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Introduction Types and composition Application

An inhibitor is a substance that when added in small concentrations to an environment, decreases the corrosion rate  Corrosion inhibitors are additives to the fluids that surround the metal or related object.  The effectiveness of a corrosion inhibitor depends on fluid composition, quantity of water, and flow regime.  A common mechanism for inhibiting corrosion involves formation of a coating, often a passivation layer, which prevents access of the corrosive substance to the metal.

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An inhibitor can be considered as a retarding catalyst There are numerous inhibitor types and compositions Most inhibitors have been developed by empirical experimentation Inhibition is not completely understood but it is possible to classify inhibitors according to their mechanism and composition

Reducing the movement or diffusion of ions to the metallic surface  .Increasing the anodic or cathodic polarization behavior (Tafel slopes)  .Introduction Inhibitors slow corrosion process by:  .Increasing the electrical resistance to the metallic surface  .

Inhibitors: types and composition Adsorption-type inhibitors  Hydrogen-evolution poisons  Scavengers  Oxidizers  Vapor-phase inhibitors  .

The effectiveness of this inhibitor depends on the chemical composition. their molecule structure and their affinities for the metal surface These are organic compounds which adsorb on the metal surface and suppress metal dissolution and reduction reactions .Adsorption-type inhibitors    Usually designated as film forming protect the metal by forming a hydrophobic film on the metal surface.

which can readily attach to the metal surface  . etc.Adsorption-type inhibitors  Ex: organic amines (pyridine. diethylamine. methylamine.) Chemisorption of an organic compound is facilitated by the presence of polar groups in the molecular structure.

these substances are very effective in acid solutions  but are ineffective in environments where other reduction processes such as oxygen reduction are the controlling cathodic reactions.Hydrogen-evolution poisons Retard the hydrogen-evolution reaction  Ex: arsenic and antimony ions  As a consequence.  .

Scavengers These substances act by removing corrosive reagents from solution  Ex: sodium sulfite(Na2SO3) and hydrazine (N2H4)  It remove dissolved oxygen from aqueous 2Na 2SO3  O2  2Na 2SO4 solutions  N 2 H 4  O2  N 2  2H2O .

Scavengers Work very effectively in solutions where oxygen reduction is the controlling corrosion cathodic reaction  But will not be effective in strong acid solutions  .

Oxidizers Used to inhibit the corrosion of metals and alloys that demonstrate activepassive transitions  Metals:iron and its alloy and stainless steels  Substance: chromate.  . nitrate and ferric salts.

Vapor-phase inhibitors These are very similar to the organic adsorption-type inhibitors  Possess a very high vapor pressure (usually about 10-2 to 10-7 mmHg)  These materials can be used to inhibit atmospheric corrosion of metals without being placed in direct contact with the metal surface  .

Continue… Are placed in the vicinity of the metal to be protected  Transferred by sublimation and condensation to the metal surface  Only effective in closed spaces such as inside packages or on the interior of machinery during shipment  .

Continue… Dicyclohexylamine nitrite (DAN) has been found especially effective for steel surfaces  But increases attack on copper alloy  Nitrobenzoate ( a universal vaporphase inhibitor): protect ferrous. copper and other alloy system  .

automotive coolants  Once-through sytems usually consume too much of the inhibiting chemical to be economically feasible  .  Ex: recirculating cooling water.Application Inhibitors find greatest use in recirculating systems.

◦ Increasing concentration and ◦ Increasing temperature Many inhibiting compounds are toxic (chromates.Application   The effectiveness of inhibitors is diminished by ◦ Increasing solution corrosivity. arsenic) and recent environmental regulations have limited their use .

Application   Many inhibitors are effective for more than one type of alloy but ◦ pH ◦ temperature ◦ and other condition are unique for each An inhibitor for one metal may be corrosive to others .

IE-ineffective. RE-reasonably effective.Metal Mild steel Table 5. A-aggressive .1: Effectiveness of inhibitors in near neutral pH waterNitrites Benzoates Borate Phosphate Silicate Chromates s E E E E s E s RE Tannin s RE Cast iron Zinc Copper Aluminiu m Pb-Sn solder E E E E E E IE PE PE A IE IE PE PE E V E E V E RE RE RE RE RE RE RE E V RE RE RE E-effective. V-variable. PE-partially effective.

Application  Three types of environment find greatest use for inhibitors 1) Natural. copper. . ◦ It has a good corrosion and scale inhibition effect on t he high hardness cooling water ◦ applicable to carbon steel. etc. supply and industrial cooling waters by nearly neutral (pH 5 to 9) range  Ex: ◦ organic phosphonate. copper alloy and stainless steel. ◦ widely used in the airconditioning cooling water in hote ls. acrylic copolymer as the main a ctive ingredient.

Application 2)Primary and secondary production of crude oil and subsequent refining processes  The main ingredient :is two-imidazoline. . gas. but also dispersed in water.  This unique feature makes it be the preferred component of gas corrosion inhibitor.  soluble in oil.

and a reduced iron build-up.Application 3) Acid solutions for pickling to remove rust and mill scale during the production and fabrication of metal parts or for postservice cleaning of such parts  Ex: The pickling operation makes use hydrochloric acid. higher efficiency. inclusive of a better finishing and appearance. that presents many benefits. .

50-100 ppm . long chain aliphatic amines such as octdecylamine at 1-3 ppm Refrigeration brines: chromates.2: Inhibitors used for industrial application Sample inhibitor CaCO3 deposition.Potable water -Recirculing cooling water -Automotive coolants -Steam condensates -Brines and seawater . benzotriazole Neutralizers: ammonia. benzoate. 3-10% Hot desalting brines: mixed chromate and phosphate. nitrate at 300-500 ppm Calcium polyphosphates at 15-37 ppm Silicates at 20-40 ppm Nitrite. polyphosphates. silicates. phosphate. zinc salts Chromate. sodium mercaptobenzothiazole. morpholine. cyclohexamine.Environment Waters Table 5. 2000-3300 ppm Diluted seawater: sodium nitrite. benzylamine. borax.

mercaptans. (0. decylamine. di-ortho-tolyl-thiourea. various amines including primary amine. sulfides. quinoline. dibenzylsulfoxides .Continue… Environment Sample inhibitor Acid pickling solution -Sulfuric acid -Hydrochloric acid Oil production and refining -Primary and secondary recovery -Refining Fatty imidazolines. amido-amines. diamines. oxyethylated primary amines.003-0. quaternized amines Imidazoline and derivatives Phenylthiourea. alkyl pyidines. phenylthiourea.01%) Pyridine. various amines.

Displacement of the corrosion potential in the negative direction indicates mainly retardation of the cathodic process (cathodic control) . Ecorr decreases and icorr decreases.Cathodic inhibitor   On addition of the corrosion inhibitor.

. which polarizes the metal by restricting the access of dissolved oxygen to the metal substrate.Cathodic inhibitor    Cathodic inhibitors are generally less effective than the anodic type. They often form a visible film along the cathode surface. The film also acts to block hydrogen evolution sites and prevent the resultant depolarizing effect.

Cathodic inhibitor  Example: ◦ ◦ ◦ ◦ Zinc hydroxide Zinc phosphate Calcium carbonate Calcium phosphate .

Anodic inhibitor   On addition of the corrosion inhibitor. Displacement of the corrosion potential in the positive direction indicates mainly retardation of the anodic process (anodic control) . Ecorr increases and icorr decreases.

Anodic inhibitor    Anodic inhibitors build a thin protective film along the anode. the appearance of the metal will be left unchanged. . The film is initiated at the anode although it may eventually cover the entire metal surface. increasing the potential at the anode and slowing the corrosion reaction. Because the film is not visible to the naked eye.

molybdate.Anodic inhibitor  Example: ◦ Chromate. Oxygen must be present in water for orthophosphate to function as an anodic inhibitor. ◦ Polyphosphate -. Chromate and nitrite are the only anodic inhibitors that function in the absence of oxygen. and nitrite -.catalyze the reaction between the metal and oxygen to form a passivating film.also catalyzes the reaction between steel and oxygen to form a passivating gamma iron oxide film. .exhibits some anodic properties but functions primarily as a cathodic inhibitor. ◦ Orthophosphate -.

. Little changes in the corrosion potential suggests that both anodic and cathodic processes are retarded.Mixed inhibitor   On addition of the corrosion inhibitor. icorr decreases but Ecorr changes very little (either positive or negative).

Mixed inhibitor   They are typically film forming compounds that cause the formation of precipitates on the surface blocking both anodic and cathodic sites indirectly. Silicates and phosphates do not afford the degree of protection provided by chromates and nitrites. copper and brass. However. sodium silicate protects steel. for example. they are very useful in situations where non-toxic additives are required. ◦ Phosphates also require oxygen for effective inhibition. Examples: ◦ Sodium silicate. protection is not always reliable and depends heavily on pH. is used in many domestic water softeners to prevent the occurrence of rust water. . In aerated hot water systems. however.

3(  a   c )icorr . a c Rp  2. Rp  The efficiency of an inhibitor can also be studied by recording polarisation curves or by polarisation resistance measurements.Polarisation resistance.

R p inhibited  R p uninhibited p%  100 R pinhibited  .Inhibition efficiency. p It is important to be able to evaluate inhibitors and determine the conditions under which they are effective.  The inhibition efficiency can be expressed by.