PREVENTION OF CORROSION BY MODIFICATION IN ENVIRONMENT

To avoid corrosion various protective method are commonly used. 1) Control of the physical, mechanical, chemical characteristics of metals and alloys. 2) Control of environment 3) Control of external source of electric potential.

Control of the physical, mechanical, chemical Characteristics of metals and alloys.

The various method based on the above principle are listed below. 1) Protective coatings. 2) Purification. 3) Heat treatment. 4) Alloying. 5) Change in design. 1) Protective coatings. The protective coatings applied to prevent corrosion can be either metallic or non-metallic type. Both metallic and non-metallic coatings applied to metals for the prevention of corrosion should have the following characteristics. a) Good corrosion resistance against medium with which it comes in contact. b) Perfect adherence to the underlying metal. c) Continuous, so as to cover the surface completely.

A)

METALLIC COATINGS.
The metal film coated on surface of the base metal may act to prevent corrosion of base metal in two ways being either cathode or anode. a) Cathodic coating: It provides physical barrier between base metal and corrosion media. E.g.Coating of gold, aluminum, chromium, brass and iron. b) Anodic coating: It provides better solvating cage or more anodic surface than base metal. E.g. coating of zinc, aluminum and cadmium on steel.

ADVANTAGES OF METAL COATINGS

1) More durable than non metallic coatings. 2) More decorative than most of other cladding. 3) Best shielding against corrosion as compared to all other metals.

METHOD OF APPLYING METALLIC COATINGS. A) Hot dipping: In this method case is dipped in molten bath of
metal to be coated. Although the method is simple but many complications are involved. Method is not very good due to following reasons. a) Uneven coating is obtained. b) Control of proper thickness is difficult.

B) Spraying: In this method the liquid metal is sprayed over

subject. The surface is grit blasted and metal is applied as a shower of tin, globules, which on striking the surface flatten to give splay porous coating.

C) Sherardizing: The coating metal in this process is taken

in powder form and base metal pieces to be coated are revolved in cylinder with that powder.

D) Mechanical cladding: This method is used for copper

And steel plates or lead on copper sheet. This method can be used only for sheets and plates.

E) Cementation: This process differ from cladding only in

Sense that in this case object is heated to sufficiently high temp, so that coating metal diffuses into it form a layer of alloy on surface.

ELECTROLYTIC COATINGS
This is most commonly employed method of coating metal nowadays. This method can be used to coat almost every metal and wide range of alloys. The object to be coated is cleaned, pickled, washed and then dipped into suitable bath. Another plate of coating metal or noble metal dipped into it. These plates are connected to DC power source supply making the object plate

as cathode. By varying c.d. distance between electrodes, temp, concentration of bath, addition of various additives various properties such as brightness, thickness, adhesiveness, hardness can be varied. Some of the most common used metals for coatings and properties of these coatings:

A)

NICKEL:
2) Highly resistance to attack by water and most aqueous solution at different pH and concentration. 3) Most resistance to alkaline. 4) Nickel coating is cathodic to iron and

Properties: 1) good wear and corrosion resistance.

Brass. USES: For protection, decoration and wear resistance on iron, steel and brass. Recently it has been used also in zinc based alloy.

B)

CHROMIUM : Properties: 1) chromium surface when exposed to air

is immediately coated with thin Film of oxide which is transparent, hard and corrosion resistance. 2) Chromium deposits has characteristics bluish white tint.

Uses: chromium coating are done on house hold

Objects to large machine tools, bearing of cylinder.

C) ZINC:
Properties: 1) Zinc is anodic to steel and
hence if the coating is non continuous and has holes etc.., steel is not corroded. 2) Zinc coating provides effective protection to steel under sea water and atmospheric condition. Uses: zinc has been coated on base metals especially on iron plates extensively.

D) COPPER:
Properties: moderately good corrosion resistance to
atmosphere and salt solutions.

Uses: copper plating usually done only as undercoats before nickel or

chromium plating.

E) ALUMINUM:
Properties: owing to fact that aluminum reacts
with oxygen and superficial inert film is formed and brings about protection. It offers little if any electrochemical protection. Uses: as a protective coating for iron and steel. B) NON METALLIC COATING: Non metallic coatings applied to prevent corrosion are of two types. 1) Inorganic coating 2) Organic coating INORGANIC COATING: The principle coatings for metals are described below: a) Vitreous enamels: they form hard glassy outside layer and protect by acting as an efficient barrier to the corrosion environment. b) Portland cement coating: they are usually several centimeters thick to give adequate protection to steel. c) Conversion coating: these coatings are formed by reactions with the metal surface and are of several distinct kinds viz phosphate coating from acid phosphate on steels, oxide coatings on steel and aluminum formed by the reaction with oxygen and water and stream. ORGANIC COATING: Organic coatings are inert organic barriers applied on the surface of materials for both corrosion protection and decoration. Organic coatings include varnishes, paints, enamels and lacquers. 2) METALLIC PURIFICATION: Pure metals are likely to resist corrosion better than metals containing impurities. In certain cases very small amount of impurity increases the corrosion resistance by several folds. Extremely pure metals corrode at a very slow rate, owing to their high hydrogen over potential. Any addition of more noble metals possessing somewhat lower hydrogen over potential will, however behave as a cathode of the local cells. The rate of corrosion therefore rapidly increases with decreases with decreasing purity of parent metal.

PURITY OF AL% 99.998 99.99 99.97 99.98 99.2

LOSS IN WEIGHT (gm/day) 6 112 6500 3600 190000

3) HEAT TREATMENT: The corrosion resistance of metals and alloys can also be minimized by the proper heat treatment. ANNEALING: it may be carried out to homogenize the microstructure, composition and reduce the internal stresses, thereby improving the corrosion resistance. E.g. Elimination of coring, or cast structure or internal stresses. HARDENING AND TEMPERING: hardening treatment increases the corrosion rate of steel because it contains single phase martensite. The tempering treatment after hardening however affects the rate of corrosion in following ways: a) Tempering at low temperature: many galvanic cells of ferrite and carbides are formed resulting in a increase in corrosion rate. b) Tempering at high temperature: the carbide agglomerate causing reduction in number of galvanic cells which results in decrease in the corrosion rate. 3) ALLOYING: An increase in corrosion resistance of most commercial metals can also be achieved by alloying them with suitable alloying elements. For maximum corrosion resistance alloy should be from solid solution. 4) CHANGE IN DESIGN: Corrosion rate can also be reduced by proper design and fabrication. In general the design should be such so as to maintain the uniform condition as far as possible throughout. Followin g steps are taken for minimize the galvanic corrosion.

a) Material should be as close as possible in galvanic series. b) Dissimilar materials should be insulated. c) The anodic material should have large area where as cathodic area should be much smaller.

MODIFICATION IN ENVIRONMENT
Corrosion is a result of interaction of materials with environment. Corrosion resistance is therefore not an inherent property of materials but depend to large extent on the nature of the environment, so as to reduce its interaction with material will provide a method of corrosion prevention. Corrosive environment can be modified by three ways. 1) Alteration of environment variables such as temp, concentration, velocity, pH etc. 2) Elimination of corrosive ingredients such as humidity, oxygen, Oxidizing agent, solid contaminates. 3) Introduction of inhibitors

1) ALTERATION IN ENVIRONMENT
A) Alteration in temperature: In most of the cases lowering the temperature of the environment reduces the corrosion rate. The degree of reduction depends upon the type of environment, metals, and alloys. Reduction in corrosion rate is large in case such as 18 Cr-8Ni in nitric acid, Monel in hydrofluoric acid, as shown in figure. (Curve A).

Reduction is less in case A) such as 18Cr-8Ni in sulphuric acid, nickel in hydrochloric acid and iron in hydrochloric acid. (In fig. curve B). In certain cases lowering temperature increases the corrosion rate. E.g. boiling sea water is less corrosive than sea water. B) Alteration in concentration: The effect of corrosive is complex. Certain cases of corrosion prevention by altering corrosive concentration.

As shown in figure lowering the concentration of corrosive reduces the concentration rate. There can be a concentration below which corrosion rate remain constant. Corrosion rate is higher at low concentration of corrosive medium and it is less at higher concentration.

C) Alteration in velocity: Corrosion rate also depend on the velocity of the environment. This may increases or decreases the corrosion rate. In most cases decreases in velocity reduces the corrosion rate. Decrease in velocity to zero can increase corrosion rate. During stagnation period corrosion rate is increased due to settling of suspended matter, establishment of metal. In cases where the corrosion process is under diffusion control and metal is ready passivated. Increase in velocity reduces the corrosion rate. (In fig curve A)

4) Alteration of pH value: high pH value of environment usually reduces the corrosion of iron and steel. The curve given in following fig

illustrates this point. It is clear that solubility of ferrous oxide rapidly above pH 9, falling to zero at pH=11.5

Corrosion rate will further increase: a) With further increase in pH b) With increase in velocity of water. c) With presence of oxygen.

2) ELIMINATION OF CORROSIVE INGRADIENTS:

A) DEHUMIDIFICATION: Dehumidification is the process of reducing
environment moisture to such an extent the amount of water condensed on metal surface is too negligible to cause corrosion.

B) ELIMINATION OF SOLID CONTAMINATION: Dissolved solid

content in water increase the corrosion rate. It can be due to two reasons. a) Solid contamination may increase the electrical conductivity. This will speed up the electrode reaction and hence corrosion rate. b) Dissolve ions can penetrate the protective coating formed by corrosion product of inhibitor on the metal.

C) ELIMINATION OF OXYGEN AND OXIDATION AGENT:

Corrosion rate can be reduced in certain cases by reducting the concentration of oxygen and oxidizing agents from the environment. As shown in above figure. C) INTRODUCTION OF AN INHIBITORS: Inhibitors prevent corrosion by two mechanisms. 1) By formation of protective layer on metal surface. 2) By reducing the corrosiveness of the environment towards the metal. Inhibitors usually retard corrosion rate in three ways. 1) By slowing down the corrosion without suppressing it completely. 2) By prolonging the incubation period of the reaction. 3) By passivating the metal surface by polymolecular film. VARIOUS TYPES OF INHIBITORS: 1) Filming inhibitors: a) Anodic b) Cathodic c) Mixed 2) Adsorption inhibitors 3) Vapour phase inhibitors. 1) FILMING INHIBITORS: The inhibitors which form a barrier, are called filming inhibitors. Filming inhibitors can be classified into anodic, cathodic, or both aspect of corrosive process simultaneously. a) Anodic inhibitors: they operate by producing a passivating oxide film mainly at those parts of the surface where metal cations are formed. b) Cathodic inhibitors: these inhibitors instead of deactivating the active sides relay upon general coverage of the metal surface. Cathodic inhibitors are generally less effective due to following reason; 1) Mechanism of corrosion prevention is indirect while anodic inhibitors directly prevent the metal from mechanism. 2) Precipitate form at cathode may not be much in soluble and may not bond to the metal surface tightly. c) Mix type: These inhibitors interfere with both anodic and cathodic reaction. An example of an inhibitive ion which may into this category is benzoate.

2) ADSORPTION INHIBITOR: Adsorption inhibitors are surface active addition agent that functions as a result of adsorption to the metal forming an impervious barrier either at anodic sides or indiscriminately over the surface. D) VAPOUR PHASE INHIBITOR: Vapour phase inhibitors are essentially soluble filming inhibitor. The vapour of which has corrosion inhibiting properties. Vapour phase inhibitor consist of nitride benzoate and carbonate anions attach to suitable heavy organic cation. ADVANTAGES OF VAPOUR PHASE INHIBITORS: 1) Easily applicable to articles. 2) No need of removal of oil or grease film before application. DISADVANTAGES OF VAPOUR PHASE INHIBITORS: 1) Accelerates the corrosion rate of certain nonferrous metals. 2) Requires effective sealing of package against loss of package against loss of inhibiting vapour. 3) This inhibitor discolors certain plastics.

APPLICATION OF INHIBITORS:
Inhibitors are used for protecting ferrous metals and nonferrous metals such as Al, Sn, Mg, Cu and their alloys.

LIMITATIONS OF INHIBITORS:
1) It is not possible to add inhibitor to all corrosive system because they may contaminate the environment. 2) Certain inhibitors are toxic in nature. They cant be used in protecting food utensils etc. 3) Most of the inhibitors cant be used at high temp. 4) Mainly used in closed system.

REFERENCES:
1) AN INTRODUCTION TO ELECTROMETTALURGY BY RAJENDRA SHARAN & SATYA NARAIN. 2) CORROSION ENGUNEERING BY MARS G. FONTANA & NOBERT D. GREENE.