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International Journal of Pressure Vessels and Piping 77 (2000) 85±90

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Flow-accelerated corrosion of pressure vessels in fossil plants


R.B. Dooley*, V.K. Chexal
EPRI 3412 Hillview Avenue, Palo Alto, CA 94304, USA

Abstract
Flow-accelerated corrosion (FAC) is a phenomenon that results in metal loss from piping, vessels and equipment made of carbon steel. It
occurs under conditions of ¯ow, geometry and material, which are common in high-energy piping and tubing in nuclear, fossil and industrial
power plants. Substantial progress has been made towards understanding the mechanism and in preventing FAC. This paper provides a
sprinkling of that knowledge with particular emphasis for fossil and industrial plants. q 2000 Elsevier Science Ltd. All rights reserved.
Keywords: Flow-accelerated corrosion; Feedwater; Hydrazine

1. Introduction EPRI, Electricite de France, and Kraftwerk Union, now a


part of Siemens.
Flow-accelerated corrosion (FAC) causes wall thinning Flow-accelerated corrosion is a process whereby the
(metal loss) of carbon steel piping, tubing and vessels normally protective oxide layer on carbon or low-alloy
exposed to ¯owing water or wet steam. If undetected, the steel dissolves into a stream of ¯owing water or a water±
degraded component can suddenly rupture, releasing high steam mixture. The oxide layer becomes thinner and less
temperature steam and water into neighboring plant areas. protective, and the corrosion rate increases. Eventually a
The escaping ¯uids can injure plant workers, sometimes steady state is reached were the corrosion and dissolution
severely, and damage nearby equipment. Over the years, rates are equal and stable corrosion rates are maintained. In
FAC has caused hundreds of piping and equipment failures some areas, the oxide layer may be so thin as to expose an
in all types of fossil, industrial steam, and nuclear power apparently bare metal surface. More commonly, however,
plants. However, often the cause of the failure was not the corroded surface exhibits a black color typical of
known by the plant owner, or if known, was not reported. magnetite.
Additionally, the power industry did not fully understand Damage caused by ¯ow-accelerated corrosion can be
the conditions under which FAC occurred, where plants characterized as a general reduction of wall thickness
should look to ®nd it, or how to best control it when it rather than a local attack, such as pitting or cracking.
was found. Although FAC occurs over a wide area within a given
This changed in 1986. On 9th December of that year, an ®tting, it is localized in the sense that it frequently
elbow in the condensate system ruptured at the Surry occurs over a limited area of piping ®tting due to
Nuclear Power Station. The failure caused four fatalities local high areas of turbulence. In this content, ªlocalizedº
and tens of millions of dollars in repair costs and lost may mean within several feet (,1 m) of the ®tting or region
revenue. FAC was found to be the cause of the failure. of turbulence. However, if one ®tting is found to be thinned,
Because of the deaths involved and the high degree of regu- then most likely there will be others that have also lost
lation applied to the nuclear power plants, a comprehensive material.
overall approach was needed. An intensive international A thinned component will typically fail due to overstress
cooperative effort was initiated to understand the parameters from operating pressure, or abrupt changes in conditions
which affect FAC. The strategy was that understanding FAC such as water hammer, and start-up loading. Large ®ttings
would allow the development of technology to help plants may rupture suddenly rather than provide warning of their
®nd damage before failure occurs, and the measures to degraded condition by ®rst leaking.
control it. The major parties in this cooperation were FAC occurs under both single and two-phase ¯ow condi-
tions. Because water is necessary in order to remove the
oxide layer, FAC does not occur in lines transporting dry
* Corresponding author. or superheated steam.
0308-0161/00/$ - see front matter q 2000 Elsevier Science Ltd. All rights reserved.
PII: S 0308-016 1(99)00087-3
86 R.B. Dooley, V.K. Chexal / International Journal of Pressure Vessels and Piping 77 (2000) 85±90

Two-phase FAC has been recognized as a worldwide Table 2


problem since about 1970. Since the mid-1980s, single- Most important fossil plant areas experiencing FAC (results from 1997
survey of 63 utilities [2])
phase FAC has been acknowledged as a major problem in
the balance-of-plant and secondary piping of US and foreign Piping around BFP
nuclear and fossil plants. The remainder of this paper Tubesheet/tubes in HP Heaters
concentrates only on single-phase FAC. Heater Drain Lines
Economizer Inlet Header Tubing
Piping to Economizer Header
1.1. Some key ®eld history
Tubesheet/tubes in LP Heaters
Deaerator shell
The technology and information developed since the Heat recovery steam generator
Surry failure have greatly reduced the incidence of FAC (HRSG) tubing
failures, particularly in the nuclear plants which have the
greatest level of implementation of the technology. Never-
reducing conditions (below 2300 mV ORP or redox
theless, instances of severe thinning, leaks, and ruptures
potential).
have still occurred. Some of the most signi®cant examples
² The feedwater oxygen levels were very low (,1 ppb).
of recent failures in nuclear plants are summarized in Table
² The heater drains are susceptible areas in plants with both
1 [1].
all-ferrous and mixed feedwater metallurgies.
Failures in fossil and industrial steam plants have not
historically been as well documented, because the plants FAC has also been commonly observed in industrial, pulp
are not as tightly regulated and because FAC has not been and paper, and chemical and petroleum plants. Most
properly identi®ed. However, as a result of recent fatalities recently it has quickly become the most important failure
at a fossil plant, the topic now has a higher priority. A recent mechanism in the heat recovery steam generators (HRSG)
survey [2] of 63 utilities ranked the most important areas of combined cycle units.
where FAC has been identi®ed in fossil plants (Table 2);
40% of the utilities had found FAC. Table 3 provides a 1.2. Key features
summary of recent (from 1982) serious fossil plant failures,
resulting in bursts, extensive plant damage, or fatalities, The FAC process produces a different surface appearance
known to be caused by FAC. for single-phase ¯ow than it does for two-phase ¯ow:
Table 3 indicates that there are a number of very impor- ² For single-phase ¯ow (liquid only): when the corrosion
tant and signi®cant features which are common to these rate is high, the metal surface is often characterized by
FAC incidents: overlapping ªhorseshoe pitsº that give a scalloped or
² The feedwater failures all occurred in the high-pressure orange peel appearance. The scalloped appearance
portions of the system up to and including the economi- usually occurs in large diameter piping where a signi®-
zer inlet header tubes. This means that the temperature cant loss of thickness has occurred.
range up to 280±3008C in fossil plants is susceptible to ² For two-phase ¯ow, the well-known ªtiger stripedº
failure. This range is above the temperature at which appearance is often observed in large pipes. The black
maximum FAC occurs in laboratory experiments and part of the surface is the corroded area. It is covered with
above the temperature where magnetite solubility is a very thin oxide ®lm. The blue to red colored part of the
maximum. surface is protected by a thick oxide ®lm. This appear-
² Each system (A±W) had stainless steel low- and high- ance is thought to be caused by a very disturbed, turbu-
pressure feedwater heaters. lent water ®lm ¯ow along the pipe wall.
² The feedwater in each case was treated with both When FAC is occurring, the oxide ®lm present on the
ammonia and a reducing agent (usually hydrazine) surface can be very thin (less than 1 mm). Under these
which means the feedwater was operating under conditions, the ®lm is nearly transparent and the surface
Table 1
has a metallic appearance. However, if the ®lm thickness
Signi®cant FAC failures in nuclear power plants since 1989 increases, the surface appears black.

Plant Date Location


2. Mechanism of FAC
S.M. de Garona (Spain) December 1989 Feedwater
Loviisa Unit 1 (Finland) May 1990 Feedwater
Millstone Unit 3 December 1990 Heater drain The phenomenon of FAC is well-understood [1]. It is a
Millstone Unit 2 November 1991 Reheater drain process whereby the normally protective magnetite (Fe3O4)
Almaraz Unit 1 (Spain) December 1991 Extraction steam layer on carbon steel dissolves in a stream of ¯owing water
Loviisa Unit 2 (Finland) February 1993 Feedwater or wet steam. This process reduces or eliminates the oxide
Sequoyah Unit 2 March 1993 Extraction steam
layer and leads to a rapid removal of the base material until,
Fort Calhoun April 1997 Extraction steam
in the worst cases, the pipe or tube bursts. The FAC process
R.B. Dooley, V.K. Chexal / International Journal of Pressure Vessels and Piping 77 (2000) 85±90 87

Table 3
Serious FAC failures in fossil plants from 1982 [3]

Plant Location Temp. Feedwater treatment pH Oxygen Feedwater heaters

A Elbow downstream of BF 3608F 1828C NH3/N2H4/Carbo-hydrazide Low , 1 ppb All-stainless


booster pump
B Elbow near El at RT plug NH3/N2H4 8.80±9.20 Low , 1 ppb
C Downstream of boiler stop 4568F 2368C NH3/N2H4 8.75 Very low , 1 ppb All-stainless
valve near El
D±W El tubes Final feedwater NH3/N2H4 9.00±9.40 Very low , 1 ppb All-stainless
Numerous Drain lines Low Very low , 1 ppb All-ferrous & mixed

can become rapid: wall thinning rates as high as 3 mm/year This dissolution process is controlled by the oxidizing/
have occurred. The rate of metal loss depends on a complex reducing potential (ORP) of the water. Basically the more
interplay of many parameters including the feedwater chem- reducing the feedwater, the higher is the dissolution and
istry, the material composition, other materials in the feed- level of corrosion products measured in the feedwater.
water systems, and the ¯uid hydrodynamics. Under alkaline, deoxygenated (reducing) conditions the
The FAC process is an extension of the generalized corro- primary reaction of iron dissolution is inhibited by increas-
sion process of carbon steel in stagnant water. The major ing pH or by decreasing the reducing environment (i.e. ORP
difference is the effect of the water ¯ow at the oxide±solu- becoming more positive). This causes a reduction of the
tion interface. FAC can be divided into coupled processes ferrous ion (Fe 21 and Fe(OH) 1) concentration.
that take into account the presence of the porous magnetite The solubility of ferrous hydroxide (Fe(OH)2) rises with
layer on the steel surface up to about 3008C (Fig. 1): increasing temperature to a maximum at around 1508C, then
decreases with a steep drop to the solubility of magnetite
² The ®rst process produces soluble ferrous ions at the between 200 and 2508C.
oxide±water interface and can be separated into three
simultaneous actions: 2.1. Factors in¯uencing FAC
± metal oxidation occurs at the iron±magnetite interface
The scienti®c basis of ¯ow-accelerated corrosion together
in water with a reducing potential (ORP , 0 mV);
with laboratory studies do not provide the utility engineer
± the ferrous species diffuse from the iron surface to the
with the tools needed to solve real plant problems. To meet
main water ¯ow through the porous oxide layer;
this need, a number of models have been developed to
± the magnetite oxide layer at the oxide±water interface
predict the rate of FAC [4±7]. There are several key para-
dissolves by a reductive process that is promoted by
meters which affect the rate of FAC; these are discussed
the presence of hydrogen.
below.
² The second process involves the transfer of the ferrous
Because the FAC process as described above involves at
ions into the bulk water across the boundary layer. The
least two steps (soluble iron production at the oxide/water
concentration of ferrous ions in the bulk water is very low
interface and transfer of the corrosion products to the bulk
compared to the concentration of ferrous ions at the oxide
solution across the diffusion boundary layer), it is necessary
solution interface. The corrosion rate (FAC) increases if
to consider both the corrosion processes (steel oxidation,
there is an increase of water ¯ow past the oxide±water
oxide dissolution, charge transfer, etc.) and mass transfer.
interface.
The role of the major in¯uencing factors can be classi®ed as
follows:
² Hydrodynamics factors, i.e. ¯ow velocity, pipe rough-
ness, geometry of the ¯ow path, steam quality or void
fraction for two-phase ¯ows.
² Environmental factors, i.e. temperature, pH, reducing
agent and oxygen concentration, oxidizing±reducing
potential, water impurities.
² Metallurgical factors, mainly the chemical composition
of the steel. The most bene®cial element has been deter-
mined to be chromium. An alloy with a nominal chro-
mium content as low as 1% will have low or negligible
Fig. 1. Schematic representation of oxide formed on iron-based feedwater FAC rates. There is evidence that even lower amounts of
surfaces during operation with deoxygenated all-volatile treatment (AVT) chromium (as low as 0.1%) may signi®cantly reduce
under reducing conditions (ORP p 0 mV). FAC in single-phase systems.
88 R.B. Dooley, V.K. Chexal / International Journal of Pressure Vessels and Piping 77 (2000) 85±90

hydrazine which does not react with oxygen thermally


decomposes to form ammonia. Recent information indicates
that in the 0±150 ppb range of hydrazine level, the FAC rate
increases with increasing hydrazine level as the oxidizing±
reducing potential (ORP) becomes more reducing. The
decrease in potential in this range leads to greater dissolu-
tion of the surface magnetite (Fe3O4) and thus to an increase
in the rate of FAC. Above the 150 ppb hydrazine level, the
potential is lowered signi®cantly enough that it leads to
slower kinetics. Thus, any further increase in the hydrazine
level leads to a decrease in the FAC rate. Therefore, a plot of
FAC rate versus hydrazine level is a bell-shaped curve with
a peak at 150 ppb.
Theoretical considerations show that FAC should be
proportional to the concentration of hydrazine to the 1/6
power, with recent laboratory data indicating that this
does not continue above 150 ppb of hydrazine or below
20 ppb.
Hydrazine is commonly added to the feedwater of the
PWR secondary circuit to keep feedwater oxygen levels
lower than 5 ppb. Hydrazine is used to maintain a reducing
environment in the feedtrain and the steam generator as a
scavenger of residual oxygen and as a pH-conditioning
agent as it decomposes to ammonia. However, to achieve
a pH level of 9.5, a concentration of about 50 ppm is neces-
sary, which is not feasible for plant applications.
Fig. 2. Fossil Plant FAC program Road Map. In fossil and industrial plants, hydrazine, if used, is added
to the feedwater immediately after the condensate polishers
or the condensate extraction pump. It is an absolute neces-
2.2. Effect of water chemistry and oxidizing reducing sity for mixed-metallurgy systems to protect the copper-
potential based feedwater heaters. However, in all-ferrous systems,
it can be eliminated in high purity …,0:3mS=cm† feedwater.
It has been frequently observed in power plants, espe- In both cases, it is not optimum practice to use the hydrazine
cially fossil and industrial plants, that the occurrence of to both alkalize the cycle and to deoxygenate.
FAC damage is very dependent on the environmental In the past, hydrazine concentrations of about 20 ppb
factors: were used to control the oxygen in the feedtrain. Recently,
(a) pH at temperature US utilities have begun adding larger amounts of hydrazine
(b) ORP which provides an indication of the balance in nuclear plants to maintain a strongly reducing environ-
between reducing agents (such as hydrazine) and oxygen. ment within the steam generators. Hydrazine concentrations
Knowledge of the level of one or the other may not be of approximately 100 ppb are used for this purpose;
suf®cient to indicate the susceptibility to FAC. Thus ORP however some utilities, outside the US have used levels
is becoming the indicator of choice. up to 600 ppb.
It should be noted that ORP, also called redox, utilizes a (c) Temperature: Temperature is an important variable
platinum measuring electrode with a Ag/AgCl reference affecting the FAC of carbon steels and low alloyed steels.
electrode to measure the potential. This measurement is The phenomenon usually occurs between 100 and 2808C.
made at ambient temperature with a sampling system in a Temperature in¯uences the rates of the oxidation and reduc-
similar manner to pH and dissolved oxygen. ORP is not a tion reactions. It also in¯uences the values of the thermo-
measurement of corrosion potential, but is an excellent para- physical properties. FAC as a function of temperature is a
meter to determine the relative corrosion potential for a dome-shaped curve with a peak near 1508C for a constant
feedwater system [12]. mass ¯ow rate, steam quality, and water chemistry. Above
Hydrazine (and alternatives) is a reducing agent added to and below the peak temperature, FAC wear rates tend to
the feedwater/condensate system in a power plant. It main- decrease. Note, however, that the peak temperature is a
tains a reducing environment in the steam generators function of the main variables affecting the FAC process;
(nuclear plants) and in the feedtrain. Hydrazine is unique but in practice the major failures have occurred in fossil and
in the chemical species in that it is reactive and unstable. It industrial plants at temperatures above this laboratory
reacts with oxygen forming water and nitrogen. Most of the derived maximum (Table 3).
R.B. Dooley, V.K. Chexal / International Journal of Pressure Vessels and Piping 77 (2000) 85±90 89

² Type C is oxygenated treatment (OT) using only ammo-


nia and oxygen.

The major difference in terms of FAC between Type A,


and Types B and C chemistries is that Type A provides a
reducing environment (ORP , 0 mV), whereas Types B
and C result in an oxidizing environment (ORP . 0 mV).
Under the reducing conditions of Type A feedwater
chemistry, the type of oxide (magnetite) which grows on
carbon steel surfaces up to about 3008C is shown schema-
tically in Fig. 1.
For ªnormalº Type A chemistry, the ORP is typically less
Fig. 3. Schematic representation of oxide formed on iron-based feedwater than 2300 mV, and the level of feedwater corrosion
surfaces during operation with oxidizing feedwater. products (measured at the economizer inlet) will be less
than 10 ppb. Most fossil plants can easily achieve 5 ppb;
3. Application of mechanism to FAC control this situation is regarded as ªnormalº and not of major
concern from an FAC viewpoint.
A comprehensive FAC program can help a utility/opera- For a unit with Type A chemistry and high rates of FAC,
tor avoid the large costs that accompany pipe/tube failure the ORP will also be less than 2300 mV; but because of the
and forced outages. The aspects of such programs for local ¯ow hydrodynamics, the total corrosion/dissolution
nuclear [8] and fossil/industrial [9] plants have been devel- process is faster. The result is more dissolution and oxide
oped. For example, Fig. 2 shows the two pronged approach particle entrainment into the ¯ow. In the worst cases, FAC
for controlling FAC in fossil plants. will be so fast that there is only a very thin layer of Fe3O4 on
The following are some of the activities in any FAC the surface. Importantly, the level of feedwater corrosion
inspection, evaluation, and mitigation program: products (measured at the economizer inlet) can be much
more than 10 ppb.
² identifying susceptible systems
Types B and C chemistries produce a completely different
² developing computer models of susceptible lines [4±7]
situation. Fig. 3 shows the typical oxide structure that forms
² selecting locations for inspection
² inspection planning [10] on carbon steel surfaces up to about 280±3008C under
oxidizing feedwater environments. Here, the surface is
² preparing for inspection
covered by a layer of ferric oxide hydrate (FeOOH),
² conducting inspections [11]
which also permeates down the pores of the magnetite.
² evaluating inspection data
So under the conditions of B and C chemistries the ORP
² qualifying the components for continued use
is greater than zero; conditions which favor the growth of
² repair or replacing thinned components
FeOOH. This formation does two things: (i) it reduces the
² optimizing feedwater chemistry.
overall corrosion rate because the diffusion (or access) of
oxygen to the base material is restricted (or reduced), and
3.1. Control of feedwater chemistry in fossil/industrial (ii) it reduces the solubility of the surface oxide layers.
plants Thus, from an FAC perspective, this surface FeOOH layer
dissolves much slower (at least two orders of magnitude
Unlike in most nuclear plants where the feedwater has to
slower) than magnetite into the ¯owing feedwater, under
be reducing to protect the steam generator, the feedwater
exactly the same hydrodynamic conditions that existed
chemistry can be changed/optimized in some fossil/indus-
previously with Type A chemistry. The overall result is
trial plants. These cycle chemistry activities have the proven
that the measured feedwater corrosion products can be
capability of reducing the generation of feedwater corrosion
much less than 1 ppb and FAC is minimal.
products, and reducing and nearly eliminating FAC depend-
There are essentially two types of all-ferrous systems:
ing on the system metallurgy and the feedwater chemistry
those containing only carbon steel in the tubing and piping,
adopted.
and those containing stainless steel tubing and carbon steel
For both all-ferrous and mixed-metallurgy feedwater
piping. As can be seen clearly in Table 3 most of the serious
systems, the feedwater treatment always needs to be all-
FAC failures in fossil plants have occurred when all the
volatile. Currently there are three types of treatment:
tubing (both LP and HP) is stainless steel, and the chemistry
² Type A is classical all-volatile treatment (AVT) using is Type A (normal AVT with hydrazine producing
ammonia and a reducing agent or oxygen scavenger ORP , 0 mV). This implies that the reducing environment
(such as hydrazine). is more severe in the HP feedwater when the tubing is stain-
² Type B is the same as Type A minus the reducing agent, less as compared to when the tubing is carbon steel or
called ªNew AVTº. copper-based.
90 R.B. Dooley, V.K. Chexal / International Journal of Pressure Vessels and Piping 77 (2000) 85±90

Table 4
Comparison of normal cycle chemistry limits at the economizer inlet for AVT feedwater and oxygenated treatments (values in parentheses represent the
achievable and desirable levels)

Cycle chemistry parameter AVT (mixed metallurgy) AVT (all-ferrous) Oxygenated treatment (OT) (all-ferrous)

PH 8.8±9.1 9.2±9.6 8.0±8.5 a


9.0±9.5 b
Ammonia, NH3 ppm 0.15±0.4 0.5±2.0 0.02±0.07 a
0.3±1.5 b
Cation conductivity (mS/cm) , 0.2 , 0.2 (,0.15) , 0.15 (,0.1)
Fe, ppb , 10 (,5) , 5 (,2) , 5 (,1)
Cu, ppb , 2 (,2)
Oxygen, ppb , 5 (,2) 1±10 30±150 a
30±50 b
ORP c, mV p0 0±80 . 100
a
For once-through units.
b
For drum units.
c
Oxidizing±reducing potential (with respect to Pt electrode vs Ag/AgCl).

Mixed-metallurgy systems can only use Type A feed- FAC programs which will ensure an adequate level of
water chemistry which maintains a reducing environment safety.
under all operating regimes to protect the copper based
tubing. This means that the carbon steel interconnecting
piping and the economizer inlet tubing must also be exposed
References
to the same reducing environment. Observation of Table 3
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fossil plant mixed-metallurgy systems; however wall loss in power plants. EPRI TR-106611R1, July 1998.
associated with FAC has been observed in fossil plants, [2] Dooley RB, Mathews J, editors. Fifth International Cycle Chemistry
and serious failures have occurred in nuclear plants with Conference. EPRI TR-108469, October 1997.
mixed-metallurgy systems; thus the carbon steel compo- [3] Dooley RB, Mathews J. The current state of cycle chemistry for fossil
plants. Fifth International Cycle Chemistry Conference. EPRI TR-
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108469, October 1997.
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