Chapter 9 Automotive Corrosion Environment

9.1 Conductivity of Water

Water is modelled as a covalently bonded molecule H
2
O. Transition of covalently bonded
water to ionically bonded water is expressed as the ionization constant K
w
for water.
H
2
O <-> (H
+
) + OH
-
Covalent bond Ionic bond
The value of this constant is temperature dependent, but at 25 C it is 1.01x10
-14
. The pH is
the square root of the ionization constant K
w
. If the H
+
ions exceed the OH
-
ions the medium
is acidic and is represented by a pH from 1 to 7. If OH
-
ions exceeds the H
+
ions the
medium is alkaline (pH from 7 to 14).
The resistivity of water varies depending on its source. Approximate value of the resistivity
(ohm meters) are given. The effect of this resistivity has a marked effect on the corrosion
profile in a given system as shown in Fig 10.1.
Table 9.1 Resistivity
Pure water 20,000,000
Distilled water 500,000
Rain water 20,000
Tap water 1-5000
River water (brackish) 200
Sea water (coastal) 30
Open sea 20-25
9.1 Conductivity of Water
Water, however, is not pure. It contains gases which dissolve in the water to produce
charge carriers, which upsets the equilibrium between the H
+
ions and OH
-
ions. Thus,
when rain water falls through the atmosphere, it dissolves carbon dioxide and both sulphur
dioxide and sulphur trioxide. These are acidic gases and dissolve in water to form a weak
acid but the number of ions is significantly increased by this up-take. Hence such as solution
will greatly assist the corrosion reaction in providing more charge carrier for the liquid
environment.
9.1.1 Dissolved gases and solids
The solubilities of oxygen, carbon dioxide and sulphur oxides in water are temperature
dependent as shown in Table 9.2 and dependent on the salinity of the water.
Table 9.2 The solubility (cubic metres per cubic metre of water under 1 standard
atmosphere) of various gases in water will affect the resistivity and aggressiveness of the
medium.
Temperature of water (
0
C)
0 20 40 60
CO
2
1.676 0.848 0.518 0.360
N
2
0.0230 0.0152 0.0119 0.010
O
2
0.047 0.03 0.022 0.019
Sulphur oxide 79.8 39.4 18.8 -
Chapter 9 Automotive Corrosion Environment
These oxides of carbon and sulphur are responsible for the industrial aggressive
environments, while the dependence of the salinity of the solubility of oxygen is thought to
account for the effect of salt concentration on corrosion rate for steel as shown in Fig 9.1
and 9.2.
Solids must ionize for the solid to be dissolved in water. Hence a salt, such as the road de-
icing salts (NaCl), will produce ions (Na
+
and Cl
-
) which will again act as charge carriers in
the liquid environment without affecting the pH. The corrosion rates show the marked effect
of the addition of these charged carriers, which increase the aggressive nature of the liquid
medium. Note that the industrial atmospheres containing sulphur dioxides are more
aggressive.
Fig 9.1 A schematic diagram indicating the
effect of good and bad resistivity of the
aqueous phase on the surface of mild steel.
Fig 9.2 The effect of salt concentration on the
corrosion rate of mild steel was studied by
using intermittent salt spray at 5 C.
Chapter 9 Automotive Corrosion Environment
In Fig 9.2, the reason for the decrease in corrosion rate with the increase in salt
concentration is due to the decrease in oxygen uptake with increase in salinity.
9.2 Road De-Icing Salts: Their equivalence to sea water
Consider an ideal situation where a piece of steel can corrode in two media: pure water and
sea water (Fig 9.1). Both sea water and road de-icing salts contain sodium and calcium
chlorides. The effect of the chloride ion upon the corrosion rate is immense.
In the pure water without chloride, the Fe
2+
ion is taken out of solution by the OH
-
ions from
the water. The insoluble ferrous hydroxide Fe(OH)
2
initially forms a film over the steel
which act as a good barrier layer through which oxygen must diffuse to get to the steel
surface so that the cathodic reaction can take place. The pH of a saturated solution of
ferrous hydroxide is 10.5 and so the steel is also in an alkaline environment. The rate of
corrosion in alkaline media is low owing to the presence of a protecting passive film on the
surface of steel.
Fe
2+
+ 2OH
-
<-> Fe (OH)
2
The iron ion Fe
2+
becomes more soluble and mobile in the presence of chlorides and so can
move away from the metal-liquid interface and react with the hydroxyl ions OH
-
away from
the dissolving area. This prevents the ferrous hydroxide film Fe(OH)
2
from being deposited
on the surface of the steel and thus there is no barrier film through which the oxygen has to
diffuse. The road de-icing salts therefore make the liquid environment more aggressive by
providing more mobility to the Fe
2+
ions, and more charge carrier (Na
+
and Cl
-
ions) in the
liquid environment. Thus the corrosion reaction is accelerated.
Chapter 9 Automotive Corrosion Environment
9.3 Effect of Dissolved Oxygen
Oxygen is removed from water by the following:
1) Corrosion of steel
2) Dissolved salts
3) Biological decay
4) Increase in temperature.
The corrosion of iron in oxygenated water is a parabolic curve. The initial corrosion rate may
reach a figure of 100 mg dm
-2
day
-1
, which rapidly falls as the ferrous hydroxide is deposited
on the steel surface (as low as 10-25 mg dm
-2
day
-1
). The corrosion reaction rate is
controlled mainly by the diffusion of oxygen to the steel surface. The corrosion rate reaches
a maximum with high oxygen levels because the excess of oxygen required by the cathodic
reaction is available to form a passive oxide film on the steel. This effect is not often
observed in automotive corrosion because most corrosion cells are formed by differences in
the replenishment rates of oxygen. Under these conditions of very high oxygen
replenishment, the metal is very susceptible to pitting corrosion, which once started will set
up and can not be destroyed once they have been set up. Localized metal penetration is the
result.
Chapter 9 Automotive Corrosion Environment
9.4 Effect of Dissolved Salts on Oxygen Uptake in Water
The amount of oxygen which water can dissolve is dependent on the concentration of
dissolved salt as shown in Fig 9.2. Here the corrosion rate at first increase with salt content
and then at 3% of sodium chloride in solution it falls to below the corrosion rate for pure
water when over 20% salt solution is dissolved. This is because the oxygen solubility falls
with salt content. The initial rise in corrosion rate with salt content, shown in Fig 9.2, is
almost certainly due to the fact that the anodes and cathodes can be further away from
each other when the medium contains salt than when the steel is in pure water. In pure
water the anodes must be near to cathodes owing to the poor conductivity of the medium.
As the salt content rises, the conductivity rises and so the distance between the local
electrodes may increase. Because of this increase in distance between anodes and
cathodes, the protective ferrous hydroxide Fe(OH)
2
is no longer deposited as the barrier
layer.
9.5 Hygroscopic Salts, Deliquescent Salts
The air which we breath consists of oxygen (23% by weight), nitrogen (75% by weight),
carbon dioxide (0.04%) and water vapour (0.7% by weight at 10C). This water vapour is
invisible in the air and only shows its presence when the air becomes cold, whereupon the
water condenses out as dew, fog or clouds. The amount of water taken in by the air is
expressed as the relative humidity:
Chapter 9 Automotive Corrosion Environment
9.5 Hygroscopic Salts, Deliquescent Salts
Relative humidity = (amount of water vapour in the air)/ (amount of water vapour required to
saturate the air) X 100
This is expressed as a percentage. A relative humidity of 30% means that the air is very dry,
while a relative humidity of 95% means that the air is very damp. Cold steel will reduce the
temperature of the adjacent air and water will condense onto the metal, giving the concept
of a metal sweating. Water vapour in the colder layer of air adjacent to the car body in the
late evenings and early mornings condense out on the car body and in crevices and on
hygroscopic salts. The main road de-icing salt are hygroscopic NaCl and CaCl
2
. Saturated
solution of salts have an equilibrium relative humidity. The relative humidity of the air in
equilibrium with saturated solution at 20C for NaCl and CaCl
2
is 76% and 36%,
respectively.
A hygroscopic salt is a compound, a salt, which absorbs water from the atmosphere to
produce an electrolyte. In some case the compound will make a pool of water at its site and
the materials is said to be deliquescent. A hygroscopic salt therefore can be considered to
be artificially increasing the relative humidity of its immediate environment. Thus the
hygroscopic salt produces an environment which is wetted earlier as the relative humidity
rises and remains wet for a longer period after the relative humidity falls. Hence the road de-
icing salts NaCl and CaCl
2
will not start to dry out until the relative humidity falls to 76% and
32%, respectively.
Chapter 9 Automotive Corrosion Environment
9.5 Hygroscopic Salts, Deliquescent Salts
There are many salts which are hygroscopic, but the main ones in the corrosion of the
motor vehicle are phosphoric acid and its salts, which arise from the metal pretreatment
process and the road de-icing salts. The excess or unreacted phosphoric acid from these
preparation should be removed with distilled water in order to make sure that the
hygroscopic contaminants are not trapped beneath the new paint films. Tap water is
unsuitable as the water contains several dissolved salts. Research has shown that
sulphates are main cause of paint breakdown by blistering. The sulphates may arise from
industrial atmospheres.
9.6 Critical Humidity
Water molecules are chemically bound to the
surface of the metal by weak van der waals
bonds. It is estimated that at a relative humidity of
55% there is a surface film some 15 molecules
thick upon the surface of mild steel, and this
increase to 90 molecular layers as the relative
humidity rises to 100%. These surface-adsorbed
layers are capable of supporting the corrosion
process above 60% relative humidity. This is very
pronounced if the atmosphere contains sulphur
dioxided (Fig 9.3).
Fig 9.3 The corrosion rate of iron varies markedly with SO
2
, humidity
and particles, accelarating quickly at a critical humidity of over 70%.
Chapter 9 Automotive Corrosion Environment
9.7 Effect of Capillary
Condensation
Some important consequences for water
ingress into porous materials such as
paint films or the narrow crevices are
as follows:
1) Water will condense more easily
upon a concave surface than on a
flat surface.
2) Water will evaporate from a convex
surface and condense upon a flat
surface or concave surface.
3) Once capillaries contain water it is
very difficult to dry them out as their
surface profile is always concave.
4) Protective coatings (e.g., paints and
chromium plating) contain micro-
capillaries which take a long time to
dry and act as preferential sites for
atmospheric condensation.
Fig 9.4 Capillary rise is inversely proportional to the
crevice gap or capillary radius r.
Chapter 9 Automotive Corrosion Environment
9.8 Effects of Surface Tension
water
Two dirt particles with a small amount of water will be attracted towards each other to
gain the minimum surface area for the amount of water present. This will ensure that the
dirt particles are in contact in three dimensions (i.e., compacted). As the amount of water
with each dirt particle increases, the minimum surface area for the associated water can
only be obtained by pushing the dirt particles apart as shown in (b). This will not be self-
compacting.
Dirt particle
water
Small amount of water leads to
compact by capillary action
Larger amount of water leads to an
open structure
(b)
(a)
1) The compact of road dirt by the phenomenon of surface tension is important in the
building-up of the aggressive micro-climate within the car body structure.
2) The small amount of water present upon each road dirt particle means that there is
insufficient water to wash away and clear the road dirt which is deposited out of
wheel spray.
3) The slower the car travel, the larger will be these water droplets, and the higher the
ratio of water to dirt which they can contain.
Fig 9.5 Effect of surface tension
Chapter 9 Automotive Corrosion Environment
9.9 Road De-icing Salts
Road de-icing consist of naturally occurring sodium and calcium chlorides mixed with fine
sands which also act as an abrasive owing to the relative speed of the car body and road.
This mixture, is spread onto the roads as a safety measure.
In some countries these salts (especially calcium chloride) are made use of to keep down
the dust on minor (dirt) roads. They keep the dust down because they are hygroscopic and
deliquescent thus absorbing the atmospheric water vapour at low humidities.
The road de-icing salt melt the snow and ice because they depress the equilibrium
temperature at which ice co-exists with its liquid (saline) state. If these The maximum
freezing point decrease is concentration dependent. Thus the freezing point of water with
soluble additions are usually shown in a phase diagram. One section of the phase diagram
for both sodium chloride and calcium chloride is shown in Fig 9.6(a) and 9.6(b) respectively.
This shows the maximum freezing point depression being -21C for sodium chloride and -
55C for calcium chloride. The addition of sodium chloride to crushed ice cubes from the
refrigerator at 0C will actually produce this temperature of -21C (if 23.31% sodium chloride
in the mixture; -55C is for 30% calcium chloride). Hence it would appear that by the
addition of road salts to our roads we are making the road and ice-colder. In actual fact we
do make them colder, but then the road can take up heat from the surrounding atmosphere
which may be at -5C. More and more ice will melt in trying to keep tehice-salt mixture at -
21C until all the ice has melted. Hence the addition of road de-icing salts to our roads will
only work if the ambient temperature is above -21C. CaCl
2
must be used where the
ambient temperature can be as low as -55C.
Chapter 9 Automotive Corrosion Environment
9.9 Road De-icing Salts
Fig 10.6 (a) and (b) show one section of the phase diagram for both sodium chloride and
calcium chloride, respectively.
(a)
(b)
Chapter 9 Automotive Corrosion Environment
9.10 Concentration of the Road De-icing Salt within Crevices
The road de-icing salts concentrate within the last areas to dry. Among the last areas to dry
are (1) hemming folds or clinches, (2) metal overlap, (3) at or between the motor vehicle
panel and decorative brightwork, plastic guards or any attachment which forms a crevice,
(4) behind the door-tailgate hinges, (5) beneath areas which have suffered paint stripping,
(6) around the door-glass rubbers and (7) around the door return, crevices and folds.
Fig 9.7 and 9.8 show diagrammatically what happens as water evaporates from a crevice
which contains a very dilute solution of road de-icing salts within the crevices area. This is
compared with a similar concentration of saline solution on a flat vertical panel Fig 8.7(b). If
the vehicle is stationary, then after, say 1 h of drying, the water profile would shrink as
shown in Fig 9.7(b). If the vehicle is now considered in motion, then a sudden bump in the
road can displace the droplet on the vertical panel to some other location.
Chapter 9 Automotive Corrosion Environment
Fig 9.7 This shows a water droplet drying (a) with and (b) a dirt particle as a
locating nucleus for water droplet. Vibration will therefore mean that water
droplet will run down the vertical panel as a result of gravity. (C) A water droplet
drying within an inter-weld which acts as a locating nucleus for the water droplet.
9.10 Concentration of the Road De-icing Salt within Crevices
Chapter 9 Automotive Corrosion Environment
Fig 9.8 the same diagrams as Fig. 9.7 except that now the substrate is coated
with a wax or oil which presents a hydrophobic surface to the saline droplet. The
right one shows a water droplet excluded from the wax-oil-coated crevice. Any
dissolved salts such as the road de-icing salts will be concnetrated outside the
crevice at the last area to dry, which is now a well oxygenated area and so the
corrosion rate will be very low.
9.10 Concentration of the Road De-icing Salt within Crevices
Chapter 9 Automotive Corrosion Environment
9.10 Concentration of the Road De-icing Salt within Crevices
Any saline solution left on the panels will dry first. The last area to dry will be the inter-welds
and so these regions will suffer an increase in the concentration of road de-icing salts within
the inter-welds.
9.11 The Motor Industries Acceleration Corrosion Tests
Over the years the raw products used in motor vehicle manufacture have undergone
accelerated corrosion tests based on the traditional laboratory tests. These acceleration test
are numerous in number and some of them are as follows: (1) The ASTM 117B salt spray
test; (2) the cupric chloride accelerated acetic acid salt spray (CASS) test; (3) cyclic
humidity test, which are probably the most reliable; (4) the Corrodkote test, where ferric
chloride is added to the acetic acid salt spray. These accelerated test do not detect a
mechanism of corrosion.
Another series can be used where the corrosive effects are much less and therefore a
longer time is required to show up corrosion and these are the field or service tests. In these
test samples are exposed to the condition which are met in practice. The corrodkote test
was the near service condition that was reached in that a corrosive acetic acid salt spray,
modified with cupric chloride and ferric chloride, was splashed onto the specimen by
rotating paddles and the soiled specimen were then exposed to a humid environment at
high temperatures.
Chapter 9 Automotive Corrosion Environment
10.11 The Motor Industries Acceleration Corrosion Tests
When it came to putting the finished motor car under an accelerated test cycle, the
conditions chosen were not the ideal to simulate service conditions. The accelerated
tests conventionally used to drive the vehicle through a salt ford or dip at low speeds (20
mph) and then to place the vehicles in a humidity chamber (100% relative humidity at
49C) and allow the vehicle to sweat for several hours. Other manufacturers have various
test methods. None of these methods will produce the small spray droplets required to
form the low momentum micro-droplets which will so easily alter direction as a result of
the pressure eddies around the vehicle body.
The large diameter spray from this 20 mph encounter with the salt dip does not produce
the (low momentum) fine particles of spray which will be self-compacting on out of sight
(or out of trajectory) ledges. Also, the high momentum (20 mph) droplet will not be draw
through the manufacturers process drainage holes by the small pressure changes
around the vehicle. This procedural test therefore leads to the acceptance of bad design
faults which lead to premature failure by corrosion as described throughout this book.
Chapter 9 Automotive Corrosion Environment