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CHE021-Applied Chemistry

Prepared by

Mr. Rahul Mehta


Lecturer Department of Chemistry Lovely Professional University, Phagwara, Punjab, India E-mail: rahul.mehta@lpu.co.in

Corrosion and its preventions

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Corrosion
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Definition
The slow destruction of a metallic material by chemical, electrochemical, or metallurgical interaction between the environment and the material is called Corrosion. e.g. Rusting of iron due to formation of hydrated ferric oxide Formation of green layer in Cu vessels due to formation of basic copper oxides.
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Cause of Corrosion

Metallurgy (Reduction)

Ore + energy

Pure Metal

Corrosion (Oxidation)

e.g., rusting of iron when exposed to atmospheric conditions. Rust is hydrated oxide (Fe2O3.xH2O).

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Types of Corrosion
Dry (or) Chemical Corrosion This type of Corrosion occurs mainly through the direct chemical action of atmospheric gases (such as O2, halogen, H2S,SO2,N2 ) to form corrosponding metal oxides, halides, sulphides,sulphates and nitrates respectively

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Oxidation Corrosion
The attack of atmospheric oxygen on metal forming metal oxide is commonly called Oxidation Corrosion. This type of corrosion occurs in the absence of moisture, i.e. why it is called Dry Corrosion.

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Mechanism of Dry Corrosion


(Oxidation) nO2+2ne2nO2- (Reduction) (Oxide ion) 2M + nO2 2 Mn+ + 2nO2(Metal oxide)
2M 2Mn++2ne-

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Metal + Oxygen Metal oxide Nature of Oxide Fim:-If the film is, STABLE, it behaves has a protective coating in nature e.g., the oxide films on Al,Pb,Cu,Pt etc., are stable and therefore further oxidation corrosion of metal is prohibited. UNSTABLE that is the oxide layer formed decomposes back into metal and oxygen. So, oxidation Corrosion is not possible. Metal oxide Metal + Oxygen e.g., Ag, Au and Pt do not undergo oxidation Corrosion.

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VOLATILE that is oxide layer volatilizes after

formation and as such leaves the underlying metal surface exposed for further attack. This causes continuous corrosion which is dangerous for the metal e.g. Molybdenum oxide (MoO3) POROUS that is the oxide layer formed having pores or cracks. In this case the atmospheric oxygen passes through the pores or cracks of the underlying metal surface. This causes continuous corrosion till complete conversion of metal into its oxide.

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Wet Corrosion
In this case Corrosion occurs in presence of air and
moisture through the formation of electrochemical cells, i.e. why wet corrosion is also known as Electrochemical Corrosion.

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Wet Corrosion
This corrosion occurs due to the existence of separate anodic
and cathodic parts, between which current flows through the conducting solution. At anodic area, oxidation reaction occurs thereby destroying the anodic metal either by dissolution or formation of compounds. Hence corrosion always occurs at anodic parts. Mn+ + ne(Oxidation)

At Anode: M

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Wet Corrosion
At cathodic part, reduction reaction occurs. At cathodic part, the dissolved constituents in the conducting
medium accepts the electrons forming ions (OH-, O2-).

The metallic ions formed at anodic part and the non metallic
ions formed at cathodic part diffuse towards each other through conducting medium and form a corrosion product somewhere between anode and cathode.

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Mechanism of Wet Corrosion


The cathodic reaction consumes electrons with
either evolution of hydrogen or absorption of oxygen which depends on the nature of corrosive environment.

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Evolution of hydrogen
This type of corrosion occurs in acidic medium e.g.,
considering the metal Fe, anodic reaction is dissolution of iron as ferrous ions with liberation of electrons.

Fe

Fe2+ + 2e- ( Oxidation)

The electrons released flow through the metal from


anode to cathode, whereas H+ions of acidic solution are eliminated as hydrogen gas.

2H+ + 2e-

H2 ( Reduction)
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The overall reaction is Fe + 2H+ Fe2+ + H2 This type of corrosion causes


displacement of hydrogen ions from the solution by metal ions.
The anodes are large areas, whereas cathodes are small areas.

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Absorption of Oxygen
At anode:
Fe Fe2+ + 2e- (Oxidation) At cathode: The released electrons flow from anode to cathode through iron metal. O2 + H2O + 2e2OH- (Reduction) Fe2+ + 2OHFe(OH)2

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If oxygen is in excess, ferrous hydroxide is easily oxidised to ferric hydroxide. 4Fe (OH)2 + O2 + 2H2O 4Fe (OH)3

The product called yellow rust corresponds to Fe2O3. xH2O.

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Differential Aeration 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 different air concentration from other part.

Experimentally it has been observed that poor


oxygenated parts are anodic.

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Differential Aeration Corrosion If a metal e.g., Zn is partially immersed in a dilute solution of a neutral salt e.g., NaCl then the parts above and adjacent to the waterline are strongly aerated and hence become cathodic. Whereas parts immersed show a smaller oxygen concentration and become anodic.
Zn Zn2+ + 2e(Oxidation) O2 + H2O + 2e2OH- (Reduction)

Zn2+ + 2OH-

Zn(OH)2

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Galvanic Corrosion

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When two dissimilar metals are electrically


connected and exposed to an electrolyte, the metal higher in electrochemical series undergoes corrosion, called Galvanic corrosion. e.g, Zinc (higher in electrochemical series) forms the anode and is attacked and gets dissolved; whereas copper (lower in electrochemical series) acts as cathode.
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Mechanism of Galvanic Corrosion

If the solution is acidic then corrosion occurs by


hydrogen evolution process and if the solution is neutral or slightly alkaline in nature then corrosion occurs by oxygen absorption process.

Zn Zn2+ + 2e- (Oxidation) 2H+ + 2eH2 ( Reduction)

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Hence, this can be minimized by


1. Avoiding galvanic couple 2.Providing an insulating material between the two metals.

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Waterline Corrosion
This is also known as differential oxygen concentration
corrosion.

In general, when water is stored in a steel tank, it is


observed that the maximum amount of corrosion takes place along a line just beneath the level of the water meniscus.

The area above the waterline (highly oxygenated) acts


as cathodic and is not affected by corrosion.
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PROTECTION FROM CORROSION


It includes coating of metal surface to avoid direct contact of air with metal. The types coatings used for protection are: 1. Metallic Coating 2. Non-Metallic Coating 3. Organic Coating But before the coating can be applied on the metal surface, metal surface should be prepared. Surface Preparations are important because it ensures uniform coating as well as the coating is firmly attached .

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Surface Preparations
The various methods used for preparing metal surface are 1. 2. 3. 4. 5. SOLVENT CLEANING ALKALI CLEANING ACID PICKLING SAND-BLASTING MECHANICAL CLEANING

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SOLVENT CLEANING:
Solvent cleaning is used to remove oils, greases, buffing compounds and fatty substances. This involves in cleaning the surfaces by the application of organic solvents like trichloroethylene, tetrachloroethylene etc. This treatment provides a metal surface, readily wetted by aqueous solution, which is particularly required for electroplating.

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ALKALI CLEANING:
Alkali cleaning agents are trisodium phosphate along with soaps and wetting agents like caustic soda. An alkali treatment is always to be followed by a very thorough rinsing with water and then immersion in a slightly acidic solution of 0.1% chromic acid or sodium or potassium chromate to remove the last traces of alkalis.
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SAND-BLASTING:
The process consists in introducing the sand an abrasive into an air stream, under pressure of 25 to 100 atmospheres. The blast is impacted on the metal surface to be cleaned. The sand-blast impact removes any scale present and also causes a certain degree of hardening of the cleaned metal surface.

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MECHANICAL CLEANING:
Mechanical cleaning removes loose rust and other impurities from the surface. This is, generally, done by hand cleaning with a bristle brush plus some abrasive like sand papers

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ACID PICKLING
Acid pickling is more convenient method of scale removal in many cases than mechanical cleaning and sand-blasting. It is, usually, accomplished by immersing the metal except Al in an acid-pickling solution. Al is picked in alkaline solution. Acid-pickling of steel is accomplished by dipping in warm dil.H2SO4 or in cold HCl solution to which some inhibitor has been added.
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Generally, there are two types of metallic coatings are protection from corrosion.
1. Anodic coatings 2. Cathodic coatings

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ANODIC COATINGS
Anodic coatings are those in which, the metal used for is more anodic than the metal which is to be protected. For example, coating of Aluminum, Cadmium and Zinc on steel surface are anodic, because their electrode potentials are lower than that of the base metal iron. Therefore sacrificially, anodic coatings protect the underlying base metal
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Galvanization
Galvanization is a process in which the iron article is protected from corrosion by coating it with a thin layer of zinc. Then after, dipped in the bath molten zinc which is at 425-4500C. So method used for Galvanization is HOT DIPPING When the iron piece is taken out it is coated with a thin layer of zinc.

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CATHODIC COATINGS
TINNING: The process of coating tin over the iron or steel articles to protect it from corrosion is known as tinning. Tin is a nobler metal than iron, therefore, it is more resistance to chemical attack. Method used is again Hot Dipping,A cleaned Iron sheet is passed through a bath molten flux. Like Zinc chloride, then through molten tin and finally through a suitable vegetable oil.

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CATHODIC COATINGS:
METAL CLADING The surface to be protected is sandwiched between two thin layers of coat metal and pressed between rollers. The coat metal has to be anodic to the base metal and only plain surfaces can be cladded. This method is used for coating Al, Cr, Ni, Duraluminium, etc.

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ELECTOPLATING
Electroplating is the electro-deposition of metal, by means electrolysis over surface of metals, alloys or non-metals. In this process Metal to be protected is made CATHODE Anode is generally of that metal whose coating is to be done. Both the electrodes are dipped in electrolyte containing same ions , whose coating is to be done.
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ELECTOPLATING
Electroplating is the deposition of a metallic coating onto the surface of an object by putting a negative charge onto the object and immersing it into a solution which contains a salt of the metal to be deposited.

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METAL SPRAYING:
In this process, the coating metal in the molten state is sprayed on the roughened surface of the base metal. The metal thus sprayed adheres to the base metal surface.

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Sprayed-coatings can be applied by the following 2 techniques.


1. Wire-gun method 2. Powder metal method

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1. Wire-gun method
Wire-gun method is more widely used for common metals. In this, the wire of the coating metal is melted by an oxy-acetylene flame and atomized by a blast of compressed air.

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2. Powder metal method


In this, finely divided powdered metal is sucked from the powder chamber and then heated as it passes through the flame of the blow-pipe. The blow-pipe disintegrates the metal into a cloud of molten globules, which are then adsorbed on the base metal surface. This method is, however, limited to lowmelting metals like Zn, Pb, Sn, etc.
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CEMENTATION
Cementation is the process in which base metal is packed in the powdered coating metal and heated to the temperature just below the melting point. Resulting in the formation of layers of alloys of varying composition. It is also suitable for coating small articles of uneven surfaces and shapes such as screws, bolts, valves and gauge tools.
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Cathodic protection

In this method, the metal structure can be protected from corrosion by connecting it with wire to a more anodic metal. As this more active metal is sacrificed in the process of saving metal from corrosion, it is known as sacrificial anode. The metals which are commonly used as sacrificial anodes are Mg, Zn, Al and their alloys. The important applications of this method is the protection of underground cables and pipelines from soil corrosion.
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