CORROSION AND ITS PREVENTION

Any process `deterioration ( or destruction) & consequent loss of a solid metallic material through an unwanted chemical or electrochemical attack by its environment, starting at its surface, is called corrosion.
oxidation Metal reduction Metal oxide

Types of corrosion: A. Dry or chemical corrosion

This type of corrosion occurs mainly through the direct chemical action of environment/ atmospheric gases such as oxygen, halogen, hydrogen sulphide, or anhydrous inorganic liquid with metallic surface.

a. Oxidation corrosion:
It occurs due to the direct action of oxygen at low or high temperatures on metal, usually in the absence of moisture. Mechanism: M M n+ + ne( loss of electron) Metal ions n/2 O2 + 2ne- nO2- ( gain of electrons) Oxide ions M + n/2 O2 M n+ + nO2- Metal oxide

Oxidation corrosion mechanism

Nature of the oxide layer

a.Stable: A stable layer is fine- grained in structure &
get adhered tightly to the parent metal surface. It is Impervious in nature. It behaves as a protective coating in nature, thereby shielding the metal surface. Consequently, further oxidation corrosion is prevented. ( e.g. Al, Sn, Pb, Cu, Pt etc.).

b.Unstable: The oxide layer formed, Decomposes

back into the metal & oxygen Pt, Ag, Au etc do not undergo oxidation corrosion

Metal

Metal oxide

Oxy

c. Volatile:
The oxide layer volatilizes as soon as it is formed, thereby leaving the underlying metal surface exposed for further attack. This causes rapid and continuous corrosion. e.g.MoO3 d. Porous: Metal oxide layer having pores or cracks . In such cases , the atmospheric oxygen have access to the underlying surface of metal , through the pores or cracks of the layer .This causes rapid and continuous corrosion. e.g. Na, K, Fe, Zn etc

PILLING BEDWORTH RULE

According to this rule if the volume of the oxide film is greater than the volume of metal, the oxide film is protective & nonporous in nature (e.g. oxides of Al, Sn, Cu, Pb, etc.) & if the volume of the metal oxide formed is less the volume of metal, the oxide film is non-protective & porous in nature (e.g. oxides of Li, Na, K,Ca, Mg, etc.)

b. Corrosion by other gases

The corrosion occurs by the gases like halogen, hydrogen sulphide, sulphur dioxide, chlorine, fluorine etc.

c. Liquid metal corrosion: It is due to the chemical action of flowing liquid metal at high temp on solid metal or alloy. The corrosion reaction involves either (i) dissolution of a solid metal by a liquid metal or (ii) internal penetration of the liquid metal into the solid metal

B. Wet corrosion or electrochemical

This type of corrosion occurs : (i) When a conducting liquid is in contact with metal or (ii) when two dissimilar metals or alloys are either immersed or dipped partially in a solution. This corrosion occurs, due to the existence of separate anodic & cathodic parts, between which current flows through the conducting solution. Corrosion always occurs at anodic areas. Cathode protected from corrosion.

Mechanism of wet corrosion: Evolution of hydrogen:

It occurs in acidic environments. Fe Fe 2+ +2 e- ( loss of electron-oxidation) These electrons flow through the metal, from anode to cathode, where H+ ions( of acidic solution) are eliminated as hydrogen gas. 2H+ +2 e- H2 ( gain of electronreduction) The overall reaction is : Fe + 2H+ Fe 2+ + H2

Mechanism of wet corrosion

b. Absorption of oxygen:
Fe Fe2++2e-( loss of electron-oxidation) 1/2 O2 +H2O +2 e- 2HO- ( gain of electron-reduction) Fe 2+ +2HO- Fe(OH) 2 If enough oxygen is present , 4Fe(OH)2 +O2 +2H2O +2 e- 4Fe(OH)3 corresponds to Fe2O3. H2O If the supply of oxygen is limited the corrosion product may be black anhydrous magnetite Fe3O4 .

Oxygen absorption

C. Galvanic corrosion:

When two dissimilar metals (Zn & Cu) are electrically connected & exposed to an electrolyte , the metal higher in electrochemical series undergoes corrosion. Mechanism Zn Zn 2+ +2 e( loss of electron)

Galvanic corrosion

D. Concentration cell corrosion:

This type of corrosion is due to electrochemical attack on the metal surface, exposed to an electrolyte of varying concentrations or of varying aeration. Differential aeration corrosion occurs when one part of metal is exposed to a different air concentrations from the other part. Zn Zn 2+ +2 e( loss of electron-oxidation) 1/2 O2 +H2O +2 e- 2HO- ( gain of electron-reduction) Zn 2+ + 2HO- Zn(OH)2

Differential aeration corrosion

Zn rod

cl

Differential aeration corrosion

Differential aeration corrosion

Factors influencing corrosion:

A Nature of the metal:

(i)

Position in galvanic series (ii) Nature of the oxide film (iii) Relatives areas of the anodic & cathodic parts (iv) Purity of metal (v) Physical state of metal (vi) Solubility of corrosion products (vii) Volatility of corrosion products

B. Nature of the corroding environment

(i) Temperature (ii) Humidity of air (iii) Presence of impurities in atmp (iv) Influence of pH (v) Nature of the electrolyte (vi) Effect of oxygen

Corrosion control:

a. Proper designing b. Using pure metal c. Using metal alloys d. Cathodic protection (i) Sacrificial anodic protection method

Fig: Sacrificial anodic protection method

( e. g. Pipe line, bridge, ship hull or boat)

eSoil

Mg Mg 2+ Pipe

(ii) Impressed current cathodic protection

e. g. water-box coolers, water tanks, buried oil or water pipes, marine pier etc
e-

Soil
(Graphite, ss, Pt)

Pipe

Impressed current cathodic protection

e. Modifying the environment:

(i) Deaeration

(ii) Deactivation(Na2 SO3, N2 H4) (iii)Dehumidification (Alumina, Silica gels) (iv) Alkaline neutralization(NH3, NaOH, lime)

f. Use of Inhibitors
(i) An anodic inhibitors: Oxygen rich compounds like chromates, phophates, tungstates of transition metals. (ii) Cathodic inhibitors: 2H+ +2e- H2(g) The diffusion of H ions is decreased organic inhibitors like amines, heavy metal soaps, mercaptans, etc, H2O+1/2O2 +2e- 2OHCorrosion is controlled by Na2 SO3 or by addition of inhibitors like Zn, Mg or Ni salts

g. Application of protective coating (i) Tinning

(ii) Galvanising

h. Electroplating
eAnode Ni Ni 2+

B
Cathode

NiSO4 electrolyte

Article

i.Cladding
In this process the base metal is sandwiched between two thin layers of coating metal & then hot rolled to produce strong bonding. Elements like Al, Ni, & Ti are used as a cladding for steel.

Corrosion current measurement

Butler-Volmer equation

ba bc icorr =2.303--------------(1/Rp)

(ba+ bc)
Where
icorr = corrosion current ba = anodic tafel slope bc = cathodic tafel slope Rp = polarisation resistance

Galvanic series

Surface area effects

Steel revets on copper bar submerged in 3% NaCl

Copper revets on steel bar submerged in 3% NaCl