Boiler Water

Treatment

1
 BOILER WATER TREATMENT
AIMS:
 Prevent scale formation in the boiler by precipitating all scale forming salts in
the form of a non-adherent sludge.
 Prevent internal corrosion of the boiler by: raising the PH, eliminating
Oxygen and helping to promote a stable oxide layer.
 Condition sludges for easy removal by blowdown.
 Prevent foaming and carry over.

BOILER FEED WATER

The feed water system is normally arranged so that the condensate is collected and
returned to the boiler. Assuming all of the condensate is returned, the boiler should
receive pure distilled feed water containing no salts. Unfortunately not all the
condensate is returned to the boiler due to leakage losses and due to steam usage
where recovery of condensate is not possible. This makes feed water make-up necessary.
Make-up water must be as pure as possible. Ideally it should be distilled
water from the evaporator. When supplies of distilled water are limited, fresh water
from ashore will have to be used. Fresh water will contain varying amounts of mineral
salts depending on its origin.
The following is a typical mass analysis of fresh water:
Sodium Chloride (NaC1) 50 ppm
Sodium Nitrate (NaNO 3) 35 ppm
Magnesium Sulphate (MgSO 4) 30 ppm
Calcium Sulphate (CaSO 4) 90 ppm
Calcium Carbonate (CaCO 3) 200 ppm

Sources of salt contamination of boiler feed water:

 Using fresh water make-up especially if it has a high salt content.
 The evaporator if water droplet carry over or priming occurs.
 The condenser if tubes are leaking.

SCALE PREVENTION
If hardness salts such as Calcium Carbonate, Calcium Sulphate and Magnesium
Sulphate are present in the boiler water they will deposit out in hotter regions of the
boiler to form scale. Scale will reduce heat transfer resulting in overheating and a loss
of boiler efficiency. In water tube boilers scale deposits can block tubes which reduces
water circulation resulting in overheating and tube failure.
Scale forming salts can be eliminated from the boiler by maintaining a
reserve of treatment chemicals in the boiler. When the hardness salts enter the
boiler they react with the treatment chemicals. The reaction produces a relatively
harmless precipitate and a harmless sodium salt.
The most common treatment chemicals for scale prevention are Tri Sodium
Phosphate (TSP - Na3PO4). Di Sodium Phosphate (NaHPO4) and Sodium Hydroxide
(Caustic Soda - NaOH). Sodium Carbonate (Soda Ash - Na 2 CO 3 ) and Calcium
Hydroxide (Lime - Ca(OH) 2 ) can also be used for pretreatment. Following are some
of the reactions that take place in the boiler:

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 Hardness Salt + Treatment = Precipitate + Harmless Salt
3CaCo3 + 2Na3PO4 = Ca3(PO4)2 + 3Na2CO3
3CaSO4 + 2Na3PO4 = Ca3(PO4)2 + 3Na2SO4
MgSO4 + 2Na3PO4 = Mg3(PO4)2 + 3Na2SO4
MgCl2 + 2NaOH = Mg(OH)2 + 2NaCl
MgSO4 + 2NaOH = Mg(OH)2 + Na2SO4
CaCl2 + Na2CO3 = CaCO3 + 2NaCl
(not precipitated)

CORROSION PREVENTION
Internal corrosion of the boiler is greatly reduced by:
1. Raising the PH of the boiler water ic. lowering the boiler water hydrogen ion
concentration. Hydrogen ions (H +), which have lost electrons, take electrons from the
metal to form Hydrogen (H 2) at the metal surface. The loss of electrons from the metal
produces metal ions (Fe +) deficient in electrons. The boiler water contains hydroxyl ions
(OH-), which have an excess of electrons. The hydroxyl ions combine with the metal
ions to form soluble ferrous hydroxide. The formation of ferrous hydroxide results in
the loss of metal ie. corrosion.
2. Removing oxygen from the boiler. When there is no oxygen in the boiler water
the hydrogen, produced in the above reaction, forms a polarising layer on the surface
of the metal stopping further corrosion. When oxygen is present it combines with
the hydrogen to form water removing the polarising layer and allowing corrosion to
continue.
Oxygen in the boiler water can also cause oxygen pitting as a result of
differential aeration producing an anode and a cathode. The resultant electron flow
between the anode and cathode causes a pit to develop. Oxygen pitting once started is
difficult to stop, it can only be arrested by cleaning the pit out mechanically or by acid
cleaning. This type of corrosion is often found at the water line where the dissolved
oxygen is released by boiling and also in idle boilers.
Oxygen also breaks down the protective oxide layer by oxidising it.
3. Promoting the formation of a stable oxide layer in the boiler. It is desirable to form
an iron oxide layer known as Magnetite (Fe 3 O 4 ) on the internal surfaces of the
boiler. The Magnetite layer once formed will stabilise and form a tenacious barrier to
further corrosion. Magnetite will be attacked by O2, forming ferric oxide which is porous,
easily removed and gives no protection against corrosion ie:
Fe3O4 + O2 = Fe2O3
4. Preventing scale build up. Corrosion can take place under scale as salts can become
concentrated by evaporation of water.
To raise the alkalinity and PH of the boiler water alkaline salts such as Na 2CO3
and NaOH can be used, NaOH is a strong alkali which raises alkalinity and PH.
Na 3 PO 4 also raises the PH as it produces NaOH in the boiler. NaOH increases the
hydroxyl ions (OH-) and therefore produces a corresponding reduction in hydrogen ions.

3
 Oxygen removal is accomplished by mechanical deaeration before the water
enters the boiler, by keeping the feed system "closed" to prevent oxygen being
absorbed by the feed water, by keeping feed temperatures as close as possible to the
saturation temperature and by chemical treatment. Sodium Sulphite (Na2 O3) is used in low
pressure boilers and Hydrazine (N2H4) in high pressure boilers.
Sulphite Reaction: 2Na2O3 + O2 = 2Na2SO4
Hydrazine Reaction N2H4 + O2 = 2H2O + N2
The formation of a stable oxide layer is assisted by the use of Hydrazine which can
convert ferric oxide to Magnetite.
SLUDGE CONDITIONING
Coagulants are used to gather the finely divided precipitated Magnesium and Calcium
Phosphate, and Magnesium Hydroxide into a non-adherent sludge which can be removed
from the boiler by periodic blowdown. Organic substances such as tannins and starches,
and inorganic substances such as sodium aluminate are used as coagulants.

Synthetic organic polymers known as polyelectrolytes are also used.

Polyelectrolytes stop the salts from depositing on metal surfaces, instead the salts
combine with the polyelectrolyte to form a free flowing sludge which is removed from the
boiler by blow down.
FOAMING AND CARRY OVER
Foaming and carry over are controlled by preventing the TDS building up by regular
blowdown. Anti-foam chemicals can also be used to reduce the surface tension of the
boiler water thus prevent foaming.

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 pH
Introduction
pH (potential of hydrogen) is a convenient way of expressing the degree of acidity
or alkalinity of water with a single numerical value. pH is a measure of the
hydrogen ion (H+) concentration in gram ions per litre. An ion is an atom or group
of atoms that has lost or gained electrons ie an electrical charge. For an ion the
number of electrons # the number of protons in the nucleus. Electrons are
negatively charged. Hydrogen ions are designated as H + as they have lost electrons
which makes them positively charged ie deficient in electrons.
Pure water (H20) has a pH of 7 at 25°C. A small quantity of the water "ionises" to
for hydrogen ions and hydroxyl ions (OH-). The sum of the hydrogen and hydroxyl
ion concentrations is always equal ie an increase in one results in a corresponding
decrease in the other.
The pH Scale
The pH scale ranges from 0 to 14 with pH 7 being neutral ie pH 7 has equal
concentrations of hydrogen and hydroxyl ions. Decreasing numbers indicate
increasing acidity and therefore increasing hydrogen concentration. The pH scale
is exponential, when descending the scale each number represents a
concentration 10 times the concentration of the previous number eg pH 4 is 10 x
more acidic than pH 5, pH 3 is 10 x more acidic than pH 4 ie pH 3 is 100 x more
acidic than pH 5. Likewise when acceding the scale pH 9 is 10 x more alkaline than
pH 8, pH 10 is 100 x more alkaline than pH 8.
The pH scale is derived mathematically from the negative log to the base 10 of the
hydrogen ion concentration in gram ions per litre ie "the log of the reciprocal of the
hydrogen ion concentration".Eg.

A pH of 10 is a very low hydrogen ion concentration ie 1/10 10 = 0.000,000,0001 gm

ions/ltr when compared to a pH of 3 which has a hydrogen ion concentration 1/10 3 =
0.001 gm ions/ltr.

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Hydrogen Ions and Corrosion
Hydrogen ions being positively charged can accept electrons from iron (Fe) resulting
in the formation of hydrogen gas (H2). The iron is now deficient in electrons (Fe+) and
it achieves electrical equilibrium by combining with hydroxyl ions in the water to form
iron hydroxide Fe(OH)3, a corrosion product. When the pH is low there is a relatively
large concentration of hydrogen ions and the corrosion process can continues at a
rapid rate resulting in general wastage of the metal surface.
The hydrogen gas produced can form a polarising layer which, if not carried away
in the water, can stifle corrosion. The presence of oxygen in the water removes the
hydrogen by reacting with it to form water thus allowing corrosion to continue. Also if
oxygen is present it reacts with the iron hydroxide to form ferric oxide (Fe2O3).

Prevention of Corrosion
Corrosion can be reduced in boilers, feed systems and other closed systems such as
fresh water cooling and brine systems by raising the pH ie decreasing the hydrogen
ion concentration. Boiler pH is kept around 10 to 11 while feed systems, cooling
systems and brine systems are kept at 8.5 to 9.
The pH can be raised by increasing the hydroxyl ion concentration eg sodium
hydroxide (NaOH) ionises to produce hydroxyl ions - NaOH ---> Na+ + OH-,
trisodium phosphate and sodium carbonate (soda ash) also increases pH. Sodium
carbonate breaks down with heat in the presence of H2O to form NaOH.

Strong acids such as sulphuric acid, hydrochloric acid and nitric acid will produce
very low pH as they ionise easily releasing hydrogen ions. CO2 from the air forms
carbonic acid also resulting in low pH.

6
 WATER TESTS - L.P. BOILERS

The following are typical boiler water tests carried out on L.P. boilers:

 PHOSPHATE RESERVE: This test is carried out to determine if there is

sufficient phosphate reserve for eliminating any scale forming hardness salts that
may enter the boiler.
Test: Filter a sample of the boiler water - the sample must be clear. Measure 5 ml into
the test tube and add 12.5 ml of molybdate reagent, stopper, mix thoroughly and
allow to stand. After approx. 2 minutes compare the resultant blue colour of the
sample with the standard colours on the Phosphate Comparitor. Record the
ppm of Phosphate Reserve.

 P ALKALINITY (Phenolphthalein Test): This test is carried out to determine if

there is sufficient alkalinity in the boiler to minimise corrosion. P Alkalinity measures
the amount of hydroxides and carbonates in the boiler water.
Test: To a filtered and cooled 50 ml sample add 4 drops of Phenolphthalein indicator
and mix. If the PH of the sample is above 8.4 it will turn pink. Add sulphuric acid 1
drop at a time until the pink disappears. The mis of acid used is proportional to the P
Alkalinity. Acid strength and size of sample determines ppm.

 CHLORIDES: This test determines the level of chlorides present in the boiler
water. A rapid increase in chlorides would indicate feed water contamination. High
chlorides lead to foaming and increased corrosion.
Test: Using the previous sample, add 10 drops of Potassium Chromate indicator.
The sample will turn light yellow. Add silver nitrate while stirring until the sample
changes to a light redish brown colour. The mls of silver nitrate used is proportional
to the chlorides. Size of sample and strength of silver nitrate determines ppm.

 TOTAL DISSOLVED SOLIDS (T.D.S.): This test is to determine the "density" of

the boiler water ie. the total dissolved solids. It can be measured with a hydrometer
when T.D.S. is above 2000 ppm and with a conductivity meter if the T.D.S is below
2000 ppm. The conductivity meter measures the ability of the water to conduct a
current. The scale of the meter is graduated in ppm. The sample should be at the
correct temperature.

 SODIUM SULPHITE RESERVE: This test determines if there is sufficient sulphite

reserve in the boiler water for the elimination of oxygen. This reduces the corrosion
risk.
Test: Using a fresh 100 ml sample immediately add 4mls of sulphuric acid and 1 ml of
starch indicator solution. Add potassium iodate-iodide until the sample begins to
turn blue as all the sulphite is converted to sulphate. Potassium iodate -iodide
used is proportional to the sulphite. The ppm of sulphite is determined from the
size of the sample and the strength of the potassium iodate-iodide used.

Other test may also be carried out such as: Hydrazine ( oxygen scavenging );
Hardness ( should be zero if a phosphate reserve is maintained); PH; Caustic
Alkalinity ( hydroxides only ); Total Alkalinity (hydroxides, carbonates and bi-
carbonates ); M Alkalinity (bi-carbonates only); Polymer if polymers are used for
scale control.
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 BOILER TESTS FOR LP BOILERS

Test/Range Test Method End Point/Result Reason for Test Control

'P' Alkalinity Phenolphthalein indicator. Titrate with dilute Sulphuric Acid (H2SO4) until the end point is Prevention of corrosion. Addition of alkaline salts:
100 to I5O ppm Indicator turns pink if the PH is reached where the sample changes from pink to clear, mis of acid Sufficiently high PH is can Sodium Carbonate (Na2CO3)
above 8.4, carbonates and used is proportional to the alkalinity expressed as ppm of be inferred from alkalinity. Tri-Sodium Phosphate (Na3PO4)
hydroxides are present. Calcium Carbonate. Size of sample and strength of acid Sodium Hydroxide (NaOH)
Determine result.
Chlorides Potassium Chromate indicator Titrate with Silver Nitrate, Chloride produces Silver Chloride Prevention of corrosion
300 ppm max. gives sample light yellow colour which is white and does not change colour of sample. When all and foaming Regular blowdown
Test uses the same sample as Chlorides are neutralised, Silver Chromate is produced which is
previous test with the addition red. The end point is reached when sample changes to red/brown.
of Size of sample and strength of Silver Nitrate determine result.
H2SO4 to make it acid.
Phosphate Reserve Colour Comparator Intensity of blue colouration produced indicates phosphate is Prevention of scale by Addition of Phosphate salt:
20 to 60 ppm Reagent: Molybdate present, phosphate reserve in ppm is read from the colour neutralising hardness salts Tri-Sodium Phosphate (Na3PO4)
comparator. Di-Sodium Phosphate a2HPO4)

Sodium Metaposphate (NaPO3)

TDS Conductivity Meter TDS is proportional to the conductivity of the water. Prevent foaming and Regular blowdown
800 to 1500 ppm Temperature of the sample must be taken into account. carryover
Sulphite Reserve Colour Comparator Compare colour of sample to standard colour chart which is Prevention of corrosion by Addition of Sodium Sulphite
50 ppm or usually supplied in the form of a disc . elimination of 02
Hydrazine Reserve Colour Comparator Compare colour of sample to standard colour chart. Prevention of corrosion by Addition of Hydrazine
0.1 to 0.3 ppm elimination of 02
Caustic Alkalinity Test for hydroxides only Barium Chloride is added first to neutralise carbonates. Test then Prevention of corrosion by Addition of alkaline salts
follows same procedure as 'P' alkalinity test. maintaining correct PH
Note: for HP boilers using Co-ordinated Phosphate treatment the
caustic alkalinity should be zero.
PH Meter, litmus paper or chemical Prevention of corrosion by Addition of alkaline salts:
9.8 to 10.5 test maintaining correct PH As for 'P' Alkalinity above
M Alkalinity Methyl Orange indicator. Use same sample as P Alklinity test, titrate with dilute Sulphuric As for P Alkalinity As for P Alkalinity
Indicator turns yellow if the PH Acid (H2SO4) until the end point is reached where the sample
is
above 4.3. changes from yellow to salmon pink, mis of acid used is
proportional to the M alkalinity expressed as ppm of Calcium
Carbonate. Size of sample and strength of acid determine result.

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 Chemicals used for Boiler & Feed water treatment

A typical treatment may contain some or all of the following;

Sodium Phosphate To prevent Calcium scales

Sodium Hydroxide To prevent Magnesium scales and minimise corrosion

Polymers To prevent scale or condition sludge so that it can be easily

blown down. They are giant molecules formed by the
combination of large numbers of simple molecules called
monomers.

Polyelectrolytes These are also large molecules of natural or synthetic origin,

made of monomers which are ionic in nature and form ions in
solution.

Polyacrylates These are ionic polymers of acrylic acid.

Polyamides These are polymers made up of monomers called amides.

Tannins/Starch Sludge conditioners which are used to keep suspended matter
from depositing on boiler surfaces..

Hydrazine/sodium Used to remove oxygen from boiler water.

sulphite

Antifoam To reduce carry over. They work by reducing the stability of water
films around steam bubbles, thus allowing them to collapse more
readily. A common type of antifoam is based on high molecular
weight compounds of silicon in the form of polyamides.

Neutralising amines To neutralise Carbolic acid in the feed system. They are
volatile compounds based on ammonia, such as
Morpholine or Cyclohexylamine.

Filming amines These are similar to the above but act more by forming
a protective film on metal surfaces of steam and
condensate lines. Octadecylamine is a common filming
amine.

In phosphate based treatment polymers are used for coagulation & dispersion of the
sludge resulting from the phosphate/ hydroxide reactions. In treatments based solely or
partially on polymers the polymer acts to prevent scale and may remove existing deposits.

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 BOILER WATER TREATMENT
Some Important Factors

Dissolved gases
Dissolved gases are present in the feed water coming either from the make -up water
or returned condensate. The principal gases are oxygen and carbon dioxide, the
presence of which can cause corrosion of the feed, economiser, boiler and
condensate systems. Both mechanical and chemical means are employed to remove
the gases. Medium and high pressure boilers invariably have a mechanical
deaerator, which will reduce levels to typically 0.005 mg/1 oxygen. In systems with an
open feed tank the levels of oxygen can be minimised by maintaining a high temperature.

Silica
Silica can cause the deposition of very insulating scales in a boiler. At high pressures,
ie. above 40 bar, silica has an appreciable volatility in steam. However, it is not
normally a problem when evaporated sea water is used as make-up because silica is
present at a low level in sea water. Shore water can have high levels of silica.

Oil
Oil contamination can be very damaging to a boiler. Slight contamination can be dealt with
by the conditioning chemicals but in general all steps should be taken to prevent its
ingress-

TREATMENT CHEMICALS

There are a number of forms of boiler water treatment that can be used depending on the
operating pressure and type of boiler. Many specialist water treatment chemi cal
suppliers have their own proprietary products and their recommendations for the
application of these products should always be followed. The recommendations of boiler
suppliers should also be followed. The following notes give the important features of the
most commonly used treatments

Caustic/Phosphate
This treatment is based on the maintenance of reserves of both caustic soda and
phosphate in the boiler water. The chemical reserves give the required alkaline
environment to prevent corrosion and protect against the ingress of hardness salts.
Calcium and magnesium salts will be precipitated according to the following reactions.

3CaC12+ 2Na3PO4--> Ca3(PO4)2+

6NaC1 MgC12 + 2NaOH -->
Mg(OH)2 + 2NaCl

In order to prevent salts being precipitated in the feed system the chemicals are
preferably added directly to the boiler. The precipitated salts are removed by blowdown.

Polymers
Specific water soluble polymers are used for coagulation, dispersion and to prevent scale
and sludge formation. The action of certain polymers is to prevent scale formation by
magnesium and calcium salts by forming a non-adherent sludge. One of the most

10
common polymers used in this treatment is a polyacrylate, used in conjunction with
either sodium hydroxide or sodium hydroxide/sodium phosphate and sludge
formation. The action of certain polymers is to prevent scale formation by magnesium
and calcium salts by forming a non-adherent sludge. One of the most common polymers
used in this treatment is a polyacrylate, used in conjunction with either sodium
hydroxide or sodium hydroxide/sodium phosphate.

The polymer treatment prevents scale deposition and minimises sludge formation. It may
also loosen any scale already present in a boiler. It is therefore preferable to introduce
such a treatment to cleanboilers only, otherwise troubles might be encountered through
the exposure of leakages at places where scale has been loosened, ie. tube expansions
etc., or blockage of tubes by the detached scale.

Oxygen scavengers
Common chemicals continuously added to the feed for scavenging oxygen are sodium
sulphite and hydrazine which react with oxygen according to the following equations:

2Na2SO3 + 02 -> 2Na2SO4

2N2H4 + 02 2NH3 + 2H2O

The use of sodium sulphite is restricted to boilers operating at pressures up to 40 bar.

Above this pressure the sulphite decomposes to give acidic products. Hydrazine has no
such restrictions, although its present day usage is declining because of its toxic nature.
There are a number of proprietary products available which do not have this disadvantage.
Amines
Amines are used to protect against corrosion. There are two distinct classes.
Neutralising amines
They are steam-volatile, and are used to neutralise carbon dioxide in steam, condensate
and feed systems. The common amities used are cyclohexylamine and morpholine, or
combinations of the two.

Filming amine
These do show a neutralising tendency, but their essential function is to protect by forming
a molecular water-repellent protective film on metal surfaces and thus prevent corrosion.
Octadecylamine is a commonly used filming amine.

Antifoams
These are complex organic compounds of high molecular mass and should be applied
according to the supplier's instructions. They are effective at reducing carry over due to
foaming and thus improving steam purity. For safety reasons it is recommended that they
are only used as an additional safeguard and are not used to allow total solids to rise
higher than would be allowed without their application.

STEAM PURITY

Many marine boilers provide steam for turbines and it is important that good
quality steam is produced. This requires the correct installation of drum internals and
selection of the appropriate boiler water conditions. Boilers with only rudimentary
drum internals will require lower concentrations to be maintained in the boiler water
than otherwise would have been necessary.
11
SAMPLING

The first requirement to be able to control feed and boiler water conditions is to obtain
representative samples. For all sample locations, where the medium to be sampled is
above 60°C it is necessary to fit a cooler. This is for both protection of the operator from
scalding and to prevent a proportion of the sample flashing off as steam, which would
give falsely high test readings. Where boiler water sampling is fitted with an internal
collection pipe it should be checked that the pipe is remote from the feed discharge.
Otherwise contamination of the sample with feed water will give falsely low test
readings. It is essential when taking a sample that the sample be run to waste for
sufficient time to flush out all lines and the collection container.

BOILER WATER TREATMENT

TROUBLES ASSOCIATED WITH WATER TREATMENT

Failure to maintain adequate water conditions can have serious consequences for boiler
operation. The main types of failure can be categorised as follows.

Overheating
This can be divided into short and long term.

Short term
This type of failure can result from either a loss of feedwater, when it is usual for a
large number of tubes to be affected, or blockage of an individual tube when the damage
is confined to the blocked or partially blocked tube. The feature of this type of failure is
that the tube swells, and the failure is thin edged, purely because the metal overheats
and becomes plastic. The internal pressure causes the material to expand like a
balloon to the point of failure. There is one exception to this and this is a short water
failure in the presence of copper. The copper reaches its melting point and a thick
edged rupture results from intergranular penetration.

If a short water failure is taken to the extreme the metal becomes so hot that the water
present dissociates into hydrogen and oxygen and the heat produced in the oxidation of
the steel is sufficient for a self-sustaining hydrogen fire to be started and which will
continue as long as water is being fed to the boiler

A further possible cause of short water failure which occurs in superheaters is by

priming when a slug of water blocks a few tubes for a short period of time but
sufficient for these tubes to overheat and possibly fail.

Long term
These arise as a result of internal deposits or oil contamination reducing heat
transfer, causing overheating and blistering of the tubes. Small longitudinal splits
develop around the blister, and through the peak of the blister the metal thins, and
finally fails as a 'creep rupture'. The presence of oil tends to make this happen very
much more quickly than with other types of deposits. This type of failure can also
occur in the steam circuits. Here the problem (assuming that the design is correct) can
be due to the use of the wrong material. More often, it is caused by excessive operational
temperatures either continuously or by a number of short term temperature escalations
12
eg. during start-up or soot blowing.

All these failures can be termed 'creep' and can be recognised by a heavily oxidised
layer and a thick edged failure with numerous small longitudinal cracks adjacent to the
point of failure.

Corrosion
Once more this general heading can be split into two distinct types.

Pitting
To complicate matters this can be further subdivided into several categories.

1 . Dissolved gas ie. oxygen or carbon dioxide bubbles, cling to the metal
surface, setting off a vigorous corrosion reaction. The pits are
characterised by being sharp edged and having no corrosion products
present. The time to failure can be very short .

2. Scab pitting is much the same as the above, and is caused by high
oxygen and low pH. Characteristic are hard scabs of corrosion product.

3. Soft scab pitting is caused by droplets of water adhering to the surface

during storage or shutdown. The corrosion products are soft and reddish in
colour.

4. Acid pitting is caused by either poorly carried out acid clean or sea water
contamination and is characterised by the base of the pits having a larger
area than the entry.

On-load corrosion

On-load corrosion is probably not as prevalent now as it was a few years ago, as we
appreciate the causes more fully, but nevertheless is one of the most common causes of
failure in medium and high pressure boiler plant. The principal cause is a deposition of
metallic oxides within the furnace. The oxides of iron and copper are transported into
the boiler and may be the result of corrosion in the condensate/feed system or
generated within the boiler itself. For example, high oxygen and low pH can cause
corrosion of the economiser and the resulting corrosion products end up in the boiler.
These corrosion products, which at the pH in the boiler are largely particulate in
nature, tend to bake out in the areas of highest heat flux ie. on the furnace side of
the tube in an area around the furnace at or slightly above the burners. The deposit
changes the form of boiling from nucleate to wick boiling. Nucleate boiling is the
normal production of steam bubbles at the tube surface in a clean deposit free tube. In
the wick boiling process boiler water enters the deposit through fine pores and is drawn
down to the metal surface by capillary action. Evaporation takes place at this
surface with the steam escaping through larger pores. The evaporation causes
concentration of boiler salts and may reach a level of many thousands times the
concentration in the bulk fluid as there is no flow at the metal surface to flush the
salts away. The concentrated boiler solution rapidly attacks the boiler steel. T he
deposit has an insulating effect and the temperature rise accelerates the rate of attack.
The tube thins, often over a considerable length, and eventually fails.

In severe cases corrosion process goes a stage further and a more catastrophic
13
failure occurs. Hydrogen is produced in the process and this can diffuse into the
metal. The hydrogen reacts with the carbon of the metal and methane is produced
under extreme pressure. This destroys the metal structure and the metal becomes weak
and brittle. The failure is often extremely violent with sections of tubing blowing out. It is
most important that the oxide deposits are removed before this process is initiated
and for this reason a regular chemical cleaning is recommended.

Wastage
General wastage on the water side is extremely rare but can be caused by marginal
water conditions. It is more normally associated with the gas side.

Corrosion associated with stress

For the sake of completeness it is worthwhile mentioning these although the
occurrence on marine boilers is rare. Under this heading we have fatigue type failures
where alternating stress eventually gives rise to failure. This process is accelerated
if there is a corrosive environment, ie. corrosion fatigue. If thermal cycling is present
then it becomes thermal fatigue.

Caustic embrittlement or gouging is no longer the problem that it was with riveted drums
etc., but it is still occasionally found at tube expansions. The mechanism is a
combination of the residual stress in the expansion joint and a high caustic concentration
as a result of leakage at the expansion joint.

14