Rao).

https://doi.org/10.1016/j.engfailanal.2018.03.013
Received 14 July 2017; Accepted 13 March 2018
Available online 14 March 2018
1350-6307/ © 2018 Elsevier Ltd. All rights reserved.
M. Ananda Rao et al. Engineering Failure Analysis 90 (2018) 14–22

Steam Inlet Feed water outlet

Pressure 17-36

Steam outlet Feed water inlet

Fig. 1. Schematic of the high pressure water heater.

Table 1
Chemical analysis of water and condensate (15 days average data).

DM Water Condensate

Conductivity 0.08 μs/cm Conductivity 5 μs/cm

pH 7.01 pH 9.22
Silica 11 ppb Silica 11 ppb
Total iron 10 ppb
Ammonia 0.8 ppm
Cationic conductivity 0.25 μs/cm

velocities and molar concentration of NaOH was established. In another seminal work by Poulson [14], the effect of the heat transfer
on the deposition of caustic and subsequent stress corrosion cracking of 316 steel was studied in an artificial crevice. The relevant
literature on the subject was also reviewed and the advantages of the devised experimental approach were discussed in detail. The
corrosion resistance of 316 L type stainless steel in caustic environment reported is reported [15–16]. Stress corrosion cracking of
different materials with possible alloy/environment combinations been tabulated and failure mechanism in stainless steels with
respect to stresses, microstructure, effect of cold work, protective films, sensitisation was discussed in detail [17–19].
In recent years, steels of higher corrosion resistance in alkali environment are desired. The objective of the current work is to
analyze the corrosion damage of a high pressure heater tube made of stainless steel SA213 TP 316L in a thermal power plant.

2. Description of high pressure water heater

To enhance the energy efficiency in a power plant, the incoming feed-water to the boiler is pre-heated by the outgoing steam. The
corrosion damage case study reported here was happened in a coal fired thermal power plant The heater tubes are made of SA213 TP
316L Pl material. The diameter of a tube is 16 mm and the wall thickness of in the tubes is 1.6 mm. The heater tubes are designed to
withstand for high pressure operation (above 104 bar) and hence referred as high pressure heater tubes. The heater in the discussion
is an heat exchange of horizontal shell and tube type as shown in Fig. 1. heat exchanger. Schematic of the heater with operational
data is presented in Fig. 1. Steam inlet (shell side) and outlet temperatures are 573 K and 373 K respectively at 17–36 bar pressure.
Feed Water enters roughly at 323 K and gets preheated to 373 K, tubes are designed to operate up to180 bar. Laboratory analysis of
water and condensate is tabulated in Table 1. Few tubes failed in the desuperheating zone (where steam enters) of the heater after
11 months of service life, against the prescribed service life of 25 years. The failure was in the desuperheating zone of the heater,
incoming steam enters in this zone and transfers most of the super heat to the boiler feedwater.

3. Details of experimental evaluation

The failed tube sample was first examined visually. The chemical composition at the failed regions of the tube were found using
optical emission spectrometer (OES-Spectrolab, Germany). The failed tube's inner and outer surfaces were examined by stereo-
microscopy (Leica, Switzerland). For further examination of the failed tube, the metallographic samples were prepared by con-
ventional polishing and examined in both etched and unetched conditions. The nature of the corrosion deposits and the presence of
any other deposition of elements were examined using SEM-EDS (Model: SEM-JEOL JSM 739A).

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M. Ananda Rao et al. Engineering Failure Analysis 90 (2018) 14–22

Fig. 2. High pressure heater failed tube (as received condition), stainless steel 316L.

Table 2
Chemical composition of the failed tube.

Element (wt%) C Si Mn P S Cr Ni Mo Fe

Failed tube 0.02 0.51 0.92 0.021 0.005 16.3 10.80 2.17 Rem
Specified composition of SA213 TP 316L ≤0.035 ≤1.0 ≤2.0 ≤0.045 ≤0.030 16.0–18.0 10.0–14.0 2.0–3.0 Rem

Fig. 3. Stereo photomicrographs (A) crack initiation sites (B) longitudinal microcracks.

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Fig. 4. Steriomicrograph shows the (A) cavities and corrosion pits inside the tube surface. (B) Pits, oxides and deposits inside of the tube.

4. Results and discussion

In the visual examination, discoloration of the tube external surface is evident as shown in Fig. 2. It clearly appears that the failure
was of transverse cracking type (perpendicular the axis of the tube) as given in Fig. 2.Table 2 gives the chemical composition of the
tube at the failed region and the composition is as per the material specification. External surface pitting is seen as the crack initiation
sites in stereomicrocopy examination as shown in Fig. 3A. Longitudinal micro cracks were seen which are perpendicular to the main
transverse crack (Refer Fig. 3B). Cavities, micro cracks and corrosion deposits on the tube's inner surface were observed and the same
are shown in Fig. 4.
The optical micrographs shown in Fig. 5 A & B show branched cracking on the external surface of the tube. The branching is
present in both longitudinal and transverse direction. No microstructural deformation was observed across the cross section except
near to the inner surface as shown Fig. 6. On further analysis, the mode of cracking is found to be intergranular cracking as shown in
Fig. 7. On external tube surface branched cracks were observed and these are generally referred as stress corrosion cracks and no
microstructural deformation was observed near to these cracks.
A scanning electron microscopy (SEM) image of a crack is presented in Fig. 8, the crack is of stress corrosion cracking type. SEM
with Energy Dispersive Spectrometry (EDS) was performed in and around the failure region to understand the cause of failure.The
analysis results obtained at three different regions, visually near, inner surface of the tube, and on outer surface were presented in
Figs. 9, 10 and 11 respectively. The EDS analysis at the region near to the crack as shown in Fig. 9 indicated the presence of
extraneous elements sodium and chlorine besides the alloying elements of SS 316L. The excess amounts of Carbon, Oxygen and
Calcium can be attributed to the CaCO3 scaling near the crack. The tube internal surface EDS analysis shown in Fig. 10 didn't revealed
the excess amounts of Na, Ca, O and C as was evident near the crack. Bulk EDS analysis on the outer surface, region away from the
crack revealed only alloying elements of SS 316 material, except oxygen as shown in Fig. 11, the extraneous elements sodium,
chlorine, carbon, Oxygen and Calcium were not present. The presence of oxygen is likely due to chromium oxide layer on the tube
surface. All the SEM images revealed the presence micro cracks on the failed tube. The impurities present on the tube surface are due
to their presence in the condensate and the chemical agents such as caustic soda, Hydrazine and phosphates added to the boiler feed
water might deposited salts of sodium and calcium.

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Fig. 5. Optical micrograph shows the (A) branched cracking on thetube external surface. (B) Crack in the unetched condition.

From optical microscopic examination results, it can be concluded that the failure of the tube is by Stress corrosion cracking
(SCC). SCC is a major cause of many service failures of boiler tubes. It occurs due to the simultaneous presence of tensile stress and the
presence of corrosion causing ions. In the case reported, the presence of Clˉ and Na causes the damage of stable passive film over the
surface at the high pressures and temperatures. Note that SS 316 L steel is widely regarded as a superior corrosion resistant material
due to added molybdenum (Mo)·However, the possible crack initiation sites in 316 L steel are secondary phase formation, inclusions,
stress induced localized areas of film rupture, in- homogeneousness in the material composition, small thickness of the protective
film, high concentration of the corrosion causing elements and stress concentration.
The cracks which ultimately led to the failure were initiated at the pits (Refer Fig. 3 A). The pitting was due to the presence of Clˉ
ions in the steam condensate (Refer Fig. 9). The presence of silicon is known to promote the pit growth. The inclusions can potentially
become pit initiation sites, as the inclusions could become very active in acidic, aqueous and chloride containing environments and
dissolve the material. This dissolution creates localized anodic areas on the metal surface and can potentially attract chloride ions.The
addition of caustic soda and the impurities present in the fresh feed water such as salts of sodium, potassium might have eventually
deposited inside the pits over the time.
Stress corrosion cracking in austenitic stainless is of two types namely, transgranular or intergranular. The cracks observed on the
tube surface were predominantly intergranular (Fig. 7) and the intergranular cracking was suspected due to the presence of high
sodium levels near the crack (SEM EDS presented in Fig. 9). Although the Clˉ ions also promote intergranular cracking in most of the
cases, the stress corrosion cracking due to chlorine was reported to be intransgranular type [19].The presence of chlorine inside the
pits and micro cracks might have accelerated the cracking. The accumulated caustic soda on the outer surface of the tube is capable of
causing stress corrosion crack propagation along the tube thickness. The presence of sodium may also be attributed to the formation
of sodium ferrites on the outer surface [7]. These ferrites which are highly porous in nature can entrap both Clˉ and caustic soda
inside their matrix creating favourable environment for corrosion. The deformation observed near the inner tube surface was due to
high water pressure and consequent induced stresses during crack propagation. The exfoliation of scaling is also possible due to
thermal and operating stresses which can lead to the dissolution of protective film with no repassivation. The scaling exfoliation
caused by thermal stresses in the tube material, induced stresses during the operation and dissolution of the film with no re-
passivation might have also resulted in the exposure of the base metal directly to the corrosion environment. Many different

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Fig. 6. Optical photomicrographs (A) at the centre of the tube cross section. (B) Deformed structure close to tube inner surface.

Fig. 7. Optical micrograph at the tube external surface, evidence of intergranular corrosion.

mechanisms have been proposed to explain the stress corrosion interactions that occur at the crack tip, and there may be more than
one process that causes SCC [19–20]. The failure mechanism model relevant to intergranular corrosions are dissolution model,
dissolution of grain boundaries, which are chemically active paths for crack propagation. In the present investigation, it was found
that crack initiation was from surface pitting; the cracks initiate from the pit on the tube surface and propagate intergranularly.
Source of pitting was chlorides present in the condensate. The pit was acted as stress raiser to initiate failure, change in the corrosive
environment was promoted by the presence of Na within the pit. As the failure mode was intergranular and branched cracking was
observed the crack propagation was by synergetic effect of both caustic and chloride attack.

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Fig. 8. SEM image of the crack, crack branching and microcracks.

Element Wt%

C 46.87
O 27.82
Na 1.48
Mg 1.00
Al 0.63
Si 1.47
Cl 0.32
K 0.43
Ca 17.14
Fe 1.87
I 0.98
Total 100.00

Fig. 9. SEM image of a typical longitudinal crack and EDS analysis at a selected location near the crack.

5. Conclusions

With the aid of characterisation it was found that extensive branching of the crack at the tube surface, which is an indication of
stress corrosion cracking. The crack was initiated from tube external surface pitting, the presence of chloride ions in the condensate
are responsible for pitting. The crack morphology on the tube surface was predominantly intergranular, the intergranular cracking
was suspected due to the presence of high Na. The accumulation of caustic that was added to regulate the pH and with the thermal
and mechanical stresses in the material have led to caustic corrosion. Presence of both chlorides and Na concentration at the pits
caused intergranular corrosion of the heater tube.

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M. Ananda Rao et al. Engineering Failure Analysis 90 (2018) 14–22

Element Weight %

C 10.35
O 17.06
Na 0.26
Al 0.28
Si 0.54
Cl 0.36
Ca 0.37
Cr 4.92
Mn 0.08
Fe 64.54
Ni 1.23
Total 100.00

Fig. 10. Scanning electron microscope (SEM) image of inside surface of the failed tube with the corresponding bulk EDS analysis in % wt.

Element Weight %

C 4.22
O 18.53
Si 1.22
Cr 19.17
Fe 49.25
Ni 7.62
Total 100.00

Fig. 11. SEM image of the outer surface away from the crack, with bulk EDS analysis in % wt.

Acknowledgement

The authors express their sincere thanks to Director, CSIR-National Metallurgical Laboratory, Jamshedpur, for his encouragement
and permission to publish this work.

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