Inhibitor

Introduction Types and composition Application

Introduction
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.

Introduction

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

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

Inhibitors: types and composition

Adsorption-type inhibitors Hydrogen-evolution poisons Scavengers Oxidizers Vapor-phase inhibitors

Adsorption-type inhibitors

Usually designated as film forming protect the metal by forming a hydrophobic film on the metal surface. 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

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

Hydrogen-evolution poisons
Retard the hydrogen-evolution reaction Ex: arsenic and antimony ions As a consequence, 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.

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

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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

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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

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

Application

The effectiveness of inhibitors is diminished by Increasing solution corrosivity, Increasing concentration and Increasing temperature Many inhibiting compounds are toxic (chromates, 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

Metal Mild steel

Table 5.1: 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

RE RE

RE RE
RE RE RE

E V

RE RE RE

E-effective, IE-ineffective, RE-reasonably effective, PE-partially effective, V-variable, A-aggressive

Application

Three types of environment find greatest use for inhibitors

1) Natural, supply and industrial cooling waters by nearly neutral (pH 5 to 9) range

Ex:
organic phosphonate, acrylic copolymer as the main a ctive ingredient. It has a good corrosion and scale inhibition effect on t he high hardness cooling water applicable to carbon steel, copper, copper alloy and stainless steel, etc. widely used in the airconditioning cooling water in hote ls,

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

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; that presents many benefits, inclusive of a better finishing and appearance, higher efficiency, and a reduced iron build-up.

Environment Waters

Table 5.2: Inhibitors used for industrial application

Sample inhibitor CaCO3 deposition, silicates, polyphosphates, zinc salts Chromate, nitrate at 300-500 ppm Calcium polyphosphates at 15-37 ppm Silicates at 20-40 ppm Nitrite, benzoate, borax, phosphate, sodium mercaptobenzothiazole, benzotriazole Neutralizers: ammonia, morpholine, cyclohexamine, benzylamine, long chain aliphatic amines such as octdecylamine at 1-3 ppm Refrigeration brines: chromates, 2000-3300 ppm Diluted seawater: sodium nitrite, 3-10% Hot desalting brines: mixed chromate and phosphate, 50-100 ppm

- Potable water -Recirculing cooling water -Automotive coolants -Steam condensates -Brines and seawater

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Environment Sample inhibitor

Acid pickling solution -Sulfuric acid -Hydrochloric acid Oil production and refining -Primary and secondary recovery -Refining Fatty imidazolines, various amines including primary amine, diamines, amido-amines, oxyethylated primary amines, alkyl pyidines, quaternized amines Imidazoline and derivatives Phenylthiourea, di-ortho-tolyl-thiourea, mercaptans, sulfides, (0.003-0.01%) Pyridine, quinoline, various amines, decylamine, phenylthiourea, dibenzylsulfoxides

Cathodic inhibitor

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

Cathodic inhibitor

Cathodic inhibitors are generally less effective than the anodic type. They often form a visible film along the cathode surface, which polarizes the metal by restricting the access of dissolved oxygen to the metal substrate. 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, Ecorr increases and icorr decreases. Displacement of the corrosion potential in the positive direction indicates mainly retardation of the anodic process (anodic control)

Anodic inhibitor

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

Anodic inhibitor

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

Mixed inhibitor

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

Mixed inhibitor

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

Polarisation resistance, Rp

The efficiency of an inhibitor can also be studied by recording polarisation curves or by polarisation resistance measurements. a c Rp 2.3( a c )icorr

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, R p inhibited R p uninhibited p% 100 R pinhibited