Module 3: Corrosion and Mechanisms

o Types of Corrosion
o Dry (Chemical) Corrosion and its Mechanism
o Corrosion by oxidation
o Corrosion by gases other than O2
o Liquid metal corrosion
o Wet (Electrochemical) Corrosion and its Mechanism
o Hydrogen evolution corrosion
o Oxygen absorption corrosion
o Galvanic or bimetallic corrosion
o Concentration cell corrosion (or water line corrosion)

o Passivity and Pitting Corrosion

o Wear and Crevice Corrosion
o Inter-granular Corrosion
o Stress Corrosion and Hydrogen Embrittlement
o Corrosion in Boilers and Superheaters

Course Outcome
▪ CO3: Illustrate mechanisms of corrosion and surface protection techniques.
Course Objective
▪ Imparting knowledge about corrosion and their mechanisms, factors affecting corrosion.
In nature, most metals (except Au, Pt, etc) exists as compounds (as their
oxides, carbonates, chlorides, silicates, etc).
These metallic compounds are thermodynamically more stable.
But, during the extraction process at high temperature, the metallic
compounds are reduced to their pure metallic state (Cu2+ → Cu0) which is
thermodynamically unstable state.
Hence, the extracted/reduced pure metal will always have a strong tendency
to convert itself into the more stable metallic oxide compound through
corrosion.

Metal Metallic compound + energy

Corrosion (oxidation)

Extraction of
metals

Chemical or electrochemical attack from the environment on a solid metal

resulting in its deterioration (or destruction or disintegration) starting at
the metal surface is called “CORROSION”.
Thus corrosion is “reverse extraction of metals”
 Types of Corrosion
a) Dry or Chemical Corrosion
(i) Corrosion by oxidation occurs when O2 present in the atmosphere
attacks the metal at low or high temperatures (usually in the absence of
moisture), thereby forming an oxide layer on the surface of the metal.
Fe → Fe2+ + 2 e- (oxidation) Oxidation corrosion results in the
½ O2 + 2e- → O2- (reduction) formation of an metal-oxide (MO) film
Fe + ½ O2 → Fe2+ + O2- (total reaction) which may be porous or non-porous.

Mechanism Fe2+ Outward diffusion of metal ions through

2+
the
scale (faster, due to small size of Fe )
Atmospheric oxygen Fe → Fe2+ + 2e- (oxidation)
(air) O2 Metal (M)
2e-
½ O2 + 2e- → O2- (reduction) O2- Inward diffusion of oxide ions through the
scale (slower, due to larger size of O2-)
Q. Why does a metal get corroded faster in coastal
environment as compared to desert environment?
Explain the corrosion type that would have occurred
in each of those 2 environments (Compare Dry and
Wet Corrosion Mechanisms).
 Types of oxide layers formed: 4 types
i) Stable oxide layer:
o It is a fine grain of metal-oxide layer which is stable, non-porous and adheres
strongly to the pure metallic surface.
o E.g. Oxides of Al, Pb, Cu, Ni and Cr which form stable, non-porous and tightly
adhering metal-oxide films (<300 Å or 30 nm thick) to the pure metallic surface
thereby preventing further oxidation corrosion.
ii) Unstable oxide layer:
o Oxide layers produced on noble metal surfaces (Pt, Ag, etc) immediately
decompose back into the metal and oxygen. thereby preventing oxidation
corrosion.
Metal + Oxygen Metallic oxide

Unstable
Exposed surface
metal oxide

O2 in air Metal oxide

decomposes
metal metal metal + O2
immediately
Q. What type of oxide is formed on the metal M and justify its impact on corrosion if VMO/VM
= 0.56 and (b) VMO/VM = 1.65 (V = volume).
iii) Volatile oxide layer:
o The metal-oxide layer volatilize (evaporate) rapidly as soon as they are
formed, thereby exposing the underlying metal surface for further
corrosion. E.g. MoO3 is volatile.
Exposed surface volatile metal oxide Fresh surface exposed for
further attack
Metal oxide
O2 in air volatilizes
metal
metal metal

iv) Porous oxide layer:

o These oxide layers have minute pores or cracks through which the
atmospheric oxygen diffuse and contact the pure metal surface, thereby
further corrosion is promoted.
Exposed surface Porous metal oxide

metal O2 in air Further attack through

metal pores & cracks continues
Q. Identify the rule that deals with volume of metal oxide formed in
dry corrosion case.
Pilling-Bedworth rule:
o An oxide is protective or non-porous if the volume of metal-oxide is equal to or
greater than the volume of the metal from which it is formed;
o An oxide is non-protective or porous if the volume of the metal-oxide is less
than the volume of the metal from which it is formed.
o Cu, Al, Ni, Cr form tightly adhering, non-porous oxide layers resulting in rapid
decrease in the rate of oxidation to zero.
o Li, Na, K, Mg form porous oxide layers and rate of oxidation continues non-stop.
ii) Corrosion by gases other than O2:
o The extent of corrosion depends on the chemical affinity between the metal and the
gas involved.
o The film formed is protective or non-porous (2Ag + Cl2 → 2 AgCl), thereby
preventing the metal from further attack.
o The film formed is non-protective or porous (Sn + 2Cl2 → SnCl4, volatile), thereby
exposing the underlying fresh metal surface for further attack.
Fe + H2S → FeS + 2H (atomic hydrogen) in which H2S gas attacks steel at high
temperature and make them brittle (hydrogen embrittlement) by forming FeS as
porous scales.
(iii) Corrosion by liquid metals:
o Liquid metal flowing at high temperature over the solid metal or alloy can
result in either the:
(a) Dissolution of the solid metal by the liquid metal (gold can be corroded
by mercury / solid zinc dissolved in liquid gallium) or
(b) Internal penetration into solid metal by liquid metal (cadmium in nuclear
reactors corroded by liquid sodium (used as coolant)).
(b) Wet or Electrochemical corrosion
This type of corrosion occurs when a metal or two dissimilar metals or
alloys are either immersed fully or partially in an electrolyte.

At the anode: M Mn+ + ne- (oxidation)

Mn+ either dissolves in solution or forms compounds such as oxides.
(a) If the corrosion product is soluble in the medium, rate of corrosion will be
high; (b) If the corrosion product is insoluble in the medium, rate of
corrosion will be very low.
 At the cathode: The metals cannot be further reduced; but the
dissolved constituents in the electrolyte accept the electrons to form
anions (½ O2 + 2e- → O2-).
Therefore, the metallic ions (at anodic part) react with non-metallic ions
(at cathodic part) and form a corrosion product at the cathode.
Q. State the conditions under which wet corrosion takes place and its 2 types with
suitable examples.
• Formation of anodic and cathodic areas
• Presence of an electrolyte
• Electrons flows between the electrodes
• Ions flow through the electrolyte
• Corrosion of anodic part (Oxidation)
• Formation of corrosion product at cathode (Reduction)

Electrochemical corrosion occurs in the following types:

1. Hydrogen evolution – type corrosion Mechanism of electrochemical
corrosion
2. Oxygen adsorption – type corrosion
3. Galvanic corrosion
4. Concentration cell corrosion
Q. Two iron cub boards were corroded. Spillage of conc. HCl in one cup board and
accumulation of some rain water in the other cup board were observed. Explain the type of
corrosion that happened in the two cases and their corrosion mechanism [Slides 9 & 10].
1. Hydrogen evolution type corrosion
occurs when base metals are in contact with an acidic solution.
Eg. At Anode : Fe Fe2+ + 2e- (oxidation)
At Cathode : 2H+ + 2e- H2 Anode : large area
The overall reaction is: Fe + 2H+ Fe2+ + H2
Cathode : small area
Metal ions produced at the anode dissolves in the electrolyte while hydrogen evolves at
the cathode. Hence, this type of corrosion causes “displacement of hydrogen ions from
the acidic solution by metal ions”.

Acidic solution (electrolyte) H+

H+
H+ Cathodic
reaction
2 H+ + 2e- → H2
Fe → Fe2+ + 2e- Fe → Fe2+ + 2e- Anodic
reaction

Anodic area Anodic area

(large) Fe Cathodic area (large) Fe
(small)
[Link] absorption type corrosion:
Occurs when base metals are in contact with neutral solutions like NaCl containing
Dissolved oxygen (DO). Rusting of iron is an example of this. Anode : small area
Anode : Fe Fe2+ + 2e- (oxidation) Cathode : large area
These electrons are used by the dissolved oxygen in aq. conditions
Cathode : ½ O2 + H2O + 2e- 2 OH- (Reduction)
The Fe2+ at the anode and OH- at the cathode diffuse and react to produce ferrous
hydroxide, Fe(OH)2 as rust: Fe2+ + 2 OH- Fe(OH)2
If sufficient oxygen is present, Fe(OH)2 gets oxidized to ferric hydroxide (yellow rust)
4 Fe(OH)2 + O2 +2H2O 4 Fe(OH)3 or 2(Fe2O3.3H2O)
Q. Elaborate on rusting of
aq. NaCl solution (electrolyte) iron under neutral and well
aerated water.
½ O2 + H2O + 2e- → 2OH-
Thin oxide
rust e- rust
film layer

Cathodic area Cathodic area

(large) Fe (large) Fe More dissolved oxygen→
more removal of
Anodic area
electrons from the
(small) caused by cracks in the oxide film
oxidation of Metal →
Fe → Fe2+ + 2e- more corrosion!!!
 Galvanic series Galvanic Series
Tendency to get oxidized is arranged in the
increasing order from bottom to top.
The species higher in the series is more
anodic and hence corrodes faster than the
metal below it.
Deals with metals and alloys.
The position changes with respect to the
combination of metals/alloys.

Q. A steel screw in a brass marine hardware corrodes. Give reason. How can you avoid this type of
corrosion?
Q. Justify which one among the following is the best design: (a). larger Copper device fitted with
smaller Zn part or (b). larger Iron device fitted with smaller Al part.
Q. You are provided with two different metals for the fabrication of a metal door. Indicate the
precautions to be taken in order to protect the metal door from corrosion.
Q. When Zinc metal is dipped in 1 N H2SO4, the initial rate of corrosion is quite slow. Upon the
addition of another metal salt, the rate of corrosion increases significantly. Identify that metal salt
and the reason behind the increase in corrosion rate.
3. Galvanic corrosion:
o Occurs when two dissimilar metals (zinc and copper) in the galvanic series are in
contact with each other (joined by welding) and exposed to corroding
environment.
o The metal with more negative potential (more higher in the galvanic series) will
become anode and corrodes.
o This type of corrosion is called galvanic “corrosion”.
Zn → Zn2+ + 2e-
o In Zn-Cu, Zn acts as anode (oxidized) and Copper acts as cathode (reduced).
o The electron flows from anode to cathode.
o E.g. steel screws in a brass marine hardware; lead-antimony solder around a
copper wire; steel pipe connected to copper plumbing
o Galvanic corrosion can be avoided or minimized by coupling metals which are
close in the electrochemical series or by using insulators.
Q. Identify the type of corrosion that occurs when metals are partly covered with dust, oil
marks, sand, etc.
4. Concentration cell or differential aeration corrosion
Is a form of electrochemical corrosion (wet-type).
It occurs when a metal surface is exposed to varying concentration of electrolyte or
varying concentration of oxygen (formed due to local temperature
differences/inadequate agitation/slow diffusion of metal-ions), thereby leading to the
formation of a concentration cell.
It is the most common type of concentration cell corrosion and it occurs when one part of
the metal is exposed to lower concentration of O2 (acts as anode) and the other part of the
metal is exposed to higher concentration of O2 (acts as cathode).
 Ex. Zinc rod dipped in brackish water solution (also called as water-line corrosion).
½ O2 +H2O + 2 e- 2 OH- Zinc rod Anode: Zn Zn2+ + 2e-
More oxygenated part
Water-line
Cathode:½O 2 + H2 O+ 2e - 2OH-
(Cathode)
e- Flow of electrons
NaCl solution
Corroding anode (less oxygenated part)
Zn2+ Zn Zn2+ + 2 e-
This type of corrosion also occurs when metals are partly covered with dust, oil
marks, sand, etc.
Cathode Sand

Anode
Metal (Less
Oxygenated
part)

Metals partly covered with dirt, dust, sand, scale, oil marks become oxygen deficient
areas – Anodes. M → Mn+ + 2e- . The other area which is more exposed to oxygen
becomes oxygen rich and acts as cathode.
Passivity:
Definition: Passivity is the phenomenon in which a metal or an alloy exhibits a much higher
corrosion-resistance than expected from its position in electrochemical series.
Reason of passivity formation: Passivity is due to formation of a highly protective, but very
thin (~30 nm thick), quite invisible film on surface of metal or alloy, making it more noble.
Characteristics of passive film: Insoluble, non-porous and self-healing film, which when
broken, will repair itself on re-exposure in presence of oxygen.
Examples: Ti, Al, Cr and Stainless steel containing Cr.
Mechanism of Passivity
• The behavior of metal and alloy can be conveniently divided into 3 regions: active, passive and
transpassive.
• In active region, behavior of this material is identical to that of a normal metal. A slight increase
in oxidizing power of the solution causes a corresponding rapid increase in corrosion rate.
• If more oxidizing agent is added, the corrosion rate
shows a sudden decrease. This corresponds to the
passive region. Further increase in oxidizing agent
produces little change in corrosion rate of material.
• During transition from active to passive region, a 10³ to
10⁶ reduction in corrosion rate is usually observed.
• Finally, at very high concentrations of oxidizers or in
the presence of very powerful oxidizers, corrosion rate
again increases with increasing oxidizer power. This
region is termed as transpassive region (Fig.).

Fig. Corrosion of active-passive metal as a function of solution oxidizing power (electrode potential).
Potentiostatic polarization curve of Flade potential of Fe
active-passive metal (Fe)
• When applied potential is withdrawn, passivity
• Active state: decays
Metal corrodes (Fe⁰ → Fe²⁺ + 2e⁻) • Passivity decays in a very short time
• Passive state: • At Flade potential, active state of the metal is
Insulative film is formed & no corrosion re-established.
occurs Important:
• Transpassive zone: P and φ are roughly equal (but not the same).
Formation of Fe³⁺ as well as O₂ evolution WHY?
➢ change in pH
➢ IR drop due to insulating film
Passivators of iron
• Passivators are inorganic oxidizing agents, which react slowly when in direct contact
with iron.
• They are adsorbed on the metal surface.
• Higher the concentration of passivator, more readily it adsorbs.
• CrO₄²⁻, NO₂⁻, MoO₄²⁻, WO₄²⁻, FeO₄²⁻
Passivity in iron alloys
• Fe alone is not naturally passive (i.e., corrodes in short time)
• Cr is a naturally passive metal (i.e., remains bright & tarnish-free)
• Fe-alloy has passive property when at least 12% Cr is added.
Theory of passivity
Oxide film theory
◦ Metal oxide or other compound is formed
◦ This oxide separates metal from the environment
◦ Eventually slows down the rate of reaction
◦ Effectiveness of corrosion reduction depends on the nature & properties of thin
protective film.
Adsorption theory
◦ Passivity is achieved due to chemisorbed film of O₂ or other passivating agents.
◦ This film separates metal from water or other corroding environment.
◦ Film may be of monolayer or multilayer.
Q. Under what conditions pitting corrosion is formed? Underline its mechanism.
2. Pitting corrosion:
Definition: Pitting corrosion is a localized accelerated attack, resulting in the formation of
cavities around which the metal is relatively unattacked.
The protective oxide layer on the metal surface gets damaged at specific points due to
chemical attack. scratches or cut edges, thereby giving rise to the formation of small anodic
and large cathodic parts.
Due to the above conditions, rapid penetration of oxygen takes
place through some cracks in the oxide film, and pitting takes
place leading to the destruction of their passivity and the metal
corrodes more and more.
Eg. Al, Ti and stainless steel undergo pitting corrosion in acidic
environment.
Presence of crevice or Damage of the passive film due to external
crack, Damage of the passive film due to Cl- ions
Wear Corrosion Occurrence of Wear depends on
 Wear is a process of removal of material • Geometry of the surface
from one or both of two solid surfaces in • Applied load
solid state contact, occurring when these • The rolling and sliding velocities
two solid surfaces are in sliding or rolling • Environmental conditions
motion together. • Mechanical, thermal, chemical and
 Wear is the progressive damage, metallurgical properties
involving material loss, which occurs on the • Physical, thermal and chemical
surface of a component as a result of its properties of the lubricant.
motion relative to the adjacent working parts.
Wear Analysis Types of wear process
❑ In analyzing a wear problem
in a machine, it is necessary Surface
Abrasion Erosion Adhesion
to determine the kind of wear Fatigue
that occurred. Solid & Fluid
Fretting
❑ Analysis requires Low stress Adhesive Pitting
Impingement
microscopic examination of High stress Seizure Spalling
Cavitation
the worn area and a close Gouging Galling Impact
Slurry
Polishing Oxidative Brinelling
look at the used lubricant. Erosion
wear
❑ Wear is generally
proportional to the applied
load and the amount of
sliding.
 Types of Wear
Adhesive Wear Polishing Wear Electro-corrosive Wear Cavitation damage
Abrasive Wear Contact Fatigue Fretting Wear False brinelling
Erosion Wear Corrosive Wear Electrical discharge Wear

1. Adhesive Wear 1.1 Adhesive wear - Prevention

• The removal of material due to adhesion
between surfaces MECHANICAL LUBRICANT
• Mild Adhesion - the removal of surface Resuce load, Use more viscous oil to
films, such as oxides, at a low rate. speed and separate surfaces
• Severe Adhesion - the removal of metal temperature
due to tearing, breaking, and melting of Improve Oil Use ‘extreme pressure’
metallic junctions. This leads to scuffing or cooling (anti-scuff) additives as
galling of the surfaces and even seizure. a sulfur-phosphorous
or borate compounds
Use compatible metals
Apply surface coatings such as
phosphating
2. Abrasive Wear 2.1 Abrasive Wear Prevention
▪ Abrasive Wear – the cutting of furrows MECHANICAL LUBRICANT
on a surface by hard particles. (For
example, sand particles between Remove abrasive by Use oil free
contact surface, or hard asperities on an improved air and oil of abrasive
opposing surface) filtering, clean oil particles
handling practices,
❖ Hard coatings can reduce abrasive improved seals, flushing
wear. and frequent oil changes
Minimize shot peening, Use more
beading, or sand viscous oil
blasting of surfaces
because abrasives
cannot be completely
removed.
Increase hardness of metal surfaces
3. Erosion Wear 4. Polishing Wear
• Cutting of furrows on a surface by • Continuous removal of surface films,
hard particles contained in a fluid laid down via a chemical reaction from
traveling at high velocity. an additive in oil or by very fine hard
particles in the lubricant, and so on.
• Polishing wear is characterized by
shiny, smooth, mirror like metal
surfaces. Fine abrasives wear away
surface films as they form and reform.
4.1. Polishing Wear prevention
3.1. Erosion Wear - Prevention
MECHANICAL LUBRICANT
MECHANICAL LUBRICANT
Remove abrasive by Use oil free of None Choose less
improved air and oil abrasive chemically active
filtering, clean oil Particles additive.
handling, improved Remove corrosive
seals, flushing and contaminant.
frequent oil changes
Reduce impact angle to Use more Remove abrasive.
less than 15o viscous oil
Increase hardness of metal surfaces
5. Contact Fatigue 6. Corrosive wear
• Cracking, pitting, and ▪ Corrosive wear- the removal of
spalling of a surface in corrosion products from a surface by
sequence due to cyclic motion, such as the rubbing off of
stresses in a contact. rust.
▪ Contact fatigue is most 6.1 Corrosive Wear prevention
common in rolling
MECHANICAL LUBRICANT
element bearings, gear
teeth, and cams. Use more Remove corrosive
5.1 Contact Fatigue prevention corrosion resistant material such as
metal (not too chemically
MECHANICAL LUBRICANT stainless) active additive and
Reduce contact Use clean, dry oil. contaminates
pressures and
frequency of cyclic Reduce operating Use improved
stress. temperature corrosion inhibitor.
Use high quality Use more viscous
vacuum melted oil Eliminate corrosive Use fresh oil.
steels. material

Use less abusive Use oil with higher-

surface finish pressure viscosity
coefficient
Crevice Corrosion
Crevice corrosion occurs between two joining surface which may be metal-metal or
metal-non metal crevice. It is localized corrosion of metal or alloy surface. In crevice
corrosion, the joining surface area has low concentration of oxygen as compare to other
area. The portion with lower concentration of oxygen become anode and portion with
higher concentration of oxygen becomes cathode. Mechanism of corrosion is similar to
absorption of oxygen step of electrochemical theory of corrosion.
 (a) (b)

(c)

▪ Microstructure of steel is made up of grains separated

by their boundaries.
▪ Bulk of the grains remain largely unaffected by
corrosion.
▪ Cr added (~12%) in stainless steel passivates the
metal surface by precipitating as chromium carbide at
the grain boundaries (GBP), resulting in localized Cr-
depleted zones (PFZ) adjacent to those grain
boundaries, leaving PFZ area vulnerable to corrosive
attack (IGC) in certain electrolytes.
Stress Corrosion Cracking
• Stress-corrosion occurs when fine cracks propagate through a metal
or alloy exposed to applied/residual stress + corroding environment.
• Stress cracking often appears as brittle mechanical fractures that
resembles a network of tree branches.
• It’s a form of galvanic corrosion, with stressed area behaving as
anodic and unstressed area as cathodic.
• Stress cracking is influenced by factors such as metal composition,
structure, temperature and chemical environment.
• Mild steel and Al cracks in presence of alkali and nitrates; Cu alloys
crack when exposed to NH3; High-tensile steels undergo brittle
cracking in aq. environments, especially when chlorides are present.
Hydrogen embrittlement – a type of stress corrosion
What is Hydrogen Embrittlement (Stress Corrosion Cracking)?
Atomic hydrogen is a cathodic product of many electrochemical reactions. Atomic
hydrogen, due to its small size and mass will easily penetrate most clean metal surfaces
and migrate rapidly to favorable sites where it precipitate as molecular hydrogen to form
small pressurized cavities/cracks/large blisters, or it may react with the base metal to form
hydrides.
The accumulation of hydrogen in high strength alloys leads to stress cracking and is often
referred to as hydrogen induced cracking or hydrogen embrittlement.
For this reason, all processes such as pickling or electroplating must be carried out under
well controlled conditions to minimize the amount of hydrogen generated.
Hydrogen may be introduced during:
1. During melting and entrapped during solidification
2. Anodic reaction during corrosion
3. Hydrogen gas welding.

28
 Choice of Materials Impacts of Hydrogen Embrittlement
All types of structural materials will be Hydrogen is one of the most influential
exposed to hydrogen at elevated pressures alloying elements.
and expected to perform their function.
Steel: transmission pipelines, compressors, Many metals and alloys readily absorb
storage containers, dispensers. hydrogen from H2(g) or other hydrogen
Al Alloy: containers, tube trucks, on-board bearing environments.
storage. Hydrogen dissolves as an interstitial and
Polymers and Polymer Matrix Composites - diffuses rapidly.
distribution pipelines, storage containers.
Stainless Steels: fuel cell containers and Hydrogen alters physical properties.
components, on-board tubing and storage. Hydrogen can dramatically alter the
Ni-Based alloys: compressors, valves, deformation and fracture behaviour of
bearing surfaces. metals and alloys by
Others: Cu alloys, Ti alloys. • Modifying normal modes of
deformation and fracture
• Precipitating as brittle metal hydrides
or H2(g) blisters
• Induce new brittle “cleavage-like”
fracture modes
• Lowering the cohesive strength of
interfaces.
Boiler Corrosion: Scale and Sludge formation in boilers
In boilers, water evaporates continuously (for steam production) and concentration
of the dissolved salts also increases continuously. When their concentration
reaches a saturation point, they precipitate in the form of scales and sludges.
• Scales: hard deposits, which stick very firmly to the inner surface of the
boiler. Scales are the main source of boiler troubles.
• Sludge: soft, loose and slimy precipitate formed within the boiler.
• Sludge can be easily scrapped off with the wire brush.
• Formed comparatively colder portions of the boiler and collects in the bends
where the flow rate is slow.
• Sludges have greater solubility in hot water than in cold water, Ex., MgCO3,
MgCl2, MgSO4, CaCl2, etc.
Disadvantage of sludge formation
• They are poor conductor of heat, so they tend to waste a portion of heat generated.
• If sludges are formed along with scales, the sludges get entrapped in the scales
and both get deposited as scales.
• Excessive sludge formation disturbs the working of the boiler by settling in regions
of poor water circulation (bends, connection points) thereby choking the pipe line.
Prevention of sludge formation
By using well softened water and by frequent blow-down operation (drawing off
a portion of the concentrated water)
Formation of scales may be due to:
(1) Decomposition of calcium bicarbonate (soft scales, low-pressure boiler)
(2) Deposition of Calcium Sulphate (hard scales, high pressure boiler)
(3) Hydrolysis of magnesium salts (soft scales, low-pressure boiler)
(4) Presence of Silica
1. Decomposition of calcium bicarbonate
• Scale composed chiefly of calcium carbonate is soft and is the main cause
of scale formation in low-pressure boilers.

Scale
• But in high-pressure boilers, CaCO3 is soluble.
CaCO3+ H2O Ca(OH)2 (Soluble) + CO2

2. Deposition of Calcium Sulphate

• Solubility of CaSO4 in water decreases with increasing temperature. It is
soluble in cold water, but almost completely insoluble in super-heated water.
• CaSO4 gets precipitated as hard scale on the heated portion of the boiler,
whereas, it is relatively dissolved in the colder portion of the boiler. This is
the main cause of scales in high-pressure boilers.
• The solubility of CaSO4 in water decreases with increase of temperature.
• CaSO4 is soluble in cold water, but almost completely insoluble in super-
heated water.
Temperature Solubility of CaSO4

15oC 3200 ppm

230oC 55 ppm
320oC 27 ppm
• CaSO4 gets precipitated as hard scale on the heated portion of the boiler,
whereas, it is relatively dissolved in the colder portion of the boiler. This is
the main cause of scales in high-pressure boilers.
3. Hydrolysis of magnesium salts
Dissolved magnesium salts undergo hydrolysis to produce magnesium
hydroxide precipitate which forms a soft type of scale.
MgCl2 + 2H2O Mg(OH)2 + 2HCl

4. Presence of Silica
Presence of silica even in small quantities deposits as calcium silicate (CaSiO3) or
magnesium silicate (MgSiO3). These deposits stick very firmly on the inner side of the
boiler surface and are very difficult to remove. Important source of silica in water is the
sand filter.
What are the disadvantages of scale formation?
1. Wastage of fuel: Due to low thermal conductivity of the scales, the rate of heat
transfer from boiler to inside water is greatly decreased. Hence, over-heating is
done which causes wastage of fuel.
Thickness of scale in (mm) 0.325 0.625 1.25 2.5 12

Wastage of fuel 10% 15% 50% 80% 150%

2. Lowering of boiler safety: Due to over-heating, the boiler material becomes softer
and weaker, may explode under high-pressure conditions.
3. Danger of explosion: When thick scales crack, water comes in contact with over-
heated boiler surface. This results in the formation of large amounts of steam which
will increase the boiler pressure and may cause even explosion.
4. Decrease in efficiency: Scales deposit in the boiler parts and block the flow of heat
and water, resulting in reduced efficiency of the boiler.
Disadvantages of hard water
1. Caustic embrittlement
2. Boiler Corrosion
1. Caustic embrittlement: is a type of boiler corrosion, caused by
using highly alkaline water in boiler.
o During softening of hard water by lime [Ca(OH)2]-soda [Na2CO3] process,
the excess Na2CO3 present in softened water decomposes to NaOH and
CO2 in high pressure boilers.

Na2CO3 + H2O → 2 NaOH + CO2

o This NaOH makes the water caustic.

o The NaOH containing water flows into minute cracks present in the boiler
by capillary action.
o As water is boiling, it evaporates and the conc. of NaOH increases slowly.
o This caustic soda attacks the boiler and forms sodium ferroate (Na2FeO2)
which makes the boiler parts brittle (embrittlement).
Concentration cell formed during caustic embrittlement
Caustic attack on boiler parts can be represented as:
+ _

Iron at rivets, Conc. NaOH Dil. NaOH Iron at

bends, joints, soln. soln. plane
etc. surfaces

o The iron in contact with dil. NaOH becomes cathode and the iron in
contact with conc. NaOH becomes anode. The anodic part slowly
corrodes and dissolves.
o Caustic embrittlement can be avoided by adding:
a) sodium phosphate (Softening agent)
b) tannin or lignin (Blocks hair line cracks)
c) sodium sulphate (Blocks hair line cracks); With increasing boiler
pressure, the amount of Na2SO4 added is also increased.

Na2SO4 /NaOH conc. 1:1 2:1 3:1

Pressure 10 atm 20 atm >20 atm
Boiler corrosion
o Decay of boiler material by chemical or electrochemical attack by
surrounding environment. Reasons for boiler corrosion are:
a) Dissolved oxygen
b) Dissolved carbon dioxide
c) Acids from dissolved salts
a) Dissolved oxygen (DO):
2 Fe + 2 H2O + O2 → 2 Fe(OH)2 (ferrous hydroxide)

4 Fe(OH)2 + O2 → 2[Fe2O3.2H2O] Rust or corrosion

DO can be removed by adding calculated qty. of sodium sulphite or

hydrazine or sodium sulphide:
2 Na2SO3 + O2 → 2 Na2SO4
N2H4 + O2 → N2 + 2H2O
Na2S + 2O2 → Na2SO4
Hydrazine removes O2 without increasing the concentration of dissolved solids. The
products (N2 and H2O) are also harmless. Hence, hydrazine is the most efficient
internal treatment chemical for the removal of dissolved oxygen.
DO can be removed by mechanical aeration also. Water spraying in a perforated plate-fitted
tower, heated from sides and connected to Vacuum pump. High temperature, low pressure
and large exposed surface reduces dissolved oxygen in water
b) Dissolved CO2:
o Dissolved CO2 forms carbonic acid which corrodes the boiler
slowly.
CO2 + H2O H2CO3
o Mg(HCO3)2 Mg(OH)2 + 2 CO2

o CO2 is removed by adding calculated quantity of ammonia:

2 NH4OH + CO2 (NH4)2CO3 + H2O

o It is also removed by mechanical aeration along with oxygen.

c) Acids from dissolved salts:

o Dissolved magnesium salts hydrolyze to form acids:
MgCl2 + 2 H2O → Mg(OH)2 + 2 HCl
o This acid reacts with boiler in chain-like reactions producing HCl:
Fe + 2 HCl FeCl2 + H2
FeCl2 + 2 H2O Fe(OH)2 + 2 HCl

o Even a small quantity of magnesium salts will cause large amount of

boiler corrosion.
Important Note: Slides 38-41 are additional content on boiler corrosion.
Just read once and understand…
Corrosion in boiler 1) Boiler water treatment
• Protective magnetic layer may be Why needed?
damaged either chemically or • To control corrosion.
mechanically. • To prevent scaling of boiler tubes
• Pitting may be occur in localized (lowers heat transfer rate)
region. • To reduce SiO2 (damages turbine
• Excess OH- concentration (chemical blades)
damage). Steps???
• Differential concentration of • Removal of dissolved gases (O2,
oxide & metal (mechanical damage). CO2).
• Addition of alkali.
• Use of inhibitors.
2) Removal of dissolved gases 3) Alkali addition
• Dissolved gases causes pitting • Alkali (NaOH) addition is usual
corrosion in tubes practice
• Deaerated by steam • Caustic embrittlement may occur.
• Deaerated by O2 scavengers (Na2SO3, • NH3 is sometimes added instead of
N2H4). NaOH.
• Dissolved CO2 should be removed • NH3 is volatile.
(carbonic acid is corrosive to steel). • Does not accumulate in crevices.
• CO2 accumulation is avoided by CO2 • Crevice corrosion does not occur.
release during boiler blowdown.
 Corrosion in boilers and super heaters
 It is degradation of metal components due to chemical reactions, primarily driven by
high temperatures, dissolved gases like oxygen, formation of carbonic acid from
dissolved CO2 gas, caustic embrittlement from high alkalinity, ash deposit in super-
heaters and impurities in the water, leading to tube thinning, pitting and cracking.
 Fire-side corrosion is major reason for failure in super heater and re-heater tubes.
 In waste-recovery boilers, chloride and sulfate dissolves the protective iron oxide
and brings the bare steel in contact with the corrosive environment, resulting in
formation of iron sulfide rather than iron oxide.
 The carbon and iron sulfide present in the ash deposits indicate reducing
conditions. Hydrogen chloride can impact iron sulfides instead of oxides to form iron
chloride as a corrosion product. The iron chloride consists of a relatively low boiling
point and forms vapors in the super-heater / re-heater temperature range. The
corrosion mechanism is by the loss of iron as a vapor.
 Furnace wall tubes are also impacted through fireside corrosion. Sodium and
potassium pyrosulfate (Na2S2O7 or K2S2O7) causes the furnace wall corrosion. Both
the elements melt below 800 oF, where the furnace wall tubes operate. The melting
point of Na2S2O7 is 750 oF and K2S2O7 is 570 oF. Combining the two compounds
can melt at even lower temperatures.
 Effects of boiler corrosion:
Lost Efficiency: Scale buildup contributes to more corrosion by trapping sodium under
the scale, pitting the inside surface. It leads to further damage inside the boiler and its
tubing. Holes in the metal result in leaks that cause severe operational problems and
boiler shut down.
Shorter Lifespan: Overlooking corrosion reduces the lifespan of the steam boiler
system. The efficiency loss degrades until the system shuts down.
Higher Costs: Corrosion can lead to excessive costs for repairing the system or
replacing damaged parts. In many cases, pitted tubes or parts need to be replaced
rather than repaired. The system should be shut down to fix the damage that reduces
productivity.
Pitting: Steam boilers having high levels of oxygen react with the metal to cause pits
on the surface. If overlooked, the pits continue to deepen till they create holes in the
metal. The holes can lead to the failure of the system.
Holes: Holes occur while operating a system with severe pitting. The pits do not repair
themselves or reverse their severity. It deteriorates as the chemical reaction that
caused the erosion continues until the metal has a breech.
Preventing Corrosion in Steam Boiler
• Monitoring the System: Maintaining the acid-base balance of the water is crucial to
prevent acidity from damaging the steam boiler.
• The pH for feed water is between 7-9, slightly alkaline.
• Sodium phosphate salts or sodium hydroxide are added to control the water within
the range. Checking the water and steam for sodium also helps in preventing
corrosion by determining the need to control the minerals present in the system.
• Adjusting Feed water: It prevents the impact of dissolved oxygen on the metal
surface of the system. Depending on the results, scavenging agents or added or a
deaerator is used for getting rid of oxygen.
Three chemicals are common for scavenging oxygen
1. Sodium sulfite: Usually used in medium or low-pressure systems
2. Hydrazine: Ideal for high-pressure boilers
3. Sodium erythorbate: Non-toxic and can replace the other two chemicals for use
in food processing.