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ANODIC PROTECTION AGAINST CORROSION AND CRACKING OF DIGESTER

VESSELS

Conference Paper · January 2003

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 TAPPI Fall Technical Conference – 2003

ANODIC PROTECTION AGAINST CORROSION AND CRACKING OF DIGESTER VESSELS

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

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

ABSTRACT
________________________________________________

Corrosion studies in a number of digester extraction liquors have confirmed that carbon steel has a profound
active/passive transition. Anodic protection of digesters relies on the ability of carbon steel to passivate. Anodic
protection has been effective in preventing stress corrosion cracking, although it may not stop the propagation of
existing stress corrosion cracks. Significant reductions in corrosion rate can be achieved by shifting the corrosion
potential from active values to passive values. Passive corrosion rates for carbon steel in high temperature
extraction liquors can still be appreciable.

________________________________________________

INTRODUCTION

This is the third in a series of three papers on protection of continuous digesters from corrosion. The previous
papers have been on thermal spray coating [1] and on stainless steel weld overlay [2]. These three alternatives for
protection of continuous digesters have previously been compared [3].

History

Anodic protection was first proposed in the late 1950's and the 1960's to protect carbon steel batch digesters from
general corrosion thinning [4-7] but its first North American application was in 1979 for corrosion protection in a
soda continuous digester [8]. Following the catastrophic failure of a continuous digester in 1980 due to caustic
stress corrosion cracking (SCC), anodic protection was one of the SCC-protective measures recommended by the
TAPPI Digester Cracking Research Committee [9]. During the 1980's numerous anodic protection systems were
installed to protect carbon steel continuous digester vessels against both SCC and corrosion [10-22]. The anodic
protection systems installed for SCC protection focused on the impregnation zone in single-vessel kraft pulping
systems or the impregnation vessel in two-vessel systems since these were the locations where almost all SCC was
found. By the 1990's anodic protection systems were increasingly being installed to protect continuous digesters
against corrosion thinning at elevations below the cooking screens and in particular the wash zone where several
cases of rapid corrosion thinning had occurred.

Corrosion Polarization Curves

Corrosion in digester liquors is an electrochemical process involving anodic (oxidation) and cathodic (reduction)
reactions. Carbon steels display active/passive behavior in digester liquors. Whether carbon steel is active
(characterized by high corrosion rates) or passive (characterized by low corrosion rates) depends on the value of the
corrosion potential of the steel in the liquor. Anodic protection can occur due to the ability of carbon steels to
passivate in alkaline pulping liquors. Anodic protection relies on shifting the corrosion potential from values
corresponding to active corrosion to more positive values that are characteristic of passivation. Figures 1 and 2 are
corrosion polarization curves showing the true relationship between corrosion potential and corrosion rate in
continuous digester and batch digester liquors, respectively [23]. The "S" shape of the corrosion polarization curves
is due to a competition between the oxidation processes of iron dissolution and oxide formation. When the
corrosion potential is below the "nose" (maximum active corrosion rate) in the polarization curve an increase in the
potential causes an increase in the rate of corrosion. Above the "nose", the corrosion rate decreases with increasing
potential in apparent contradiction to the belief that a greater driving force should provide yet higher corrosion rates.
This is because the process of oxide formation becomes thermodynamically possible at the potential of the "nose"

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and occurs in addition to the dissolution process. As the potential is further increased the surface of the steel is
covered with an oxide film of high resistivity and the corrosion rate (leakage through defects in the passive film or
repairs to the passive film) becomes small and independent of potential.

As can be seen from the corrosion polarization curves in Figures 1 and 2, active corrosion in both continuous and
batch digester liquors is characterized by values of corrosion potential below approximately -50 millivolts versus a
molybdenum reference electrode (-50 mV vs Mo). The active corrosion maximum (or "nose") in continuous
digester extraction liquors often occurs at -150 mV vs Mo. In batch digester liquors the "nose" occurs at a lower
potential value, possibly -200 mV vs Mo. Corrosion rates under conditions of active corrosion may be very high.
Some continuous digesters have corroded at rates of ¼ inch per year (6 mm/y). Carbon steel tends to passivate at
potentials higher than -50 mV vs Mo. Corrosion rates in the passive state can be well below 10 mils per year (0.2
mm/y). Anodic protection used against corrosion thinning has a control potential that is within the passive range
(e.g., +50 mV vs Mo) but not high enough to waste current on oxidation of sulfide in the liquor. The control
potential may have to be "fine-tuned" in order to obtain the lowest possible passive corrosion rate.

Anodic protection used against SCC takes advantage of the fact that SCC occurs only within a narrow range of
potentials just above the active/passive transition in the polarization curve [24-26]. The potential range where SCC
can occur is narrow, perhaps only 50 mV wide. The location of the SCC zone on a corrosion polarization curve
would be from -50 to 0 mV vs Mo, in the region where corrosion rates decrease with increasing potential. Anodic
protection used against SCC usually implies controlling the system at a potential of approximately +100 mV vs Mo
to be certain that the digester wall is outside the range where SCC can occur.

ANODIC PROTECTION SYSTEM DESIGN

Anodic protection systems are comprised of rectifiers, cathodes, reference electrodes, and associated cabling. The
rectifiers are installed outside the digester and provide the necessary current for anodic protection. As mentioned
above, corrosion is an electrochemical process. Electrons are released by the oxidation reactions and are consumed
by the reduction reactions. By impressing a current on the digester wall the potential can be shifted in the positive
(anodic) direction. The rectifiers must be capable of providing sufficient current to move the corrosion potential
past the active corrosion "nose" and into the passive zone. The cathodes and reference electrodes are installed inside
the digester. The reference electrodes are used to sense the potential of the digester wall and to provide feedback to
the rectifier such that the current output can be adjusted to reach and hold the desired control potential. Start-up of
an anodic protection system after a shutdown usually requires a short period of high current output to passivate the
digester wall. Once passivation has been achieved the current required to maintain the passivity is usually quite
small.

Cathodes

There are several different configurations of cathodes that can be used in anodic protection systems. The first
anodic protection systems in continuous digesters had pipe cathodes that were installed around the central pipe.
There was an insulating PTFE layer between the pipe cathode and the central pipe to prevent short-circuiting of the
current between the cathode and central pipe. There were problems with the bolting of the pipe cathodes that led to
their being replaced by linear cathodes that required less maintenance. Linear cathodes must be of carbon steel
construction as stainless steel cathodes crack due to hydrogen charging. Figure 3 shows a typical entry for linear
cathodes that is located inside and beneath the central pipe support shroud. The central pipe support shroud protects
the horizontal cathode runs from damage by the chip plug. Figure 4 shows the linear cathodes adjacent to the central
pipe where PTFE insulated stand-offs prevent short-circuiting to the central pipe. Shorter linear cathodes are used in
the impregnation zone for protection against SCC. Longer linear cathodes are used to provide current to lower
elevations for protection against corrosion. PTFE insulation is wrapped around the upper elevations of the long
cathodes to prevent current being unnecessarily consumed in the upper part of the digester. "Tee cathodes" provide
better current distribution above and below a junction with a buss bar (Figure 5). There have been some cases of
damage (pitting, SCC) of the stainless steel central pipe from the adjacent linear cathodes under conditions of
excessive rectified current output. The central pipe can be protected by installation of carbon steel shields on the
central pipe (Figure 6).

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Wall-mounted cathodes can be either vertical (Figures 7) or circumferential (Figure 8) in orientation. Each wall
mounted cathode requires its own buss bar and penetration through the digester wall. Vertically-oriented cathodes
are typically spaced as evenly as possible around the digester. More vertical cathodes are required at lower
elevations in the digester where the circumference is greater. Anodic protection against corrosion using vertical
cathodes may be problematic if they extend across elevations in the digester where the corrosion environment is
significantly different. Circumferential cathodes may offer better corrosion control at different elevations. The
wall-mounted cathodes have a frame that is welded to the digester wall. It is claimed that the compression of the
chip plug as it passes over a circumferential wall-mounted cathode aids in movement of the plug. The cathode
elements in the center of the wall-mounted cathodes have PTFE insulation to prevent current short-circuiting to the
support (Figure 9). The cathode elements are carbon steel. The cathode frames may be either stainless steel or
carbon steel. Stainless steel cathode supports are welded to the digester wall using stainless steel electrodes, and
carbon steel cathode frames are welded to the digester wall using stainless steel electrodes.

Circumferential rod-type cathodes can be installed below headers where they are protected from damage by the chip
plug (Figure 10). Depending on the circumference of the digester there may be one or two buss bar penetrations for
each circumferential rod-type cathode. Figure 11 shows a buss bar for a rod-type cathode. Rod-type cathodes have
also been installed to protect the carbon steel digester wall adjacent to the top edge of stainless steel weld overlays
from a form of preferential corrosion called "fingernailing". Rod-type cathodes installed below headers can provide
protection to the digester wall behind the screens above. Circumferential rod-type cathodes have also been installed
behind blank plates in an impregnation vessel to provide protection against SCC (Figure 12).

Blank plate cathodes can protect carbon steel blank plates from corrosion (Figures 13 and 14). There are typically
three blank plate cathodes located around the digester circumference in a zone where there are several elevations of
blank plates. Replacement of corroded carbon steel blank plates using stainless steel may be an alternative to
installing blank plate cathodes.

Cathodes can also be installed above the internal cone for protection against both SCC and erosion corrosion.
Figures 15 and 16 show two kinds of cathodes above the internal cone, one made using pipes and the other using
rods in the form of a cage or "crown". Anodic protection systems above the internal cone may have anti-scaling
capabilities that help the top separator basket keep clean during operation, but the results have been mixed.

Reference Electrodes

Reference electrodes for anodic protection systems must be robust and capable of surviving for years in a continuous
digester environment. Lack of robustness rules out the use of laboratory reference electrodes such as the saturated
calomel electrode in digesters. Some reference electrodes are retractable (Figure 17) which permits replacement of
the electrodes while the digester is operating. Most reference electrodes are fixed and cannot be replaced until the
digester is empty during a shutdown. The reference electrodes used most commonly in anodic protection systems
are pieces of molybdenum, silver, or stainless steel. Figure 18 shows the appearance of a molybdenum reference
electrode on the inside of a digester. Only the tip of a ⅛ inch (3mm) diameter molybdenum wire is exposed to the
digester environment. The molybdenum reference electrode relies on the redox potential for the corrosion of
molybdenum to molybdenum sulfide (MoS2)being reasonably stable in alkaline liquors . The Mo/MoS2 potential
actually varies with the concentration of sulfide in the liquor so it is not a "reproducible" reference; however, it has
sufficient stability for use in kraft continuous digesters. The same argument applies for the silver electrode that
relies on the redox potential of the corrosion of silver to silver sulfide (Ag2S). The Ag/Ag2S potential is also not
constant or "reproducible" but has sufficient stability for use in kraft continuous digesters. The stainless steel
reference electrode (typically type 304L) relies on the observation that stainless steels are invariably passive in
continuous digester liquors. This is not necessarily the case in batch digester liquors. The potential of the stainless
steel may be affected by the presence of oxidants in the liquor so is not "reproducible" but it is sufficiently stable for
use in kraft continuous digesters.

Both the molybdenum and stainless steel reference electrodes assume nearly equal potentials in kraft digester
liquors. A high input impedance voltmeter attached across them would measure 0 volts. The silver-silver sulfide
electrode (also known as the SSSE) typically has a potential that is approximately 50 mV lower than either the
molybdenum or the stainless steel electrodes in continuous digester liquors. This difference in reference electrode
potentials must be taken into account when comparing corrosion potential data using different reference electrodes.

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Reference electrodes are usually installed at multiple elevations in a continuous digester. Each reference electrode
has its own nozzle. The core samples from cutting the holes for the nozzle are useful for confirming the thickness
and condition of the digester wall. Reference electrodes are typically installed flush with the digester wall so that
they are not damaged by the movement of the plug. Reference electrodes have also been installed behind screens
and blank plates.

EVALUATING ANODIC PROTECTION BEFORE INSTALLATION

It may be prudent to install reference electrodes in a continuous digester even if no decision has been made to
proceed with the installation of an anodic protection system. The reference electrodes will tell the anodic protection
system designers and/or mill engineers where the protection is most needed. Also the reference electrodes can be
used to provide an "early warning system" against the sudden onset of rapid corrosion thinning. This would be
characterized, for example, by a decrease in corrosion potential values from the passive range (e.g., above -50 mV
vs Mo or SS) into the active range (below -50 mV vs Mo or SS). This knowledge would allow measures to be taken
to slow the rate of corrosion such as: decreasing the temperature, cessation of pulping of corrosive wood species, or
addition of caustic to raise the residual alkali level.

Anodic protection has been very successful in protecting digesters against SCC. There is probably little need to re-
invent the wheel by doing testing to verify this well-established fact. The situation with anodic protection against
corrosion thinning at lower elevations in continuous digesters is less clear. There are some situations that may make
it difficult to lower corrosion rates to an acceptable value. These include digesters where the:

(1) extraction temperature is in excess of 338ºF (170ºC),

(2) wood species being pulped is highly corrosive (e.g., western red cedar or Douglas fir),
(3) residual alkali level is very low (e.g., less than ~3 g/L NaOH).

Laboratory corrosion testing should be done prior to purchasing an anodic protection system to verify that anodic
protection is capable of lowering the corrosion rates to acceptable values. The acceptable value of corrosion rate
will depend on the remaining corrosion allowance in the digester but is generally taken to mean less than 10 mpy
(0.1 to 0.2 mm/y). One way to determine the ability of anodic protection systems to provide corrosion thinning
protection is to acquire corrosion polarization curves such as shown in Figures 1 and 2. These tests are done in
autoclaves containing samples of digester extraction liquor heated to the actual extraction temperature of the digester
to be protected. Potentiostatic polarization is used to hold the potential of specimens (usually carbon steels such as
SA516-Grade 70 or SA285-Grade C) for a suitable time period (e.g., 5 days) to obtain a measurable weight loss so
that the corrosion rate can be calculated. The corrosion polarization curve in Figures 1 is the result of six different
tests at different corrosion potentials comprising the range of potentials that may occur in a continuous digester.
Alternatively, a single test could be done at the proposed anodic protection control potential to verify that the
corrosion rate is reduced to acceptably low values. However, this may not be the optimum set point and it is
possible that the corrosion rate may be further reduced at another set point.

Contact electric resistance (CER) measurements have been used to evaluate the ability of carbon steel to passivate in
digester liquors [27]. In CER testing, a probe of the material of interest (carbon steel) is repetitively brought into
contact with and disconnected from an iridium probe. The resistance measured across the probes will be very high
(e.g., 1000 ohms) if the probes develop an insulating passive film. The resistance will remain very low (e.g., less
than 1 ohm) if no passivating film is developed or if the passive film is poor. CER testing at the intended anodic
protection control potential will also provide information on how much time is required to achieve passivation, as
evidenced by the change in resistance from low to high values. If the time to passivate is lengthy it is possible that
significant corrosion thinning could occur during that interval of time.

ANODIC PROTECTION SYSTEM INSTALLATION

Nondestructive testing of all wall penetrations should be done both before and after installation of the nozzles. All
welding to the digester shell should be performed using a preheat temperature appropriate for the carbon steel wall.
It is particularly important to inspect those parts of the circumferential weld seams that will be covered by the
cathodes before wall-mounted cathodes are installed. The weld crowns are usually ground flush with the digester
wall for the cathode installation, providing good conditions for this inspection

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MONITORING ANODIC PROTECTION SYSTEM PERFORMANCE

Measurements of the reference electrode potentials and the rectifier outputs can help determine if an anodic
protection system is functioning properly. Anodic protection systems can also be remotely monitored by the system
providers. This service is usually well worth the effort since the anodic protection providers have an obvious
interest in having their systems operate successfully. A significant change in parameters such as a drop in corrosion
potential from passive to active values or a large increase in rectifier current may indicate failure of a circuit, a
reference electrode, or a cathode. Operation for weeks or months at maximum rectifier output may cause damage to
the digester wall or central pipe so it may be necessary to turn a particular circuit off if the situation cannot be
corrected externally. Modern anodic protection systems typically have considerable redundancy and may tolerate
the loss of a reference electrode or cathode until the next opportunity for replacement, usually the annual shutdown.

Although monitoring of the effectiveness of anodic protection systems against SCC has been done using pre-cracked
double cantilever beam specimens [14], monitoring is best accomplished by annual inspections at selected locations
that have been ground smooth (Figure 19). Grinding is an essential first step for crack inspection – subsequent
inspections of the same location may only require light sanding or buffing). The absence of re-cracking in a digester
that had experienced SCC is a good indication that the anodic protection system is working. The finding of small
cracks may be more due to the limitations of the nondestructive testing method (magnetic particle testing) than to
the inability of anodic protection to prevent cracking. Even where the goal is to remove all cracks from welds in a
digester during each shutdown, cracks not detected in one shutdown may be detected during a subsequent shutdown.
A period of 3 years may be required to eliminate cracks from an anodically protected digester.

The performance of some anodic protection systems to protect against corrosion thinning has been monitored using
thin layer activation (TLA). Coupons of carbon steel are irradiated by a particle beam from a nuclear reactor. The
coupons have a low level of radioactivity and are installed on the wall of the digester (Figure 20) for external
monitoring using a Geiger counter. The half-life decay of the radioactivity of the specimens has to be taken into
account. TLA coupons have been used to confirm the effectiveness of anodic protection during digester operation
by confirming that corrosion rates were lowered to very low values [28, 29].

The most effective means for evaluating the effectiveness of anodic protection against corrosion thinning is
ultrasonic thickness testing (UT) on a reproducible grid during the annual internal inspections of the digester.
Sixteen-point grids that are 1 foot (30 cm) square are particularly useful. Ideally, the UT measurements should be
taken using the same instrument, transducer, calibration block, and operator. The operator should scan each 2-inch
(50 mm) spot to find the lowest reading. Ideally the grids should be established before an anodic protection system
is installed so that baseline data are available. It is good to have several of these UT grids so that the effectiveness
of anodic protection can be monitored at different elevations in the digester Figures 21 and 22 show the same
sixteen-point UT grid after 1 and 2 years, respectively, of operation of an anodic protection system in a continuous
digester. There was essentially no change in the wall thickness over the 1 year period.

LIMITATIONS OF ANODIC PROTECTION

It is hoped that when an anodic protection system installed the problems of cracking and corrosion will be
eliminated. There are limits to effective anodic protection, however, that arise from the condition of the digester, the
condition of the anodic protection system, or from certain operating conditions that may lessen the ability of anodic
protection systems to passivate the digester.

Pre-existing Cracks

Data shows that anodic protection can prevent the initiation of SCC. However, anodic protection may not stop the
growth of existing cracks. While one may rely on anodic protection to passivate the surface of the digester wall and
shallow cracks; it is problematic whether anodic protection can passivate the metal surfaces inside cracks deeper
than approximately ⅛ inch (3 mm).

As previously mentioned, it is possible for some cracking to go undetected and then be discovered during a
subsequent inspection. This gives rise to the question as to whether the cracking occurred while the anodic

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protection system was energized. There is often a time period between the installation and energizing of a new
anodic protection system. If the digester is left unprotected for 1 or 2 months prior to energizing the anodic
protection system, it is entirely possible that SCC can initiate and grow during this time to a depth that may be
greater than ¼ inch (6 mm).

Due to the unpredictable nature of SCC and the numerous cases of through wall cracking that have occurred in less
than 1 year, it is recommended that all SCC be removed from digesters during the annual shutdowns. In many cases
the amount of cracking is so extensive that it is not possible to remove all SCC within a normal shutdown interval of
1 week. If cracks are left unremoved, it must be remembered that there is a risk with possible serious consequences
associated with this decision. There are external methods for detecting cracks that can be used to provide some
sense of security but in the author's experience external crack monitoring has not been sufficiently reliable.

Hardware Problems

There have been great advances in the reliability of anodic protection system hardware (cathodes, reference
electrodes, rectifiers, cabling) over the past 20 years. Nonetheless, problems still occur. The most significant
problems are due to breakage of the cathodes. Figures 23 and 24 show breaks in a liner cathode and a rod-type
cathode, respectively. The breaks in the cathodes are often at welds that were poorly made. All welds in linear or
rod-type cathodes should have good (preferably full) penetration. Stainless steel electrodes should never be used to
weld segments of carbon steel cathodes due to the high susceptibility of stainless steel to hydrogen charging and
embrittlement, yet sometimes stainless steel is used with the predictable consequences of cracking and failure.

It is important that the PTFE insulation on linear cathodes be maintained regularly since breaks in the insulation may
result in current flowing to locations where it is not needed or wanted. There may be high current flow to the central
pipe at the location where the insulation ends. Figure 25 shows a case where the rectifier was operating at maximum
output for a long period of time. The welds in the cathode elements of wall-mounted cathodes are susceptible to
cracking (Figure 26) possibly due to hydrogen charging.

Scaling

There is some evidence to suggest that anodic protection may reduce the amount of carbonate scaling on the digester
wall. Systems installed for anti-scaling purposes typically have a higher control potential than anodic protection
systems installed to protect against SCC. It is possible for carbonate scaling to occur on the cathodes that may in
turn affect the ability of the cathodes to provide corrosion protection (Figure 27). In one continuous digester scale
deposits rich in zinc have been observed on the wall between the wall-mounted cathodes (Figure 28). These zinc-
rich scales do not respond to muriatic acid cleaning.

Damage during Acid Cleaning

Anodic protection systems do not provide protection during muriatic acid cleaning. If the anodic protection system
is left energized during an acid cleaning, severe pitting corrosion of the digester wall, the stainless steel central pipe,
and the screens can occur. Despite this knowledge, there have been a number of cases where the anodic protection
systems were left energized during acid cleaning and damage has occurred.

High Corrosion Rates in Hot Liquors

The passive corrosion rate of carbon steel can be appreciable in very hot extraction liquors. Both active and passive
corrosion rates increase with increasing temperature. In some digester liquors, the passive corrosion rates can be
unacceptably high in extraction liquors at temperatures in excess of 170ºC. Figures 29 and 30 both show the
increase in corrosion rate of carbon steel with increasing temperature in extraction liquors from two continuous
digesters. These data were obtained by the same method described earlier for the determination of the corrosion
polarization curves in Figures 1 and 2. Control at a positive potential significantly lowers the corrosion rate from
the values under active corrosion (control at -100 mV vs Mo in the case of Figure 29; open-circuit potential of
approximately -120 mV vs Mo in the case of Figure 30). Lower passive corrosion rates may be obtained by fine-
tuning the control potential.

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CASE HISTORIES

The author has been involved with the inspection of numerous continuous digesters having anodic protection
systems and with quality control during the application of several new anodic protection systems. Following are a
number of case histories of the used of anodic protection against SCC and corrosion thinning. These goals have
been achieved in the vast majority of anodic protection systems.

Mill A. Continuous Digester with Severe Stress Corrosion Cracking

The digester was built in 1967 and only partially post-weld heat treated (as was and still is permitted by the ASME
Boiler and Pressure Vessel Code). It experienced a catastrophic failure in 1980 due to caustic SCC of the weld
seams in the impregnation zone (the zone that was not heat treated). After the digester top was rebuilt there was a
recurrence of SCC at welds in the impregnation zone. Stainless steel weld overlay bands were applied to protect the
weld seams. Severe SCC occurred in the carbon steel adjacent to the overlay band edges. The anodic protection
system was installed in 1985 for SCC protection. Originally, a clamp-on cathode was installed around the central
pipe. There were problems with broken buss bars over the next few years. Linear cathodes were installed in 1992 to
replace the clamp-on cathode. A top separator cathode was installed in 1989 for protection against erosion corrosion
pitting. No SCC of the digester has been reported in 18 years.

Mill B. Continuous Digester Susceptible to Stress Corrosion Cracking

The digester was built in 1964 and only partially post-weld heat treated. This system was installed in 1986 for SCC
protection out of concern that the digester was susceptible to SCC. After installation of the anodic protection
system, no SCC of the digester shell was detected for 15 years. In the later 1980's a tee cathode was installed to
provide better current distribution lower in the digester where corrosion thinning had been detected. In 2001, the
anodic protection system was inadvertently turned off for several months. SCC was encountered during the next
internal inspection but fortunately it was not widespread. The system has been turned back on.

Mill C. Continuous Digester with Stress Corrosion Cracking

The digester was built in 1967. Inspection in the early 1980's revealed SCC of the weld seams in the impregnation
zone. Weld overlay banding was done in an attempt to protect the weld seams in the impregnation zone. An anodic
protection system was installed in 1986 for SCC protection in this zone. Originally it had a clamp-on cathode but
this failed and was replaced using linear cathodes. Thermal spray coating of the circumferential weld seams was
also tried and appeared to be compatible with the anodic protection system. During my last inspection of this
digester there were plans to install tee-cathodes to provide protection from corrosion thinning at lower elevations.
This digester had experienced severe corrosion due to hot acid cleaning. In 1998, SCC was found near the top of the
stainless steel central pipe in close proximity to the linear cathodes.

Mill D. Continuous Digester with Original Weld Defects

The digester was built in 1962 and was completely post weld heat treated. An anodic protection system was
installed in 1986 due to concerns that underbead cracking (an original weld defect) found in the welds could
propagate as SCC when exposed to the digester environment by corrosion. The system originally had a clamp-on
cathode that was subsequently converted to linear cathodes. No SCC of the digester welds was detected after
installation of the anodic protection system. In 1998, SCC was found near the top of the stainless steel central pipe,
in close proximity to the buss bars where the PTFE insulation was removed. Carbon steel shields were installed to
protect the central pipe from further damage.

Mill E. Hardwood and Softwood Continuous Digesters with Rapid Corrosion Thinning

The hardwood digester was built in 1966 and only partially post-weld heat treated. This digester has not
experienced SCC. In the 1990's, corrosion thinning of the digester wall was observed between the extraction
screens and the cooking screens and stainless steel weld overlay was applied to a total of two rings in this zone. An
anodic protection system with wall-mounted and rod-type cathodes was installed in 1997 to protect the digester from

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corrosion thinning and the impregnation zone from SCC. Corrosion rates have been reduced to acceptably low
values.

The softwood digester was built in 1984 and post-weld heat treated per ASME Code (this may mean that it was not
completely post-weld heat treated). In 1997, stainless steel weld overlay was applied to protect two rings in the
digester where the remaining corrosion allowance was small. An anodic protection system with wall-mounted and
rod-type cathodes was also installed in 1997. In 1998, corrosion at a rate of 40 mpy (1 mm/y) was observed in the
carbon steel adjacent to the weld overlay. The control potential was changed after potentiostatic polarization testing
and contact electric resistance testing. The carbon steel corrosion rate has reportedly been acceptable since the
change in the control potential was made.

Mill F. Continuous Digester with both Stress Corrosion Cracking and Rapid Corrosion Thinning

The digester was built in 1965 and was partially post-weld heat treated. In the 1990's extensive SCC was found in
the impregnation zone in both the welds and the base metal. It was not possible to remove all the SCC within the
time constraints of a normal shutdown. In addition, the wash zone (between the wash screens and the extraction
screens) had experienced severe corrosion thinning and had been built up three times using carbon steel. An anodic
protection system was installed in 1998 to protect the digester against both SCC and corrosion thinning. There was
concern about the ability of the anodic protection system to protect against corrosion thinning since the residual
hydroxide content in the liquor was very low. Corrosion rates, however, have been reduced to very low values. The
initiation of SCC has been prevented in those locations where the cracking was removed by grinding or a
combination of arc gouging plus grinding. A multi-year program is underway to completely eliminate SCC from the
digester.

Mill G. Impregnation Vessel with Severe Stress corrosion Cracking and Continuous Digester with Corrosion

The impregnation vessel (IV) and digester were built in 1979 as part of a two-vessel system. The IV was not post-
weld heat treated while the digester was completely post-weld heat treated. In the 1980's, most of the
circumferential weld seams in both vessels were banded using nickel-base weld overlay. Inspection of the IV in
1999 revealed widespread SCC adjacent to the weld overlay bands, in the vertical weld seams, and in the base metal.
The cracking was so extensive that it was not possible to remove all of the SCC. On two occasions the IV
developed through-wall leaks due to SCC. An anodic protection system with wall-mounted cathodes was installed
in 2000 to protect the IV from further cracking. There was a 2-month delay in energizing the anodic protection
system which meant that areas cleared of SCC experienced re-cracking. In 2001, a new IV was constructed using
type 2205 duplex stainless steel and the old IV was scrapped. The cathode above the internal cone was reinstalled in
the new IV for anti-scaling purposes. The anodic protection system was installed in the digester in 1990 and
included wall-mounted cathodes, rod-type cathodes, and blank plate cathodes. There has been no appreciable
corrosion or SCC since the anodic protection system was installed. Figures 21 and 22 show the sixteen-point UT
grids from this digester.

Mill H. Continuous Digester with Rapid Corrosion Thinning

The digester was built in 1991 as part of a two-vessel system. Rapid corrosion thinning was observed soon after it
entered service. The corrosion was between the wash screens and the cooking screens, and between the cooking
screens and the extraction screens. In 1997, 4015 ft2 (373 m2) of the corroded area was overlaid using stainless
steel. Subsequently, severe preferential corrosion ("fingernailing") was noted in the carbon steel adjacent to the top
edges of the weld overlay bands. There was also severe corrosion of the carbon steel blank plates. SCC had also
been observed in the carbon steel adjacent to a stainless-capped weld seam near the top of the digester. An anodic
protection system was installed in 2001 using wall-mounted, rod-type, and blank plate cathodes to protect the
digester against SCC and corrosion thinning. In 2002, corrosion was observed below the wash screens - a location
that was not included in the original anodic protection system. A new rod-type cathode was installed below the
wash screens at that time.

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Mill I. Black Liquor Accumulator with Corrosion Thinning.

The accumulator was built in 1995 using SA516-Grade 70 carbon steel. It is part of a rapid displacement heating
batch digester system and is used to hold hot black liquor at 338ºF (170ºC). The vessel experienced severe
corrosion in the bottom half. An anodic protection system was installed in 2001 to protect the accumulator from
corrosion thinning using a single pipe cathode that extended from the top to the bottom of the vessel, located slightly
off-center. Inspection in 2002 revealed that the rapid corrosion thinning had been effectively stopped. Inspection of
the weld seams for cracking (for the first time) revealed cracks up to ¼ inch (6 mm) along the toes of three of the
circumferential weld seams. No metallurgical samples were taken so the mechanism of the cracking cannot be
confirmed as SCC. These weld seams had been restored in a previous inspection and there may have been cold
cracking. Whatever the cause, the cracking likely pre-dated the installation of the anodic protection system.

CONCLUSIONS

1. Anodic protection is an excellent method for protecting continuous digesters against SCC.
2. Anodic protection can protect digesters against corrosion thinning.
3. Anodic protection may not prevent the growth of pre-existing stress corrosion cracks.
4. Anodic protection against thinning is problematic in some digesters with hot liquors.

REFERENCES

1. Wensley, A., Thermal Spray Coatings for Corrosion Protection of Continuous Digesters and Flash Tanks,
TAPPI Engineering Conference, San Antonio (2001).
2. Wensley, A., Weld Overlay for Corrosion Protection of Continuous Digesters, TAPPI Fall Technical
Conference, San Diego (2002).
3. Wensley, A., Corrosion Protection of Kraft Digesters, Paper No. 01423 presented at the NACE Corrosion 2001
Conference, Houston (2001).
4. Mueller, W.A., Anodic Protection of Alkaline Pulping Digesters, Pulp & Paper Magazine. Canada, Vol. 60,
pp. T3-T8 (1959).
5. Watson, T.R.B., Anodic Protection of Alkaline Pulping Digesters, Pulp & Paper Magazine. Canada, Vol. 63,
pp. T247-T248 (1962).
6. Watson, T.R.B., Anodic Protection of Kraft Digesters, Materials Performance, Vol. 3 No. 6, pp. 54-56 (1964).
7. Banks, W.P., Hutchison, M., and Hurd, R.M., Anodic Protection of Carbon Steel Alkaline Pulp Digesters,
TAPPI J. Vol. 50 No. 2, pp. 49-55 (1967).
8. Bennett, D.C., Anodic Protection for Corrosion Protection in a Soda Continuous Digester, Proceedings of the
3rd International Symposium on Corrosion in the Pulp & Paper Industry, Atlanta, pp. 323-328 (1980).
9. Yeske, R.A., Stress Corrosion Cracking of Continuous Digesters for Kraft Pulping, Institute of Paper
Chemistry Project 3544, Final Report to the Digester Cracking Research Committee (1983).
10. Munro, I., Anodic Protection of Continuous Digesters to Prevent Corrosion and Cracking, Proceedings of the
TAPPI Engineering Conference, pp. 181-185 (1983).
11. Thomas, P.H., The Fight Against Corrosion on a Kamyr Continuous Digester, Proceedings of the 5th
International Symposium on Corrosion in the Pulp & Paper Industry, Vancouver, pp. 29-34 (1986).
12. Savisalo, H., Pulliainen, M., and Kerola, T., Corrosion of Kraft Continuous Digesting: The Results of In-situ
Electrochemical Testing, 5th International Symposium on Corrosion in the Pulp & Paper Industry, Vancouver,
(1986).
13. Singbeil, D. and Garner, A., Anodic Protection to Prevent the Stress Corrosion Cracking of Pressure Vessel
Steels in Alkaline Sulfide Solutions, Materials Performance, Vol. 26 No. 4, pp. 31-35 (1987).
14. Wensley, D.A., Corrosion Control in a Kraft Continuous Digester, Proceedings of the 6th International
Symposium on Corrosion in the Pulp & Paper Industry, Helsinki, pp. 7-19 (1989).
15. Chakrapani, D.G., Monitoring of Cracking and Corrosion in Continuous Digesters through Corrosion Test
Coupons and Metallurgical Specimens, Proceedings of the 6th International Symposium on Corrosion in the
Pulp & Paper Industry, Helsinki, pp. 20-34 (1989).
16. Singbeil, D., Does Anodic Protection Stop Digester Cracking? Proceedings of the 6th International
Symposium on Corrosion in the Pulp & Paper Industry, Helsinki, pp. 109-116 (1989).

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17. Pulliainen, M. and Savisalo, H., Experiences of Corrosion Control in Continuous Hydraulic and Two Vessel
Digesters by Anodic Protection, 6th International Symposium on Corrosion in the Pulp & Paper Industry,
Helsinki, (1989).
18. Kiessling, L., Application of Anodic Protection to a Preimpregnation Vessel, Proceedings of the TAPPI
Engineering Conference, pp. 659-665 (1989).
19. Smith, D., Oei, J., and Rutley, J., Kamyr Digester Shell Corrosion Reduction using Anodic Protection (1992).
20. Kiessling, L., A Study of the Influence of Modified Continuous Cooking Processes on the Corrosion of
Continuous Digester Shells, Proceedings of the 8th International Symposium on Corrosion in the Pulp & Paper
Industry, Stockholm, pp. 12-19 (1995).
21. Kiessling, L., Anodic Protection, AF-IPK Fibreline Conference, Stockholm (1995).
22. Hovland, H., Reduction of Corrosion Rates in a Continuous Digester after One Year with Anodic Protection,
AF-IPK Fibreline Conference, Stockholm (1996).
23. Wensley, A., Corrosion in Batch and Continuous Digesters, Proceedings of the 9th International Symposium on
Corrosion in the Pulp & Paper Industry, Ottawa, pp. 27-37 (1998).
24. Singbeil, D. and Tromans, D., Stress corrosion Cracking of Mild Steel in Alkaline Sulfide Solutions,
Proceedings of the 3rd International Symposium on Corrosion in the Pulp & Paper Industry, Atlanta, pp. 40-46
(1980).
25. Yeske, R.A. and Guzi, C.E., In-situ Studies of Stress Corrosion Cracking in Continuous Digesters, TAPPI J.
Vol. 69 No. 5, pp. 104-108 (1986).
26. Crowe, D.C., Stress Corrosion Cracking of Carbon Steel in Kraft Digester Liquors, Proceedings of the 6th
International Symposium on Corrosion in the Pulp & Paper Industry, Helsinki, pp. 35-47 (1989).
27. Saario, T., Development and Applications of the Contact Electric Resistance Technique, Report TKK-V-A13,
Helsinki University of Technology (1995).
28. Boulton, L.H., et al, The Effects of Anodic Protection on Carbon Steel Corrosion Rates in a Continuous Kraft
Digester as Measured by TLA, Proceedings of the 6th International Symposium on Corrosion in the Pulp &
Paper Industry, Helsinki, pp. 67-83 (1989).
29. Wallace, G. and Boulton, L.H., TLA Monitoring of an Anodic Protection System, Appita, Vol. 45 No. 2, pp.
78-82 (1992).

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100

50
Potential, mV vs Mo
0

-50

-100

-150

-200

-250
0 20 40 60 80 100 120 140 160
Corrosion Rate, mils per year

Figure 1. Corrosion polarization curve for carbon steel in a softwood (pine) continuous digester
extraction liquor at 338ºF (170ºC).

100

50
Potential, mV vs Mo

-50

-100

-150

-200

-250
0 20 40 60 80 100 120
Corrosion rate, mpy

Figure 2. Corrosion polarization curve for carbon steel in mixed white and black liquors (3:1
volume ratio) at 338ºF (170ºC).

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Figure 3. Entry for cathode buss bars beneath the central pipe shroud.

Figure 4. Buss bars for linear cathodes mounted on stand-offs along the central pipe.

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Figure 5. Tee-type linear cathode.

Drip Pan

Figure 6. Carbon steel shield to protect the central pipe from damage.

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Figure 7. Vertical wall-mounted cathodes.

Figure 8. Horizontal wall-mounted cathode.

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Figure 9. Closer view of wall-mounted cathode.

Figure 10. Rod-type cathode installed below a screen header.

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Figure 11. Buss bar for rod-type cathode.

Figure 12. Rod-type cathode installed behind blank plates (temporarily removed).

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Figure 13. Blank plate cathode.

Figure 14. Area surrounding a blank plate cathode.

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Figure 15. Pipe cathode located above the internal cone.

Figure 16. Cage or "crown" type cathode located above the internal cone.

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Figure 17. External view of a retractable reference electrode probe.

Figure 18. Internal view of a molybdenum reference electrode.

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Figure 19. Location ground free of SCC for monitoring of an anodic protection system.

Figure 20. Thin-layer activation coupon installed on the inside wall of a digester.

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1.6 0.4 0.3 0.7 0.6 3.2 0.3 0.4 0.3

Figure 21. Sixteen-point UT grid (measurements taken after 1 year of anodic protection).

Figure 22. Sixteen-point UT grid (measurements taken after 2 years of anodic protection).

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Figure 23. Break in a linear cathode.

Figure 24. Break in a rod-type cathode.

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Figure 25. Central pipe damage from high current flow where the PTFE insulation ends.

Figure 26. Crack in a weld in a wall-mounted cathode element.

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Figure 27. Scaling of a linear cathode.

Figure 28. Zinc-rich scale on the digester wall between vertical cathodes (after acid cleaning).

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350

300

Corrosion Rate, mils per year 250

200 Active
Passive
150

100

50

0
120 130 140 150 160 170 180
Temperature ºC

Figure 29. Increase in active and passive corrosion rates with increasing temperature in extraction
liquor from a northeastern digester pulping softwood.

400

350
Corrosion Rate, mils per year

300

250 Active

200 Passive

150

100

50

0
150 160 170 180 190
Temperature, ºC

Figure 30. Increase in active and passive corrosion rates with increasing temperature in extraction
liquor from a northwestern digester pulping softwood.

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