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Stress Corrosion Cracking of Stainless Steel Components in Steam Service

Article · January 2001

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 STRESS CORROSION CRACKING OF STAINLESS STEEL
COMPONENTS IN STEAM SERVICE

Mel J.Esmacher, P.E.

BetzDearborn
P.O. Box 4300
The Woodlands, TX 77380

ABSTRACT

The paper discusses stress corrosion cracking (SCC) of stainless steel components due to the ingress of
caustic into steam systems. Also reviewed are case histories in which laboratory investigations assisted in
identifying the root causes involved and proper corrective actions to resolve this problem.

Keywords: caustic, steam, stress corrosion cracking, superheater, stainless steel.

INTRODUCTION

A serious threat to service reliability in many industries is the sudden fracture of stainless steel components
employed in steam service, such as superheater tubing, expansion joints, steam lines and turbine parts. After
reviewing metallurgical failure analysis test results, caustic-induced stress corrosion cracking (SCC) is frequently
discovered to be the cause of this brittle cracking.

In many ways, caustic SCC of stainless steel represents a forgotten phenomenon, since it was researched,
studied and quantified in the ‘60s and ‘70s. As a result, material selection for steam system components is now
routinely made with the understanding that steam purity guidelines will be strictly followed. However, this
assumption is continually challenged by inadvertent ingress of caustic via boiler water chemistry upsets,
carryover of boiler moisture/salts into the steam system, contamination of desuperheating (or attemporating)
water injected into steam as a means of temperature control, or accidental entry of caustic process streams into
steam headers or boiler condensate return. In fact, it is not unusual to find that after 10 years of uneventful
service, a single upset in caustic contamination of steam produces complete component failure within a few
hours or days.

This paper will outline the mechanism of caustic SCC in stainless steel alloys, review case histories to
examine instances of operational upsets that put stainless steel components at risk, and discuss possible
corrective actions tat can reduce the incidence of failure.

MECHANISM

Austenitic (300 series) stainless steels (SS) have a significant sensitivity to the combination of stress and the
presence of caustic in high temperature steam environments, similar to caustic embrittlement of carbon and low-
alloy steels. As with most metals that are susceptible to SCC, decreasing levels of applied stress in caustic
(20% NaOH and 20% KOH test solutions at 300 °C in 347 SS) have been shown to increase the time for
failure (Figure 1), suggesting that stress relief annealing could be a possible remedy. 1,2 However, other studies
have shown that the minimum stress threshold for caustic SCC in 300 series austenitic stainless steels can be
extremely low (less than one) as compared higher nickel alloys such as alloys 800, 690, and 600 (Figure 2). 3
In addition, stress-relief annealing has yielded little to no improvement whatsoever in 300 series stainless steels
in resistance to cracking in hot, concentrated caustic solutions. 4,5 This is in contrast to the success of thermal
stress relieving in higher nickel alloys to reduce caustic SCC susceptibility. 6

In addition to being subject to cracking with only a slight amount of residual or applied stress, the speed of
an advancing stress-corrosion crack front for stainless steel alloys in caustic solutions is much greater than that
observed in carbon or low-alloy steels. Crack growth in 347 grade SS has been shown to have an extremely
high rate of initial propagation, as much as 6.25mm (0.25 in.) per hour. 7 In fact, it has been shown that less
than 0.2% hydroxide in water may cause cracking in austenitic stainless steels in a few hours under
concentrating conditions. 8

Unlike the mostly intergranular crack propagation in caustic SCC of carbon and low-alloy steels, highly-
branched transgranular crack paths are commonly seen and are often indistinguishable from chloride-induced
SCC in austenitic stainless steels. 9 Microscopic elemental analysis techniques, such as scanning electron
microscope – energy dispersive X-ray analysis (SEM-EDXA), along cracks or on fracture surfaces can help
differentiate between transgranular cracks caused by chloride SCC and caustic SCC in stainless steel.
However, it should be noted that branched intergranular crack paths are also witnessed in caustic SCC of
austenitic stainless steel, especially in lower concentration caustic solutions like 10% sodium hydroxide at 316
°C. 10

The speed of caustic crack growth in austenitic stainless steels is due to breakdown of the primary passive
film and localized anodic dissolution at film breakage locations in the active-passivation transition zone, with
transpassive Cr dissolution playing a dominant role in the process. 11,12 In addition, the stability of
hydroxyanions (such as HFeO 2- and HNiO 2-) in high pH may prevent a passive, protective film from forming,
especially at higher operating temperatures. 13
 Temperature can also determine whether caustic SCC occurs in stainless steel alloys. For types 304, 347,
316 and 321 stainless steels, a “tentative safe limit” of 50 °C in concentrated caustic has been proposed (Figure
3). 14 However, as shown in Figure 3, an inherent danger of caustic cracking within a 100-300 day period
appears imminent as temperatures approach 100 °C. At temperatures from 175 °C to 300 °C (and above),
cracking failure within 24 hours has been documented as a function of caustic concentration. 15

The composition of stainless steel alloys used in steam service does have some influence on resistance to
caustic-SCC. For example, molybdenum is considered to be detrimental in relation to caustic-induced
cracking, due to extension of the potential range for cracking in hydroxide solutions. 16 Low to moderate nickel
levels exert a negative effect, while increased nickel content (above 30% Ni) in an austenitic alloy is very
beneficial. 17 This is consistent with the service experience of increased caustic-SCC resistance of Incoloy 800,
Inconel 600, and ultimately alloy 201, and is especially pronounced at higher caustic concentrations. 18 Inconel
600 is resistant to brittle, intergranular caustic-SCC in concentrated caustic solutions up to the melting point of
sodium hydroxide (317 °C, 603 °F).19 However, rapid intergranular cracking has been observed in Inconel
600 at temperatures at or near this melting point in steam environments. 20,21 Chromium additions also help
austenitic stainless steels resist SCC, especially in oxygenated caustic solutions. 22,23

CASE HISTORY EXAMPLES IN LITERATURE

From the wealth of research data on rapid caustic-SCC of stainless steel, it is clear that it is cause for
concern whenever steam purity has been compromised by sodium hydroxide ingress. Numerous failure analysis
reports detail the rapid nature of steam system component failure due to carryover of caustic into a high-
temperature steam system. In regards to gross carryover in extremely high temperature steam (700-930 °C),
the presence of molten caustic salts has been documented to trigger catastrophic oxidation in Incoloy 800 and
304H SS components. 24 In these cases, molten salts created excessively high corrosion penetration rates
(complete failure of a three-ply Incoloy 800 expansion joint within three days of installation), so cracking
damage was not the failure mechanism.

Another paper discusses the performance of 321SS versus replacement Inconel 600 expansion bellows at
45 kg/cm2 (650 psi) pressure at 400 °C (750 °F). 25 The original 321SS bellows failed, and both the 321SS
and Inconel replacement joints failed within 10 days of installation. Due to the high steam temperatures, the
presence of caustic collected in the bellows (from an intermittent carryover of boiler water salts) was extremely
aggressive, producing rapid failure regardless of the alloy choice.

Another example of carryover-induced caustic SCC of stainless steel is a report of 304H superheater tube
weld support cracking at steam temperatures of 510 - 538 °C (950- 1000 °F) at 10.5 Mpa (1500 psi) operating
pressure. 26 In this case, weld supports cracked catastrophically within hours of a caustic regenerate ingress into
the boiler water system (due to a failed check valve in the demineralizer system) and subsequent carryover.
Unfortunately, the sodium analyzer in the steam system was not operating at the time of the upset, so the system
operator had little information of the severity of the steam contamination event.
 In addition to carryover, inadvertent caustic contamination of desuperheating water can be a source of
steam contamination and resulting SCC of stainless steel. Inspection of broken grade 286A precipitation
hardened turbine packing springs confirmed severe intergranular cracking and the presence of 20-30% sodium
in deposits near the failure. 27 Boiler feedwater with free caustic (sodium hydroxide) present was being used
for a source of desuperheater water. The suggestion was made to move the point of caustic injection into the
feedwater downstream of where the feedwater was taken off for desuperheating water in order to avoid the
inadvertent caustic contamination of the steam system.

OTHER CASE HISTORIES

Expansion Joints on Steam Dryer Cans

A report of repetitive 321SS expansion joint fracturing in a 10.4 kg/cm2 (150 psi) papermill steam dryer
application was received following an electrical outage at the plant. The magnitude of the problem was not
initially known, but later became obvious after replacement joints failed within hours of replacement. Figures 4,
5 and 6 show the failed expansion joint. There did not appear to be any gross deposits on the cracked metal
surfaces. However, cross-sectional metallography revealed extensive branched transgranular cracking, initiating
on the steam side surface (Figures 7 and 8). One of the secondary crack sites was bent open and studied in a
scanning electron microscope (SEM), equipped with an energy dispersive X-ray analysis (EDXA) system
(Figures 9 and 10). SEM-EDXA of the corrosion product on the fracture surface (Figure 11) showed
approximately 27% sodium concentration. It was subsequently discovered that during a power failure in the
plant, a steam header had become depressurized, and a caustic process chemical had “backed up” into the
steam header. The coating of caustic residue inside the steam header from that one-time excursion was
sufficient to crack every replacement expansion joint attempt that was subsequently made downstream. This
pattern of caustic-SCC continued until the entire steam header system was shut down and water-washed.
Since that corrective action, not a single stainless steel steam expansion joint has failed in the system.

Superheater Bend Cracking

After 10 years of service in a boiler operating at 60 kg/cm2 (865 psi), a 304SS superheater tube failed
catastrophically due to brittle cracking in a bend (Figures 12, 13 and 14). Metallographic cross-sectioning
confirmed extensive transgranular SCC (Figures 15 and 16). SEM-EDXA confirmed approximately 10%
sodium present in the internal deposits inside the superheater bend. Follow-up investigating confirmed that the
sodium salts had been transported into the superheater loop, as it was later admitted that the boiler “carries over
quite frequently”. Corrective action in this case was aimed at eliminating the frequent carryover problem, which
was suspected to stem from periodic operational upsets. This type of physical carryover of water droplets into
the steam phase entering into a superheater bank can be induced by excessively high water levels in the steam
drum, inadequate or malfunctioning steam separation equipment, or periodic surges related to load changes.
28,29 Also, as part of a corrective action plan, effective steam purity monitoring techniques should be in place to
document the frequency and severity of carryover events. 30, 31

Stress-relief annealing of replacement bends was suggested in this case, as the cracks were only present in
the bends. Bends and welded areas in stainless steel superheater banks are frequently the first areas to crack
rapidly when exposed to caustic carryover. However, as it discussed earlier, it is unlikely that stress relief
annealing alone will be sufficient to resolve caustic-SCC susceptibility, especially in a situation of frequent
carryover events.

Gasket Joint
Analysis of a 25-year-old 304 stainless steel handhole gasket from a 41.4 kg/cm2 (600 psi) boiler identified
failure due to pitting and cracking (Figures 17 and 18). Although not dealing with a steam system, this case
history is interesting because of the severity of cracking damage from salts concentrated by evaporation of
escaping water as it flashed to steam. SEM-EDXA testing confirmed the presence of concentrated potassium
species. It was therefore confirmed that water seepage caused steam to flash at the joint, and potassium
hydroxide concentrated within the crevice area as general deterioration of gasket occurred and the seal became
compromised. Like sodium hydroxide, potassium hydroxide can be a potent caustic SCC agent, and in this
case a combination of both intergranular and branched transgranular SCC was observed (Figures 19 and 20).
Due to successful long service, replacement with similar 304SS gasket material was suggested. It was deemed
unlikely that leakage and flash concentration of caustic would occur if the replacement gasket was installed
correctly. If repetitive failure occurred in the future, a more caustic-SCC resistant alloy featuring higher nickel
may be necessary, such as Incoloy 800, Inconel 600, or nickel alloy 201.

CONCLUSIONS

It should be pointed out that the above examples of rapid stainless steel component SCC failure run the
gamut from heavy carryover and subsequent caustic accumulation to minor (one-time excursion) events of
caustic in steam. However, the result is frequently the same: brittle cracking of vulnerable stainless steel tubing,
turbine packing springs and expansion joints. Although high caustic concentration and high operating
temperatures tend to produce the most severe failures, both laboratory tests and field experience have shown
than even relatively dilute sodium or potassium hydroxide solutions may cause cracking within a few hours when
concentrating conditions are present on austenitic stainless steels. Therefore, efforts directed at detecting and
minimizing caustic intrusion into steam systems by maintaining appropriate monitoring of feedwater, condensate
return, and steam purity, should be considered whenever the risk of caustic SCC is present in steam systems.
In steam systems subject to repetitive austenitic SS caustic-SCC problems where remedial actions have not
been completely effective, upgrading to higher nickel content alloys should be considered to improve service
performance.
 REFERENCES

1. J. A. Sedriks, Corrosion of Stainless Steels, (New York: John Wiley & Sons, 1979), p. 178.

2. J.E. Truman, “Methods Available for Avoiding SCC of Austenitic Stainless Steels in Potentially Dangerous
Environments,” Stainless Steels, ISI Publication 117, (London: The Iron and Steel Institute, 1969), p.101.

3. J.A. Sendriks, S. Floreen, McIlree, “The Effect of Nickel Content on the Stress Corrosion Resistance of
Fe-Cr-Ni Alloys in an Elevated Temperature Caustic Environment,” Corrosion, 32,4, (1976).

4. I.L. Wilson, F.W. Pement, R.G. Aspden, “The Effect of Alloy Structure, Hydroxide Concentration, and
Temperature on the Caustic Stress-Corrosion Cracking of Austenitic Stainless Steels”, Corrosion/72, paper
no. 61, (Houston, TX: NACE International, 1972).

5. A.R. McIlree, H.T. Michels, “Stress Corrosion Behavior of Fe-Cr-Ni and Other Alloys in High
Temperature Caustic Solutions,” Corrosion, 3, 2 (1977).

6. Ibid, p.66.

7. Wheeler, G.C., “A Look at Caustic Stress Corrosion”, Power, Sept.1960, p. 87.

8. Howells, E., “ Caustic Stress Corrosion Tests on Stainless Steel”, Corrosion Technology, Nov. 1960,
p.369.

9. C.P. Dillon, D.R. McIntyre, MTI Publication No. 15: Guidelines for Preventing Stress Corrosion Cracking
in the Chemical Process Industries, (Columbus, OH: Materials Technology Institute of the Chemical
Process Industries), p.41.

10. I.L.W. Wilson, R.G. Aspden, “Caustic Stress Corrosion Cracking of Iron-Nickel-Chromium Alloys”,
Stress Corrosion Cracking and Hydrogen Embrittlement of Iron Based Alloys, Conference held at Unieux-
Firminy, France, June 12-16, 1973, NACE-5, 1977.

11. R. W. Revie, Uligh’s Corrosion Handbook, (New York: Wiley & Sons, 2000), p. 195.

12. J.H. Zheng, W.F. Bogaerts, “Transpassive Chromium Dissolution – Interaction with Stress Corrosion
Cracking of Austenitic Stainless Steel in Caustic Solution”, Second International Conference on Corrosion-
Deformation Interactions, Sept. 1996, (London: Institute of Materials, 1997), p.116.

13. G.J. Theus, R.W. Staehle, “Review of Stress Corrosion Cracking and Hydrogen Embrittlement in the
Austenitic Fe-Cr-Ni Alloys”, Stress Corrosion Cracking and Hydrogen Embrittlement of Iron Based
Alloys, Conference held at Unieux-Firminy, France, June 12-16, 1973, NACE-5, 1977.

14. P. Cohen, The ASME Handbook on Water Technology for Thermal Power Systems, (New York: The
American Society of Mechanical Engineers), p.864.
15. M.O. Speidel, “Stress Corrosion Cracking of Austenitic Stainless Steels,” ARPA Handbook on Stress
Corrosion Cracking, R.W. Staehle, M.O. Speidel, eds.

16. R. W. Revie, Uligh’s Corrosion Handbook, (New York: Wiley & Sons, 2000), p.201.

17. G. Rondelli, B. Vicentini, M.F. Brunella, A. Cigada, “Effect of Alloy Element Contents on Caustic Stress
Corrosion Cracking of Several Stainless Steels”, Werkstoffe und Korrosion, 44, 2, (1993) pp. 57-61.

18. J. A. Sedriks, Corrosion of Stainless Steels, (New York: John Wiley & Sons, 1979), p.175.

19. L.D. Kramer, S.T. Michael, F.W Pement, “Service Experience and Stress Corrosion of Inconel 600
Bellows Expansion Joints in Turbine Steam Environments,” Materials Performance, 14, 9, (1975), p.25.

20. Ibid.

21. A.W. Loginow, “Failure Analysis of Expansion Bellows in High Pressure Steam”, Materials Performance,
18, 10 (1979).

22. J. A. Sedriks, Corrosion of Stainless Steels, (New York: John Wiley & Sons, 1979), p. 175.

23. J.A. Sedriks, J.W. Schultz, M.A. Cordovi, “Inconel Alloy 690 – A New Corrosion Resistant Material,”
Boshoku Gijutsu 28, 82-95, (1979).

24. J.P Ribble, M.J Esmacher, “Molten Salt Attack of Alloy 800H and Cast Stainless Steel Superheater
Components Resulting From Steam-Side Carryover Deposition”, Corrosion/96, paper no. 543, (Houston,
TX: NACE International, 1996).

25. A.W. Loginow, “Failure Analysis of Expansion Bellows in High Pressure Steam”, Materials Performance,
18, 10 (1979).

26. M. J. Esmacher, “Stress Corrosion Cracking of Stainless Steel Superheater Tubing”, Handbook of Case
Histories in Failure Analysis: Vol. 2, ASM, (Metals Park, OH, 1993), p.227-229.

27. M. J. Esmacher, “Avoiding Problems in Diagnosing Boiler Tube Failure Mechanisms,” presented at the
International Water Conference, Pittsburgh, PA, 1998.

28. D. J. Kotwica, “Deposit-Related Failures of Boiler Superheater Tubing and Steam Piping,” Corrosion/95,
paper no. 615, (Houston, TX: NACE International, 1995).

29. D.G. Chakrapani, “Corrosion and Material Problems in Cogeneration Boiler Systems of the Pulp and
Paper Industry,” presented at the 10th International Conference on Metallic Corrosion, 1988.
30. J. O. Robinson, “Effective Monitoring Improves Industrial Steam Plant Performance,” Corrosion/90, paper
no. 177, (Houston, TX: NACE International, 1990).

31. A. Whitehead, R. T. Bievenue, “Steam Purity for Industrial Turbines”, GE Power Systems, Oct. 1988.
 FIGURE 1 - Effect of applied stress on time to FIGURE 2 - Threshold stress intensities in
failure of Type 347SS in oxygenated NaOH and deaerated 50% NaOH at 316 °C (600 °F). 1,3
KOH solutions at 300 °C (Sedriks, Truman 1,2)

FIGURE 3 - Temperature and NaOH FIGURE 4 – 321SS cracked steam expansion

concentration effects on the SCC susceptibility of joint samples.
austenitic stainless steels.14,15

FIGURE 5 – Circumferential internal cracking FIGURE 6 – Close-up view of branched

that caused steam leak. cracking at edge of a fracture site.
 FIGURE 7 - Photomicrograph of internal FIGURE 8 – Photomicrograph showing
caustic SCC in the expansion joint. 200x, cracking tip morphology. 500x, electrolytic
electrolytic etch: 10% oxalic acid. etch: 10% oxalic acid

FIGURE 9 – SEM photomicrograph showing a FIGURE 10 – SEM photomicrograph

crack surface opened up, adjacent to fracture. showing corrosion product present on the
500x. expansion joint fracture surface. 1000x
 FIGURE 11 – SEM-EDXA of corrosion product on expansion joint fracture surface.

FIGURE 12. 304SS superheater tube with FIGURE 13. View of circumferential fracture at
fracture at the bottom of the bend. bottom bend in the superheater tubing.
 FIGURE 14 - Internal cracking adjacent to FIGURE 15 - Photomicrograph showing
fractured edge in the superheater tubing. internal caustic-SCC in the superheater
bend. 37x, electrolytic etch: 10% oxalic
acid

FIGURE 16 - Photomicrograph showing FIGURE 17 - Failed 304SS handhole

caustic-SCC in the superheater bend. 200x, gasket.
electrolytic etch: 10% oxalic acid
 FIGURE 18 - Cracking of stainless steel FIGURE 19 - Photomicrograph showing
band in gasket, after cleaning. intergranular caustic-SCC in the 304SS
gasket. 100x, electrolytic etch: 10% oxalic
acid.

FIGURE 20 - Photomicrograph showing transgranular

caustic-SCC in the 304SS gasket. 200x, electrolytic
etch: 10% oxalic acid.

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