CORROSION AND ITS CONTROL

CORROSION AND ITS CONTROL

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

 Corrosion is a phenomenon of gradual deterioration of metals or its alloys by the action of environment to their respective chemical compounds. Theories of corrosion:
1. Dry (Chemical or Direct) Corrosion 2. Wet corrosion (Electro chemical)

1) 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.

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. Ex.: oxides of Al, Sn, Pb, Cu, etc.

ii) unstable: 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 Pilling-Bed worth 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.

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.

Hydrogen corrosion: A different type of dry corrosion attack by hydrogen gas on metals is known as hydrogen embrittlement. it is due to the formation of atomic hydrogen as a result of chemical or electrochemical reaction at metal surface.

Liquid metal corrosion: It is due to chemical action of flowing liquid metal 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

2) WET OR ELECTROCHEMICAL CORROSION: This type of corrosion occurs Where a conducting liquid is in contact 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.

The principle types of electrochemical corrosions are 1. Hydrogen evolution corrosion 2. Oxygen absorption corrosion

Evolution of Hydrogen type: Usually corrosion occurs in acidic medium Fe metal converts into ferrous ions at anode by liberation of the electrons.

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.

These electrons flow through the metal from anode to cathode The hydrogen ions present at cathode eliminated as H2 gas.

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

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

Types of corrosion 1. Galvanic corrosion 2. Waterline corrosion 3. Soil corrosion 1) Galvanic Corrosion: When two dissimilar metals are electrically connected and 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.

3) Underground or Soil Corrosion: The corrosiveness of the soil depends on Soil acidity Degree of aeration Electrical conductivity Soil moisture Soil texture

According to particle size soils are classified as

1. Gravelly or Sandy Soil:

It is very porous and aerated. If a metal is buried in such soil corrosion occurs similar to wet corrosion 2) Water-logged Soil: Amount of oxygen available is very small, but bacteria may present and cause microbiological corrosion 3) Intermediate character corrosion: Fine gravel, sand and salt containing soil may produce intense corrosion. If air pockets are present, differential aeration corrosion may occur.

 Factors influencing the corrosion: The rate and extent corrosion of corrosion depends on Nature of metal Nature of corroding environment

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: The over voltage of the metal in the corrosive environment is inversely proportional to corrosion rate. 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

Purity of the metal: Impurities in the metal cause heterogeneity and form electrochemical cells. higher the percentage of impurity , faster is the rate of corrosion of the anodic metal. Physical state: The smaller the grain-size of metal is contact with greater amount of environment, 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 corrosion rate.

2. Nature of the corroding environment: Temperature: With increase of temperature of environment reaction as well as diffusion rate increases there by corrosion rate also enhanced. Humidity: Corrosion of a metal becomes faster in humid atmosphere is that gases and vapours, water vapour acts as electrolyte, system becomes electro chemical cell. PH: Acidic media is more corrosive than alkaline and neutral media. e.g. : Zn suffers minimum corrosion at PH = 11, which is rapidly corroded even in weakly acidic

Formation of O2 concentration cell: with the increase in supply of oxygen to the moist metal surface the corrosion is promoted. less oxygen concentration parts become anodic, more gets cathodic leads to formation of o2 concentration cell. Anodic part suffers from corrosion. at cathode 2 H2O +O2 +4 e- 4 OHat anode Fe Fe 2+ + 2e- ( corrosion )

 CATHODIC PROTECTION The principle of this method is that the base Metal to be made as cathode by connecting it to powerful anode metal plate There are two types 1.Sacrifical anodic protection The metallic structure to be protected is connected through a metallic wire to a more anodic metal so that all the corrosion will take place only the anodic metal. Metals commonly used as sacrificial anodes are zinc aluminum mg. Applications This methods are to protect underground pipelines

 2.Impressed current cathodic protection In this method an impressed direct current is sent in the opposite direction of the corrosion current to nullify it. Usually a battery is an one terminal connected with an insoluble anode graphite electrode immersed in a backfill containing coke, gypsum, sodiumsulphate. The terminal of the battery is connected to the metallic structure to be protected, witch act as the cathode Application; This method usually applied to underground water pipe lines, oil pipe lines, marine piers

Introduction: 1. Protective coatings function as a continuous physical barrier between the coated surface and the environment 2. Besides corrosion protection, it also acts as a decorative smooth polished surface. Surface coatings-methods of application on metals: 3. Hot dipping it is a process of coating the base metal by immersing it in the molten coat metal. Ex: Galvanising, Tinning, Metal cladding, Electro plating.

PROTECTIVE COATINGS

Galvanising: Dipping the base metal iron in the molten coat zinc Tinning : Dipping the base metal iron in the molten coat tin

Galvanising:
It is the process of coating of iron or steel with a thin coat of zinc by immersing it in molten zinc to prevent rusting. Iron or steel first cleaned by acid pickling using dil. H2SO4 sol.at 60-90oC for 15-20 min. The base metal is then dipped in molten zinc maintained at 415-430oC. The surface of the bath is covered with NH4Cl flux to prevent oxide formation on the surface of molten zinc. The coated base metal is then passed through rollers to correct the thickness of the film and finally annealed temp. of 250oC and cooled slowly.

 Uses : Galvanising is mainly used for the protection of iron from the atmospheric corrosion in the form of sheets, wires, pipes, nails, bolts, screws etc. Since some of the zinc compounds are poisonoius, galvanised utensils cannot be used for preparing or storing food stuffs.

Tinning: This is the process of coating over mild steel sheets, iron sheets by immersing it in the molten tin to prevent rusting. The steel is first passed through dil. H2SO4 to
H2SO4 remove surface impurities. Then it is passed through a bath of molten tin covered with a flux of ZnCl2.

After the coating of tin, the sheet is passed through palm oil. The palm oil protects the immediate tin coated hot surface against oxidation.

Finally the sheet is passed through a rollers to produce the thin coat of tin of uniform thickness. Uses: Used for coating the steel, copper and brass sheets used for making containers for storing food stuffs.

TINNING:

Metal Cladding: It is the process of sandwiching the base metal between two thin layers of coating metal by hot rolling the composite to produce a firm bonding. The coat metals are usually metals of least reactivity and higher in the electrochemical series. The cladding layer should be very thin and its thickness is only 5% of the total composite metal.

Cu, Ni, Al, Ag, Pt, Ti are some of the metals used as coat metal sheets in metal cladding. Duraluminium sandwiched between aluminium sheets and hot rolled to produce the composite (Alkad) which is free from stress of corrosion.

METAL CLADDING:

Electroplating:
Electroplating or electro deposition is the process by which the coat metal is deposited on the base metal by passing direct current through an electrolytic solution containing the soluble salt of the coat metal. Eg: Copper plating The copper plating of a material where CuSO4 is the electrolyte,copper rod is placed as the anode and the material to be coated is placed as the cathode.The following ionisation rxn of electrolyte takes place. CuSO4 ----------Cu+2 + SO4-2

On passing current Cu+2 ions of the electrolyte get deposited at the cathode. In electrolytic process like electroplating, cathode is negative and anode is positive. Cu+2 + 2e- --------- Cu (at cathode) SO4-2 --------- SO4 + 2e-(at anode) For Cu coating an acid bath consists of 15-30% CuSO4 and 5% Conc H2SO4 along with small amount of additives like boric acid,gelatin etc., are mixed and used as electrolyte. CuSO4 ----------- Cu+2 + SO4-2 H2SO4 ----------2H+ + SO4-2

The ionisation rate of sulphuric acid and copper sulphate is very much less due to common ion effect and controlled deposition of Cu+2 ions on the surface of cathode takes place.At normal temp. a current density of about 0.5 to 1.5 ampere/dm2 is used. Uses: It is done on metals and non metals to improve the surface appearance, resistance to corrosion, wear resistance,chemical resistance and surface hardness. Mainly used in automobile, aircraft, locks, jewellery, type writers, watches etc..

ELECTROPLATIN G

Organic surface coatings: These are inert organic barriers applied on

metallic surfaces and other constructional materials for both corrosion protection and decoration. The protective value of such a coating depends on 1) Its chemical inertness to the corrosive environment, 2) Its good surface adhesion, 3) Its impermeability to water, salts and gases as well as , 4) Its proper application method.

Paints : Paint is a mechanical dispersion mixture of 1 or more pigments in a vehicle vehicle is a liquid, consisting of non volatile, film forming material, drying oil and highly volatile solvent, thinner. when a paint is applied to a metal surface the thinner evaporates, while the drying oil slowly oxidizes forming a dry pigmented film.

Constituents of paints : Pigments, Drying oil, Thinner driers, Extenders/filters, Plasticizers, Anti skinning agents.

(1) pigments:

Provide Capacity to paint Desired colour Wear resist & abrasion resist. Impermeability to moisture give protection to by reflecting U.V light
White:White lead, Zinc ride Red: Red lead, chartered Blue: Prussian blue Black: Carload black Characteristics of good pigment: Chemically insert Non toxic Opaque Cheap

(2) Drying Oil: Are glycerol esters of high mol. weight. Fatty acids present in animal and vegetable oils. Ex:- linsed oil, soyabean, dehydrated caster oil. Dying oil, linsed oil Semi drying oil, soybean oil, Fish oil Non drying oil, mustard oil, Sunflower oil Function of Drying Oil: Main Film forming constituent Vehicle or medium Toughness Adhesion Water-proof ness

(3) Thinner: Reduces paint viscosity to suitable level Dissolve additives in vehicle Suspend pigments Increase penetration power and elasticity of paint film Help in drying of the paint as it evoparates. Eg :Turpentine, mineral spirits, benzene.

(4) Drier: O2 carrier catalysts Accelerate drying process through oxide, polymerization and condensation. Eg: Resonates, Tungstates and naphtates of Co, Mn, Ph and Zn. (5) Extenders (or) Fillers: To reduce the cost To reduce cracking of dry paint film To fill void in film Act as carrier few pigment colour. (6) Plasticisers: To provide elasticity to film To minimize its cracking Ex: Triphenyl phosphate, Tricresyl phosphate

(4) Drier: O2 carrier catalysts Accelerate drying process through oxide, polymerization and condensation. Eg: Resonates, Tungstates and naphtates of Co, Mn, Ph and Zn. (5) Extenders (or) Fillers: To reduce the cost To reduce cracking of dry paint film To fill void in film Act as carrier few pigment colour. (6) Plasticisers: To provide elasticity to film To minimize its cracking

(7) Anti skinning agents: Poly hydroxy phenols. Pigment Volume Concentrator( PVC) = in paint. If PVC is more Bind annuity decrease Wash ability Opacity of white paint is created by difference in refractive indices vehicle and pigment.