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CORROSION

Definition of corrosion: Corrosion is defined as the destruction of metals or alloys by the surrounding environment through chemical or electrochemical reactions. Example: When iron is exposed to air in the presence of moisture, hydrated ferric oxide (rust) is formed.
Fe2+ + 2OHFe(OH)2
Fe2O3.3H2O rust(brown colour)

2Fe(OH)2 + 11/2 O2 + H2O

Electrochemical theory of corrosion: According to electrochemical theory, when a metal such as iron is exposed to corrosive environment, following changes occur. A large number of tiny galvanic cells with anodic and cathodic regions are formed.

Fe2+ Fe2+
Anodic region Electrons

OH- OHCathodic region

O2 H2O

Iron Metal

1. 2. 3.

Oxidation of metal takes place at the anodic region. e.g. Fe Fe2+ + 2 eThe Fe2+ ions dissolve, so corrosion takes place at the anodic region. The electrons travel through the metal from the anodic region to cathodic region. Reduction of O2 or H+ takes place at the cathodic region. O2 + 2H2O + ne4OHThe metal is unaffected at the cathodic region.

4. Fe2+ and OH- ions travel through the aqueous medium and form corrosion product.
Fe2+ + 2OHFe(OH)2

5 The corrosion product may undergo further oxidation to form rust. Fe2O3.3H2O 2Fe(OH)2 + 11/2 O2 + H2O

Reactions: Reaction at anodic region: As mentioned above, oxidation of metal takes place at anode.
Fe Fe2+ + 2e-

Reactions at cathodic region: At cathode, the reaction is either a) liberation of hydrogen or b) absorption of oxygen. a) Liberation of hydrogen ( in the absence of oxygen) In acidic medium the reaction is.
2H+ + 2eH2

In neutral or alkaline medium, the reaction is 2H2O + 2e2OH- + H2 b) Absorption of oxygen ( in the presence of oxygen) In acidic medium, the reaction is 4H+ + O2 + 4e2H2O In neutral or alkaline medium, the reaction is O2 + 2H2O + ne4OHOverall reaction:
Fe2+ + 2OHFe(OH)2
Fe2O3.3H2O

2Fe(OH)2 + 11/2 O2 + H2O

Different types of corrosion:


1. Differential metal corrosion:

Zn metal

Fe metal

Fe metal

Cu metal

Anode Cathode Anode Cathode This type of corrosion occurs when two dissimilar metals are in contact with each other and are exposed to a corrosive environment. The two metals differ in their electrode

potentials. The metal with lower electrode potential acts as anode and the other metal with higher electrode potential acts as cathode. The anodic metal undergoes oxidation and gets corroded. A reduction reaction occurs at the cathodic metal. The cathodic metal does not undergo corrosion. The reactions may be represented as follows:

Cell reactions: At anode : M Mn+ + ne- (Oxidation of metal M)

4OH- (Reduction of oxygen) Higher the potential difference between the anodic and cathodic metals, higher is the rate of corrosion.
Example: When iron is in contact with zinc, iron acts as cathode and zinc acts as anode because zinc has lower electrode potential compared to iron. Therefore zinc undergoes corrosion. On the other hand, when iron is in contact with tin, iron acts as anode because iron has lower electrode potential compared to tin. Hence iron undergoes corrosion. Other examples: 1. Steel screws in copper sheet. 2. Steel screws with copper washer. 3. Bolt and nut made of different metals.

At cathode : O2 + 2H2O + 4e-

2.

Differential aeration corrosion:

Iron More O2, (Cathode)

Less O2, (Anode) Wate r

This type of corrosion occurs when two different parts of the same metal are exposed to different oxygen concentrations. (e.g. An iron rod partially dipped in water.) The part of the metal which is exposed to less oxygen concentration acts as anode. The part which is exposed to more oxygen concentration acts as cathode. The anodic region undergoes corrosion and the cathodic region is unaffected. The reactions may be represented as follows:

Cell reactions: At anode : M Mn+ + ne- (Oxidation of metal M) 4OH- (Reduction of oxygen)

At cathode : O2 + 2H2O + 4e-

Other examples: 1. Part of the nail inside the wall undergoes corrosion. 2. When a dirt particle sits on a metal bar, the part under the dirt undergoes corrosion. 3. Partially filled iron tank undergoes corrosion inside water.

3. Pitting corrosion: This is an example of differential aeration corrosion. When a small dust particle gets deposited on a steel surface, the region below the dust particle is exposed to less oxygen compared to the remaining part. As a result, the region below the dust particle acts as anode undergoes corrosion and forms a pit. The remaining region of the metal acts as cathode and is unaffected.

The reactions may be represented as follows:

Cell reactions: At anode : M Mn+ + ne- (Oxidation of metal M) 4OH- (Reduction of oxygen)

At cathode : O2 + 2H2O + 4e-

Formation of a small anodic area and a large cathodic area results in intense corrosion below the dust particle.

4. Water line corrosion: This is an example of differential aeration corrosion. More oxygen, (Cathode)

Rust

Less Oxygen (Anode)

Water

When a steel tank is partially filled with water for a long time, the inner portion of the tank below the water line is exposed only to dissolve oxygen, where as, the portion above the water line is exposed to more oxygen. Thus the portion below the water line acts as anode and undergoes corrosion. The upper portion acts as cathode and is unaffected. A distinct brown line is formed just below the water line due to the deposition of rust. The reactions may be represented as follows:

Cell reactions: At anode : M Mn+ + ne- (Oxidation of metal M) 4OH- (Reduction of oxygen)

At cathode : O2 + 2H2O + 4e-

Other example: Ships which remain partially immersed in sea water for a long time undergo water line corrosion.

5. Stress corrosion:

Boiler Anode Cathode


Soft water = Very dilute NaOH

Stress corrosion occurs when stressed region of metals are exposed to corrosive environments. The stressed region acts as anode and undergoes corrosion. The unstressed region acts as cathode and is unaffected. Stress corrosion is highly specific in nature. For corrosion to occur, the presence of both stress and a specific corrosive environment are necessary. For example, stressed regions of mild steel undergo stress corrosion in the presence of NaOH solution. Caustic embrittlement in boilers is an example of stress corrosion. Here alkaline (NaOH) water enters the hairline cracks on the boiler wall (mild steel). The water evaporates off leaving behind a concentrated solution of NaOH in the crack. When the concentration of NaOH increases to 10%, an electrochemical cell is set up with the stressed region acting as anode. The iron surrounded by dilute NaOH acts as cathode. The anodic region undergoes corrosion leading to crack propagation which may result in boiler failure. (It is a stress corrosion occurring in mild steel when exposed to alkaline solutions at high temperature and stress. The boiler water, usually contains a certain proportion of sodium carbonate added for water softening purposes. In high pressure boilers, the carbonates breaks up to give respective hydroxide and carbon dioxide, and make boiler water alkaline.
Na2CO3+H2ONaOH+CO2

This very dilute alkaline water flows into the minute hairline cracks and crevices by capillary action. The water evaporates and increases the concentration of the alkali. This concentrates alkali dissolves iron as sodium ferroate in crevices, cracks and the metal under stress. The sodium ferroate decomposes into magnetite and alkali is regenerated in the process as per the following reactions.
NaOH +Fe Na2FeO2+H2 Na2FeO2+H2O NaOH +Fe3O4

This type of stress corrosion in boilers in the presence of alkaline medium, called caustic embrittlement. This can be prevented by the addition of the substances such as sodium sulphate,
tannin, etc., which blocks the cracks and crevices, thereby prevents the penetration of alkali.)

Factors affecting the rate of corrosion

Primary Factors (Related to metal) Environment) Factors are:1. Nature of the metal 2. Physical state of the metal 3. Hydrogen over voltage 4. Nature of the protective layer Factors affecting the rate of corrosion:

Secondary factors (Related to 1. pH of the medium 2. Temperature 3. Area effect 4. Polarisation

1. Nature of the metal: Metals with lower electrode potentials are more reactive and are more susceptible to corrosion. For example, elements such as Mg and Zn, which have low electrode potentials, are highly susceptible to corrosion. Noble metal such as gold and platinum, which have higher electrode potentials, are less susceptible to corrosion. Exceptions: Metals and alloys which show passivity are exceptions for this general trend. Such metals form a protective coating on the surface which prevents corrosion. 2. Nature of corrosion product: If the corrosion product is insoluble, stable and nonporous, then it acts as a protective film which prevents further corrosion. The film acts as a barrier between the fresh metal surface and the corrosive environment. On the other hand, if the corrosion product is soluble, unstable and porous, then the corrosion process continues even after the formation of corrosion product. Example: Aluminium, titanium and chromium form a protective film of metal oxide on the surface. Stainless steel forms a protective film of Cr2O3 on the surface. But in the case of Zn and Fe, the corrosion products formed do not have protective value. 3. Difference in potential between anodic and cathodic regions: Larger the potential difference between the anodic and cathodic regions, higher is the rate of corrosion. For example, the potential difference between iron and copper is 0.78 V, and between iron and tin is 0.3 V. Therefore, corrosion is faster when iron is in contact with copper. The use of dissimilar metals should be avoided wherever possible. Otherwise, the anodic metal gets corroded.

4. Anodic and cathodic areas: Smaller the anodic area and larger the cathodic area, more intense and faster is the corrosion. For example, a broken coating of tin on iron surface results in intense corrosion at the broken region. Iron is anodic to tin. Exposed region of iron acts as anode with small area. Tin acts as cathode which has large area. 5. Anodic and cathodic polarizations: The polarization at anode and cathode decreases the rate of corrosion. Anodic polarization occurs due to the accumulation of metal ions in the vicinity of anodic region. This retards the formation of new metal ions by oxidation. Thus the corrosion process is retarded. Cathodic polarization occurs due to the accumulation of hydroxyl ions in the vicinity of cathodic region. This accumulation retards the movement of cathodic reactant (oxygen) towards the cathodic surface. Hence, the rate of cathodic reaction decreases. A retarded cathodic reaction results in retardation of anodic reaction also. Thus the corrosion process is slowed down. 6. Hydrogen over voltage: When the cathodic reaction is liberation of hydrogen, a high hydrogen over voltage retards the cathodic reaction. A retarded cathodic reaction retards the anodic reaction also. Thus the corrosion process is slowed down. (Note: Theoretically, certain potential difference between anode and cathode is required for the hydrogen evolution to occur at cathode. But in practice, the potential difference required is more than the theoretical value. This excess potential difference is called hydrogen over voltage.) 7. pH of the medium: In general, lower the pH of corrosion medium, higher is the corrosion rate. (Exception: Metals like Al, Zn etc. undergo fast corrosion in media with high pH.) Iron does not undergo corrosion at pH greater than 10. This is due to the formation of protective coating of hydrous oxides of iron. Between pH 10 and 3, the presence of oxygen is essential for corrosion. If the pH is less than 3, corrosion occurs even in the absence of oxygen. 8. Temperature: Higher the temperature, higher is the rate of corrosion. In general, the rate of a chemical reaction increases with increase in temperature. Corrosion is one such chemical reaction. Therefore, the rate of corrosion increases as the temperature increases.

Increase in temperature increases the ionic conductivity of the corrosive medium. This also contributes to the increase in corrosion rate.

Corrosion control
1.

Anodizing (Anodizing of aluminum): When aluminum metal is made anodic in an electrolytic bath with sulphuric acid or chromic acid as the electrolyte, a thin layer of aluminium oxide (Al2O3) is formed on the surface. This process is called anodizing of aluminium or anodic oxidation of aluminum. When anodized aluminium is exposed to a corrosive environment. the Al2O3 layer on the surface acts as a protective coating. Hence corrosion is prevented. Other metals such as Mg, Ti etc. can also be anodized. (Note: On anodizing, Al2O3 is formed on the surface as a porous layer. The layer may be made compact by sealing, which involves heating with boiling water or steam. During sealing, Al2O3 is converted into Al2O3.H2O which occupies higher volume. Therefore, the pores are sealed.) Applications: Metals such as Al, Mg, Ti etc. are anodized to control corrosion.

2. Phosphating: Converting the surface metal atoms into their phosphates by chemical or electrochemical reactions is called phosphating. The phosphating bath contains three essential components: (i) free phosphoric acid, (ii) a metal phosphate such as Fe, Mn phosphate and (iii) an accelerator such as H2O2. Phosphating not only improves the corrosion resistance but also imparts good paint adhesion quality to the surface. Applications: Phosphate coating is given as an under layer before painting the car bodies, refrigerators and washing machines.

Inorganic coatings (Chemical conversion coatings) These coatings are produced at the surface of the metal by chemical / electrochemical reactions. These coatings are applied on the article for decorative effect and to increase the corrosion resistance of the base metal. These serves as an excellent base coating for paints and enamels. Examples: Anodising and Phosphating

Anodising

Phosphating

These coatings are generally produced These coatings are generally applied on non-ferrous metals like Al, Zn, Mg frequently to iron, steel and zinc and to and their alloys by anodic oxidation a lesser extent on Al, Cd and Sn. (electrochemical) process. These are produced by the chemical The base metal is made as anode. reaction of the base metal with Anodising of Al: It is carried out to aqueous solution of phosphoric acid produce a porous/nonporous coating. and phosphate of Fe, Mn or Zn. The porous coating is obtained by The reactions are slow, hence it is anodic oxidation. The electrolysis is enhanced by using accelarators along conducted in an acid bath, at moderate with the phosphating mixture. o temperature 30-40 C, using moderate The most common mode of current densities, in which the base metal is acceleration is by addition of oxidizing made as anode. The commonly used baths agents, such as nitrate, nitrite, chlorate are H2SO4 / Chromic acid / Phosphoric acid and hydrogen peroxide. /oxalic acid. The thickness of the film The chemical reaction between the increases with progressive oxidation. Outer base metal and the phosphating most layer of the oxide film is very porous mixture results in the formation of and soft, these pores are sealed by surface film consisting of crystalline exposing to the boiling water. In this Mn-Fe Phosphate, Zn-Fe Phosphate process the metal oxide layer changes into etc. These coatings are applied by its mono hydrate. immersion or spraying or brushing. These coatings do not offer complete The non porous coatings are produced resistance to the atmospheric by using non-corrosive electrolytes like corrosion. boric acid and borax. These coatings are These are used as a primer coat for applied on electrolytic condensers. paints, enamels, etc. The anodised coatings are thicker than the natural oxide film and possess improved corrosion resistance as well as resistance to mechanical injury. 3. Organic coating: (Coating with paints and enamels): Metal corrosion may be controlled by the application of an organic coating of paint on the surface. The organic coating acts as a barrier between the metal surface and the corrosive environment. A primer coat such as phosphate coating is generally applied as an undercoat before painting. Organic coatings are applied by different methods such as brushing, spraying, roller coating etc.

4.

Galvanizing: Galvanizing is the process of coating a metal surface such as iron with zinc metal. Galvanizing of iron is an example of anodic metal coating on the surface of a cathodic metal.

Galvanization is carried out by hot dipping method. It involves the following steps.

Dc Power

Al2O3

H2CrO4 Cathode The metal surface is 1.

2. 3. 4. 5.

Anode A washed with organic solvents to remove organic matter on the surface. Rust is removed by washing with dilute sulphuric acid. Finally, the article is washed with water and air-dried. The article is then dipped in a bath of molten zinc. (Molten zinc is covered with a flux of ammonium chloride to prevent the oxidation of molten zinc.) The excess zinc on the surface is removed by passing through a pair of hot rollers.

Application: Galvanization of iron is carried out to produce roofing sheets, fencing wire, buckets, bolts, nuts, pipes etc. (Note: Even if the Zn coating falls off at some places, the base metal (Fe) does not get corroded at those places. This is because the base metal acts as cathode. In corrosion process, the cathodic metal always remains unaffected.) (Note: Galvanized articles are not used for preparing and storing food because zinc dissolves in dilute acids producing toxic zinc compounds)

5. Tinning: Tinning is the process of coating the surface of a base metal (such as iron) with tin. Tinning of iron metal is an example of cathodic metal coating on an anodic base metal. Tinning of iron is carried out by hot dipping method. It involves the following steps. 1. 2. 3. 4. 5. 6. The metal surface is washed with organic solvents to remove organic matter on the surface. Rust is removed by washing with dilute sulphuric acid. Finally, the article is washed with water and air-dried. It is then passed through molten zinc chloride flux. The flux helps the molten tin to adhere strongly on the surface. It is then dipped in a bath of molten tin. The excess tin on the surface is removed by passing through a series of rollers immersed in palm oil. The oil prevents the oxidation of tin coating.

Applications: Tin-coated steel is used for manufacturing containers. (Note: In tin-coated iron, if a small crack is formed in the tin coating, an intense and accelerated corrosion of iron occurs at the exposed region because of the formation of a small anodic area (iron) and large cathodic area (tin)). (Note: Copper utensils are coated with tin to prevent contamination of food with poisonous copper salts.)