electrons pass into the electrolyte it is dissociated into positive and negative ions, as shown by the formula: -2H,02H" + 20H”. Simultaneously the electrons couple back with the hydrogen ions to form two full Hydrogen atoms, which join together diatomically to form hydrogen gas. This is termed as being evolved, or given off from the cathode. The hydroxyl ions return to the anode through the electrolyte carrying the electrons. The corrosion triangle, as shown below, can illustrate the electrical circuit. The electron circuit can be seen to be from anode A, to cathode C, through the electrolyte E, back to A. ~ <% Clechrons Figure 1.2 The corrosion triangle. The chemical reaction From the above we can see that no chemical reaction, (combination of elements) has occurred at the cathode, or in the electrolyte. The chemical reaction, the formation of corrosion products, only occurs at the anode. The positive iron ions, Fet+, receive the returning hydroxyl ions and ionically bond together to form iron hydroxide, which is hydrous iron oxide, rust, and is shown by the formula: Fe"* + 20H"> Fe (OH) It is now apparent that corrosion only occurs at the anode, néver at the cathode, hence the term cathodic protection. If a structure can be made to be the. cathode in a circuit, it will not corrode. The corrosion triangle shows the three elements needed for corrosion to occur, anode, cathode and electrolyte. If any one of these three is removed from the triangle, corrosion cannot occur. The one most commonly eliminated is the electrolyte. Placing a barrier between the electrolyte and the anodic and cathodic areas, in the form of a coating or paint system does this. If electrolyte is not in direct contact with anode and cathode, there can be no circuit, and so no corrosion. + The basic corrosion reaction, as explained above, occurs fairly slowly at ambient temperatures. In common with all chemical reactions certain factors can increase the reaction rate, listed below are some of these. Temperature. Steel, in common with most_metals, is thermodynamically unstable. The hotter the steel is the faster the corrosion will occur. £ Hyaroscopic salts. Wil attract water and dissolve in it. When salls are present on a substrate and a coating is applied over them, water will be drawn through the film and the resulting solution builds up a pressure under the film. Eventually the film is forced up to form blisters. These blisters are called Rev2 January 2010 T WI wows cenree Corrosion Fon warenats Copyright © TWI Ltd 2010 SOWING TECHNOLOGYosmotic or hygroscopic blisters, and are defined as ‘pinhead sized water filled blisters’: Sulphates and chlorides are the two most common salts, chlorides ‘predominant in marine environments, and sulphates in industrial areas and sometimes agricultural 3 Aerobic conditions. (presence of oxygen): By introducing oxygen into the cathodic reaction the number of Hydroxyl ions doubles. This means that double the number of iron ions will be passivated and therefore double the corrosion rate. Shown by :- 2120 + O2 + 4e > 40H. <4” Presence of some types of bacteria on the metal surface, for example sulphur edi ucing bacte ‘bacteria, better known as SBS, or, metal eating microbes (MEMs). os pt ol 5 Acids and alkalis. -4C) +. - nN _N@eH — riat— gut In descending order, the further down the jist the metal is, the more reactive it is, and so, the more anodic it is, the metal loses its electrons to become reactive ions. The degree of activity can be expressed as potential, in volts. The list can be called a galvanic list, but when the free potentials of the metals are known it can also be galled the electro motive forces series 6f)the electro-chemical series. Below is a list of some metals in order of nobility with potentials as measured using a copper/copper sulphate half cell reference electrode, in seawater at 25°C. noha mere cleere Material Known potential av, values Graphite + 0.25 v Pettive Titanium 0.0v Silver =0.4Vv ‘ Nickel 200 =0.15¥, Lead =0.2v ‘Admiralty brass =0.3V Copper =0.35 Vv, Tin Mill scale Low alloy stee! ild steel ‘Aluminium alloys Zinc Magnesium dgnotal ~ elechon From the list above it can be seen that millscale is immediately above steel on the galvanic list. This means that millscale is cathodic to steel, and if left on the surface of steel will accelerate the corrosion of the steel substrate. + Mill scale is formed during the rolling operation of steel sections eg RSC, RSA, RSJ The oxides of iron form very quickly at temperatures in excess of 580°C. The first Rev 2 January 2010 TWI won cenme Corrosion FOR MATERIALS Copyright © TWI Ltd 2010, CL ‘erat eeeno.o0roxide formed is FeO, iron oxide, the next is FesO, and last of all FesO3. Common names in order ar@ WUSlite, magnetite and haematite. These oxides até Compressed during the rolling operation to produce blue millscale. The thickness of millscale varies from 25 to 100um. Because millscale is only produced during rolling, when it has been removed by any surface preparation method, it can never recur. | 2m ‘Rev 2 January 2010 = " Corrosion TWI worn cenrre Tgp vonwnrenns Copyright © TW Ltd 2010 VIM nc seen.0cy