2001 TAPPI JOURNAL PEER REVIEWED PAPER

ALTERN ATIVE MATERIALS FOR FLOOR AND LOWER WATERWALL TUBES IN

BLACK LIQUOR RECOVERY BOILERS

Angela Wensley, Ph.D., P.Eng.

Pulp and Paper Corrosion Specialist
Angela Wensley Engineering Inc.
15397 Columbia Avenue
White Rock, BC, Canada
V4B 1K1

ABS TRACT

Cracking or corrosion thinning has necessitated the replacement of type 304L-clad composite
tubes in floors and lower waterwalls in many cases. Although replacement is often done in kind,
there are a number of alternative materials that may have improved resistance to cracking and
thinning. This paper discusses several of these alternatives that range from carbon steel to
composite tubes clad with alternative alloys, or to tubes with weld overlaid, thermal sprayed, or
diffusion coatings. Also discussed is the damage that can be done to the tubes before they ever
enter service.

INTRODUCTION

For many years it was believed that type 304L-clad composite tubes were the solution to
waterwall corrosion problems in black liquor recovery boilers. Type 304L-clad tubes have
demonstrated a far superior resistance to sulfidation than do conventional carbon steel tubes. In
the 1980's, cracking problems were encountered using 304L-clad composite tubes at smelt spout
openings and preferential corrosion of the 304L-cladding was also observed at primary and
secondary air port openings. Cracking of 304L-clad composite tubes in recovery boiler floors
became a serious concern in the early 1990's. Cracking of 304L-clad composite tubes at primary
air ports was first reported in the 1980's and has become a more widespread problem in the late
1990's. The cracking and corrosion problems have prompted interest in replacing the 304L-clad
composite tubes in locations where this material is clearly unsuitable for service. Floor tube
replacement is sometimes necessitated due to severe deformation of the floor tubes by the
"falling Volkswagen" phenomenon. Other forms of mechanical damage (such as rodding
damage) can also require the replacement of waterwall tubes at smelt spout openings and at
burner ports.

Cracking
1
Cracking was reported in 304L-clad composite tubes at smelt spout openings in the early 1980's .
Since this time the cracking problem with 304L-clad composite tubes have been reported in the

2001 TAPPI JOURNAL PEER REVIEWED PAPER 1 AUGUST 2001/VOL. 84: NO. 8
waterwall, waterwall openings, and floor tubes 2-16. Based on this author's extensive experience
in inspections of composite tube recovery boilers, the cracking of 304L-clad composite tubes can
be said to either have a random "mosaic" appearance or a circumferential orientation. A range of
appearances between these two kinds is also possible. The mechanism and causes for the
cracking are still the subject of ongoing investigations.

The thermal expansion difference between type 304L stainless steel cladding and the underlying
carbon steel tube (usually SA210-Grade A1) is likely the major contributor to the tensile stresses
that are required for cracking. As-manufactured 304L-clad composite tubes panels can have
high residual stresses from the co-extrusion, bending, and welding processes. Thermal
treatments ( normalizing) are applied to severely bent 304L-clad composite tubes such as those
formerly widely used at smelt spout openings in an attempt to reduce the magnitude of residual
stress. In service the cladding would be expected to expand more than the underlying carbon
steel and develop a compressive stress state. When placed out of service as in a shutdown the
cladding could return to a state of high tension. It has been demonstrated that stress corrosion
cracking of 304L stainless steel can occur in waterwash solutions that come in contact with
17,18
smelt, a possible explanation for floor tube cracking .

Figure 1 is a view of mosaic cracking that occurred in 304L-clad composite tubes in a smelt run
on a recovery boiler floor. Exploration of these cracks by grinding revealed that the mosaic
cracking in this and numerous other boilers is almost always confined to the stainless steel
cladding. M osaic cracking can be unpredictable in the tubes or locations where it occurs.
M osaic cracking has occurred in the smelt runs, in front of the smelt spout openings, and at
seemingly random locations on boiler floors in those 304L-clad composite tube boilers. Floor
tube mosaic cracking sometimes correlates with the locations of floor supports (Figure 2) or
bends in the tubes where the floor has deformed from falling saltcake. The floor cracking in
smelt run composite tubes can also be most severe where there is excessive corrosion of studs in
the adjacent studded carbon steel floor tubes. In recovery boilers that experience cracking of
primary air port opening composite tubes mosaic cracking typically occurs in the lower crotch of
the opening (Figure 3) or adjacent to the termination of the membrane below the opening
(Figure 4). M osaic cracking can also occur on waterwall tubes particularly those that are
adjacent to the smelt spout opening tubes (Figure 5).

Figure 1. Mosaic cracking in a smelt run 304L clad composite tubes on either side of a floor
membrane.

2001 TAPPI JOURNAL PEER REVIEWED PAPER 2 AUGUST 2001

Figure 2. Mosaic cracking in 304L-clad composite tubes located above a floor support plate.

Figure 3. Mosaic cracking in a primary air port 304L-clad composite tube.

Figure 4. Mosaic cracking adjacent to a membrane in a primary air port 304L-clad composite
tube.

2001 TAPPI JOURNAL PEER REVIEWED PAPER 3 AUGUST 2001

Figure 5. Mosaic cracking in a 304L-clad composite tube adjacent to an Alloy 825-clad smelt
spout opening.

Circumferential cracking has mostly been a problem in smelt spout opening 304L-clad
composite tubes, sometimes occurring within months of the installation of a new opening. This
problem became so endemic in composite tube boilers by the late 1980's that the first shift to
alternative tube cladding materials occurred in smelt spout openings. The newer metallurgies
prolong the service life but may eventually crack given a long enough period of service ( Figure
6). Circumferential cracking of 304L-clad tubes has also been observed at primary air port
opening tubes in a number of recovery boilers. When it occurs, primary air port tube cracking
tends to occur in the lower crotch area on the tubes above or beside the termination of the lower
membrane (Figure 7). Excavation by grinding and metallographic examination have revealed
that some circumferential cracks have propagated through the stainless steel cladding and into
the underlying carbon steel. Such cracks tend to be straight in cross section appearance.
Cracking of primary air port opening tubes has been observed after as little as 18 months of
service. Although primary air port cracking may initially be detected in only one location or on
one wall in the boiler with additional time and better inspection the cracking in those boilers is
observed on an increasing number of tubes on all four walls.

Figure 6. Circumferential cracking in a smelt spout opening Alloy 825-clad composite tube.

2001 TAPPI JOURNAL PEER REVIEWED PAPER 4 AUGUST 2001

Figure 7. Circumferential cracking in primary air port 304L-clad composite tubes.

M osaic and circumferential cracking may be found at different locations on the same 304L-clad
composite tubes whether located on the floor, at a smelt spout opening, or at a primary air port
opening. When the cracking is found the usual option is to remove the cracks by grinding.
There is a tendency to weld repair the grinding excavations particularly if the grinding exposes
the underlying carbon steel. Pad weld repairs are susceptible to recracking ( Figure 8). Carbon
steel that is exposed by the grinding removal of cracks from primary air port opening tubes may
not necessarily require weld repair since there is much experience with exposed carbon steel at
air port tubes ("balding"). See the next section on Corrosion.

Figure 8. Cross section of cracking in a weld repair on a 304L-clad composite tube adjacent to
a smelt spout opening.

In some boilers the cracking of 304L-clad composite tubes has reportedly been monitored rather
than removed. Where there are cracked floor or waterwall tubes there will always be concern
about the safety of operating the boilers. This is particularly true if there is uncertainty about the
existence of cracks or whether all cracking has been found and removed. Penetrant testing (PT)
is the most widely-used technique used to find cracks in primary air port and smelt spout opening
tubes. PT requires a better surface preparation than is currently used in most boiler inspections

2001 TAPPI JOURNAL PEER REVIEWED PAPER 5 AUGUST 2001

and without superior surface preparation has not been reliable in finding all the cracking that
19
may exist in composite tubes . PT can reveal significant cracks not found by conventional
surface preparation if an abrasive flap wheel is used. Higher-sensitivity eddy current testing
(ET) has been successful for detecting cracks in floor tubes. Acoustic emission (AE) testing has
also been used to detect cracks in recovery boiler floors.

Corrosion

Type 304L-clad tubes are highly resistant to sulfidation and normally do not experience
appreciable thinning. Localized cold side wastage of the stainless cladding at primary and
20-25
secondary air port openings has been attributed to hydroxide condensation . Hydroxide
corrosion results in the complete loss of the stainless steel cladding and the resultant exposure of
the underlying carbon steel that is known as "balding" (Figure 9). When the cold side corrosion
phenomenon was first discovered there was a concern that the underlying carbon steel would
corrode at a faster rate than would the stainless steel cladding. This has not turned out to be the
case since carbon steel resists hydroxide corrosion better than does type 304L stainless steel.
"Balding" has been left in some boilers for many years, continuing to grow in extent but not
appreciably in depth. Pad weld repairs to "balded" areas using type 309L stainless steel corrode
as rapidly as the type 304L stainless steel tube cladding. Pad weld repairs using nickel-base
alloys reportedly have better corrosion resistance than repairs made with type 309L stainless
25
steel or with pure nickel .

Figure 9. "Balding" of a primary air port 304L-clad composite tube viewed from the windbox
with the casting removed.

25
Falat has proposed that fireside "balding" at air ports is due to high temperature sulfidation by
molten salts (sulfate/sulfide/carbonate melt) rather than by molten hydroxides. This is an
environment similar to that seen by a smelt spout opening but at a higher temperature. Oxidation
of sulfide-rich smelts may provide an energy source for high temperature excursions that have
been reported.

In those boilers where "balding" is a problem at primary air port 304L-clad composite tubes it
affects an increasing number of openings over time eventually until virtually all of the openings
have "balding." "Balding" and cracking have been observed in close proximity on the same

2001 TAPPI JOURNAL PEER REVIEWED PAPER 6 AUGUST 2001

primary air port opening tubes. This suggests that the corrosion and cracking mechanisms are
related.

Butt weld caps in 304L-clad composite tubes made using stainless steel filler metal (usually type
309L) can be susceptible to corrosion that can expose the underlying carbon steel butt weld to
the furnace environment (Figure 10). It is likely that owing to dilution effects some of these butt
weld caps have poorer chemistry and are not as corrosion resistant as either the tube cladding or
other weld caps made with less dilution.

Figure 10. Corrosion of a butt weld between 304L-clad composite tubes.

ALTERN ATIVE MATERIALS

The following materials are alternatives to in-kind replacement of type 304L-clad composite
tubes:

1. Bare carbon steel.

2. Studded carbon steel.
3. Thermal spray coated tubes.
4. Chromized tubes.
5. Nickel-base composite tubes.
6. Weld overlaid tubes.

The following sections describe some of the benefits and drawbacks of these various alternatives.

Bare Carbon S teel

Replacement of cracked composite tubes using bare carbon steel tubes has been done in the
floors of some recovery boilers. In these cases the cracking was unanticipated and there was no
time to have any other tubes delivered on site (Figure 11). Bare carbon steel tubes have bought
the necessary time for floor replacement 1 year later. It is probable that bare carbon steel tubes
could survive for a longer period of time in lower-pressure boilers but carbon steel replacement
is not considered a permanent or long-term solution for high-pressure boilers.

2001 TAPPI JOURNAL PEER REVIEWED PAPER 7 AUGUST 2001

Figure 11. Panel of bare carbon steel tubes installed in a 304L-clad composite tube floor.

S tudded Carbon S teel

Before composite tubes were widely adopted by the pulp and paper industry pin studded carbon
steel tubes were the "standard" for floor (Figure 12) and lower waterwall tubes (Figure 13) in
26, 27
many recovery boilers . Even today there are numerous boilers using studded waterwall and
floor tubes. Studded carbon steel tubes have once again become a preferred choice for
replacement of cracked composite tubes in sloped floor boilers. M oving the butt weld line
between the 304L-clad composite tube waterwall and the studded carbon steel floor to the
bottom of the waterwall (Figure 14) may be helpful in minimizing the corrosion of the carbon
steel tubes next to the butt welds that has occurred in some boilers (Figure 15).

Figure 12. Carbon steel floor tubes with studs.

2001 TAPPI JOURNAL PEER REVIEWED PAPER 8 AUGUST 2001

Figure 13. Carbon steel wall tubes with studs around the primary air ports.

Figure 14. Butt weld line between floor and front wall 304L-clad composite tubes.

Figure 15. Corrosion of carbon steel tubes and studs adjacent to floor 304L-clad composite
tubes.

2001 TAPPI JOURNAL PEER REVIEWED PAPER 9 AUGUST 2001

One problem with studded floors is that the studs corrode (Figure 16) and presumably lose their
effectiveness in holding a layer of frozen smelt against the tubes. Eventually either the studs
require maintenance or the studded floor panels must be replaced. Because of the difficulties in
obtaining adequate cleanliness of tubes that have been in service it is preferable to re-stud on top
of the worn studs (these can be prepared to a fresh surface by grinding) instead of applying new
studs directly onto the tube surface (where less-efficient power wire brushing is the most
practical alternative). The use of chromized studs may not provide extra service life as
chromized studs tend to fracture in service (Figure 17).

Figure 16. Corroded carbon steel studs on a carbon steel floor tube.

Figure 17. Fractu red ch romized studs on floor carbon steel tubes.

Thermal S pray Coated Tubes

Thermal spray coatings properly applied can provide excellent protection for both carbon steel
and composite tubes. Coatings have been applied using both the twin-wire arc spray (TWAS)
and high velocity oxygen fuel (H VOF) processes. HVOF coatings tend to be less porous and
more resistant to permeation by the furnace environment. Proper surface preparation (a white

2001 TAPPI JOURNAL PEER REVIEWED PAPER 10 AUGUST 2001

metal grit blast) is essential for a coating to be successful. If the required surface preparation is
not obtained the mechanical bond with the tube surface is impaired and the coatings can fail by
spalling. The service life of a well-bonded thermal spray coating is determined by the rate of
penetration of the environment that results in a corrosion front progressing through the coating
thickness converting the metallic coating into a nonprotective sulfide corrosion product. The
coatings require periodic maintenance to ensure their serviceability.

Thermal spray coatings of an alloy having a 50% Cr/50% nickel composition have been used to
extend the life of new (carbon steel), corroded (carbon steel and composite), or cracked
(composite) waterwall and floor tubes. It is essential that all detectable cracking be removed
before coating is considered as an option for extending the life of cracked tubes. Thermal spray
coatings have been applied over floor and lower waterwall 304L-clad composite tubes where the
existing cracking that was detected by penetrant testing was removed by grinding (Figure 18).

Figure 18. Thermal spray coating of 304L-clad composite tubes.

Chromized Tubes

Chromized tubes (carbon steel tubes that have a diffusion coating of chromium) have been
widely used in both the waterwalls and floors of decanting floor boilers 28. Chromized tubes in
general serve well but can experience problems such as pitting (Figure 19). Spalling and
"balding" of chromized tubes have also been observed but these cases are rare. The performance
variability of chromized tubes may be due to variations in the chromizing process itself. A
nondestructive method for measuring the thickness of the chromized layer has not yet been
perfected. M easurement of the chromium content of the surface using a portable x-ray
fluorescent alloy analyzer is not sensitive enough detect small changes in thickness. M agnetic
susceptibility instruments intended to read ferrite contents in stainless steel welds can provide
useful information on chromizing thickness although the necessary calibration standards have
not yet been produced.

As the chromizing process has gained wider acceptance applications for use have expanded to
include tube installations in other types of boilers, superheater tube bends, generating bank tube
ends, smelt spouts, and studs.

2001 TAPPI JOURNAL PEER REVIEWED PAPER 11 AUGUST 2001

Figure 19. "Pitting" of chromized tubes.

Nickel-Base Composite Tubes

Alternative alloys for co-extruded composite tube cladding include variations of both Alloys 825
and Alloy 62529-31. These alloys have a better match of thermal expansion coefficients compared
with that of the underlying carbon steel. Alloy 625 has the best match of thermal expansion
coefficient. The first application using nickel-based alloy composite tubes was in smelt spout
openings where the service life was greatly improved. M odified Alloy 825 smelt spout openings
eventually experience cracking (Figure 6). M odified Alloy 825 composite smelt spout opening
tubes are also susceptible to what appears to be erosion or sulfidation caused by the flowing
smelt (Figure 20). There have been reports that Alloy 625-clad tubes at primary air ports have
no better resistance to "balding" than type 304L-clad tubes. Corrosion of the butt weld caps has
been observed in waterwalls where Alloy 825 composite tubes are joined to 304L-clad
composite tubes (Figure 21). Butt weld cap corrosion may be due to excessive dilution of the
filler metal with the carbon steel or to insufficient metal in the cap.

Figure 20. Location of erosion thinning of smelt spout opening Alloy 825-clad tubes.

2001 TAPPI JOURNAL PEER REVIEWED PAPER 12 AUGUST 2001

Figure 21. Corrosion of butt welds between 304L-clad and Alloy 825-clad composite tubes.

Weld Overlaid Tubes

Carbon steel tubes that are spiral welded in the shop using a gas metal arc weld overlay
composed of nickel-base Alloy 625 have been used for: (1) replacement of smelt runs in
recovery boiler floors (Figure 22), (2) smelt spout openings (Figure 23), and (3) primary air port
openings (Figure 24). The thermal expansion coefficients of Alloy 625 and carbon steel are
closely matched. This situation should improve resistance to cracking but is not a guarantee.
The spiral-welded tubes can be normalized after manufacture to further reduce residual
32
stresses . In one boiler Alloy 625 weld repairs to 304L-clad composite tubes were found to be
25
highly resistant to hydroxide corrosion although rapid corrosion of spiral weld overlaid tubes
has been observed at primary air port openings in another boiler. The sulfidation resistance of
Alloy 625 tubes may not be as good as that of 304L-clad composite tubes. The chromium
content of an Alloy 625 weld deposit is diluted with the carbon steel substrate that may affect
corrosion resistance. Since this is a relatively new tube alternative more time and service
experience is required before any definitive statements can be made concerning the servicability
of Alloy 625 overlaid tubes compared with the other materials discussed above.

Figure 22. Floor with spiral weld overlaid Alloy 625-clad tubes.

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Figure 23. Smelt spout opening made using spiral weld overlaid Alloy 625-clad tubes.

Figure 24. Primary air port opening made using spiral weld overlaid Alloy 625-clad tubes.

Field-applied gas metal arc weld overlay of waterwall tubes using ER309L stainless steel has
33
also been accomplished in many boilers . ER309L weld overlay is normally used to protect
entire carbon steel waterwalls or the more localized thinning that sometimes affects the carbon
steel tubes above the composite tube cut line. Figure 25 shows the visual quality of field weld
overlaid waterwall tubes. The higher chromium content of the type 309L tends to impart good
sulfidation resistance to the tubes.

2001 TAPPI JOURNAL PEER REVIEWED PAPER 14 AUGUST 2001

Figure 25. Waterwall tubes weld overlaid in-situ.

DIS CUSS ION

The quality of the replacement floor or waterwall tubes is dependent on rigorous inspection and
quality assurance before and during installation. All too often the quality of type 304L-clad
waterwall panels has been poor. Painting of new waterwall or floor panels by the manufacturer
before delivery can obscure fabrication and workmanship defects. Painting may have some
function for protection of carbon steel tubes from corrosion in transit but does nothing to protect
the more corrosion resistant materials discussed above. On unpainted 304L-clad tubes or panels
may be found evidence of local spot heating (Figure 26), severe scratching or scoring (Figure
27), undocumented weld repairs, and other defects. There is no reason to assume that
manufacturing defects would be absent from any of the replacement alternative materials.

Figure 26. Damage from local spot-heating of new 304L-clad composite tube.

2001 TAPPI JOURNAL PEER REVIEWED PAPER 15 AUGUST 2001

Figure 27. Mechanical damage at a primary air port opening from cold bending of 304L-clad
composite tube.

Visual inspection of new panels in the shop is often enough to obtain better quality. For thermal
spray coatings an independent monitoring of the surface preparation and coating thickness using
magnetic lift-off (M LO) gauges is recommended. For chromized coatings thickness monitoring
using a portable x-ray fluorescence analyzer (for chromium) or a magnetic susceptibility (ferrite)
instrument should be done. For co-extruded composite tubes it is best to have baseline cladding
thickness data obtained using properly calibrated M LO instruments so that any thinning can be
detected after the tubes have been in service. Thickness measurement on spiral weld overlay
tubes is problematic since the thickness of the weld overlay can vary from 1.5 to 2.4 mm (55 to
85 mils) around the circumference of a single tube. One can, however, obtain useful thickness
information if M LO measurements are done at reproducible locations.

I recommend obtaining samples of the tubes that are being installed. These can be cross
sectioned and examined using a metallograph to observe problems with the microstructure,
interface, thickness, and the presence of any defects that may affect service life. Composition
and hardness should also be measured to confirm that these are within acceptable ranges. The
tube samples should be exposed to the same thermal treatments as the tubes that will go into
service. This may include normalizing of severely bent tubes at waterwall openings or spot
heating.

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2001 TAPPI JOURNAL PEER REVIEWED PAPER 16 AUGUST 2001

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Received: September 15, 2000

Accepted: M ay 22, 2001

This paper was accepted for abstracting and publication in the August 2001 issue of TAPPI
JOURNAL.

TAPPI Website: www.tappi.org

2001 TAPPI JOURNAL PEER REVIEWED PAPER 18 AUGUST 2001