Flow-Accelerated Corrosion: A Critical Issue Revisited

07/01/2007

By Brad Buecker, Contributing Editor

Sudden failures of high-pressure, high-temperature feedwater piping by flow-accelerated-corrosion
(FAC) continue to claim lives in the utility industry, which is, of course, the ultimate catastrophe. The
conventional condensate/feedwater treatment of oxygen-scavenging/pH-conditioning, used for many
years by utilities throughout the country, has proven to be the culprit. The reducing environment
generated by this chemistry will induce FAC, where gradual thinning of pipe or tube walls in a very
localized area leads to sudden and catastrophic failure. The following discussion of FAC, and methods
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to prevent it, is taken from a seminar given at the 2007 Electric Utility Chemistry Workshop.

Fundamental Feedwater Chemistry

Mild steel is the universal material for condensate/feedwater piping as it offers excellent strength at
economic value. However, iron is just one of several metals that exhibit amphoteric behavior, in that the
corrosion rate is minimized within a narrow pH range and increases as conditions move either to acidic
or strongly alkaline territory. Figure 1 outlines the general corrosion pattern for iron and shows that in
acid or alkaline conditions, corrosion rates can be quite significant.

Click here to enlarge image

The safe range for condensate/feedwater systems is much more restricted than that shown on the
graph and is typically held between the pH values of 9.0 and 9.6.
When a steam generator is placed on line, and where subsequent oxygen concentrations in the
condensate and feedwater remain at levels within a low part-per-billion (ppb) concentration, steel
develops a protective coating of iron oxide known as magnetite (Fe3O4). This mechanism also occurs on
boiler waterwall tubes.
Similarly, copper alloys develop a protective layer of cuprous oxide (Cu2O). Formation of protective
oxide layers is a very important concept.
Optimizing chemistry in the condensate/feedwater system is critical for two reasons. First, to prevent
corrosion of the piping and heater tubes themselves, and second to minimize the formation and
transport of corrosion products that travel to the boiler and beyond. The two primary corrosion control

issues in condensate/feedwater systems involve pH and oxygen. It is these control issues that influence
FAC.
As outlined above, excursions of pH outside a relatively narrow range induce corrosion, most notably in
iron-based materials. Feedwater piping and heat exchanger tubes exhibit minimal corrosion at a mildly
alkaline pH. For a feedwater system of all steel metallurgy the optimum pH range is 9.2 to 9.6. (These
conditions are different in oxygenated treatment systems, as will be described in a later section.)
Corrosion control in mixed-metallurgy systems is more complicated. Admiralty brass exhibits minimum
corrosion within a pH range of 8.5 to 9. Copper-nickel alloys, particularly the 90-10 material, are most
stable around a pH of 9.3. So the question becomes, What is the best pH for a system containing
carbon-steel piping and copper-alloy heat exchanger tubes? In years past, a commonly recommended
pH range for mixed-metallurgy systems was 8.8 to 9.1, but this recommendation was recently raised to
9.0 to 9.3.
Ammonia or organic amines are the pH-conditioning chemicals of choice. Amines decompose to
produce ammonia in feedwater. However, in high-pressure utility boilers where the steam is quite pure,
decomposition of amines can potentially introduce unwanted organic acids and CO2 to the turbine. For
this reason, some experts recommend ammonia as the best pH-conditioning chemical.

Dissolved Oxygen Corrosion and Treatment Issues

Uncontrolled oxygen ingress into a steam generator can cause problems, as Figure 2 illustrates.

Figure 2 Oxygen pitting of an economizer tube

Photo courtesy of Mel Esmacher, GE Water Systems.

Click here to enlarge image

So, virtually all conventional utility steam generators have been designed with condenser air removal
compartments, deaerators in the condensate/feedwater system and chemical feed systems to inject not
only the pH-conditioner but also an oxygen scavenger/metal passivator into the feedwater. The latter
constitutes the primary difficulty.
Into the 1980s (in the United States at least), conventional wisdom called for complete removal of
oxygen from feedwater. It was thought-incorrectly as we shall see-that the total absence of oxygen was
best for corrosion control in the feedwater network. Thus, mechanical oxygen removal was
supplemented with chemical treatment. The workhorse for many years was hydrazine (N2H4), which
reacts with oxygen as follows:
Hydrazine proved advantageous because it does not add any dissolved solids to the feedwater, it reacts
with oxygen in a one-to-one weight ratio and it is supplied in liquid form at 35 percent concentration.
A primary benefit of hydrazine is that it will passivate oxidized areas of piping and tube materials as
follows:

Hydrazine residuals were typically maintained at relatively low levels of perhaps 20 to 100 ppb.
Hydrazine or its safer alternatives are now no longer recommended unless the feedwater system
includes copper-alloy heater tubes.

Flow Accelerated Corrosion

The use of a pH-conditioner and oxygen scavenger-particularly the latter-constitutes what is known as
an all-volatile treatment (reducing) AVT(R) program. In the 1980s and 1990s, researchers began to
discover that AVT(R) was the cause of previously unspecified problems. Most notable is the dissolution
of magnetite at a temperature range and chemical conditions common to the feedwater network.
A special note should be made that pH in high-purity water, like condensate and feedwater, is a direct
function of the ammonia concentration. It is the lower pH, at low ammonia concentrations in a reducing
environment, which is responsible for magnetite dissolution. This explains why corrosion can be much
higher at an NH3 concentration of 0.1 ppm than in any other case. (Figure 3.) The ammonia does not
attack the magnetite directly.

Click here to enlarge image

While it is well documented that dissolved oxygen can induce serious boiler and feedwater corrosion,
especially during unit shutdown, the complete removal of oxygen during normal operation can be very
troublesome. FAC develops at flow disturbances and direction changes; for example, feedwater and
economizer elbows, reducers, and tees, steam attemperating lines: essentially all flow-disturbed areas
touched continuously by feedwater, in strongly reducing environments.

To understand the problem, first consider the nature of the protective magnetite (Fe3O4) layer. The
compound is actually a joint mixture of FeO and Fe2O3 that often exhibits a rippled pattern. Iron exists in
a +2 (ferrous) oxidation state in FeO and +3 (ferric) in Fe2O3. The ferrous ions are those that are
susceptible to FAC and in affected zones the ions migrate out of the magnetite matrix. The reducing
environment continually regenerates ferrous iron, whose constant migration weakens the wall structure
and eventually reduces pipe strength to the point of sudden failure. From a straight-on view, the
corrosion has the texture of an orange peel. Figure 4 illustrates a side-view of FAC.

Figure 4 Feedwater pipe thinned by FAC.

Photo courtesy of Mel Esmacher, GE Water Systems

Click here to enlarge image

As is clearly evident, the pipe wall gradually thins. Catastrophic failures occur when the affected area
can no longer withstand the inside pressure. Sudden ruptures of high-temperature feedwater lines have
killed approximately 10 utility workers at several stations in the last decade or so. It is imperative that
potentially affected areas be checked ultrasonically for wall thinning, particularly at plants that once used
or continue to use AVT(R).
FAC has also been a problem in heat recovery steam generator (HRSG) waterwall tubes that have
many tight-radius elbows. The low-pressure circuits of HRSGs often operate near the temperature of
highest corrosion potential (Figure 3), which exacerbates FAC potential. A particular difficulty with
HRSGs is that the two or three semi-independent waterwall circuits make chemistry control rather
difficult. One extra-cost solution for controlling FAC in HRSGs in the design phase is to specify tube
material, at least in elbows, of 1.25 percent chrome steel. This material is resistant to attack.

FAC Prevention
Often, chemical methods are effective for controlling FAC. Sometimes only mechanical means are
suitable.
Oxygenated treatment (OT) is a feedwater treatment that also serves to protect the boiler. In an OT
program, oxygen is deliberately introduced to the condensate and feedwater system. Two variations of
oxygenated treatment are most popular. In the first, oxygen is injected alone without any pH-

conditioning chemicals. This program is known as neutral water treatment (NWT). More often, ammonia
is injected for pH control. This is known as combined water treatment (CWT).
OT was developed in Germany some 30 years ago for replacement of AVT(R) in once-through steam
generating units. The program was adopted by other European utilities and has gained large
acceptance at once-through utilities in the U.S. The treatment requires the controlled injection of oxygen
into the condensate/feedwater system. Common injection points are just after the condensate polisher
and again at the deaerator outlet. In CWT programs, which are most common in the U.S., oxygen is
dosed to maintain a 30 to 150 ppb residual. Ammonia is added to raise the pH within a range of 8.0 to
8.5. Typically, 20 to 70 ppb of ammonia will produce this pH.
The chemistry of oxygenated treatment is interesting and explains why the program has become
popular. In conventional AVT(R) programs, it may be difficult to keep dissolved/suspended iron
concentrations in the feedwater below 2 ppb and excursions above 10 ppb are not uncommon. Iron
particulates are the primary product that carries over to the boiler. With oxygen injection however, the
base layer of magnetite becomes covered and interspersed with an even tighter film of ferric oxide
hydrate (FeOOH). This compact layer is more stable than magnetite and releases very little dissolved
iron or suspended iron-oxide particles to the fluid. A properly orchestrated OT program should lower
feedwater iron concentrations to less than 1 ppb.
The keys to an OT program are controlled oxygen feed and high-purity condensate, where cation
conductivity can be maintained 0.15 S/cm. Such parameters are typical in once-through units
anyway, as makeup and feedwater must be highly pure because contaminants would enter the steam
directly. Pure feedwater in once-through units is usually a given, as these steam generating systems are
always equipped with condensate polishers. OT has also been applied to a number of drum units
throughout the world, as it is a condensate/feedwater treatment and thus can function regardless of
boiler design. OT cannot be used in systems that contain copper-alloy feedwater heater tubes, as
copper corrosion would be much too severe.
An issue that has come to light regarding OT programs is that of two-phase FAC. At points in the steam
generating system, particularly deaerators and feedwater heater drains, zones of physical separation
between water and steam will develop. Chemicals in the feed solution that prevent FAC may settle in
one phase leaving the other without protection. Thus, FAC can occur when all chemistry parameters are
seemingly in acceptable ranges. Two-phase FAC is virtually impossible to control chemically. The issue
can be addressed mechanically by utilizing 1.25-chrome steel in affected areas, as was mentioned
earlier for HRSG elbows.
An offshoot of OT is a program developed by EPRI known as all-volatile treatment (oxidizing), or
AVT(O). The idea continues to be establishing a FeOOH layer on the feedwater piping, but by a less
intensive mechanism. What the researchers found is that in condensate/feedwater networks where
condenser air in-leakage is minor and where condensate dissolved oxygen levels stay at or below 10
ppb, discontinued feed of the oxygen scavenger allows the FeOOH protective layer to form naturally. As
with OT, this program is only for systems with all-ferrous metallurgy. One difference from OT, however,
is that the pH should be maintained within a range of 9.2 to 9.6. An operating guideline is cation
conductivity 0.2 S/cm. Excursions in dissolved oxygen concentration and cation conductivityparticularly the former-indicate excess air in-leakage within the condenser. Increased air in-leakage also
introduces excess carbon dioxide, which influences corrosion. Thus, for a unit on AVT(O) any air inleakage difficulties that raise condensate dissolved oxygen levels much above a mid-teen ppb
concentration should be investigated and corrected as quickly as possible.
For mixed-metallurgy systems, OT and AVT(O) are not acceptable, as they would initiate excessive
copper corrosion. However, operation with complete absence of oxygen leads to FAC. So, the correct
program is to feed an oxygen scavenger, but at reduced concentrations to minimize FAC. This can be
quite difficult when relying upon standard dissolved oxygen and oxygen scavenger analyses. The
technique of oxidation-reduction potential (ORP) monitoring is becoming popular for mixed-metallurgy
condensate/feedwater chemistry. In short, on-line ORP monitors measure the electrochemical potential
of the solution versus a standard electrode, most commonly silver/silver chloride.
A general rule-of-thumb is that the oxygen scavenger should be fed to maintain an ORP within a range
of -350 to -300 millivolts (mV). This corresponds to a range of -150 to -100 mV for a standard hydrogen
electrode (SHE). However, chemists have found that this guideline should not be considered an
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absolute. A better plan is to set up comprehensive tests that include dissolved iron and copper
analyses, and coordinate the optimum ORP range with minimized copper and iron concentrations.

The important point is that plant personnel establish chemistry to prevent severe copper corrosion but
also to prevent FAC. Feedwater heater tubes can be replaced. Human life cannot.