Corrosion

SCIENCE OF CORROSION
Most of the metals (Except Au, Pt) exist in nature in combined state as their Oxides due to its reactivity. These are reduced to get Metals (Extraction of metals) Extraction of the metals is a reduction process. When the metals are exposed to environment destruction starts at the surface. This destruction may be due to direct attack of chemical or electrochemical Reverse of extraction of metals is called Corrosion Any process of destruction or deterioration of metals through chemical or electro chemical attack by its environment is called Corrosion
Dr. E. Laxminarayana
Mail: elxnkits@yahoo.co.in
Types of corrosion:
1. 2. 3. 4. 5. 6. 7. Dry (Chemical or Direct)Corrosion Wet corrosion (Electro chemical) Underground (soil) Corrosion Pitting Corrosion Stress Corrosion Galvanic Corrosion Concentration cell (Deferential aeration) Corrosion
Dry corrosion or Chemical corrosion: This type of corrosion occurs through the direct chemicals There are three main types of chemical corrosion Oxidation corrosion Corrosion by other gases (SO2, CO2, Cl2 etc.,) Liquid metal corrosion Oxidation corrosion:
It occurs by the direct attack of oxygen at low or high temperatures on metals. It is caused in absence of the moisture. At low temperature alkali and alkaline earth metals are rapidly oxidized and at high temperature almost all metals (except Au, Ag, and Pt) are oxidized.
2M O2 M + O2
2 M2+ + 2e- (Oxidation) 2 O2- (Reduction) Metal oxide
SCIENCE OF CORROSION Mechanism: Oxidation occurs first at the surface of the metal and the resulting metal oxide forms a barrier. Either metal ion diffuse out side or oxide must diffuse inwards through the scale. Diffusion of metal ion out side is much faster than the oxygen diffusion Nature of oxide formed: This oxide plays an important role in oxidation corrosion. 1.Stable: A stable layer is fine grained and gets adhered to the parent metal surface. So, it acts as protective layer Further corrosion is prevented for these metals. E. Laxminarayana Dr. Ex.: oxides of Al, Sn, Pb, Cu, etc. Mail: elxnkits@yahoo.co.in
If the oxide formed is unstable, decomposes back into the metal and oxygen. So, corrosion is not possible. Ex.: oxide of Pt iii) Volatile: If the oxide formed is volatile in nature it volatizes as soon as it is formed. So, corrosion rate increases rapidly. Ex.: oxide of Mo
iv) Porous: i.e., having pores or cracks. This causes continuous corrosion. Ex.: oxide of K, Na, etc. This is explained based on the PillingBerworth Rule According to this rule an anode is protective or non-porous, if the volume of the oxide is greater than the volume of metal. It is explained based on the ratio of the metal oxide volume to the metal volume. Porous layers usually contain PBR less than 1 and non-porous layer greater than 1.
SCIENCE OF CORROSION Corrosion by other Gases: The gases like SO2, CO2, Cl2, H2S etc. may also cause corrosion. The extent of the corrosion depends on the chemical affinity between metal and the gas. The degree of attack depends on the formation of protective or non-protective films on the metal surface. Liquid metal corrosion: It is due to chemical action of flowing liquid etal at high temperature on solid metal or alloy. It involves either dissolution of a solid metal by a liquid metal; or internal penetration of liquid metal into the solid metal
SCIENCE OF CORROSION WET OR ELECTROCHEMICAL CORROSION: This type of corrosion occurs Where a conducting liquid is in conducting with metal or When two dissimilar metals or alloys are immersed partially in a solution. Two metals act as electrodes and current flows through the conducting solution. At anode oxidation reaction takes place, so anodic metal is destroyed. Hence, corrosion always occurs at anode. But the cathode is not affected.
Mechanism of action: The stability of the metal ion formed at anode is stabilized either by Evolution of hydrogen (or ) Absorption of Oxygen. Evolution of Hydrogen type: Usually corrosion occurs in acidic medium Fe metal converts into ferrous ions at anode by liberation of the electrons.
Fe
Fe+2 + 2e- (oxidation)
These electrons flow through the metal from anode to cathode The hydrogen ions present at cathode eliminated as H2 gas.
2H+ + 2e-
H2 (Reduction)
Fe + 2H
Fe
+2
+ H2
SCIENCE OF CORROSION This type of corrosion causes displacement of H+ ions from acidic solution by metal ions. In this type of corrosion anodes are large areas; where as cathodes are small areas. Absorption of Oxygen: Common example is rusting of iron in neutral medium (NaCl) The surface of iron always coated with iron oxide. If some cracks are developed on this metal oxide, anodic areas are created; while the well metal parts act as cathodes. In this type of corrosion anodes are small areas; where as cathodes are large areas.
At anode:
Fe Fe+2 + 2e- (oxidation)
At cathode: The liberated electrons are absorbed by dissolved oxygen.
O2 + H2O + 2e-
2 OH-
The Fe+2 and OH- diffuse and combine to form Fe(OH)2
Fe+2 + OH-
Fe(OH)2
SCIENCE OF CORROSION If enough oxygen is present it will be oxidized to form ferric hydroxide or yellow rust. If oxygen is limited the corrosion product will be black rust / anhydrous magnetite. Galvanic Corrosion: When two dissimilar metals are exposed to an electrolyte, the metal which has higher oxidation potential values undergoes corrosion. Ex. Daniel cell In acidic solution evolution of the H2 takes place: While in alkaline or in neutral solution, oxygen absorption occurs.
Zn Zn
+2
+ 2e
(oxidation)elxnkits@yahoo.co.in Mail:
Concentration cell Corrosion: It occurs due to electro chemical attack. If a metal surface is exposed to either electrolyte of different concentration or of different aeration. It has been found experimentally that poor oxygenated areas act as anode and the metal part strongly aerated become cathode. Ex. Zn metal dipped in NaCl solution.
SCIENCE OF CORROSION Factors influencing the corrosion: The rate and extent corrosion of corrosion depends on Nature of metal Nature of corroding environment
SCIENCE OF CORROSION 1. Nature of the metal: Position in galvanic series: When two metals are electrical contact in presence of an electrolyte the more active metal undergoes corrosion. The rate depends on the difference in their position in galvanic series. Greater the difference is the faster the corrosion of the anode. Over voltage: When a metal, which occupies high position in galvanic series, is placed in 1N H2SO4 it corrodes and produces small EMF. If a few drops of CuSO4 is added corrosion rate accelerates. Relative areas of anodic and cathodic parts: Corrosion rate is rapid, when anodic Dr. E. Laxminarayana areas are small because of the demand for e-. Mail: elxnkits@yahoo.co.in
SCIENCE OF CORROSION Purity of the metal: Impurities in the metal cause heterogeneity and form electrochemical cells. Physical state: The smaller the grain-size of metal is greater will be solubility, hence rate of corrosion increases. Nature of surface film: It can be explained based on the specific volume ratio. Specific volume ratio = vol. of metal oxide / vol. of metal Greater the specific volume ratio, lesser the oxidation. Solubility: Solubility increases the rate of corrosion. Volatility: Volatility increases the rate of corrosion.
SCIENCE OF CORROSION 2. Nature of the corroding medium: Temperature: Corrosion rate increases with increasing temperature. Humidity: As the humidity present in the air increases corrosion rate increases. Critical humidity is the relative humidity above which the atmospheric corrosion rate of metal increases sharply. Presence of the impurities: If the impurities like CO2, SO2, H2S etc. increases rate corrosion. Presence of suspended particles also increases rate corrosion
SCIENCE OF CORROSION pH: Acidic media is more corrosive than alkaline and neutral media. Formation of O2 concentration cell:
Galvanising
Tinning
Metal cladding:
Electroplating:
e-
Anode
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Corrosion

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SCIENCE OF CORROSION

2 M2+ + 2e- (Oxidation) 2 O2- (Reduction) Metal oxide

Fe+2 + 2e- (oxidation)

At cathode: The liberated electrons are absorbed by dissolved oxygen.

The Fe+2 and OH- diffuse and combine to form Fe(OH)2

Cathode Article to be Protected

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