Engineering Failure Analysis 14 (2007) 731–738

www.elsevier.com/locate/engfailanal

Failure analysis of bank front boiler tubes

M.R. Khajavi, A.R. Abdolmaleki *, N. Adibi, S. Mirfendereski
Industrial and Environmental Protection Division, Research Institute of Petroleum Industry, P.O. Box 18745-4163,
Pazhooheshgah Bulevard, Khairabad Junction, Old Qom Road, Tehran, Iran

Received 10 September 2005; accepted 31 October 2005

Available online 25 October 2006

Abstract

Waterside corrosion problems can seriously affect reliability of boiler systems. Two significant of waterside corrosion
mechanisms are caustic corrosion and phosphate corrosion. Two critical factors contribute to these failures. The first is
availability of NaOH or of alkaline-producing salts. The second contributing factor is the mechanism of concentration.
In this paper a case study on bank front tubes are presented. Different tests and examinations including visual examination,
optical microscope, SEM, and XRD revealed the root causes of this boiler-tube failure were caustic and phosphate
corrosion.
Ó 2006 Elsevier Ltd. All rights reserved.

Keywords: Boiler tube; Failure analysis; Caustic corrosion; Phosphate corrosion; Mechanism

1. Introduction

Water and water chemistry are important factors in the promotion of waterside or internal surface corro-
sion and influence the useful life of tube steels [1].
The corrosion resistance of the boiler tube depends on the pH level of the water and the amount of con-
taminants. The protective magnetite is unstable and will solubilize at pH values below 5 and above 12
[1,3]. The inability to maintain pH greatly increases the probability of serious waterside corrosion. Boiler
water treatment controls should provide a moderately alkaline environment to keep the oxide film in place
[1]. A significant factor in waterside corrosion is the amount of corrosion product deposition on the tube wall
[1–3]. Deposition can cause overheating and circulation restrictions. Both conditions frequently result in
unscheduled outages.
Deposit buildups are most likely to occur where flow is disrupted by bends, welds with backing rings or
protrusions; at regions of high heat flux; and on horizontal or slanted tubes that are heated from above or
below [1]. Deposits are 50–100 times more likely to occur in high heat transfer areas [2].
Depending on which contaminants are present during the chemical unbalance, different failure mechanisms
will be experienced [1].

*
Corresponding author. Fax: +98 21 590 10 94.
E-mail address: abdolmalekiar@ripi.ir (A.R. Abdolmaleki).

1350-6307/$ - see front matter Ó 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.engfailanal.2005.10.017
732 M.R. Khajavi et al. / Engineering Failure Analysis 14 (2007) 731–738

2. Caustic corrosion

Caustic corrosion refers to the corrosive interaction of sufficiently concentrated sodium hydroxide with a
metal to produce distinct hemispherical or elliptical depressions. The depressions may be filled with dense cor-
rosion products that sometimes contain sparkling crystals of magnetite [5]. Caustic corrosion is sometimes
referred to as ‘‘caustic attack’’, ‘‘caustic gouging’’ or ‘‘ductile gouging’’ [1,5].
The susceptibility of steel to attack by sodium hydroxide is based on the amphoteric nature of iron oxides;
that is, oxides of iron are corroded by both low-pH and high-pH environments. High-pH substances, such as
sodium hydroxide, will dissolve magnetite:
4NaOH þ Fe3 O4 ! 2NaFeO2 þ Na2 FeO2 þ 2H2 O ð1Þ
When magnetite is removed, the sodium hydroxide may react directly with the iron:
Fe þ 2NaOH ! Na2 FeO2 þ H2 ð2Þ
Caustic corrosion results in irregular wall thinning or gouging of the tube’s waterside surface and failures are
the result of the corrosion metal loss. As the wall thickness is reduced by corrosion, the hoop stress imposed by
the water pressure is increased and a ductile tensile failure results. Considerable wall thinning can occur (up to
75% wall thickness) before failure [1].
Two critical factors contribute to caustic corrosion. The first is the availability of sodium hydroxide or of
alkaline-producing salts (i.e., salts whose solution in water may produce base). Sodium hydroxide is often
intentionally added to boiler water at noncorrosive levels; it may also be introduced unintentionally. Poorly
controlled or malfunctioning chemical-feed equipment may also cause excessive alkalinity [5].
The second contributing factor is the mechanism of concentration. Because sodium hydroxide and alkaline-
producing salts are rarely present at corrosive levels in the bulk environment, a means of concentrating them
must be present [5]. Two basic concentration mechanisms exist:

2.1. Departure from nucleate boiling (DNB)

The term nucleate boiling refers to a condition in which discrete bubbles of steam nucleate at points on a
metal surface [5].

2.2. Steam blanketing

Steam blanketing failures result from stratification of steam/water mixture such that concentrations of
caustic can occur and produce corrosion. The corrosion occurs at an interface between the water and steam
where deposits can form. This leads to a localized but highly corrosive situation that results in wall thinning
and stress rupture of the tube steel [1,7].
The stratified flow of steam/water occurs when the velocity of fluid is not sufficient to maintain turbulence
and produce thorough mixing of the phases. The steam/water stratification can occur especially at low loads.
Steam blanketing failures have been experienced in horizontal roof tubes and sloping wall tubes [1].

3. Phosphate corrosion

Congruent phosphate control theory assumes that orthophosphates do not significantly chemically interact
with tubing alloys, deposits, or corrosion products; such assumptions are frequently wrong [8]. Some boiler-
tube failures attributed to caustic gouging actually have been caused by reaction of sodium phosphate species
with boiler-tube steel, boiler-tube oxides, or both. This is referred to as ‘‘phosphate corrosion’’. This produces
unique wastage morphologies and characteristic corrosion products of NaFePO4 [8,9]. Iron phosphate forma-
tion is reported as also being associated with phosphate corrosion [8]. Phosphate attack at lower sodium to
phosphate ratios produces welldefined depressions or gouges [8,9].
It has been reported that when a solution of trisodium phosphate is concentrated at elevated temperature,
crystals of disodium phosphate precipitate out and the supernatant liquid is rich in NaOH [6].
 M.R. Khajavi et al. / Engineering Failure Analysis 14 (2007) 731–738 733

Fig. 1. Control diagram for a coordinated pH–phosphate program. Corrosion is prevented if water chemistry is maintained within the
control box for a given pressure [7].

Na3 PO4 þ H2 O $ Na2 HPO4 þ NaOH ð3Þ

To eliminate the formation of free caustic, a mole ratio of Na to PO4 of 2.6 is recommended [6,8,9]. This is
accomplished by adding a mixture of Na3PO4 and Na2HPO4. A ratio of 65% Na3PO4 to 35% Na2HPO4 cor-
responds to a mole ratio of 2.6 [6].
Two critical factors contributing to the phosphate corrosion are [9]:

(1) NaOH availability: The chemical treatment based on applied phosphate, because of precipitation/depo-
sition at high temperatures.
(2) Concentration mechanism: There are two concentration mechanisms. The first is the DNB that allowed
the deposition of the phosphate. The second was the formation of a steam blanket that allowed concen-
tration of the caustic soda.

Fig. 1 illustrates the phosphate–pH relationship recommended to control boiler corrosion. For a 1000 psig
industrial boiler, caustic concentration is avoided by maintaining the pH and phosphate levels below the 2.8–1
sodium to phosphate molar ratio control line. Deposition of acidic sodium phosphate salts in a 1000 psig sys-
tem can be minimized or eliminated if the pH and phosphate levels are maintained above the 2.2–1 sodium to
phosphate molar ratio control line. People treating an industrial boiler with a coordinated pH–phosphate pro-
gram often mistakenly believe that the water chemistry is ‘‘in control’’ as long as pH and phosphate levels are
maintained below the upper sodium to phosphate control limit for a given pressure. The importance of staying
above the 2.2–1 control line is often not recognized [7].

4. Remedies

Different corrective or diagnostic actions may be employed to combat or prevent the caustic or phosphate
corrosion depending on root cause [1–7,9].

5. Case study

In this study failure of a refinery boiler tube has been investigated. The received tube was subjected to a
series of examinations, including visual examination and photographic documentation, stereoscopic micros-
copy, optical microscopy, scanning electron microscopy (SEM), and X-ray diffraction (XRD).

5.1. Results

5.1.1. Visual examination

The failed tube was a section of bank front tubes. When the tube was split lengthwise, two longitudinal
grooves were found extending from near the bend towards steam drum. There was no evidence of corrosion
734 M.R. Khajavi et al. / Engineering Failure Analysis 14 (2007) 731–738

on vertical surfaces, but the slanted section of the tube suffered from severe corrosion and metal loss. A thick-
lipped rupture was evident near the bend. The failure resulted from wall thinning on the internal surface.
Visual examination revealed that before the onset of grooves, there was a sponge-like area on both sides,
and at the top side of both grooves, there was a sparkling dark gray area. Fig. 2 illustrates the appearance
of the internal surface of the tube.

5.1.2. Stereoscopic microscopy

In order to further documentation, some photographs were taken from the internal surface and the thick-
lipped rupture area. Fig. 3 features the thick-lipped rupture near the bend.

5.1.3. Optical microscopy

Cross sectional and longitudinal samples were cut from the corroded areas. After preparation and etching
with natal, they were examined to study the microstructure and morphology of the corroded areas. Metallo-
graphic examination showed the presence of pits (Fig. 4). Using the polarized light the deposition and pene-
tration of copper was revealed (Fig. 5). The metallographic appearance of base alloy indicated no change in
the microstructure (Fig. 6).

5.1.4. SEM examination

SEM was used to study the morphology of the corroded surface, while energy dispersive X-ray (EDX) anal-
ysis was carried out on the corroded areas to identify various elements in the corrosion products. Different

Fig. 2. Internal surface of the damaged tube.

Fig. 3. Thick-lipped rupture and its surrounding area.

M.R. Khajavi et al. / Engineering Failure Analysis 14 (2007) 731–738 735

Fig. 4. Pits near the grooves.

Fig. 5. Deposition of copper was revealed using polarized light.

Fig. 6. Microstructure of the base alloy in corroded area.

736 M.R. Khajavi et al. / Engineering Failure Analysis 14 (2007) 731–738

Fig. 7. Feature of the porous deposit at sides of the grooves and its elemental analysis.

samples revealed the presence of Fe, O, P, Na, Cu, Ca, Si, Mg, and S. Fig. 7 illustrates feature of the deposits
at sides of the groove and its elemental analysis.

5.1.5. XRD examination

XRD analysis at different locations showed the principle constituents (Table 1).

5.2. Discussion

There were parallel grooves along the sides of the slanted section (Fig. 2). Considerable metal loss resulted
in thick-lipped rupture. Before the beginning of the grooves, there was a sponge-like (porous) area. The inter-
nal corrosion extended in some areas across the top zones of the tubes as dark gray sparkling deposits. All
these visual evidences were the characteristics of phosphate corrosion. Due to the mentioned mechanisms
and factors for caustic corrosion and phosphate corrosion, and upon examination evidences, also according
to the refinery’s information that boilers operate at low water level, two possible causes exist for the observed
waterside corrosion.
As mentioned, the first contributing factor is the availability of NaOH or of alkaline-producing salts. The
analysis of deposits using SEM-EDX revealed the presence of P and Na. From system information, the boiler
water was treated using a coordinated pH–phosphate program involving trisodium and disodium phosphates.
If proper water chemistry control is not maintained, phosphate compounds may precipitate or deposit and
leave free NaOH. So the presence of phosphorus in the deposits indicates that there was a precipitation of
phosphates because no other source is possible for phosphorus. The produced NaOH can concentrate by per-
meating the deposits to high-pH levels. At high-pH levels, the protective magnetite oxide layer is solubilized
and corrosion occurs.
The other assumed mechanism is steam blanketing. The DNB mechanism is impossible because of no
change in microstructure of the base alloy due to overheating (Fig. 6).
According to the operational data, boiler operates at low water level. This results in stratification of water
and steam phases (steam blanketing). Inadequate waterside circulation can lead to the formation of thick

Table 1
Compositions of the deposits
Location Composition
Vertical section 1-Fe 2-FeO 3-Fe2O3 4-Fe3O4
Slanted section 1-Cu 2-Fe 3-Cu2O 4-FeO 5-Fe2O3 6-Fe3O4
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deposits in localized zones along a water line. Corrosives may concentrate by permeating the deposits, result-
ing in gouging along the water line. In horizontal or slanted tubes, a pair of parallel trenches will form. The
result of visual examination indicates such grooves (Fig. 2).
Results of XRD examination indicate that the amount of protective Fe3O4 is less than other compounds
found in deposits. This disclosed that most of the compounds in deposits were non-protective and they
may precipitate as porous.
Calcium, magnesium, iron, copper, aluminum, and silica are common contaminants in boiler feedwater
that can form deposits [2]. Formation of porous deposits can result in concentration of NaOH to high-pH
levels, and ultimately lead to degradation of the base alloy. Analyses using EDX reveals the presence of all
these elements. In the following, the possible sources of these elements are discussed.

5.2.1. Copper
Copper is used extensively in steam generation systems for water heating, steam condensing, and process
temperature control. Dissolution and/or exfoliation of copper oxidation products concerns boiler operators
because the release of corrosion products not only decreases the lifetimes of copper-containing components
but also increase boiler deposits. This leads to impeded heat transfer, localized corrosion, and difficulties in
subsequent boiler cleaning [10].
Effluent copper concentrations were measured as a fraction of pH, temperature, flow rate, amine type,
amine concentration, and dissolved oxygen concentration. Temperature had the largest impact on copper con-
centration. As the temperature was raised from the expected in condensate systems to that expected in feed-
water heaters, the average copper concentration increased dramatically. All other factors except flow rate had
smaller but significant effects on copper concentration. Changing flow rate had no effect [10].

5.2.2. Sodium and phosphorus

Source of these two elements is chemicals used for water treatment. Sodium can present due to different
sources and mechanisms, as mentioned. Trisodium phosphates may precipitate at high temperatures or at
abnormal conditions, and leave phosphorus and sodium.

5.2.3. Other elements

Calcium, magnesium, iron, copper, aluminum, and silica are common contaminants in boiler feedwater [2].
Zeolite used for boiler makeup water is one of the possible sources for aluminum, silisium, and sodium (or its
substitutes, i.e., calcium or potassium). Copper-base alloys containing aluminum may be considered as
another possible source for aluminum.
According to the refinery data sulfite is not used as an oxygen scavenger so sulfur may be introduced from
well water.

6. Conclusion

Corrosion failures frequently are caused by a combination of ineffective control of water chemistry, defi-
ciencies in design and material selection, and operational problems. In this study precipitation of sodium phos-
phate compounds from boiler water containing trisodium phosphate and also operation at low loads were
recognized as root mechanisms. In addition to increasing the load and observing the upper and lower limits
of Na to PO4 ratio for a given pressure, there are other remedies including accurate monitoring of water
chemistry.

References

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[5] Port RD, Herro HM. The NALCO guide to boiler failure analysis. McGraw-Hill Publication; 1991.
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