Desalination 222 (2008) 682688

Stress corrosion cracking (caustic embrittlement) of super heater tubes

K. Abouswa, F. Elshawesh*, A. Abuargoub
Libyan Petroleum Institute, P.O. Box 6431, Tripoli, Libya email: fawzielshawesh@yahoo.com
Received 4 February 2007; accepted 10 February 2007

Abstract After two years of non-continuous service of three boilers, weld seams for the super heater and header tubes showed severe circumferential cracking and failure. Extensive cracking was noticed after emergency shutdown to investigate the cause of tubes leakage. On-site investigation revealed the fact that tubes were suffered from extensive circumferential cracking initiated at the weld heat affected zone (HAZ) area. Over the cracked area thick crystalline white deposit was visible. The analysis using X-ray diffraction revealed that the white deposits compose mainly of sodium carbonate (nitrite) which resulted from the oxidation of caustic soda. Little amount of burkeite and thermonarite were also detected. Detailed investigation such as the visual, microscopic and metallographic examination revealed the fact that circumferential cracks were initiated at the heat-affected zone and propagated through the grain boundaries (intergranular). However, at and adjacent to the weld seams the fracture was not intergranular (quasi-cleavage) owing to the non-granular martensitic structure. Scanning electron microscope (SEM) confirms the finding that the fracture morphology was mainly intergranular at the parent metal and quasi-cleavage around the weld seams. All the above mentioned findings confirm that the cracking of boiler tubes was mainly by caustic embrittlement owing to the high concentration of caustic soda. Keywords: Boilers; Heat affected zone; Caustic soda; Intergranular; Welds

1. Introduction Caustic embrittlement has long been a serious form of boiler metal failure. The actual chemical attack (corrosion process) of the metal is normally
*Corresponding author.

undetectable, with failure occurring suddenly and often with catastrophic results. Caustic embrittlement of metal boiler result from the fact that failure occur in the presence of a highly concentrated caustic solution, and stressed metal and this usually result in sudden failure or what called by brittle failure with no apparent

Presented at the conference on Desalination and the Environment. Sponsored by the European Desalination Society and Center for Research and Technology Hellas (CERTH), Sani Resort, Halkidiki, Greece, April 2225, 2007.
0011-9164/06/$ See front matter 2008 Elsevier B.V. All rights reserved. doi:10.1016/j.desal.0000.00.000

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deformation of the metal prior to actual failure (complete separation). Generally, the microscopic examination of a properly prepared section of failed part show a characteristic pattern with cracking progressing along defined paths or grain boundaries in the crystal structure of the failed metal. Three factors are required for caustic embrittlement: (1) Leakage of boiler water must occur so as to permit escape of steam and subsequent concentration of boiler water at point of leakage. (2) Attack of the boiler metal by concentrated caustic soda (NaOH), originating from the concentrated boiler water. (3) High metal stress (residual such as weld or applied) in the area of concentration and attack. In the current case, the three points are fulfilled and the failure can be attributed to caustic embrittlement or to the general term as stress corrosion cracking. 2. Investigation Conducted scrutiny visual examination revealed the fact that all examined super heater tubes were found to suffer from severe cracking at the circumferential welded join, as shown in Figs. 1 and 2. Some of cracks were observed

Fig. 2. Close view for the failed super heater tube.

to propagate around and remote from the hook. This may be attributed to cold worked microstructure of the U-bend super heater tubes. This can be confirmed by metallographic examination and hardness measurements. Nevertheless, the cracking first initiated and propagated at the circumferential weld and afterward propagated in the parent metal. The weld protrusion from the root pass (internal surface of super heater tubes), was found to be high and not smooth (irregular) and expected to act as a preferred location for settlement of caustic soda (local caustic concentration), at which cracking can initiate and propagate. Whitish deposit at the cracked circumferential welds was observed, as shown in Fig. 1. In another hand, almost all examined circumferential weld joints of steam out let header showed several longitudinal cracks initiated from the circumferential weld and extended towards opposite directions. General view for cracking is shown in Fig. 3. 2.1. Hardness measurements Hardness measurement was conducted across the weld metal, heat affected zones (HAZ) and parent metal. The results are shown in Table 1. The results of the hardness measurement indicate that the weld metal hardness for super heater was high compared with out let tube/header.

Fig. 1. General view for the received sample of super heater tube.

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Fig. 3. Close view for the failed out let header.

Fig. 4. Macroscopic view for the propagated cracks in the super heater tube.

In general, the hardness of the weld metal for both tubes was found to be higher than that of heat affected zone (HAZ). This of course will assist in initiation of cracking within the weld metal (low toughness and strength). 2.2. X-ray diffraction A sample of white deposit was subjected to chemical analysis using X-ray diffraction and found to be composed mainly of sodium carbonate (caustic soda CO2-carbonation of caustic soda), NaOH and sign of sulfidation. Black, adherent and rough deposit scale-like was analyzed using EDAX and mainly found to be composed of deteriorated film of magnetite Fe3O4. 2.3. Macroscopic examination The result of visual examination was confirmed by the microscopic examination using
Table 1 Hardness measurements readings (Hv) across the weld metal, heat affected zone and parent metal Locations Weld metal HAZ Base metal Super heater tube 203 155 147 Steam out let header 172 164 157

special and low magnification microscope. Super heater tube showed fine circumferential cracks on both external and internal sides of the failed tube, as shown in Fig. 4. However, the observed fine cracks were originated from the internal side of super heater tube. This was confirmed by examined tube fracture surface, as shown in Fig. 5. It can be observed that the crack originated at weld heat affected zone (coarse grains-low toughness and strength) and propagated partly through the weld metal and partly through the parent metal. General view of the fracture morphology of the failed super heater tube was brittle.

Fig. 5. Macroscopic view for the failed super heater tube at the heat affected zone (HAZ). It can be observed that crack is originated at the high stressed (HAZ).

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Fig. 6. Severe corrosion pits at area around the weld metal (HAZ).

Fig. 7. Metallographic photograph shows intergranular cracks along the grain boundaries.

Severe pitting corrosion was observed in the internal side of the steam tube over an extended area around the weld metal. As mentioned above, the oxygen pits most likely occurred during down time period (shut down) (Fig. 6). 2.4. Metallographic examination In order to establish the crack path and confirm the finding that both super heater tubes and out let header are failed as a result of caustic embrittlement, detailed metallographic examination shall be conducted. This shall aim to verify whether the crack was propagated through the grain boundaries (intergranular) or across the grains (transgranular). Several specimens were cut from the three received samples and subjected to detailed metallographic examination. In case of super heater tubes the crack was found to initiate at the weld metal, and areas adjacent to weld bead (Heat Affected Zone) and in some cases at the weld defect (undercut). The crack path was mostly through the grain boundaries (intergranular) at the parent metal, as shown in Fig. 7. At weld and area adjacent to weld mixed mode fracture compose of intergranular and transgranular was predominant. This due to coarse grains and

presence of widmenstaten structure (coarse grain) at welded areas where needle type of martensitic structure, as shown in Fig. 8 is expected [1]. In case of steam out let header the cracks were found to initiate at the circumferential weld metal and propagate towards opposite direction following the preferred path which is the grain boundaries when passing the parent metal. In consistent with the super heater tubes the cracking was mainly intergranular at the parent metal and mix mode (IG&TG) when passing through the weld metal and heat affected zone. This result shall be confirmed by the utilization of the scanning electron microscope (SEM).

Fig. 8. Metallographic photograph shows cracks within the martensitic structure.

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Fig. 9. Scanning electron microscope shows intergranular fracture typical of caustic embrittlement.

Fig. 11. Fractographic scanning electron microscope shows typical fracture morphology (quazi cleavage) within the martensitic structure.

2.5. Scanning electron microscope (SEM) Intergranular and little transgranular fracture modes were predominant on the examined fracture surface, as shown in Fig. 9. The fracture surface of cracks propagated through the parent metal was mainly intergranular accompanied with little faceted intergranular fracture, as shown in Fig. 10. Crack morphology through the HAZ and weld metal was slightly different, as shown in Figs. 11 and 12. This due to difference in the microstructure at (HAZ), where coarse grains and needle-like martensitic structure are predominant. Similar fracture morphology was evident on the steam out let tube/header samples. Intergranular fracture was the predominant fracture morphology on the examined samples when cracks passing the parent metal. This result confirms the finding that both tubes (steam super heater and out let tubes) were fractured in a brittle manner by the stress corrosion cracking or what known by the caustic embrittlement) as a result of high concentrated caustic soda in the boiler water.

Fig. 10. Fractographic scanning electron microscope shows intergranular fracture typical for caustic embrittlement.

Fig. 12. Fractographic scanning electron microscope shows typical fracture surface within the weld metal.

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3. Failure mechanism The results of the conducted investigation revealed the fact that all welds for both super heater and out let tubes are failed in a brittle manner after exposure to high alkaline solution rich with sodium hydroxide (NaOH). The general failure scenario for both tubes can be given as follows: Leakage of boiler water from super heater tubes, out let, or any other location led to escape of steam and subsequent high concentration of boiler water with caustic soda (NaOH) or what known by high water concentration. Welded joint which are the most stressed area (residual stress) are attacked by highly concentrated solution/steam rich with sodium hydroxide. This causes failure in the magnetite film-like scale and direct exposure of tube substrate to highly concentrated caustic soda. The first leakage at any welded joints is expected to aggravate the situation through the continuous increase in the concentration of NaOH, hence more cracking and failure in short period of time. This is the case when leaks are left for sometime before shut down. Most of the super heater tubes and out let tube/header(s) are covered with whitish deposit around the leaked/cracked areas (welded joints). Results of X-ray diffraction confirmed the fact that this whitish deposit was mainly compose of sodium carbonate ( as result of reaction of residue of caustic soda with carbon dioxide in the air), and little of sodium hydroxide. The proposed failure mechanism for both tubes (super heater & out let), can be given as follows:

weld (i.e. weld metal, heat affected zone (HAZ) and weld defect such as under-cut). Super heater tube(s) crack propagation was circumferential as a result of tension action (hanged tubes in addition to up/down movement of tubes during operation) [2]. SEM and metallographic examinations showed that the crack path was mainly through the grain boundaries particularly in the parent metal and mix mode at the heat affected zone where the microstructure is compose of needle-like structure of martensite and widman-staten structure of coarse grains [5]. 3.2. Failure of out let tube (header) Out let tube header was failed in the same manner by the stress corrosion cracking or caustic embrittlement after exposure of circumferential welded joints to steam/water rich with high concentrated caustic soda [4]. The cracks initiated at most stressed areas which are welded joint and propagated towards both directions (up/down streams). In this case, the action of hoop stress was predominant mechanism for crack propagation. The crack path was found to be through the grain boundaries (inter-crystalline) particularly in the parent metal [3]. This is typical failure by caustic embrittlement. Severe pitting attack was visible around the welded joint. Actually oxygen pits were found over all the received samples of the out let tube/header. This type of attack is expected to occur during downtime or several shut-down encountered the non steady operated boilers. Boiler water shall be drained from super heater tubes and steam out let header during shut down. Alternatively, the remained water shall be inhibited by proper type/quantity of inhibitor. 4. Conclusion (1) Both super heater tubes and steam out let header were failed catastrophically (sudden) by the stress corrosion cracking (caustic

3.1. Failure of super heater tubes The direct contact of highly concentrated caustic soda (expected to be higher than 40%) initiated internal minute cracks at most stressed area in the super heater tubes of circumferential

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embrittlement). This due to high concentration of the caustic soda added to the boiler water to control pH (pH 9.0 or more). (2) Although caustic soda was known as effective pH control (increase pH), however, was not considered during the design stage of boilers. Consultation with boiler manufacturer shall be made before taken this action. Usually with addition of caustic soda to boiler post heat treatment shall be made on all welded joints. (3) Leakage(s) of one or more of tubes (super heater or steam out let header) result in escape of steam hence increase in the concentration of water boiler. Attack of the most stressed areas of tubes (welds and adjacent areas), with highly concentrated caustic soda, results in catastrophic sudden failure. (4) Cracking path for both tubes (super heater and out let) was mainly through the grain

boundaries typical of caustic embrittlement of carbon steel boiler components. (5) The observed misalignment of welded joints and presence of weld defects (under-cuts), in addition to the continuous tension action (hanged tubes), imposed on the super heater tubes suggested that these tubes are first leaked (failed) area. References
[1] [2] E.D.D. During, Corrosion Atals, Elsevier, 1997. R.H. Jones, Stress corrosion cracking materials performance and evaluation, ASM International, Materials Park, OH, 1992. R.N. Tuttle and R.D. Kane, Compilation of classic papers, Part 2. J. Kolts and S.W. Ciaradi, Corrosion Resistant Alloys in Oil and Gas Production, Vol. I, 1996. J.K. Lawrence, Corrosion, ASM Handbook, Vol. 13, ASM International, Materials Park, OH, 1996.

[3] [4] [5]