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6/21/2018 Corrosion and Deposits

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Corrosion Types
The majority of metals are found in a mineralise oxidised ore state, as oxides, chlorides, carbonates,
sulphates, sulphides etc. The metal is extracted form the ore by a reduction process resulting in a high
energy state. The metal will then tend to restore back to the low energy level through interaction
with environment and oxidation.

Certain metals form a stable oxide layer which acts to inhibit further corrosion. Others form a much
more porous less stable oxide layer typically have much higher levels of diminution ( material loss).

Iron has a number of different oxides depending on the amount of Oxygen present. Magnetite with a
low oxygen content is very stable and tenacious and provides a good protective barrier. Haematite has
a higher oxide content and tends to be porous and less stable.

Direct chemical-higher temperature metal comes into contact with air or other gasses (oxidation,

Principle type of Corrosion


Hydrogen Evolution (low pH Attack)

Ionic Bonds
Ionic bond are relatively week bonds were an atom hands over an electronic to another
electron making it positively charge due to the excess of protons and the receiving atom
negatively charged due to the excess of electrons. A typical example of this is Sodium
Chloride Salt

Valent Bonds
For the purpose of understanding corrosion atoms can be imagine to consist of a nucleus
containing positively charge Protons and neutral Neutrons surrounded by negatively
electrons. These electrons orbit in distinct discrete layers each of which must be filled
before the next highest layer can contain and electron.

The numbers of electrons that must appear in each of these shells is well understood. For
example the first layer must have 2 electrons, the second layer 8.

Hydrogen has one protons and a single electron and is therefore neutrally charged. But
requires an additional ‘Valence’ electron to fill the shell

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Oxygen has 8 Protons and 8 electrons, the first Shell requiring 2 electrons is therefore full
but the second Shell ,requiring 8 electrons is not full as there are only 6 remaining
electrons. It therefore requires 2 Valence electrons to complete this shell.

Atoms can share there electrons with other atoms in co-valent bonds. A water molecule
consists on 2 Hydrogen atoms with 2 covalent electron sharing bonds with an Oxygen
atom.
Atoms may share more than one electrons in multiple bonds

In water a small portion of the Water molecules and split with the electron from one of the
hydrogen atoms being shed to the remaining Hydoxide molecule. The hydrogen ion with one
proton but no electrons is positively charged and the Hydroxide ion with 9 protons (8 in
oxygen and 1 in hydrogen) and 8 electrons is negatively charged.

The positively charged hydrogen ion will seek to draw and electron to form mono-atomic
hydrogen. The mono-atomic hydrogen is highly reactive and will react with anything
available including other mono-atomic hydrogen to form the stable diatomic form of
Hydrogen.

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

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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.

The Ferrous Hydroxide formed dissolves in the water and therefore there is general wastage

Oxygen Absorption ( High Oxygen Corrosion)

pH between 6- 10, Oxygen present. Leads to pitting. Very troublesome and can be due to ineffective feed
treatment prevalent in idle boilers. A scab forms of Ferrous Oxide and Ferrous Hydroxide which the
Hydroxyl ions can penetrate.

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 deposit attack, the area under a deposit being deprived of oxygen become
anodic. More common in horizontal than vertical tubing and often associated with condensers.

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
The three critical factors are
the prescience of water or moisture
prescience of dissolved oxygen
unprotected metal surface
The corrosiveness of the water increases with temperature and dissolved solids and decreases with
increased pH
Aggressiveness generally increases with increased O2
The three causes of unprotected metal surfaces are
following acid cleaning
surface covered by a marginally or non protective iron oxide such as Hematite (Fe2O3)
The metal surface is covered with a protective iron oxide such as magnetite (Fe3O4 , black) But
holidays or cracks exist in the coating, this may be due to mechanical or thermal stressing.

During normal operation the environment favours rapid repair of these cracks. However, with high O2
prescience then corrosion may commence before the crack is adequately repaired.

General Wastage Common in boilers having an open feed system

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-Most serious form of corrosion on the waterside


-Often found in boiler shell at w.l.
-Usually due to poor shape
Pitting -In HP blrs found also in screen and generating tubes and in
suphtr tubes after priming.

Corrosion Fatigue Cracking

Corrosion fatigue cracking occurs were there is a combination of cyclical loading and stressing within a
corrosive environment.
Cases are found in areas associated to restraint or changes of section such as tube mounting arrangements as
well as as a result of aggressive load changes and in particular due to incorrect start up procedures from cold.
Rapid re-starting with water thermal stratification within the Tubes.

Corrosive environment aggravates through removal of protective magnetite layers.

Failure identification is due to thick edge most commonly in the form of Pin homes but also as cracks.
Catastrophic rupture may occur in the region or the membrane tube welds.

Common in wall and superheater 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 steam 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.

Cracks are Trans-Crystalline ( trans granular)

Caustic Cracking (embrittlement) or Stress Corrosion


Cracking

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Steel is formed iron ferrite grains bounded by cementite ( iron carbide). Stress Corrosion Cracking occurs
when there is a high pH environment and sufficient tensile stress.

It was a common failure on older riveted boilers where localised leakages, thermal gradients etc caused
increased local densities of water the Sodium Hydroxide used as the water treatment.

Modern water treatments limiting, or eliminating the use of NaOH and improved control of pH water has
all but been eliminated this as an issue.
It can however be found in water tubes , suphtr and reheat tubes and in stressed components of the
water drum.

The required stress may be applied ( e.g. thermal, bending etc. ) or residual ( e.g. welding)
Boiler steel is sensitive to Na OH , stainless steel is sensitive to NaOH and chlorides.

A large scale attack on the material is not normal and indeed uncommon. The combination of NaOH ,
some soluble silica and a tensile stress is all that is required to form the characteristic intergranular
cracks in carbon steel.

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


NaOH concentration may be as low as 5% but increased susceptibility occurs in the range 20- 40 %
Failure is of the thick walled type regardless of ductility.
Whitish highly alkaline deposits or sparkling magnetite may indicate a corrosion sight.
To eliminate this problem either the stresses can be removed or the corrodent. The stresses may be hoop
stress( temp', pressure) which cannot be avoided bending or residual weld stresses which must be
removed in the design/ manufacturing stage.
Avoidance of the concentrations of the corrodents is generally the most successful. Avoid DNB , avoid
undue deposits prevent leakage of corrodents, prevent carryover.

Proper water treatment is essential.

Caustic Corrosion
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Takes place at high pressure due to excessive NaOH


In high temperature, high evaporation rates leading to local concentrations nearly
coming out of solution and form a thin film near heating surface.
Magnetite layer broken down
Soluble compound formed which deposits on metal as a porous oxide
Local concentrations may cause a significant overall reduction in alkalinity.
If evaporation rate reduced alkalinity restored.

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)

Caustic ( or ductile ) gouging refers to the corrosive interaction of concentrated NaOH with a metal
to produce distinct hemispherical or elliptical depressions. Depression are often filled with corrosion
products that sometimes contain sparkling crystals of magnetite.

Iron oxides being amphoteric (reactive with acids and base chemicals) are susceptible to corrosion
by both high and low pH enviroments.

High pH substances such as NaOH dissolve the magnetite then attack the iron.
The two factors required to cause caustic corrosion are;
the availability of NaOH or of alkaline producing salts. ( e.g. intentional by water treatment or
unintentional by ion exchange resin regeneration.)
Method of concentration, i.e. one of the following;
Departure form nucleate boiling (DNB)
Deposition
Evapouration

Departure from Nucleate Boiling (DNB)

Under normal conditions steam bubbles are formed in discretely. Boiler water solids develop
near the surface of these bubbles and concentrate at their edges. As the Bubble lifts from the
surface of the metal water inrushes and clears the solids before they can accumulate and stick
to the metal.

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However at increased steam generation the rate of bubble formation may exceed the flow of rinsing
water , and at higher still rate, a stable film may occur with solid 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. A similar effect may be seen in Vacuum water makers and appear as rings of scale formations

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

Evaporation at waterline
Where a waterline exists corrosives may concentrate at this point by evaporation and corrosion
occurs.

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Prevention
Rifling is sometimes fitted to prevent DNB by inducing water swirl.
Reduce free NaOH by correct water treatment
Prevent inadvertent release of NaOH into system (say from an ion exchange column regenerator )
Prevent leakage of alkaline salts via condenser
Prevent DNB Prevent excessive waterside deposits
Prevent creation of waterlines in tubes- slanted or horizontal tubes are particularly susceptible to
this at light loads were low water flows allow steam water stratification.

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
A typical sequence would be ;
NaOH removes the magnetite
free hydrogen is formed ( hydrogen in its atomic rather than diatomic state) by either the reaction
of water with the iron reforming the magnetite or by NaOH reacting with the iron
This free hydrogen can diffuse into the steel where it combines at the grain boundaries to form
molecular hydrogen or reacts with the iron carbide to form methane
As neither molecular hydrogen or methane can diffuse through the steel the gasses build up ,
increasing pressure and leading to failure at the grain boundaries
These micro cracks accumulate reducing tensile stress and leading to a thick walled failure.
Sections may be blown out.
This form of damage may also occur in regions of low pH
For boilers operating above 70 bar , where high pH corrosion has occurred the possibility of
hydrogen damage should be considered

High temperature corrosion.


Loss of circulation , high temperature in steam atmosphere, or externally on suphtr tubes

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
The main concentrating mechanism is evaporation and hence DNB should be avoided

Careful watch on reserves and O2 prescience should be maintained


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
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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 )

FEED SYSTEM CORROSION.

Graphitization
Cast iron , ferrous materials corrode leaving a soft matrix structur of carbon flakes
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 205oC or higher)
Very low sea water flow condensers also susceptible.
Nickel oxidised forming layers of copper and nickel oxide
Ammonium corrosion
Ammonium formed by the decompositin of hydrazine
Dissolve cupric oxide formed on copper or copper alloy tubes
Does not attack copper, hence oxygen required to provide corrosion,Hence only possibel at the lower
temperature regions where the hydrazine is less effective or inactive,
The copper travels to the boiler and leads to piting.

Deposits and scales found in boilers


Definition: material originating elsewhere and conveyed to deposition site; Oxides formed at the site are
not deposits.

Water formed and steam formed deposits

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May occur anywhere
Wall and screen tubes most heavily fouled , superhtr has deposits formed elsewhere and
carried with the steam or carryover. Economisers ( non-steaming) contain deposits moved
from there original site.
Tube orientation can influence location and amount of deposition.
Deposits usually heaviest on the hot side of the steam generating tubes. Because of
steam channelling, deposition is often heavier on the top portion of horizontal or slanting
tubes
Deposition occurs immediately downstream of horizontal backing rings.
Water and steam drums can contain deposits, as these are readily accessed then inspection of the
deposition can indicate types of corrosion. e.g. Sparkling black magnetite can precipitate in stm drums
when iron is released by decomposition of organic complexing agents.

DEPOSITS
Iron oxides
Magnetite (Fe3O4)
A smooth black tenacious , dense magnetite layer normally grows on boiler water side surfaces. taken
to indicate good corrosion protection as it forms in low oxygen levels and is susceptible to acidic
attack
Heamatite (Fe2O3)
is favoured at low temperatures and high oxygen levels can be red and is a binding agent and tends to
hold over materials in deposition. This is an indication of active corrosion occurring within the
boiler/feed system

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Other metals
Copper and Copper oxide is deposited by direct exchange with iron or by reduction of copper oxide by
hydrogen evolved during corrosion . Reddish stains of copper are common at or near areas of caustic
corrosion. Copper Oxide appears as a black deposits. It is considered very serious corrosion risk
because of the initiation of galvanic corrosion mechanisms.
Galvanic corrosion associated with copper deposition is very rare in a well passivated boiler. Zinc and
nickel are very often found near copper deposition , nickel being a particularly tenacious binder
Rapid loss of boiler metals can occur. Copper can appear in various forms as a deposit in the boiler. As
a copper coloured metallic deposit, usually in a corrosion pit, as a bright red/orange tubercules on the
boiler metal surface or as a brown tear drop shaped formation.
Copper is generally an indicator of corrosion (or possible wear) occurring in the feed pump whether in
the condensate lines or in the parts of a feed pump. A possible cause of this is the excessive
treatment of hydrazine which decompose to ammonia carrying over with the steam to attack such
areas as the air ejectors on condensers.
Copper oxide formed in boiler conditions is black and non- metallic.

SALTS

The least soluble salts deposit first


Calcium carbonate-effervesces when exposed to HCl acid
Calcium sulphate-Slightly less friable then CaCO3
Magnesium Phosphate-Tenacious binder, discoloured by contaminants
Silicates-Insoluble except in hydroflouric acid E.G. Analcite

Water soluble deposits can only be retained if local concentration mechanism is severe. Presence of
NaOH , NaPO3 Na2SO3 should be considered proof of vapouration to dryness.

Calcium and magnesium salts exhibit inverse solubility. As the water temperature rises their solubility
reduces, at a temperature of 70'C and above they come out of solution and begin to deposit. Feed
water must be condition to remove the hardness salts before the water enters the boiler. The purity of
the water is related to the steam conditions required of the boiler.

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Hydrolyzable salts such as MgCl can concentrate in porous deposits and hydrolyze to hydrochloric acid
Scaling mechanism examples
Calcium Carbonate
Cacium Carbonate is formed by the thermal decomposition of Calcium BiCarbonate and apperas as a pale
cream to yellow scale
Ca(HCO3)2 + Heat = CaCO3 + H2O + CO2
Magnessium Silicate
Tor form requires sufficient amounts of magnessium and silicate ions coupled with a deficiency in OH- alkalinity
Mg2+ + OH- = MgOH+
H2SiO3 = H+ + HSiO3-
MgOH- + HSiO3- = MgSiO3 + H2SO4
Thus this rough tan scale can be prevented by the maintenace of alkalinity levels
Calcium Phosphate (hydroxyapatite)
Ca10(PO4)6(OH)2
Found in biolers using the phosphate cycle treatment method this is a tan/cream deposit. This is generally
associated with overdosing a boiler but can occur where insufficient disperseing agent reduces the effects of
blow down.
In anouther form Ca3(PO4)2Ca(OH)2 it is associated with correct treatment control
Scales forming salts found in the boiler
Calcium Bi-Carbonate 180ppm
Slightly soluble
>65oC breaks down to form CaCO3 +CO2, remaining Calcium carbonate insoluble in water
Forms a soft white scale
Magnesium BiCarbonate 150 ppm
Soluble in water
at more than 90oC breaks down to form MgCO3 and CO2 and then Mg(OH)2 and CO2
Forms a soft scale
Calcium Sulphate 1200 ppm
Worst scale forming salt
> 140oC (sat. press 2.5bar) or >96000ppm will precipitate out
Forms a thin hard grey scale
Magnesium Sulphate 1900ppm
Precipitates at high temperatures and about 8 bar
Forms sludge
Magnesium Chloride 3200ppm
Breaks down in boiler conditions to form MgOH and HCl
forms a soft white scale Rapidly lowers pH in the event of sea water contamination of the boiler
initiating rapid corrosion MgCl2 + 2H2O---> Mg(OH)2 + 2HCl HCl + Fe --->FeCl + H 2FeCl +
Mg(OH)2 ---> MgCl2 + 2FeOH This series is then repeated. Effective feed treatment ensuring
alkaline conditions controls this problem
Sodium Chloride 32230 to 25600 ppm
Soluble <225000ppm
forms a soft encrustation
Free irons promote galvanic action
Other deposits-
Amorphous Silicon dioxide (SiO2) - trace
at high tempos and pressures (>40bar) silica can distill from the bioler as Silicic acid and can
sublime and pass over into the steam system as a gas. Here it glazes surfaces with a smooth
layer, which due to thermal expansion crack and roughen the surface. Troublesome on HP
blading. Can be removed only by washing with Hydroflouric acid.
Magnessium Silicate 3MgO.2SiO2.2H2O (Serpentine) is formed in water with proper treatment
control

Dissolved solids in fresh water

Hard water
-Calcium and magnesium salts
- Alkaline
-Scale forming
.
.
Soft water

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-Mainly sodium salts
- Acidic
- Causes corrosion rather than scale

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