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Corrosion Control September 2003 . UMIST Corrosion and Protection Centre Module 0 – Introduction to Corrosion Module Notes .

the Corrosion and Protection Centre. UMIST.2003.This document is © 2002 . All rights reserved .

Further. the layer next to the metal surface may contain anti-corrosion pigments and is known as a primer. As well as a good quality © 2002 . polymer interaction in the dry state or by further polymerisation during the drying process. • Describe four factors that affect anodic inhibitor performance. Paints and Organic Coatings A paint consists of a mixture of different materials each constituent possessing a specific function. the binder is the component in the paint which is responsible for the adhesion of the paint to a substrate. Corrosion and Protection Centre. pH. A key feature of a paint coating is that it can be applied in a series of multiple coats. 2. Each layer will have a specific function. a precipitated film. a continuous polymeric phase which is responsible for the cohesion of the dried film either by a physical polymer. Corrosion Control . to adjust the viscosity of the wet paint. e. Solvents and thinners are low molecular weight highly volatile compounds that make the liquid paint less viscous and evaporate during the drying process. namely an adsorbed layer. 5. aggressive ion concentration. namely. The main constituent is known as the binder. Plasticisers are non polymeric compounds and are sometimes added to improve the flexibility of the final dried film. They may also provide mechanical reinforcement to the dried film. a passive film. The layer next to the environment is known as the top-coat. 7. The second major constituent is the pigment. high pressure gas pipelines made from steel. 1. An example of the use of cathodic protection would be its use in the protection of underground. Extenders are solid particles whose main function is to lower the overall unit cost. UMIST Module 0. 3. Driers are salts of transition metals added to catalyse the autoxidation drying reaction for air-drying systems. the inhibitor concentration. 4. solid particles dispersed in the binder which originally were designed to provide colour and opacity but with anti- corrosive paints imparts to the final dried film a specific anti-corrosion function. and the specific metal being inhibited.2003.Corrosion Control • Learning outcomes – at the end of the course you should be able to … • Define the main components of a paint and their functions • State and use the four criteria necessary for CP to be successful • Explain the difference between sacrificial and impressed systems • Describe the three types of surface film formed by inhibitors. Cathodic protection Cathodic protection is a useful and practical example of an electrochemical cell. and may contain UV absorbing pigments. 6.g.Page 1 .

or.g.2003. in general. in the impressed system is usually an inert metal (or sometimes graphite). there are only two ways in which inhibitors can exert their action: • by forming an adsorbed layer on the metal surface. • by forming a three-dimensional film either a passive film or a precipitated film. • The sacrificial anode cathodic protection case may be thought of as a useful case of galvanic corrosion.Page 2 © 2002 . Broadly. or even aggressive. and some of the other classifications may be more useful. Corrosion Control . aluminium and magnesium. and that substances that are inhibitors in one environment for one metal may be ineffective. The structure needing protection usually mild steel is one electrode. Module 0. However. particularly (b). or thicker precipitated films formed from solution species. the corrosion control of such pipelines is also ensured by their being cathodically protected. In the impressed current case. UMIST . In practice. The third feature is that there must be electron conduction between the two electrodes. 2. The electrochemical reaction at the anode generates electrons. Current may be supplied spontaneously. 4. There must be electrolyte contact between the two electrodes. the cathode and receives electrons. or the cell may be driven using a DC source in an Impressed current cathodic protection system. alloys of zinc. 3. as in a sacrificial cathodic protection system. there can be a variety of different mechanisms. but within each of these. four areas are important. In both cases. Corrosion and Protection Centre. it is the electrochemical oxidation of the environment. It follows that the decision as to whether a substance is or is not an inhibitor may depend on the nature of both the metal and the environment. and in the sacrificial system is a reactive metal.coating. this involves connecting the pipeline to a source of electrons. without significantly changing the concentration of corrosive species. if the metal and/or the environment is changed. inhibitors used in acid solutions or in oxygen-free neutral solutions work by adsorption on the surface whereas in aerated systems inhibition is a result of three-dimensional films. reduces the corrosion rate of the metal. The electrode reactions in the sacrificial anode case are electrochemical oxidation of the anode itself. Inhibitors and Water treatment Definition of an Inhibitor A corrosion inhibitor is a substance which. when added in small quantities to a normally corrosive environment. The other electrode is an anode. These are the basis of the classification of inhibitors as either interface or interphase. 1. thin oxides on iron. These three dimensional films may be either passive films e.

because of their solubility in acid. although the general principles apply to other metals. e. © 2002 . for aerated near-neutral solutions. according to their mechanism of action. their chemical structure.Page 3 . The mechanism of inhibition may be different in acidic and neutral solutions. UMIST Module 0. a process known as chemisorption. P.2003. The adsorption of an inhibitor molecule or ion may depend on the other species present in the solution.g. their chemical properties etc. O. This classification also. Some of the classifications that have been used are: adsorption / film forming anodic / cathodic organic / inorganic oxidising / non-oxidising safe / dangerous These classifications are not mutually exclusive and. Inhibitors for acid solutions usually function by adsorption on the metal surface. divides inhibitors according to the mechanism by which they act. which possess lone pairs of electrons which can be donated to the metal to form a chemical bond. and typically contain elements in Groups V or VI of the periodic table. and both reactions are under activation control. N. These N-containing inhibitors include aliphatic amines (primary. their usefulness depends on the system. aromatic amines and heterocyclics. secondary. Inhibitors that reduce the rate of the anodic reaction more than they reduce the rate of the cathodic reaction will cause a rise in corrosion potential. so these two cases will be considered separately. S or As. and different types of inhibitor are effective in these two environments. cationic inhibitors may adsorb more strongly if there is also anion adsorption. and for this reason many nitrogen-containing inhibitors are more effective in hydrochloric acid (where chloride may adsorb) than in sulphuric acid. Corrosion Control . Even a small reduction in the kinetics of either process will reduce the corrosion rate. Corrosion and Protection Centre. Most attention will be given to the corrosion of iron and steel. and if this is known the effects of solution composition variables such as chloride concentration can be predicted. to some extent. In many cases it is convenient to classify inhibitors according to which electrode reaction they affect and this is the basis of the anodic/cathodic classification. Inhibitors that affect both processes are known as mixed inhibitors.Classification of Inhibitors Inhibitors can be classified in many ways. Inhibitors for Acid Environments In this case the corrosion reactions are metal dissolution with hydrogen evolution as the cathodic reaction. For example. These reactions occur in the absence of surface films of oxides or corrosion products. tertiary and quaternary).

resulting in plugging of the defects by iron compounds. hydroxide. since there are essentially two ways of reducing the corrosion rate in these environments. In particular. the action of anodic inhibitors is very dependent on the inhibitor concentration. and the solution pH. or (b) to cause the steel to form or retain a protective oxide film which acts as a barrier to metal dissolution. The classification as oxidising or non-oxidising is based on whether dissolved oxygen is necessary for the maintenance of a passive surface. oxygen transport. This sudden change occurs because the uninhibited corrosion rate is controlled by the rate of oxygen transport to the surface and small changes in the anodic kinetics do not affect the overall rate. since inhibitors for oxygen-free near-neutral solutions. carbonate. but much of the available evidence is consistent with the effect of the inhibitors being at defects in the oxide film. and not necessarily on the intrinsic chemical properties of the inhibitor. in oil production. Anodic Inhibitors These are effective because they maintain a passive oxide film on the metal surface. It is convenient here to consider anodic and cathodic inhibitors separately.2003. UMIST . Inhibitors for Near-Neutral and Alkaline Environments This section considers inhibitors that work in the presence of oxygen. are of the type discussed above. such as thiourea and its derivatives. With Module 0. and the above is a simplification. for example. the rate is determined by the transport of oxygen to the metal surface. and the metal would become active. as may be found. borate. As regards the mechanism by which these inhibitors act. the aggressive ion concentration. Corrosion Control . benzoate. i. The two ways of reducing corrosion rate are (a) to reduce the rate of this rate determining step. reduction of the oxide film would occur. The inhibitors prevent this process by reducing the rate of metal dissolution at the defects. Whilst this mechanism is still the subject of discussion. In the absence of inhibitors metal dissolution would proceed and eventually the reduction of oxygen on the oxide surface would be incapable of providing the required anodic current.e. there are several properties of anodic passivating inhibitors that are well established and of considerable practical importance. there are still several hypotheses. but above the critical concentration the rate reduces essentially to zero. molybdate etc). In addition they are sensitive to the nature of the metal and to the temperature. For an actively corroding steel surface the corrosion rate is under cathodic control. If insufficient inhibitor is present there is little if any effect on corrosion rate. Corrosion and Protection Centre. They include oxidising inhibitors (chromate. so that the corrosion rate is now controlled by the anodic process (anodic passivating inhibitors). nitrite etc) and non-oxidising ones (phosphate.For sulphuric acid the common inhibitors are S-containing. by the formation of a electronically non-conducting film on the metal surface (cathodic inhibitors).Page 4 © 2002 .

Corrosion and Protection Centre. are sensitive to pH. although for many inhibitors this critical pH is well below those likely to be encountered in their application. but not for cast iron or zinc. These are not sensitive to the presence of aggressive ions. which will react with hydroxide produced at the surface to give a zinc hydroxide precipitate. The disadvantage is that they do not prevent corrosion but merely reduce the corrosion rate.Page 5 . These inhibitors are also sensitive to pH. like anodic inhibitors. Since anodic inhibitors influence the metal dissolution reaction they tend to be sensitive to the nature of the metal. and therefore depends on the inhibitor. UMIST Module 0. Cathodic Inhibitors These are substances that reduce the rate of oxygen reduction at the metal surface by precipitating on the surface a film that restricts the diffusion of oxygen to the metal. The critical minimum concentration is dependent on the aggressive ion concentration. they are not greatly affected by the presence of aggressive ions and they are effective on a wide range of metals. and the corrosion rate falls. and nitrite. The optimum pH is related to the solubility of the compound that forms the protective surface film. but several advantages. benzoate is effective for steel. with more inhibitor required as the aggressive ion (e.g. For example. such as zinc. Typical are the divalent metal cations. For chromate about 100 ppm is required in distilled water but this increases to about 1000 ppm in the presence of even 50 ppm chloride. accelerates the corrosion of lead-tin solders. since they act by reaction with cathodically produced hydroxide. Corrosion Control . chloride or sulphate) concentration increases. Cathodic inhibitors have one major disadvantage over anodic inhibitors. and there is often a linear relationship between the logarithm of the aggressive ion and inhibitive ion concentrations as shown below. They. unlike the anodic inhibitors. but against this they are effective at much lower concentrations (typically 20-50 ppm). with a minimum pH below which they do not work. but here this is not a sharp change from protection to corrosion. and even a small cathodic effect will lead to a reduction in corrosion rate. while effective for a wide range of metals.2003. Another feature of some anodic inhibitors which can give concern in practice is that if they are present in insufficient amounts the may cause the corrosion to be localised (pitting) without any reduction in the total amount of metal lost. © 2002 . The minimum concentration required for protection in distilled water is often around 10-3 M in distilled water.sufficient anodic inhibitor the anodic dissolution process becomes the rate-determining step. unless these in some way change the nature of the precipitate.

such as in power generation.Page 6 © 2002 . To prevent the build up of scale forming salts a portion of the water is discharged to waste (blowdown) and the water topped up with fresh make-up water. the presence of fouling deposits can make corrosion worse due to differential aeration effects. Open recirculating systems are commonly used for large installations. For example. surfaces causing less efficient cooling. particularly the heat exchanger. Open recirculating systems where after passage through the heat-exchanger the water is cooled by passage down a cooling tower and then recirculated to the heat-exchanger.Principles of Water Treatment The aim of water treatment is not simply to reduce corrosion although this is part of the requirements in most systems. These rely on evaporation. Corrosion Control . UMIST . Module 0. and when there is a limited supply of suitable water. Cooling Systems These can be divided into the following types. These require a plentiful supply of cooling water and since the water only passes through the heat-exchanger once the cost of any treatment chemicals must be low. • fouling. The three phenomena are interrelated and in some circumstances the optimum treatment is a compromise between prevention of the various problems. Once-through systems are also used in power generation especially for plants situated on coasts or the shores of lakes. and • corrosion. and so the circulating water becomes concentrated. and on the composition of the water in the system. pumps and filters and creating locally different environments under the deposits. causing blockage of pipes.) and the maintenance of effective heat transfer is generally the major consideration. due to looser deposits of organic or inorganic origin.2003. Closed recirculating systems where the cooling water is cooled by passage through a radiator before recirculation. Corrosion and Protection Centre. Also. the formation of dense adherent deposits on the metal. In such systems the problems to be overcome can be broadly divided into three categories: • scaling. via cooling towers. boilers etc. since the scales can restrict oxygen access to the metal surface. the prevention of scale formation tends to increase corrosion rates. The relative importance of the various factors depends on the operating conditions of the system. The majority of areas where water treatments are carried out involve the use of natural waters in heat transfer applications (cooling systems. Once-through systems where the water is drawn in from the water source. flows through the heat-exchanger and is then discarded to waste.

Corrosion Cooling systems are mostly aerated. Closed recirculating systems discharge heat to the atmosphere via a heat exchanger and evaporation of the water is prevented. as is discharge of treatment chemicals to the environment. As such the corrosion rate is largely influenced by the rate of oxygen transport to the metal surfaces. Fouling The origins of fouling deposits can be either inorganic or microbial. although scaling of surfaces other than in heat exchangers can reduce their corrosion rate. the capital cost of cooling towers is avoided. The main effect of scaling is a reduction in heat transfer.Page 7 . Corrosion and Protection Centre. The corrosion that occurs in locally anaerobic conditions is treated by attempting to prevent such environments existing. UMIST Module 0. growths of iron bacteria and massive algal growths. Problems in Cooling Systems Scaling Due to the depositon of scales such as calcium carbonate.2003. or • insoluble corrosion products The range of organic fouling material includes slimes formed by bacteria. © 2002 . and inhibitor treatments are based upon this corrosion mechanism.Against this. • reactions between the water and chemical additives. Corrosion Control . and operate at near neutral pH. Inorganic deposits can arise from: • sediments carried into the system with the make up water. although small areas may be anaerobic. such as silt.

UMIST .Page 8 © 2002 . Corrosion and Protection Centre.Module 0. Corrosion Control .2003.