CORROSION AND ITS CONTROL

Corrosion can be defined as spontaneous destruction or deterioration of a metal by chemical, electrochemical or biochemical reaction.
Eg: Rusting of iron, basic copper carbonate Corrosion can be viewed as the reverse process of extractive metallurgy.

CORROSION CLASSIFICATION:

A)
B)

Dry or Chemical Corrosion

Wet or Electrochemical Corrosion

A) Dry or Chemical Corrosion: This type of corrosion occurs by direct chemical reactions between the environment and the metals and alloys. Presence of an electrolyte is not at all essential for the corrosion to occur. Therefore this kind of corrosion is also known as dry corrosion. eg: Direct chemical action of environmental gases such as oxygen, halogens, hydrogen sulphide, sulphur dioxide, nitrogen or anhydrous inorganic liquid with the metal.

Wet or Electrochemical Corrosion

Wet corrosion occurs due to the existence of separate anodic and cathodic areas, between which current flows through the conducting solution. At the Anode: M(s) Mn+ + neAt the Cathode: i) Hydrogen evolution ii) Absorption of oxygen depending upon the nature of corrosive environment.

 Hydrogen evolution:
2H+ (aq) + 2e- H2

Reduction of oxygen in acid medium

O2 + 4H+ + 4e- 2H2O (l)

Reduction of oxygen in neutral medium

O2 (aq) + 2H2O + 4e- 4OH-(aq)

Mechanism of rusting
Rusting take place when iron is exposed to oxygen in the presence of humidity/moisture. At the anode: Fe Fe2+ + 2e At the cathode: O2 + 2H2O + 4e- 4OHFe2+ (aq) + 2OH- Fe(OH)2

 In presence of enough oxygen: 4Fe(OH)2 + O2 + 2H2O 4Fe (OH)3 or 2Fe2O3.6H2O Yellow rust In presence of limited oxygen:
3Fe(OH)2 + 1/2O2 Fe3O4.3H2O Fe3O4 (anhydrous). (magnetite) Black rust.

Types of corrosion
1. 2. 3. 4. 5. Galvanic corrosion. Differential aeration corrosion. Waterline corrosion. Pitting corrosion. Stress corrosion.

Galvanic corrosion.
Occurs when ; Two dissimilar metals are in contact with an electrolyte. Anode: Metal with lower value of standard electrode potential. Cathode: Metal with higher value of standard electrode potential.

 The less resistant metal becomes anodic and the more resistant metal cathodic. Consider Fe (Eo= -0.44V)Zn ( Eo = -0.76V) Sn (Eo = -0.14V) Cu (Eo =+ 0.36V)

Examples: Zinc and copper couple. Steel screws in a brass marine hardware. Lead antimony solder around the copper

wire.

 Factors affecting galvanic Corrosion:

The nature and the aggressiveness of the environment. Depends largely on the type and the amount of the moisture present. Accelerated corrosion due to galvanic effects is usually greatest near the junction. Cases: Steel screws in a brass marine hardware. Lead-antimony solder around the Cu wire.

Differential aeration corrosion

Occurs when: The metal is exposed to different air or oxygen concentrations. (Oxygen concentration cell) Anode: Part of the metal exposed to lower concentration of oxygen. Cathode: Part of the metal exposed to higher concentration of oxygen. Consequently, poorly oxygenated region undergoes corrosion.

Example : A metal (Zn) partially immersed in a dilute solution of NaCl At the anodic area: Zn Zn+2 + 2eAt the cathodic

area: O2 + 2H2O + 4e- 4OH-

Waterline corrosion
A form of differential aeration corrosion. occurs when: Un-agitated water is kept in an iron tank. Anode: Iron surface just below the waterline (Poorly oxygenated part) Cathode: Iron surface above the waterline (More oxygenated part)

Examples: Ocean going ships Un-agitated water stored in a tank.

 Water line corrosion:

P A
C

F F

Pitting corrosion.
The important reasons for the pitting corrosion are: *Surface roughness or non uniform finish * Scratches or cut edges. *Local straining of metal due to non uniform stress. *Depositions of extraneous matter such as sand, scale, water drop, dust etc.

Example 1.

Pitting corrosion is characterized by small anodic area and large cathodic area, resulting in

accelerated corrosion at the anodic area. It is an

autocatalytic process, with the initially formed pit produces conditions which are both stimulating and necessary for the continuing activity of the pit.

Reactions:
At the anodic area: Fe Fe2+ + 2e At the cathodic area: O2 + 2H2O + 4e- 4OHFe + 2OH- Fe (OH) 2

4Fe (OH)2 + O2 + 2H2O 2Fe2O3.6H2O (Yellow rust)

3Fe (OH)2 + 1/2 O2 Fe3O4.3H2O (Black rust)

 Examples:
*Deposition of extraneous matter (dust, sand, etc.,) on the surface of the metal *Peeling of tin coat on iron. Pitting is dangerous because it is a localized and intense form of corrosion and failure occurs with extreme suddenness.

Stress Corrosion.
Stress corrosion also known as stress corrosion cracking refers to cracking of metal caused by the combined effect of a tensile stress and a specific corrosive environment on the metal. Here, the corrosive agents are highly specific and selective.
Caustic alkalis and strong nitrate solution for mild steel Traces of ammonia for brass Acid chloride solution for stainless steel

Examples: *Season cracking of brass *Caustic embrittlement of steel

 The metal atoms under stress are always higher energy levels as compared to the one free from stress. The stressed part of the metal therefore becomes more active than the stress free part. Hence: Anode- stressed part. Cathode- stress free part. Stressed part undergoes corrosion.

Caustic Embrittlement
This is a dangerous form of stress corrosion observed in boiler. Water fed into boilers may contain free alkali (Lime soda process). Na2CO3(aq) + H2O 2NaOH + CO2(g) Local stresses exist in metal sheets of boiler under rivets. Minute cracks develop on the metal sheets when the stress is relieved.

 NaOH concentration cell forms between the stressed and unstressed part of the metal. Iron/ Concentrated, Dilute / Iron (stressed) NaOH NaOH (unstressed) ANODIC CATHODIC

3Na2FeO2+ 4H2O 6NaOH + Fe3O4 + H2 6Na2FeO2+6H2O + O2 12NaOH +2Fe3O4 When iron changes to these oxides metallic properties like malleability and ductility are lost. It becomes brittle. The brittleness is caused by caustic alkali.

 Prevention: * Na2SO4,tannin or lignin is added to water. *Boiler can be constructed by welding the sheets to avoid local stresses. *Caustic embrittlement is avoided by using demineralised water

Factors Affecting Corrosion Rate

Primary Factors: Factors related to the corroding metals. Nature of metal. Relative electrode potentials of metals. Relative cathodic and anodic area. Hydrogen overvoltage.

Secondary Factors: Factors related to the environment. Concentration and nature of electrolyte.

pH of the medium.
Temperature.

Polarization
Humidity

Galvanic Series
The galvanic series can be defined as the series prepared by studying the corrosion of metals and alloys in a given environment like sea water. Need for galvanic series: Electrochemical series does not account for the corrosion of all metals and alloys (Eg: Zn/Al couple)

Characteristics of e.m.f.Series
Electrode potentials are measured by dipping pure metals in their salt solution of 1M concentration without any oxide film on it. The positions of a given metal in electrochemical series is fixed In electrochemical series, metals and non metals are present

Characteristics of Galvanic Series

Developed by studying corrosion of metals and alloys in unpolluted sea water., without their oxide films. The position of a given metal may shift in it as metal takes active and passive states. Comprises of metals and alloys. Position of a metal, when present in the form of an alloy is different from that of pure metal.

Galvanic Series
Galvanic Series: Mg Active Mg alloys Zn Al Cd Mild Steel Cast Iron . . . . . . Ag Ti Graphite Au Pt

E.M.F. Series Li+ + e- Li (Base) K+ + eK Ca2+ + 2e- Ca Na+ + e- Na Mg2+ + 2e- Mg Al3+ + 3e- Al Zn2+ + 2e- Zn Cr3+ + 3e- Cr Fe2+ + 2e- Fe Ni2+ + 2e- Ni Sn2+ + 2e- Sn Pb2+ + 2e- Pb Fe3+ + 3e- Fe H+ + e H2 Cu2+ + 2e- Cu Ag+ + e- Ag Pt4+ + 4e- Pt Au+ + e Au F2 + e- F- (Noble)

Protection Against Corrosion

Various methods available for corrosion prevention are listed below: Selection of material & design improvement. Change of metal. Change of environment. Use of coatings for separating metal from environment. Change of metal electrode potential.

Selection of Materials.
Noble and pure metals show greater resistance to corrosion. Suitable alloying of metals. Residual stress in fabricated articles should be avoided. Avoid the use of two dissimilar metals having large difference in their electrode potentials.

Proper Designing:
Simplify forms. Avoid crevices. Avoid residual moisture. Avoid sharp corners and bends. Avoid galvanic corrosion. Avoid mechanical stresses.

General Rules For Design.

Avoid sharp edges

Allow free circulation of air

Cathodic Protection.
Corrosion of a structure can be controlled if it can be changed into the cathodic part of a corrosion cell. This is called cathodic protection. Two different methods: a) Sacrificial anode method. b) Impressed current method.

Sacrificial Anode Method.

Anodic part: More reactive metal. Cathodic part: Structure to be protected. The anode is sacrificed to protect the structure.

 Zn, Al and Mg are more reactive metals than Fe and hence they become anodic part in contact with Fe. Effective only when proper quantities of sacrificial anodes are used. Number and spacing of anodes depend upon the system to be protected.

 Examples: *Ship's steel hulls, offshore drilling platforms, oil and gas under sea pipelines, containers used to store water and other liquids are protected by this method. Advantages: *No external power supply is necessary. *Can be used in remote and difficult to reach areas. *Low installation cost. *Minimum maintenance cost.

Impressed Current Method

Impressed Current Method.

The metallic structure is made cathode with the use of impressed current by connecting it to the positive terminal of the external power source. The anode may be made up of steel, graphite and platinum group metals. The inert anode is surrounded by back fill consisting of coke breeze, gypsum to improve electrical contact.

 Advantages: * Applicable to large objects. * Uncoated parts can be protected. Limitations: * Larger installation cost. * Higher maintenance cost.

Anodic Protection
Passivity: Certain metals and alloys (Al, Ti, Cr, Mo, Ni etc.,) lose chemical reactivity under specific environmental condition. It is based upon the ability of a metal or an alloy to undergo passivation in the surrounding environment.

 When a passivating metal is immersed in an electrolyte with increasing oxidising power behaves as shown in the following graph.

ANODIC PROTECTION:
Trans passive region

 Potentiostatic method:

 Advantages: *Its applicability even in extremely corrosive environment. *Low current demand. Limitations: *It is restricted to the metals that show active-passive behaviour. *Its initial installation cost is high. *Cannot reduce the corrosion rate to zero unlike cathodic protection. *This needs continuous supply of electric current.

Surface Coating.
A protective coating on the surface of metals and alloys isolates them from corrosive environment, thereby preventing corrosion. Types: *Metallic coating. *Organic coating. *Inorganic coating.

Metallic Coating.
Coating of a metal on a substrate metal requiring protection against corrosion is metallic coating. Types: *Anodic metal coating: Coating the substrate metal with a more anodic metal. Eg: Galvanizing. *Cathodic metal coating: Coating the substrate metal with a more cathodic metal. Eg: Tinning.

Galvanizing.
Giving a Zn metal coating on iron and mild steel is known as galvanizing. When the coating breaks or cracks zinc acts as anode and the substrate iron and mild steel acts as cathode. Zinc becomes sacrificial anode and provides protection to iron and mild steel. Sheets, pipes, wires are usually galvanized.

Process.
Done by hot dipping process. Objects are degreased, pickled and cleaned. They are dipped in molten zinc bath(425430oC) NH4Cl flux is spread over the bath to prevent its oxidation. Excess liquid Zn is squeezed out and the objects with Zn coating are cooled.

Tinning
Giving a coating of tin on iron and mild steel is called tinning. Tinning protects the article until the coating covers the surface completely, by isolating it from the environment. When the coating cracks or breaks intense or pitting corrosion of the articles at the exposed region occurs. This is because tin is cathodic with iron and small anodic regions are in contact with large cathodic area.

 Tinning is done by hot dipping. Steel sheet is degreased , pickled and cleaned. It is dipped in molten tin(250oC). It is covered with ZnCl2 and NH4Cl flux to protect liquid tin from oxidation by air. Excess tin in then squeezed out from it by passing through rollers kept in palm oil.

Applications: As tin salts are nontoxic, Therefore tinned iron and mild steel sheets are used to prepare tins, cans and containers for storing food materials. Galvanized sheets cannot be used to prepare tins or cans for storing food materials, because zinc salts are toxic.

INORGANIC METAL COATING

Inorganic coatings are chemical conversion coatings. The surface layer of the metal is converted into a compound, by chemical or electrochemical reactions, which forms a barrier between the underlying metal surface and the corrosion environment

 Anodized coating
This coating is produced by non porous

metals like Al,Zn,Mg and their alloys by anodic process in which the basic metal is made as the anode in an electrolytic bath of suitable composition and by passing direct electric current.

 Methods used for getting anodized aluminium are 1. An organic dye is adsorbed on the freshly anodized surface and it is then sealed with boiling water. 2.A metal which has to be diposited is used as anode in presence of highly oxidizing electrolyte and the current is passed continuously to get the passive layer on the base metal. It is used as soap boxes tiffin carriers, window frames, etc

 Phosphate coating.
It is generally done on steel surface by converting the surface metal atoms into their phosphates by chemical or electrochemical reactions. Chemical phosphating includes dipping and spraying and electrochemical phosphating includes cathodic and anodic phosphating.

 The phosphating bath contains three essential components: 1. Free phosphoric acid 2. A primary metal phosphate 3. An accelerator such as nitrates, nitrites , chlorates

 ORGANIC COATING
Coating of metal surface with organic material. Paints and lacquers are the widely used anticorrosion coatings . The function of organic coatings are 1. The coating serves as a barrier between the metal surface and the corrosion environment 2. The pigments (red lead, zinc chromate, etc.) or drying oils(linseed oil,wood oil, etc) present in the paint often exert an inhibitive action by electrochemical and other means.

The requirements of good coating are

The film formed should be continuous,

uniform and impervious to air and water.

Should be chemically inert to the corrosion

environment
Should have reasonably long life.

Should have proper application methods.

 Surface preparation
Application of several coats of paints of

different composition.
Fillers such as nitrocellulose, epoxides etc.

are applied on the well dried primed surface

in order to improve the external appearance.

Surface are smoothened by emery paper

before applying the finishing or top coats.

 Organic coating are applied by different methods such as brushing spraying dipping, roller coating etc . Break down of the organic coating cause severe corrosion of the exposed metal parts.

Corrosion Inhibitors.
An inhibitor is a substance when added in small quantity to the electrolyte medium, inhibits the anodic or cathodic reactions. Types of inhibitors: *Anodic Inhibitors *Cathodic Inhibitors

Anodic Inhibitors.
Substances used to stop anodic reaction. They form insoluble compounds with the metal ions formed at the anodic part . These insoluble compounds form a protective film on the anode surface. This film isolates the anode from the electrolyte medium and stops its corrosion. The anions such as chromate, tungstate, molybdate, phosphate etc., are used to arrest anodic process.

 Effective only when they are added above their critical concentrations. If the added inhibitor is insufficient, it cannot plug all the anodic sites. This leads to severe pitting corrosion.

Cathodic Inhibitors.
Substances used to retard cathodic reaction. They form a protective film on cathodic surface and isolate it from the electrolyte medium thereby preventing corrosion. Two major reactions taking place on cathodic surface depending on the nature of corrosive environment are: *Hydrogen evolution type *Oxygen absorption type

 Hydrogen evolution: 2H+ + 2e- -------->H2 (acid medium) This reaction can be prevented either by *Retarding the diffusion of H+ to the cathode. *Increasing hydrogen over voltage.

 Addition of certain organic compounds, containing N or S, retards the diffusion of H +. Such substances when added to corroding environment are adsorbed on the cathodic sites forming a protective film that suppresses cathodic reaction. Eg: Urea, thiourea, mercaptans and heterocyclic compounds.

 Substances added deposit as adherent metallic film on the cathode areas and thereby prevents the evolution of H2. Oxides of Arsenic, antimony or salts like sodium meta arsenite are used since hydrogen overvoltage for these metals is quite high.

 Oxygen absorption type: (in neutral or slightly alkaline medium) O2 + 2H2O + 4e- -------> 4OH This reaction can be easily stifled either by removing the oxygen from the corrosive media or by decreasing the diffusion rate of oxygen to cathode. Reducing agents such as N2H4, Na2SO3 etc remove oxygen from the corroding environment by combining with it. N2H4 + O2 ----------> N2 + 2H2O.

 Decreasing the diffusion rate of oxygen is achieved by adding salts such as ZnSO4,MgSO4,NiSO4 etc., to the aqueous environment. They undergo hydrolysis and form a deposit of their insoluble hydroxide on the cathodic sites. Zn2+ + 2OH- -----------> Zn(OH)2. The protective film being impermeable to oxygen prevents its further diffusion to cathodic sites.

 The action of an inhibitor depends on the nature of the metal to be protected as well as corrosive environment. It is therefore necessary to choose an appropriate inhibitor for a particular system.