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Corrosion and tube failure caused by water chemistry
Metals obtained from their oxide ores will tend to revert to that state. However , if on
exposure to oxygen the oxide layer is stable , no further oxidation will occur. If it is
porous or unstable then no protection is afforded.
(porous)
Boiler corrosion
General Wastage
Pitting
Cases found in water tube blrs where due to alternating cyclic stresses set up in tube
material leading to a series of fine cracks in wall. Corrosive environment aggravates.
Trans crystalline
more in depth: Occurs in any location where cyclic stressing of sufficient
magnitude are present
Rapid start up and shut down can greatly increase susceptibility.
Common in wall and supht tubes, end of the membrane on waterwall
tubes, economisers, deaerators . Also common on areas of rigid constraint such as
connections to inlet and outlet headers
Other possible locations and causes are in grooves along partially full
boiler tubes (cracks normally lie at right angle to groove ), at points of intermittent
stm blanketing within generating tubes, at oxygen pits in waterline or feed water
lines, in welds at slag pockets or points of incomplete fusion , in sootblower lines
where vibration stresses are developed , and in blowdown lines.
Concentrations of the corrodent may build up in a similar way to those caustic corrosion
i.e.
DNB
Deposition
Evaporation at water line
And also by small leakage
Caustic corrosion at temperatures less than 149oC are rare
Caustic corrosion
More in depth:
1.
2.
3.
4.
Generally confined to
Water cooled in regions of high heat flux
Slanted or horizontal tubes
Beneath heavy deposits
Adjacent to devices that disrupt flow ( e.g. backing rings)
High pH substances such as NaOH dissolve the magnetite then attack the
iron.
i)Departure
form
nucleate
boiling
(DNB)
Under normal conditions steam bubbles are formed in discrete parts. Boiler water
solids develop near the surface . However on departure of the bubble rinsing water
flows in and redissolves the soluble solids
However at increased rates the rate of bubble formation may exceed the
flow of rinsing water , and at higher still rate, a stable film may occur with corrosion
concentrations
at
the
edge
of
this
blanket.
The
magnetite
layer
is
then
attacked
leading
to
metal
loss.
The area under the film may be relatively intact.
ii),
Deposition
A similar situation can occur beneath layers of heavy deposition where bubbles
formation occur but the corrosive residue is protected from the bulk water
iii),
Evaporation
at
waterline
Where a waterline exists corrosives may concentrate at this point by evaporation and
corrosion occurs.
prevention's
Hydrogen attack
If the magnetite layer is broken down by corrosive action, high temperature
hydrogen atoms diffuse into the metal, combine with the carbon and form methane.
Large CH-3 molecules causes internal stress and cracking along crystal boundaries
and sharp sided pits or cracks in tubes appear.
more in depth: Generally confined to internal surfaces of water carrying
tubes that are actively corroding. Usually occurs in regions of high heat flux, beneath
heavy deposits, in slanted and horizontal tubes and in heat regions at or adjacent to
backing rings at welds or near devices that disrupt flow .
Uncommon in boilers with a W.P.of less than 70 bar
Chelant corrosion
Concentrated chelants ( i,e. amines and other protecting chemicals) can attack
magnetite
,
stm
drum
internals
most
susceptible.
A surface under attack is free of deposits and corrosion products , it may be very
smooth
and
coated
with
a
glassy
black
like
substance
Horse shoe shaped contours with comet tails in the direction of the flow may be
present.
Alternately deep discrete isolated pits may occur depending on the flow
and turbulence
be avoided
Low pH attack
Pure water contains equal amounts of hydrogen and hydroxyl ions . Impurities
change the balance . Acidic water has an excess of hydrogen ions which leads to
hydrogen evolution.See previous notes on Hydrogen Evolution
For hydrogen absorption to occur no oxygen needs to be present, a pH of
less than 6.5 and so an excess of free hydrogen ions is required.
The Protective film of hydrogen gas on the cathodic surface breaks down as the
hydrogen
combines
and
bubbles
off
as
diatomic
hydrogen
gas.
May occur due to heavy salt water contamination or by acids leaching into the
system from a demineralisation regeneration.
Localised attack may occur however where evaporation causes the
concentration of acid forming salts . The mechanism are the same as for caustic
attack. The corrosion is of a similar appearance to caustic gouging
Prevention is the same as for caustic attack . Proper maintenance of
boiler water chemicals is essential
Vigorous acid attack may occur following chemical cleaning .
Distinguished from other forms of pitting by its being found on all exposed areas
Very careful monitoring whilst chemical cleaning with the temperature being
maintained below the inhibitor breakdown point. Constant testing of dissolved iron
and non ferrous content in the cleaning solution should be carried out.
After acid cleaning a chelating agent such as phosphoric acid as
sometimes used . This helps to prevent surface rusting , The boiler is then flushed
with warm water until a neutral solution is obtained.
Oxygen corrosion
Uncommon in operating boilers but may be found in idle boilers.
Entire boiler susceptible , but most common in the superheater tubes (reheater tubes
especially where water accumulates in bends and sags )
In an operating boiler firstly the economiser and feed heater are
effected.
In the event of severe contamination of oxygen areas such as the stm
drum water line and the stm separation equipment
In all cases considerable damage can occur even if the period of oxygen
contamination is short
Bare steel coming into contact with oxygenated water will tend to form
magnetite
with
a
sound
chemical
water
treatment
program.
However , in areas where water may accumulate then any trace oxygen is dissolved
into the water and corrosion by oxygen absorption occurs( see previous explanation )
Oxygen Absorption
in addition to notes above pH between 6- 10, Oxygen present.
Leads to pitting. Very troublesome and can be due to ineffective feed treatment
prevalent in idle boilers. Once started this type of corrosion cannot be stopped until
the rust scab is removed , either by mechanical means or by acid cleaning.
One special type is called pitting were metal below deposits being
deprived of oxygen become anodic . More common in horizontal than vertical tubing
and often associated with condensers.
The ensuing pitting not only causes trouble due to the material loss but
also acts as a stress raiser
i.
ii.
iii.
i.
ii.
iii.
Dezincification
Brass with a high zinc content in contact with sea water , corrodes and the copper is
redeposited. Inhibitors such as arsenic , antimony or phosphorus can be used , but
are
ineffective
at
higher
temperatures.
Tin has some improving effects
Exfoliation (denickelfication)
Normally occurs in feed heaters with a cupro-nickel tubing ( temp 205 oC or higher)
Very
low
sea
water
flow
condensers
also
susceptible.
Nickel oxidised forming layers of copper and nickel oxide
Ammonium corrosion