CORROSION OF BOILER TUBES SOME CASE

STUDIES1
Anees U. Malik, Ismail Andijani, Mohammad Mobin,
Fahd Al-Muaili and Mohammad Al-Hajri

Saline Water Desalination Research Institute

Saline Water Conversion Corporation (SWCC)
P O Box 8328, Al-Jubail- 31951
Kingdom of Saudi Arabia
Email: rdc@swcc.gov.sa

ABSTRACT

Failure of boiler tubes by corrosion attack has been a familiar phenomenon in power
plants resulting in unscheduled plant shut down, in consequence, there are heavy losses
in industrial production and disruptions to civil amenities. The failure of boiler tubes
appears in the form of bending, bulging, cracking, wearing or rupture, causing leakage
of the tubes. The failure can be caused by one or more modes such as overheating,
stress corrosion cracking (SCC), hydrogen embrittlement, creep, flame impingement,
sulfide attack, weld attack, dew point corrosion, etc.

In this presentation, information related to boiler tube failures are given in the form of
some case studies. The case studies are comprised of failures occurred due to SCC,
overheating, flame impingement and creep. The description of the failure, possible
causes and mechanism(s) will be presented followed by conclusions and
recommendations.

INTRODUCTION

The failure of industrial boiler has been a prominent feature in fossil fuel power plants.
The contribution of one or several factors appears to be responsible for failures,
culminating in the partial or complete shut down of the plant resulting in heavy losses
in industrial production and disruption to civil amenities. The use of inferior tube
materials, use of high sulfur or/and vanadium containing fuels, exceeding the design
limit of temperature and pressure during operation, poor maintenance and aging are
some of the factors which have a detrimental effect on the performance of materials of
construction. The failure of boiler tubes appeared in the form of bending, bulging,

1
Published in the Proceeding of 4th SWCC Acquired Experience Symposium held at Jeddah in 2005,
pp. 739-763.
wearing or rupture, decarburization, carburization causing leakage of the tubes. The
failure can be caused by one or more modes such as overheating, SCC, hydrogen
embrittlement, creep, flame impingement, sulfide attack, weld attack, dew point attack,
hot corrosion, etc.

In the present paper, information related to boiler tube failures are given in the form of
five cases studies.

CASE - I :
Flame Impingement of Water Wall Tubes - Shoaiba Phase- II
During unit reliability operation by Shoaiba plant engineers, flame impingement test
was conducted on water wall tubes for a few hours and it was found that flame touched
the rear wall of the furnace. It was decided by the Plant management to send some
tubes to R&D Center for investigating the effect of flame impingement on water wall
tubes.

Physical Inspection
Out of the 6 tubes provided for analysis, 3 tubes (# 1 to 3) were from flame
impingement area, 2 tubes (#4 and 5) from non-flame impingement area and one tube
(#6) was unused tube for comparison purposes (Fig. 1). The tubes were in services
since August 2000 at variable boiler load conditions. All the tubes were electrical
resistance welded seam (ERWS), however, the location of the seam was not visible by
naked eye. The position of the seam in the tube was located by grinding, polishing and
deep etching of the tube.

The original thickness of the tube was 6.2 mm and the material composition
corresponded to SA 178C.

Steam side (internal surface) of the tubes (#1 to 5) contains very thin adherent dark grey
colored scales. The results of analysis steam side scales indicate high concentrations of
Cu (19-28%) and Ni (6 to 11%) along with Zn, P, Ca and Al in significant
concentrations (Table 1).
There is much higher concentration of Cu and Ni in steam side scales in tubes from
flame impingement zone. All these compounds are contaminated with magnetite scales.
The analysis of fire side (external) scales shows the presence of S and V. The source
appears to be fuel (Table 1, Fig.2).

Microstructural Studies
The microstructures of the cross-sections of unused, non-flame impingement zone and
flame impingement zone tubes were studied. The microstructures of the cross-sections
of all the tubes were observed at the seam area. In general, the microstructures of the
seam areas show contour shaped structures in which contours in opposite directions can
be seen along a vertical axis. Some typical microstructures are discussed below:

(i) Unused Tube (#6): Contour type with well defined central line structure is
pearlitic-ferritic type with no decarburization layer (Fig. 3).
(ii) Non-Flame Impingement Zone Tube (#4 and 5) : Diffused line along the opposite
contours with no decarburization (Fig. 4).
(iii) Flame Impingement Zone Tubes (# 1 to 3): There are following cases:
(a) When the seam is not facing flame directly, there is a contour structure but no
evidence of decarburization (Fig. 5).
(b) When the seam is directly facing the flame (#1), refinement of the grains
along the vertical axis can be seen with a well-defined decarburized layer
(Fig. 6). This tube appears to be most affected by flame impingement.

In all the tubes, there is reduction in wall thickness (5 to 8%) after operation.

Conclusions
1. No decarburization was found in the unused tube and non-impingement zone
tubes. However, in flame impingement zone tubes, a well-defined decarburized
layer is present in area between the opposite contours.
2. A clear decarburization layer is probably only when the seam of the boiler tube is
directly facing the flames.
CASE - II :
Creep Failure of Boiler Reheater Tubes in a Power Plant
R&D Center received 2 reheater boiler tubes (#3 and 4) for analysis. The boilers were
commissioned about 24 years ago and had been in operation for more than 150,000 hrs.

Following were the salient features of the boiler tubes:

• Tube material : Medium carbon steel SA 192
• Nature of the tube : Seamless
• Outer diameter : 57.15 mm
• Nominal thickness : 3.4 mm
• Working pressure : 345 psig

Metallography
Photograph of the reheater tubes # 3 and 4 is shown in as received condition (Fig. 7).
External surface appeared reddish brown.

Steam Side Scales

The steam side scales contain dark grey magnetite. The inner surface is covered with
small and big pits with hematite stringers (Figs. 8 and 9). Tubes are shown after
cleaning (Fig. 10).

Microstructural Studies
The microstructures of the boiler tubes (#3 and 4) were studied by observing the
structures of cross-sections through a photometallurgical microscope. The main
observations were as follows:
(i) Cross-section of boiler unit # 3, steam side: Ferritic-pearlitic structure, there is
dispersion of carbides and accumulation at grain boundaries (Fig. 11).
(ii) Cross-section of boiler unit #3, fire side: Carbides are dispersed in ferrite matrix
and precipitated at the grain boundaries (Fig. 12).
(iii) Cross-section of boiler unit # 4, steam side: Pearlitic structure. Dispersion of
carbides in the matrix, precipitation of carbide at the grain boundaries and
spheroidization of carbides. Presence of voids is also indicated.
(iv) Cross-section of boiler unit # 4, fire side: Pearlitic structure. Huge dispersion of
carbides, spheroidization and accumulation of carbide at the grain boundaries
(Fig. 13).

Discussion

Microstructural studies reveal the following features:

(i) Structure is ferritic-pearlitic
(ii) Dispersion of carbides in the ferritic matrix
(iii) Accumulation of carbides at the grain boundaries
(iv) Spheropidization of carbides
(v) Presence of voids in some cases

The afore-mentioned observations provide strong evidence for a creep induced failure
of type II which appeared to be dominant during current operation of the boiler.

No cracking or leakage was found in the tube which indicates that stage III creep has
not yet reached, so tubes can be used for some more time.

Scale density and scale thickness values of the boiler tubes are high but still they can be
operated without cleaning.

Conclusion

The results of metallographic studies point out the involvement of creep type II
behavior in reheater tubes from boiler unit # 3 and 4.

Recommendation

As the reheater tubes from boiler unit # 3and 4 appear to be under deterioration due to
the influence of creep type II behavior. Therefore, the replacement of the tubes shall be
required in near future. A better tube material like a low alloy steel shall be a better
choice at the operating boiler temperature above 500 oC.
CASE - III :
Failure of High Temperature Superheater Tube of Boiler # 63, Al-Jubail Plant
The boiler # 63 had been in operation for more than 15 years. It was found that
superheater tube # 67 had failed at 2 locations. The failed portions were from the same
pendant.

The first portion of the failure was found at the bottom of the first loop near the
upstream side of the first bend (Fig. 14). This portion was sent to ANSALDO for
investigation.

The second portion of the failure was found at the bottom portion of the third loop
upstream of the weld point (Fig. 15). This portion of the tube consisting of outlet and
inlet tubes were sent to R&D Center for investigation. The pipe sheared at the bottom
portion. From the photograph, it is observed that the failure of the tube occurred by
rupture at the bottom portion of the third loop upstream side of the weld joint (Fig. 16).

Specifications of the unit # 63 boiler are given in Table 2.

SEM Studies
The inner section of the ruptured tube outlet and inlet are marked 1 to 5 indicating
different locations. (Fig. 17).

The fractography of the tube sample at locations 1 and 3 was carried out by SEM.
Whilst at location 1 (expanded portion) there are clear indications of intergranular
cracking originated from the outside surface (Fig. 18), the cracks at location 3
(protruded portion) are intergranular as well as transgranular (Fig. 19). The cracks at
location 5 (inlet of tube) are transgranular (Fig. 20). All cracks showed multiple
direction of propagation which are typically arising out of stresses in the scales and the
metal at high temperature.

Quantification of the Scales

The quantification of scale densities carried out near fracture surface of the tubes, as
determined by acid dissolution technique was found to be 483 and 219 mg/cm2 for
superheater inlet and outlet tubes (both third loop), respectively. The scale densities
seem to exceed the limits set by Otker Jonas for chemical cleaning of the boiler tubes.

Discussion
The presence of thick scale deposition in the fractured boiler tubes would result in
overheating leading to fracture under operating pressure-temperature conditions. The
presence of trans and intergranular fracture in SEM further proves the consequences of
thick scale deposition over steam side.

Conclusions
(i) Optical and SEM studies and quantification of the scale densities indicate the
cause of superheater tube is overheating.
(ii) Overheating of the tube at the bottom of 3rd loop near the upstream side is due to
heavy scale deposition.

Recommendations
(i) In view of abnormal deposition of scales at various locations of superheater
tubes, chemical cleaning of all high temperature superheater tubes be carried out
to avoid failure in future.
(ii) Periodic evaluation of superheater tubes for its scale density and tube life should
be planned in every maintenance schedule in consultation with R&D Center.

CASE - IV :
Failure Analysis of Failed Generation Bank Tube in Boiler # 4, Madina-Yanbu
Plant

Medina-Yanbu plant has 5 identical boilers and the manufacturer is MHI. Boiler No. 4
has failure at the generation bank tube zone. The boiler had been in service for approx
23 years. T&I report indicated rupture of the tube # 9 and leakage in the tube # 2 (at 6
O’clock position).

Figure 21shows drawing of the boiler front indicating the location of generation bank
tubes.
Physical Examination
Figure 22 shows ruptured generation bank tube in as received condition. Figure 23
shows inside water drum at the end of ruptured generation bank tube and Figure 24
shows broken away refractory laying between bank tubes and rear wall tubes. Pits and
tube thinning were noticed near the ruptured side indicating localized corrosion and
metal loss (Fig. 25). The pits are indicative of corrosion and thinning indicates partial
dissolution of metal due to corrosion near the rupture.

After removal of internal and external scales, the photograph of internal surface shows
presence of small pits (Fig. 26). The corrosion inside the tube could be the result of
dissolved oxygen in water which was further confirmed by heavy corrosion inside the
water drum (Fig. 23).

Microstructural Studies
Cross-sections of the ruptured tube samples were selected for microstructural studies.
Sample at the end of rupture shows transgranular crack propagation (Figs.27 and 28).

Presence of S, V, Ca and K in the fire side scales (EDX analysis) indicates that fuel oil
containing these impurities (Fig. 29). Due to rupture, there is contamination of S and V
in the scales from the outside combustion gases ( Fig. 30).

Discussion
Hydrojetting is carried out during shut down by using alkali (10% NaOH) to remove
heavy external deposits on the tube. The S-containing deposits are acidic in nature
forming aqueous solution of acid (mainly H2SO4) and salts by reacting with alkali.
During hydrojetting of the boiler tubes, low pH liquid (pH~2) is formed as affluent
where most of the liquid is drained off, some liquid remained adsorbed on the
refractories. The acidic liquid adsorbed by the refractories attacked the adjacent
metallic tubing. With time this gradually thinned down the metal and ultimately due to
high pressure (70 mm Hg) inside the tube, rupture of the tube occurred.

During the start of shut down period, the combustion gas contaminated with S also
condensed as H2SO4 at the dew point temperature and initiated dew point corrosion. V
compounds present in the combustion gases react with scale/corrosion products in
presence of oxygen forming low melting vanadates which undergo flushing reaction
resulting in accelerated or hot corrosion of metal. The thinning of the wall tube by
residual adsorbed acid along with combination of dew point and hot corrosion resulted
in rupture of the tube.

Conclusion
The rupture of the boiler tube occurred as a result of combination of 3 processes
namely, (i) thinning of wall tube by residual adsorbed acid attack (ii) dew point
corrosion and (iii) hot corrosion.

Recommendations
(i) Inspection of rest of the generation bank tubes, which are vulnerable to attack by
acid adsorbed at the refractories should be checked for corrosion.
(ii) During hydrojetting, pH of the washing affluent of the boiler tubes at different
locations should be monitored and should not be below 7.5.
(iii) It is advised to keep the S and V contamination level in the fuel oil to minimum
by using appropriate additive.

CASE - V :
Failure Investigations of Boiler Tubes, Al-Khafji Plant
Two pieces of wall tubes of rolled area of water drum from boiler # 200 were received
for investigation by the R&D Center.

The specifications of the boiler tube and operation parameters were as follows:
Nature of the failure
flared
Boiler No.
Years in service
Drum pressure
Tube orientation
Wall tube material
Tube dimension
No. of failed tubes
: Cracks on wall tubes just above expanded and
Area at water drum
: # 200
: About 13 years
: 20 bars
: Vertical
: ASTM 178A
: 60.8 mm x 3.2 mm
: 8, 2 received for investigation
Physical Inspection
Figures 31 shows photograph of the wall tubes in as received condition. In the thick
walled fracture, the cracks appeared to be originating from outside.

Microstructural Studies
The cross-sections of the samples reveal branching associated with the cracks. The
cracks are continuous, intergranular, transgranular or mixed type, running through the
wall tubes (Fig. 32 and 33).

EDAX Studies
EDAX of the cracked area revealed presence of elements like S, V, Cl, Fe, Ni, Mo and
Cu (Fig. 34).

Discussion
Presence of intergranular and transgranular multi-branch cracks and occurrence of thick
walled fracture indicate failure caused by stress corrosion cracking (SCC). There are
two principal causes that govern SCC in the boiler environment. First, the metal in the
affected region must be stressed to a sufficiently higher level. Second, concentration of
a specific corrodent at the stressed metal site must occur. Both the above mentioned
factors are observed to play a role ion SCC of the tube.

Just above the failure site a hole was detected in the super heater inlet header tube. In
order to take out the tubes from the drum, huge amount of green fluid was found while
removing the refractory insulation. It is quite possible that steam leaked from the
superheater and might have condensed at the bottom of the furnace. The condensate
dissolved the soot containing sulfur and vanadium and through the ceramic, led it
seeped down to the outer surface of the drum. Due to dissolution of S and V from soot
and SO3 gas from the combustion gases, condensate must be very corrosive.

Boiler wall tubes are joined to the water drum by expanding and flaring the tubes in the
drum plate hole. It seems during fabrication the tube ends were not stress relieved and
when these tubes with enough residual stresses came into contact with corrosive
 condensate, a synergic interaction of tensile stress and a corrodent occurred and
resulted into SCC.

Conclusions
Corrosive condensate formed by the condensation of leaked out steam from superheater
tubes, initiated SCC of wall tubes fixed in the water drum.

Recommendations
(1) The boiler components should be stress free this can be done by altering
operational parameters or redesigning the affected components.
(2) Residual stresses can be relieved by proper annealing.
(3) Presence of corrodent in boiler tube auxiliaries which is responsible for SCC, can
be avoided by keeping internal surfaces sufficiently free of deposits, preventing
in-leakage of condensers, heat exchangers and process steam.

Table 1. Chemical Composition of External and Internal Deposits

S. Description of Tube Parameters (weight %)

Deposits
No. Sample V Si Cr Fe Mn Cu Ni Zn Al Ca
1 External Flame Impingement
0.5 < 0.1 < 0.1 62.5 - - - - - -
Zone (fire side)
2 External Flame Impingement
1.5 < 0.1 < 0.1 62.5 0.4 - - - - -
Zone (wall side)
3 External Non Flame Impingement
1.2 0.2 < 0.1 57.8 - - - - - -
Zone (fire side)
4 External Non Flame Impingement
0.5 < 0.1 < 0.1 58.7 0.4 - - - - -
Zone (wall side)
5 Internal Flame Impingement 11.
- - - 24.5 0.8 27.8 3.3 < 0.1 0.5
Zone 2
6 Internal Non Flame Impingement
- - - 41.2 0.6 19.3 5.8 2.2 < 0.1 0.5
Zone
Table 2. Operational and Design Parameters of Boiler Unit # 63
Design Operation
… Maximum continuous evaporation, kg/hr 730,000
… Maximum design pressure, Bar ga. 113.0
… Pressure at super heater outlet, Bar ga. 93.08 92
… Super heater steam temperature oC 515 oC 512
… Feed water temp. at economizer inlet oC 235 oC 224
Air Temperature:
… Air heater inlet oC 72 oC -
… Air heater outlet oC 315 oC -
Flue Gas Temperature:
… Furnace exist temperature oC 750 oC -
… Primary superheater inlet temperature oC 820 oC -
… Air heater inlet temperature 360 oC 337
… Air heater outlet temperature oC 146 oC 105

Feed Water:
… Feed water inlet temperature oC 235 oC 224
… Feed water pressure after regulator Bar ga 1 oC 102
… Feed water temperature entering boiler drum oC 312 oC 301

Steam:
… Steam drum pressure Bar ga. 100.18 390 oC
… Secondary superheater outlet pressure bar ga. 93.08 92
… Secondary superheater outlet temperature oC 515 oC 504 oC

Figure 1. Photograph of fire side water wall tubes in as received conditions

cps

50 Fe

40

30

20 O

10 V
Fe Fe

Si S
Cr Mn
0
0 5 10 15 20
Energy (keV)

Figure 2. EDX profile of external deposits (fire side) collected

from the boiler tubes from non flame impingement
zone

Figure 3. Microstructure at the center of the weld seam in the

unused tube x 100
Figure 4. Microstructure at the center of the weld seam in the
tube # 4 from non flame impingement zone X 100

Figure 5. Microstructure at the center of the weld seam in the

tube # 3 from flame impingement zone X 100

Figure 6a. Photomicrograph of boiler tube (#1) showing

refined grains with evidence of decarburization (fire
side) X 100
 Figure 6b. Photomicrograph of boiler tube (#1) showing refined
grains with evidence of decarburization (steam side)
X100

Figure 7. Photograph of the reheater tubes, Ghazlan Unit # 3

and #4- as in received condition

Figure 8. Photograph of the splitted reheater

tube Unit # 3 showing steam side –
magnified view
Figure 9. Photograph of the splitted reheater tube
Unit # 4 showing steam side – magnified
view

(a)

(b)

Figure 10. Photograph showing (a) reheater tube Unit

# 3 (steam side) after cleaning (b) reheater
tube Unit # 4 (steam side) after cleaning
Figure 11. Photograph of a cross-section of reheater tube Unit # 3
showing steam side scales X 200

Figure 12. Photomicrograph of a cross-section of reheater tube

Unit # 3 showing fire side scales X 200
Figure 13. Photomicrograph of a cross-section of reheater tube
Unit # 4 showing central portion X200

Figure 14. Photograph showing longitudinal open crack at

the bottom of I loop upstream side of the I bend of
Boiler # 3
Figure 15. Photograph showing ruptured and sheared tube at
the bottom of the 3rd loop upstream side of boiler #
63

Figure 16. Inlet and outlet portions of the ruptured tube at

the bottom of the 3rd loop upstream of boiler #
63, HTSH Pendent 67 – As received condition
Figure 17. Inner section of ruptured superheater tube # 63
(Outlet) 3rd loop (HTSH Pendent # 67)

Figure 18. SEM fractograph of the tube (sample location #

1) (I.G.C.)
Figure 19. SEM fractograph of the tube (sample location # 3) (T.G.C.)

Figure 20. SEM fractograph of the tube (sample location # 5) (T.G.C.)

Figure 21. Schematic drawing of the boiler front indicating the

location of generation bank tubes
Figure 22 Ruptured generation bank tube # 9 in as received
condition showing front view.

Figure 23. Pictures of ruptured generation bank tube # 9 (end

shown inside water drum)
Figure 24. Pictures of broken away refractory installed on the area
between generation bank tubes and rear well tubes

Figure 25. Picture of the portion of ruptured generation

tube showing localized attack and metal loss

Figure 26. Photograph of the ruptured tube after removal of

the scales (external side) showing pitting and
thinning of the tube
Figure 27. Photomicrograph of a cross-section of boiler tube #
9 at a location where the rupture zone ends

Figure 28. SEM photograph of sample #2 showing a deep

transgranular crack

cps

Fe
20

15

V
10

O Al

S
5
Fe Cu
Cu Si
Ca V
K
Mn Ni Cu
0
0 5 10 15 20
Energy (keV)

Figure 29. EDX profile of the outside scale deposits

formed on bank generation tube # 9
cps
60

Fe

50

40

30

O
20

Si
10
Fe
Fe Al K Mn
Mg
S K V

0
0 5 10 15 20
Energy (keV)

Figure 30. EDX profile of the scales formed at the steam side (inner) of
generation bank tube # 9

Figure 31. As received cracked samples of boiler

wall tube taken out from the water
drum
 Figure 32. Micrograph of the cross-section of the stress
corrosion cracks in the boiler tubes shown in
Fig. 41. X 200

Figure 33. Micrograph showing intergranular mode of SCC X400

Figure 34. Energy dispersive X-ray analysis (EDAX) of the
cross-section of the cracks showing presence of S, V
and Cl at the crack