Corrosion: Destruction or deterioration of materials due to their reaction with the environment.

Inorganic materials are more corrosive than organic materials.

How does corrosion affect costs:

Direct:

 Material loss
 Cost of replacement/repair
 Cost of maintenance
 inability to use materials.
 over-design to allow for corrosion.

Indirect:

 loss of appearance.
 Loss of production
 Loss of valuable products
 Loss of safety

Classification of corrosion:

 High and low temperature corrosion

 Direct combination (oxidation) and electrochemical corrosion
 Wet and dry corrosion. Where liquid phases are present or not present/above dew point of
environment respectively. Example: Dry chlorine is non-corrosive to steel, but moist chlorine
is extremely corrosive.

Corrosion principles:

 Choice of materials affected by corrosion behaviour.

 Thermodynamics and electrochemistry
 Metallurgy (corrosion resistance)
 Physical chemistry (mechanism of corrosion

Corrosion rates:

This is the rate in mills/yr or thousandths of an inch/year.

RATE=
534∗W
D∗A∗T
, where W :weight ( mg ) , D :density
g
cm
3 ( )
, A :area ( in ) , T :time(hr)
2

In SI units, the rate is shown as mm/yr.

76.6∗W 2
RATE= , where Areais∈(c m )
D∗A∗T
To calculate the amount of metal removed during corrosion we can use Faraday’s equation:

I∗t∗M
w= , where I :current ( A ) , t :time ( s ) , M ( atomic mass ) , w : weight corroded (g)
n∗F
If we were given current density which is i (lowercase i) it means the current is expressed as current
density where the units are μA/cm2. i=I/A. We modify the equation giving us:

i∗A∗t∗M 2
w= , where A :area(m )
n∗F
We can also convert corrosion rates to penetration rates:

ai g
penetration=k , wherea : atomic weight , i: curren density , n: no of electrons lost , D: density ( 3 )
nD cm
K is a constant that depends on the rate desired: 0.129(mpy), 3.27(μm/yr) or 0.00327(mm/yr)

Example: Find the penetration rate of iron at a rate of 1 μA/cm 2 . The density of iron is
7.86g /cm 3 and dissolves as ferrous ions (Fe 2 + )

Since the state is 2+, n=2. We can now sub all the values into the penetration equation:

0.129 ( 55.8∗1
2∗7.86 )
=0.46 mpy

What affects corrosion?

 Composition of the environment and metal

 Movement of the environment
 Temperature
 Pressure
 Differences in the environment on a micro scale
 Time of exposure
 Surface condition, structural or physical condition of the metal
 Existence of imposed electrical potentials.

The electrochemical Cell, it is a 4-component setup:

 The anode where corrosion of the metal takes place.

 The cathode where the second metal provides a surface for the environment to react.
 The electrolyte
 The electrical connection to allow current to flow.

Anodes go through oxidation and cathodes go through reduction (RED CAT).

Cathode reactions:
In nature, neutral or basic environments containing oxygen, the reaction is:
−¿¿
−¿❑ 4 O H ¿
O2 +2 H 2 O+4 e →

If the solution is acidic then:

−¿❑2 H 2 O ¿

O2 +4 H + ¿+ 4 e ¿
→

Thermodynamics in corrosion:

Metals have a negative free energy. This indicates that they are reactive to the environment in which
they perform. ΔG=−nFE , where n :number of electrons , E :electrode potential

A standard electrode potential is the potential developed at 298.15K and when the oxidation and
reduction rates are equal.

If they are not equal, then it is shifted from its equilibrium value. This is called polarization.

Nernst equation:

This equation is used to determine the potential when the system is not at its standard potential.

˚ RT
E=E − ∗ln ( Q )
nF
We can modify the Nernst equation to determine if the cell is spontaneous:

˚ RT
∆ V =(V 2 ¿ ¿ ˚−V 1 )− ∗ln ( Q ) ,if ∆ V >0 thenis spontaneous ¿
nF

Activation Polarization:

Activation polarization takes place in 4 steps:

 Step 1: Adsorption (when something gets deposited and accumulated on a surface) of H +

ions onto the metal surface (this is the rate limiting step).
 Step 2: Electron transfer from the metal to the hydrogen atoms (this is the rate determining
step).
 Step 3: Combining of 2 hydrogen atoms to form hydrogen molecules.
 Step 4: The hydrogen molecules combine to form bubbles which is then diffused through the
solution. This step is used to determine if the reaction is occurring.

n a=± β∗log
() i
io
, where na :overvolatage , i:current density

This equation is used to determine magnitude of polarization as overvolts. β and io are constants for
the half cell. This relationship holds for both the anode and cathode.
At equilibrium the rate of reduction = rate of oxidation which can be calculated using:
i0
rate= , wherei 0 isthe exchange current density
nF

Concentration polarization:

 This polarization is caused by concentration changes in the environment adjacent to the

surface.
 If the chemical species participating in corrosion is in short supply, the mass transport to the
surface can become rate controlling.
 At slow reaction rates and/or high concentrations, there will always be enough ions near the
electrode surface hence the reaction can proceed unhindered.
 At high reaction rates and/or low concentrations, the ions are not replaced fast enough by to
keep up with the reaction rate.
2.303 RT i
 To calculate overvoltage, we use the following formula: n c= log ⁡(1− )
nF iL

Combination polarization:

 This is the curve of log current density vs overvoltage of the activation polarization and the
concentration polarization.
 Activation part has a linear curve, and the concentration polarization decreases rapidly until
the i=iL.

Please look at the graphs on pages 70-72 they give more information on this that I can’t show cos I’m
lazy.

Passivation:

Passivity: Characteristic of a metal where it does not become active in the corrosion due to the
formation of a metal oxide layer on the surface of the metal that protects it.

There are 2 theories for passivation:

 Adsorption film theory: Passive metals are covered by chemisorbed films of oxygen.
 Oxide film theory: A passive film of reaction products acts as a diffusion barrier.

What affects passivation?

 Presence of other ions in corroding solution. It alters the character of the film produced
which can increase or decrease the corrosion rate.
 The tendency of the metal to form a film.
 Rate of flow of solution
 Increase in temperature, this affects the solubility of protective films.

Wet and dry corrosion:

  Wet/aqueous corrosion: the major form of corrosion which occurs at room temperature and
in the presence of water.
 Dry/gaseous corrosion is significant mainly at high temperatures.

Wet corrosion can be classified as:

 Uniform or general
 Galvanic or 2 metal.
 Crevice
 Pitting
 Dealloying
 Intergranular
 Velocity assisted
 Environmental assisted cracking

Forms of corrosion:
 Uniform
 Galvanic
 Pitting
 Intergranular
 Selective leaching or parting
 Erosion
 Stress
 Special forms
 Hydrogen damage
 Biological corrosion
 Metal-gas reaction

Uniform corrosion:

 Is a chemical/electrochemical reaction that proceeds uniformly over time over the entire
surface.
 The metal becomes thinner until it fails.
 It is prevented by coating, inhibitors, and cathodic protection.

Galvanic corrosion:

 It only occurs when 2 dissimilar metals immersed in a corrosive or conductive solution have
contact.
 The driving force is potential.
 The less resistant material is the anode and the more resistant is the cathode.
 The cathode has very little to no corrosion.

What affects galvanic corrosion?

 Environmental effects
 Distance
 Area: the ratio of area between the anode and cathode. The greater the current density the
greater the corrosion.

Prevention:
  Avoid electrical contact of the metals by using insulation.
 Apply coatings but ensure they are in good repair.
 Use inhibitors
 Avoid an unfavourable area effect.
 Use metal combinations with similar electrode potentials.

Crevice corrosion:

 Occurs due to small volumes of stagnant solution collecting in crevices and other shielded
areas on the metal surface.

Prevention:

 Avoid crevices in design.

 Fill existing crevices with sealant.
 Remove dirt and deposits regularly.
 Use solid, non-absorbent gaskets instead of fibrous gaskets.

Pitting corrosion:

 Form of extremely localised attack.

 Small holes or cavities.
 Makes the surface look rough.
 It is autocatalytic in nature.

What affects pitting?

 Solution and composition.

 Velocity, it usually occurs at stagnant conditions hence increase in velocity decreases pitting.
 Metallurgical variables

How can it be prevented?

 Methods used for crevice corrosion can be applied.

 Material selection

Intergranular corrosion:

 Attack at grain boundaries of a metal and adjacent to it. The grain boundaries corrode but
the interior does not.
 It is caused by impurities collected at grain boundaries.

Selective leaching:

 Caused by preferential removal of one element from a solid alloy.

 Overall dimensions don’t change.
  Can be prevented by change in environment, inhibitors and using alloys less susceptible to
leaching.

Erosion corrosion:

 Occurs due to relative motion between the corrosive fluid and the metal surface.
 The rapid movement causes mechanical wear effects or abrasion.
 Passive films can act as protection.
 Soft metals and mechanically worn metals are more susceptible to erosion corrosion.
 Velocity plays a big role in erosion corrosion.

How can it be prevented?

 Change the environment.

 Use materials with better resistance to erosion.
 Use coatings
 Cathodic protection.

Stress corrosion cracking:

 Happens due to a simultaneous action of tensile stress and due to a specific corrosive
medium.
 The metal looks unattacked but fine cracks progress through it.
 Increases design stress.

Important variables:

 Temperature
 Metal and solution composition.
 Stresses
 Not all metals and environments cause SCC.
 Nature of cracking: transgranular (across) or intergranular (along)

Prevention:

 Decrease the stress level

 Reduce temperature
 Add inhibitors
 Change environment
 Change metal if environment can’t be changed
 Apply cathodic protection