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Corrosion
i) Mechanisms Galvanic corrosion occurs when a metal or alloy is electrically coupled to a different metal or alloy. Galvanic
attack can also occur when different electrical potentials are created on a metal surface by for example: Scratches,
differential stresses conductive deposits. Copper can be deposited on steel boiler surfaces during acid cleaning procedures
if the cleaning programme is not controlled to ensure all the copper is complexed. Caustic corrosion can occur either as a
result of steam blanketing (which allows salts to concentrate on boiler metal surfaces) or by localised boiling beneath porous
deposits. Either situation creates conditions where caustic in the boiler water is concentrated many times and reacts with the
protective magnetite layer destroying it and forming localised attack. Under the deposit concentrated sodium hydroxide
forms soluble ferrites which decompose at high temperatures to produce caustic resulting in a self-supporting corrosion
mechanism. 3Na2 FeO2 + 4H2O ↑ Fe3O4 + 6NaOH + H2 Acidic corrosion is due to low make-up or feedwater pH. Low
pH conditions can also be caused by contamination of the system due to:
Improper operation of demineralisation units
Process contamination of condensate
Cooling water contamination from condensers
Usually acid attack leads to general corrosion but it may be localised in areas of high stress such as tube ends. Oxygen
corrosion is the most common type of corrosive attack that occurs in boilers. Dissolved oxygen in the feedwater will attack
any of the pre-boiler systems – feed line, feedwater heaters, and economiser. The point of attack varies with boiler design
and feedwater distribution. When oxygen enters the boiler most is flashed off with the steam, the remainder can attack the
boiler metal. Whilst corrosion increases with both oxygen concentration and temperature the most serious aspect of oxygen
corrosion is that it usually occurs as pitting corrosion. Oxygen attack is an electrochemical process described by the
reactions: Anode Fe ↑ Fe2+ + 2e Cathode ½ O2 + H2O + 2e ↑ 2OHOverall Fe + ½ + H2O ↑ Fe(OH)2
ii) Effects Galvanic corrosion can show itself either as general corrosion localised/pitting attack especially if it is due to
copper plating out on a steel surface. Caustic corrosion usually is seen as an irregular attack, often referred to as ‘gouging’.
It may be associated with deposition depending on how the attack has originated. Acidic corrosion usually is seen as a
general thinning of tube metal walls, although it can be localised at areas of high stress such as tube ends. Oxygen attack is
almost invariably seen as pitting corrosion. As pits can penetrate deep into the metal oxygen corrosion can result in rapid
failure of feed lines, economiser tubes and boiler tubes. Attack may only occur at a specific location or it may cover an
extensive area. The effect is seen as well defined pits or a pock-marked surface. The pits vary in shape but are
characterised by sharp edges at the surface. Active oxygen pits have a reddish brown oxide cap, which if removed exposes
black iron oxide within the pit.
iii) Treatments Specific treatments are not applied to prevent galvanic or caustic corrosion. They are prevented by correct
operational procedures eg if deposition is prevented one mechanism by which caustic attack can occur is eliminated. Boiler
water treatment is applied specifically to maintain pH and to minimise oxygen concentration. pH control is important for the
following reasons:
Corrosion rates of metals used in boiler systems are sensitive to variations in pH
Low pH or insufficient alkalinity can lead to acidic attack.
Speed of oxygen scavenging reaction is pH dependent
Most low and medium pressure boiler operations monitor boiler water alkalinity because it correlates closely with pH. The pH
or alkalinity level maintained in a boiler system depends on factors such as pressure, metals, feedwater quality. Alkalinity
(and pH) levels are increased if needed by addition of caustic soda.
Oxygen Control
A well designed feedtank/deaeration system is essential to remove as much oxygen as possible. The remaining oxygen is
then removed chemically by the use of chemicals known as oxygen scavengers. The most widely used chemical in
low/medium pressure boilers up to 50 bar is sodium sulphite. The chemical removes oxygen according to the equation.
2Na2 3O3 + O2 ↑ 2Na2SO4 In theory therefore 7.88ppm sodium sulphite combines with 1ppm oxygen. In practice an
excess is used to compensate for purity of the chemical, to ensure complete reaction and to ensure there is a reserve of
sulphite maintained in the boiler. Sodium sulphite and concentrated solutions are widely used because of their (relative) low
cost, ease of handling and easy analytical technique. The reaction with oxygen can be catalysed by the addition of heavy
metal salts such as cobalt, nickel, manganese. Catalysed sulphite should be used when: