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Trethwey & Chamberlain-----Ch-13

Wranglen-----Ch-13
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Case study-1
A series of heat exchangers cooled with
recirculating treated watergave over 10
years problem-free service.
In an emergency untreated river water was
used for 48 hours.
Five units failed because of SCC several
weeks later.
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Case study-2
Copper based alloysexcellent service in
seawater
Failed in few months
Sulfidethe culprit in estuarine water
Thin Sulfide filmcathodic to copper
produces severe pitting at breaks in the
film
Inhibitor0.01% sodium
dimethyldithiocarbamate
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If the bulk environment is gaseous
Methods used to reduce corrosion rate in
atmosphere are:
Lower the relative humidity
Eliminate volatile components
Change temperature
Remove contaminants

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If the environment is a liquid
electrolyte
Modifications include:
Lowering ionic conductivity
Altering pH
Reducing oxygen
Changing temperature
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If the environment is soil.
Control is by:
Surface coating
Cathodic protection
Use backfill to
Improve drainage
Control pH
Change conductivity
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Atmospheric Corrosion
Waterfrom rain, mist or condensation
Heavy rainsbeneficial if the structure is
properly designed
Mist and condensationwet internal and
external surfaces and cause corrosion
Many metals corrodes if relative humidity
exceeds 60% --if 80%, rust on iron becomes
hygroscopic
The rate and severity of attack is not determined
by oxygen but determined by conductivity which
depends on salt contentsvary from area to
area.
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CO
2
in rural areasproduces slightly acidic
solution
SO
2
, SO
3
, nitrous compounds, H
2
S and
ammonium ions contaminate industrial areas
Chloride ionsat marine locations
Effect of temperature
An approx. rule; rate of reaction doubles for
every 10
o
C rise in temperature
However, at higher temp. solubility of oxygen is
reduced, limiting the cathodic reactions
Change in temp affects the relative humidity and
can cause dew point condensation
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Dew point condensation
If the temp falls below the dew point, the
air becomes saturated with water vapors
and free water condenses on exposed
surfaces which are relatively cool.
The droplets can collect in water traps
produce pools of free electrolyte in
sheltered areas, causing corrosion inside
the structure.
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Corrosion in automobile exhausts
If the temp of flue carrying the burnt fuel gas
falls below its dew point before it is released
to atmosphere, condensation takes place.
The fuel gases usually contain sulfur oxides
and nitrogen compounds. These dissolve in
water and form aggressive electrolytes.
Deposits of carbon forms galvanic couples
with the base metal and corrosion originates
from internal surfaces.

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Sulfur trioxide
Produces sulfuric acid
Raises dew point of the gas
Causes condensate to form at a higher temp
Vanadiumanother common fuel impurity
Acts as a catalyst to convert SO
2
to SO
3
in a
combustion chamber
Fuel gas with no SO
3
has dew point 38-46
o
C
Dew point with 5 ppm SO
3
100
o
C
Dew point with 40 ppm SO
3
168
o
C

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Control of Atmospheric Corrosion
Corrosion begins when relative humidity
>60%
Air in warehouses can be heated to decrease
humidity
But it does not eliminate water; condensation still
can cause corrosion
Freeze drying
To reduce relative humidity 30-40%
Use of Desiccants
Should be non-corrosive, cheap and easy to
handle
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Vapor-Phase Inhibitors (VPIs)
Used to protect steel components during
transportation.
Volatile components that spread to occupy
the available free space
They dissolve in moist film and inhibit
corrosion
Beneficial for ferrous materials
Harmful to non-ferrous metals, paints and
plastics
Should be used with care.
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VPIs compounds consist of a volatile cation
and a non-volatile anion
The cations form a thin adsorbed film on the
surface and has two important functions:
1) It is hydrophobic
2) It controls the pH of any moisture layer which
forms on its surface
Carbonates and Nitrites are two typical anions
They are carried with the volatile cation to
deposit on the metal surface.

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Two common VPIs for Steel and Al are:
1. Dicyclohexylamine nitrite (DCHN)
2. Cyclohexylamine carbonate (CHC)
DCHN
Has low vapor pressure
Takes longer time to produce effective film
Maintains protection for longer duration
VP~0.027 Pa at 25C, pH~6.8 in water
1 gram saturates 550 m
3
of air and protects
steel
Inhibits corrosion for several years in secure
packaging
Harmful to non-ferrous, paints, plastics, dyes
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CHC
Has hi VP; 21.3 Pa at 25C, pH 10.2 in water
More quick protective coating
Much shorter life
More useful in containers and stores opened
periodically; VPI can be renewed regularly
and protection is maintained rapidly once the
unit is closed.
No inhibition on Cd
Increases attack on Cu, brass and Mg
Harmful to plastics and paints
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Mixtures of two VPIs are frequently used.
Boratesfor Zinc
Chromatesfor Cu and Cu-alloys
Desiccants or VPIs are used in confined
spaces
All wooden crates should be lined with
polyethylene, tar papers, bitumen-coated
Kraft paper etc, to keep the woods vapors
away from the metal
Preservatives and fire retardants applied to
wood can also increase risk of corrosion
damage to metals when placed in contact
with wood.
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Modification of electrolyte
Corrosion rate is controlled by the slowest of the
cell processes.
May be anodic or cathodic reaction
The presence of any dissolved ions will affect the
corrosion rate by some or all of the following:
Changing the conductivity of the electrolyte
Attacking or strengthening passive films on the metal
surface
Changing the pH
On MS, Anions are aggressive at low conc. and
attack the film.
At higher conc. they may become inhibitive and
suppress anodic dissolution
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An inhibitive anion is adsorbed on the metal
at weak points in the film. It then
Suppresses anodic dissolution of the film
Allows oxide formation to take place and
strengthen the film.
On the other hand, dissolved cations which
are more noble than the metal, can plate on
to the metal surface and cause pitting due to
galvanic corrosion
Reducing conc. of ions in an electrolyte,
reduces ionic current and change anodic
processes.
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Anodic inhibitors
Increase polarization of the anode
An inhibitive anion is adsorbed on the metal at
weak points and produce thin passive film or salt
layer of limited solubility
It then strengthens the oxide film
The inhibitive role of some anions is very weak
and they can be considered aggressive towards
oxide film
The most powerful aggressive ions towards MS
surfaces are:
Sulfates
Thiosulphates
Sulfites
Thiocyanates
Chlorides
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For iron & steels; two types
One, which require dissolved oxygen, such as
Molybdtaes
Silicates
Phosphates
Borates
Second, which are themselves oxidizing, such as
Chromates
Nitrites
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Insufficient amount of inhibitor is
dangerous
Corroding area decreases
Intensity of attack on local anodes
increases
Total corrosion first increases and
then decreases ending into complete
control
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Cathodic inhibitors
Affect oxygen and hydrogen cathodic
reactions
For oxygen cathodic reactions;
2H
2
O + O
2
+ 2e
-
4OH
-
the inhibitor reacts with hydroxyl ions to precipitate
insoluble compounds
the compounds covers the cathodic sites
prevents access of oxygen to the cathodic sites
widely used inhibitors are:
salts of Zn & Mg
which form insoluble hydroxides
salts of Ca
which produce insoluble carbonates
polyphosphates
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For hydrogen cathodic reactions;
Cathodic polarization of the system controls
hydrogen evolution
Salts of As, Bi, Sb are added
Form a layer of adsorbed hydrogen on the
surface of the cathode
Organic compounds are also used which
are non-toxic.
Cathodic inhibitors are safe
Too little inhibitors do not harm the system,
because only cathodic sites are covered
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A combination of both anodic and cathodic
inhibitors are used.
Typically, chromate/polyphosphate/zinc
system
Many inhibitors are organic molecules with
groups of atoms
They are adsorbed or desorbed from metal
surface
These bulky molecules limit the diffusion of
oxygen or they trap metal ions, on the surface
and reduce the rate of dissolution.
E.g. as little as 0.2% agar-agar in distilled
water will reduce the corrosion rate to only
2.7% of rate without agar-agar.
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Removal of oxygen from the solution also reduces
the corrosion rate
Solubility of oxygen at 25
o
C ~ 8.5 ppm in tap water
At 60
o
C ~ 5.6 ppm
At 100
o
C zero
Solubility of oxygen at 25
o
C in seawater ~ 6.5 ppm
Level of diffusion of oxygen in the solution decreases
with depth
Oxygen reduction reaction for pH>7
2H
2
O + O
2
+ 4e
-
4OH
-
Oxygen reduction reaction for pH<7
O
2
+ 4H
+
+ 4e
-
2H
2
O
Corrosion rate of low carbon steel in tap water at 50
o
C
7.5 mm/yr at 6 ppm oxygen
1 mm/yr at 1 ppm oxygen
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Examples of reduced corrosion with
decreased level of dissolved oxygen are:
domestic central heating system using
copper pipes and steel radiators
car engine cooling circuit; cast iron blocks
linked to copper radiators
bimetallic corrosion is initially activated
but diminishes when dissolved oxygen
is consumed and then a black
magnetite layer is formed on steel,
giving protection to it.
3Fe(OH)
2
Fe
3
O
4
+ H
2
+ H
2
O
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Control of aqueous environments
In low temp once-through system using
fresh water
A low cost inhibitor may be used to produce a
thin protective scale
This scale
Is mostly composed of calcium- and magnesium-
carbonates
Should be of negligible thickness
Should be self-healing
Must not grow to impede the flow of water or alter
heat flow
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Production and maintenance of such a scale
requires careful control of water chemistry
Solubility of calcium carbonate in water is very
low
Therefore, the film is precipitated from the
bicarbonate ions produced from dissolved
carbon dioxide
CO
2
+ H
2
O H
2
CO
3
H
+
+ HCO
3
-
If calcium salts are present:
CaCO
3
+ H
2
O + CO
2
Ca(HCO
3
)
2

If too little CO
2
, no scale is formed
Excess CO
2
re-dissolves the film in acid solution
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CO
2
is very soluble in cold water
In boiling condition gas is ejected out
Due to formation of thick scales, differential
aeration cells may be developed.
In case of water boilers, thick scales may
also cause
Reduced heat transfer rates
Loss of efficiency
Increased risk of buckling
Increased risk of forming ash deposits on the hotter
areas at fire side of boiler tubes.
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Amines have a considerable inhibitive effect
Control the harmful effect of CO
2
Neutralizing amines such as Morpholine; added
in small quantities
They are volatile and weakly alkaline
The alkaline vapors dissolve in the condensates to
neutralize the carbonic acid which forms as the CO
2

redissolves
Filming amines such as Octadecylamine
Are volatile but insoluble in water
The vapor is driven off with steam but condenses on
the cooler metal surface to form an oily hydrophobic
layer.
Deaeration can also reduce oxygen;
frequently applied in oilfields.
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Oxygen scavengers
Sodium sulphite
Ammonium bisulphite
Hydrazine;
preferred in high pressure system
N
2
H
4
+ O
2
2H
2
O + N
2

If does not react with oxygen then decomposes as
3N
2
H
4
4NH
3
+ N
2

ammonia acts similar to amines but both
hydrazine and ammonia are dangerous for Cu
base alloys
therefore excess conc. of hydrazine is limited
to very low level i.e. 0.1 ppm
excess sodium sulphite is aggressive to steel
surface
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in modern plants, max dissolved oxygen is
limited to 0.03 ppm
in high pressure power stations oxygen in
feed-water is kept below 0.007 ppm