Corrosion in metals

Galvanic Action
Corrosion within cooling systems can occur if the coolant, i.e. water, has not been properly treated. The
corrosion can take the form of acid attack with resultant loss of metal from a large area of the exposed
surface, or by Oxygen attack characterised by pitting. A primary motive force for this corrosion is Galvanic
action
The Galvanic Series.
Or lectromotive series for metals
Cathode
Gold and !latinum
Titanium
"ilver
"ilver solder
Chromium#$ickel#%ron &!assive'
Chromium#%ron &!assive'
"tainless "teel &!assive'
Copper
(onel
)*+,* Cupro#$ickel
-)#,, $ickel#Copper
.ydrogen
lead
Tin
/#0 Tin lead "older
1ron2es
1rasses
$ickel
"tainless#"teel 03#3 &Active'
"tainless "teel 03#3#, &Active'
Chromium %ron &Active'
Chromium#$ickel#%ron &Active'
Cadmium
%ron
"teel
Cast %ron
Chromium
4inc
Aluminium
Aluminium Alloys
(agnesium
Anode
The metals closer to the anodic end of the list corrode with preference to the metals towards
the cathode end.
A galvanic cell can occur within an apparently .omogeneous material due to several processes
on of which is differential aeration where one area is exposed to more oxygen than another. The area with
less oxygen becomes anodic and will corrode.
Galvanic action within metal
Galvanic action due to temperature gradient
This situation can exist in cooling water systems with complex layout of heat exchangers and
passage ways within the diesel engine. "ystems containing readily corrodible metals such as 2inc, tin and
lead alloys can complicate and intensify problems by causing deposit formations.
Differential Aeration
#5here only a single metal exists within a system corrosion can still take place if the oxygen content of
the electrolyte is not homogenous. "uch a situation can occur readily in a 6acket water system as regions
of stagnant flow soon have the oxygen level reduced by the oxidation of local metal. The metal ad6acent
to water with reduced levels of oxygen become anodic to metals with higher oxygen content electrolyte in
contact with it. Generally, the anodic metal is small in comparison the cathode i.e. the area of stagnant
flow is small compared to the area of normal flow of electrolyte, and high rates of corrosion can exist. One
clear case of this is the generation of deep pits below rust scabs.
Corrosion of Metals
Steel (Fe)
5ill readily corrode by the reaction with oxygen in the water primarily by galvanic action.
The %ron reduces to %ron ions at anode, the oxygen is reduced by combining with water and
electrons passed from the anode &by iron changing to ions' to hydroxyl ions. Temperature, p. and the
concentration of oxygen all affect the rate of corrosion.
The oxygen reacts with the 7e
/8
to form .ematite &7e/O,' . This is a reddish brown loose
deposit. 5ith reduced oxygen content the formation of (agnetite &7e, O9' will occur. This is a more
tenacious layer and forms a protective boundary on the metal preventing further corrosion. This layer may
be removed in low p. or high p. conditions.
"cabs and tubercles of 7erric oxides and 7erric hydroxides form over an active pit.
Stainless Steels
These are alloys of steel with high chromium content &around 00:'. The alloying process results in a
material with excellent corrosion resistance. Oxygen combines with the chromium and iron to form a
tenacious self healing oxide layer.
The disadvantage of stainless steel is that in low oxygen environments, such as boil feed, the
corrosion resistance is actually reduced. %n addition stress corrosion cracking and pitting can occur when
in the presence of chlorine ions. %n this way stainless steel is not recommended in situations were
stagnant sea water might exists at it could perforate ;uicker than mild steel. The chlorine ions are the
correct right si2e to enter the atomic matrix of the metal and their concentration accelerates corrosion by
the propogation of cracks. Catastrophic failure can occur.
Copper(Cu) and Copper allos
<sed in heat exchangers due to there high heat conductivity. Copper corrosion in oxygenated water is
slow due to the time taken for oxygen to diffuse throught the oxide layer.
As copper is a relatively soft metal water velocities must be kept low. %ts presence can lead to
heavy pitting if deposited in steel systems. Ammonia in the water can remove the oxide layer and
promote rapid corrosion
Aluminium (Al)
%s essentially inert in neutral water up to about 03*=C. %t is ampoteric meaning it will corrode rapidly in
high and low p. conditions. %n the presence of "odium Carbonate or sodium hydroxide at p. above > this
corrosion is particularly severe. These conditions may exist were boiling occurs concentrating hydroxyl
ions.
!inc (!n)
%s anodic to steel and is often used as a protective coating on steel in a process called galvanising. %t is
ampoteric, corrosion increases in high and low p. conditions.
Note! At temperatures above 60'C the anodic/cathodic relationship with steel is reversed. This is of
particular importance in engine cooling sstems. The author has !oined a vessel were the third
engineer was merril fitting anodes to the clinder heads of a daihatsu generator engine. The fact
that the engine was fresh water cooled with inhibitor treatment also was ignored
%f galvanised pipes are to be fitted in a cooling circuit the coating must first be removed by
controlled acid washing.
Factors affecting corrosion rates
Temperature
As a rule of thumb for each 0*=C rise in temperature doubles the rate of corrosion.
The rate of oxygen diffusion increases in an open system with temperature up to around 3*=C.
A rapid tailing off then occurs due to the solubility of oxygen. 7or this reason open system feed tanks seen
on many vessels have heating coils which maintain the temeprature at 3?=C or higher.. %n a closed system
there is no such tail off as the oxygen cannot escape
p"#Al$alinit
The electrochemical nature of the metal will determine its corrosion rate with respect to p.. The corrosion
rate of iron reduces as the p. increases to about 0, due to the reduced solubility of the 7e ions.
Aluminium and 2inc, being ampoteric, have rates of corrosion that increases with p. higher or lower than
neutral