Corrosion

Corrosion is the deterioration of materials by chemical interaction with their

environment. The term corrosion is sometimes also applied to the degradation of
plastics, concrete and wood, but generally refers to metals.

Effects of corrosion

Losses are economic and safety:

• Reduced Strength
• Downtime of equipment
• Escape of fluids
• Lost surface properties
• Reduced value of goods

The consequences of corrosion are many and varied and the effects of these on the
safe, reliable and efficient operation of equipment or structures are often more
serious than the simple loss of a mass of metal. Failures of various kinds and the need
for expensive replacements may occur even though the amount of metal destroyed is
quite small.

TYPES OF CORROSION

• 1. DRY or CHEMICAL CORROSION

• 2. WET or ELECTROCHEMICAL CORROSION

DRY CORROSION: This type of corrosion occurs by direct chemical attack of

atmospheric gases like O2 , halogens, hydrogen sulphide etc. on the metal surface. it is
further of following types:

(a) Corrosion by O2 or Oxidation corrosion.

It is due to chemical attack of O2 on the metal resulting the formation of metal

oxide layer as:

2M + nO2-------- 2MOn(metal oxide)

Passive nature of metal:Some metals like Ti, Al, Cr show more corrosion resistance
than expected from their position in the electrochemical series. These are called
passive metals. This is due to formation of thin protective layer on metal surface.

Nature of Metal oxide layer :

(1) Stable: It acts as a barrier between metal and O2, So prevents further corrosion.

(2) Unstable: It decomposes back to metal and O2. Ag, Au, Pt are protected by this
manner.

(b) Corrosion by other gases.Corrosion is also caused by some other gases like Cl2 ,H2S,
SO2 etc. This type of corrosion depends on chemical affinity between metal and gas.

WET CORROSION:This type of corrosion occurs when a liquid medium is involved.

One part behaves as anode and undergoes oxidation and other part acts as cathode
and undergoes reduction.

Liquid medium involved acts as electrolyte. It is further of two types:

(a)Evolution of H2 type corrosion: It occurs in the acidic environment.

At anode:M-------- M n+ + ne- (oxidation)

At cathode: 2H + + 2e- ----- H2 (reduction)

(b) Absorption of O2 type corrosion

If the layer of iron develops some cracks, this damaged surface acts as anode while
the other intact metal behaves as cathode. Presence of moisture acts as electrolyte.

The reactions occuring are:

 • Fe -------> Fe+2 + 2 e- (oxidation)

O2 (g) + 2H2O + 4e- ------> 4OH- (reduction)

2Fe+2 + 4OH- --------2Fe(OH)2

In the presence of excess oxygen, Fe(OH)2 oxidises to Fe(OH)3 as:

4Fe(OH)2 + O2 + 2H2O---- 4Fe(OH)3

This ferric hydroxide formed decomposes to hydrated ferric oxide as:

Fe(OH)3 --------- Fe2O3.xH2O (Rust)

OTHER TYPES OF CORROSION

• Waterline Corrosion.
• Filiform Corrosion
• Pitting Corrosion.
• Intergranular corrosion.
• Errosion corrosion.
• Stress Corrosion.
• Crevice Corrosion.
• Galvanic Corrosion.
Differential Aeration Corrosion

Differential Aeration Corrosion

Definition: Corrosion of metals arising as a result of the formation of an oxygen concentration cell due to
the uneven supply of air on the metal surface is known as differential aeration corrosion.

Differential aeration corrosion occurs when a metal surface is exposed to differential air concentrations or
oxygen concentrations. The part of the metal exposed to higher oxygen concentration acts as cathodic
region and part of the metal exposed lower oxygen concentration acts as anodic region. Consequently,
poorly oxygenated region undergoes corrosion.

At the anode (less O2 concentration), M ------------Mn+ + ne

At the cathode (more O2 concentration), H2O + ½ O2 + 2e------ 2OH-

The examples of differential aeration corrosion include:

1. Half immersed iron plate in aqueous solution.

2. Steel pipe carrying any liquid exposed to atmosphere.
3. Ocean going ships.
4. Steel storage tanks.

WATERLINE CORROSION: This type of corrosion is observed in the water tanks where
water remains collected for a long time. It is found just below the line of water, so
called waterline corrosion.

Waterline corrosion:

Waterline corrosion is a case of differential aeration corrosion, more prevalent in cases such as ocean
going ships, water storage steel tanks, etc., in which a portion of the metal is always under water.
The waterline corrosion takes place due to the formation of differential oxygen concentration cells.
The part of the metal below the water line is exposed only to dissolved oxygen while the part above the
water is exposed to higher oxygen concentration of the atmosphere. Thus, part of the metal below the water
acts as anode and undergoes corrosion and part above the waterline is free from corrosion. A distinct brown
line is formed just below the water line due to the deposition of rust.

FILIFORM CORROSION: is a special form of corrosion that occurs under some thin coatings in the
form of randomly distributed threadlike filaments. Filiform corrosion is also known as "underfilm
Corrosion" or "filamentary corrosion".

Filiform corrosion of a tin-coated steel

Filiform corrosion occurs on metallic surfaces coated with a thin organic film that is typically 0.1 mm
thick. The pattern of corrosion attack is characterized by the appearance of fine filaments emanating
from one or more sources in semi-random directions. The filaments are fine tunnels composed of
corrosion products underneath the bulged and cracked coating.

Filiform corrosion can be visually recognized without using a microscopy. Filiform corrosion has been
observed on surfaces of coated steel, magnesium, and aluminum with thin coatings of tin, silver, gold,
phosphate, enamel, and lacquer. Filiform corrosion has also been observed on paper-backed
aluminum foils.
Filiform corrosion usually does not weaken the material or significantly reduce its functionality, but
causes an aesthetic defect. The filaments usually start from an edge or a defect in the surface
coating and move ahead semi-randomly forming long filaments with an active head and corrosion
product tail. The corrosion occurs only in the active head of the filaments, never in the inactive tails.
The filaments tend to move in somewhat straight lines and do not cross each other.

• The relative humidity of the atmosphere is the single most important factor to initiate filiform
corrosion. Most favourable humidity grade for filiform corrosion is 65-90%.
• The type of the coating on the surface is less important and thus filiform corrosion can be seen
even under metallic coatings.

The prohibitive factors, however, seems to be the use of a coating of very low moisture
permeability. Filiform corrosion is more often seen on aluminium substrates, zinc coated steel being
less prone to this type of corrosion defects.
Mechanism

The chemical character of the solute in the cell fluid presents a point of interest.
There are several iron (I1) organic salts, such as ferrous acetate, with high solubility.
These organic substances may already be at the metal-film interface, or may be extracted from the film
By the moisture which diffuses through the film.
To summarize the electrochemical and osmotic effects concerned
in this study, Figure 3 represents a cross section parallel
Pitting corrosion
Pitting is a form of extreme localized attack that results in holes in the metal. These holes may be large or small in
diameter, but generally they are small. Pits are

Fig. a. Pitting corrosion

Sometimes isolated or so close together that they look like a rough surface. Generally a pit may be
described as a cavity or hole with the surface diameter about the same or less than the depth (Fig.
a).

Pitting is one of the most destructive forms of corrosion. It causes equipment to fail because of
perforation with only a small percent weight loss of entire structure. It is often difficult to detect pits
because of their small size and because the pits are often covered with corrosion products.

The presence of extraneous impurities (like sand, dust) embedded on the surface of metals also
leads to pitting. Due to the difference in oxygen, the part underneath the impurity becomes anodic
area and the large part the catholic area. Once a small pit is formed, the rate of corrosion increases.

Mechanism

Figure above shows the mechanism of pitting corrosion of iron surface in the chloride medium.
The metal below the dust is exposed to lower oxygen concentration and undergoes corrosion. The
accelerated corrosion takes place below the deposit because of small anodic area and large cathodic
area.
Preventive measures
1. Preparing surfaces with best possible finish.
2. Remove all contanminants.
3. Designing and fabricating to avoid trapped and pooled liquid.
Erosion-corrosion:

Combined chemical attack and mechanical wear (e.g., pipeelbows).

Brass water pump

Crevice corrossion
 Crevice corrosion at a latter stage

Methods and procedures for combating or minimizing crevice corrosion are as

follows:
Use welded butt joints instead of riveted or bolted joints in new equipment .Sound
welds and complete penetration are necessary to avoid porosity and crevices on
the inside (if welded only from one side). Close crevices in existing lap joints by
continuous welding, caulking, or soldering. Design vessels for complete drainage;
avoid sharp corners and stagnant areas. Complete draining facilitates washing and
cleaning and tends to prevent solids from settling on the bottom of the vessel.

Mechanisms of Galvanic Corrosion

What causes galvanic corrosion? Different metals and alloys have different electrochemical potentials (or corrosion
potentials) in the same electrolyte. When the corrosion potentials of various metals and alloys are measured in a
common electrolyte (e.g. natural seawater) and are listed in an orderly manner (descending or ascending) in a tabular
form, a Galvanic Series is created. It should be emphasized that the corrosion potentials must be measured for all
metals and alloys in the same electrolyte under the same environmental conditions (temperature, pH, flow rate etc.),
otherwise, the potentials are not comparable.
The potential difference (i.e., the voltage) between two dissimilar metals is the driving force for the destructive attack
on the active metal (anode). Current flows through the electrolyte to the more noble metal (cathode) and the less
noble (anode) metal will corrode. The conductivity of electrolyte will also affect the degree of attack. The cathode to
anode area ratio is directly proportional to the acceleration factor.
The electrochemical series list of metals which arranged in order of their standard potentials to hydrogen electrode.
Prevention
How to prevent galvanic corrosion?
Galvanic corrosion can be prevented through a number of methods:
 Select metals/alloys as close together as possible in the galvanic series.
 Avoid unfavorable area effect of a small anode and large cathode.
 Insulate dissimilar metals wherever practical
 Apply coatings with caution. Paint the cathode (or both) and keep the coatings in good repair on
the anode.
 Avoid threaded joints for materials far apart in the galvanic series.

If protection for both types of metal is desired, then a third more active metal must be added – a Sacrificial Anode. The most
common metal is zinc although magnesium and aluminum are also used. This active metal becomes the anode for both metals. In
the example below, the zinc or aluminum sacrifices itself to protect the other two metals, hence the term “sacrificial anode”.
As sacrificial anodes corrode and deteriorate they must be replaced.