CORROSION Corrosion can be generally defined as “Degradation of a metal by chemical or Electro-chemical means”. From this definition it is obvious that two mechanisms are involved, firstly an electrical circuit and secondly a chemical reaction. Electrical Circuit In a corrosion circuit the current is always D-C- (Direct Current). It is conventionally thought that a current passes from positive + to negative -, i.e. from anode to cathode, In fact electrons are flowing in exactly the pppostte direction, fom cathode 10 anede. For corrosion circuit to exist three things are needed: a) Anode ‘An anode is a positively charged area. It becomes positively charged because the atoms release two electrons each, thus causing an imbalance between protons and electrons, positive and negatively charged units. In it’s passive state, the iron atom has 26 of each, protons and electrons, when the two electrons are released the atom still has it’s 26 protons, but now only 24 electrons. In this state the atom is now an ion, overall positively charged by two units and written as Fe"”. (An ion is a charged particle, and can be positive or negative, a single atom or a group of atoms, known as a molecule.) This losing of electrons can be shown as: - Fe -> Fe" + 3e. The Fe** is called a positive iron ion. An ion can be positive or negative and is a charged particle, an atom or a group of atoms. A passive iron atom Fe 26 protons and An iron ion Fe“, 26 protons and only 26 electrons. 24 electrons Nucleus Figure 1.1 iron atoms Painting Inspection Grade 3/2. Rev | April 2004 “EWI WORD carne rox Corrosion ul MATERIALS JOINING CLM vecuso.ocy Copyright © 2003, TWI Lid“b) Cathode A cathode is a negatively charged area where there are more electrons than needed in its passive state. These are electrons released from the anode. At the cathode the electrons enter into the electrolyte to pass back to the anode. ©) Electrolyte An electzolyte is a substance, which will conduct a current and be broken down by it, (dissociate into ions). Water is the most abundant electrolyte and also very cfficient. Acids, alkalis and salts in solution are also very efficient electrolytes. As the electrons pass into the electrolyte it is dissociated into positive and negative ions, as shown by the formula: -2H)O->2H* + 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 retum 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. E A c 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 pi iron ions, Fe+, re ionically bond together to form ion hydroxides See eee en by the formula: Fe* + 20H Fe (OH), It is now apparent that corrosion only occurs at the anode, never 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 accur. 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. Painting Inspection Grade 3/2, Rev I April 2004 "TWI woup centre ron Corrosion 12 77g MATERIALS JONING VLM vecewovocy Copyright © 2003, TWI Lid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. 1 re Temperature. Steel, in common with most metals, is thermodynamically unstable. The hotter the steel is the faster the corrosion will occur. ogmopic Higer : : lygroscopié Salis. A hygroscopic salt is one, which will attract water and dissolve in it. When salts 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 osmotic or hygroscopic blisters, and are defined as ‘pinhead sized water filled blisters’, Sulphates and Chlorides are the two most common salis, chi redominant_ in marine environments, and sulphates in industrial areas and sometimes agricultural, 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. 2H,O + 02+ 4e > 40H-(AccHaration Cot esi on) 4 Presence of some types of bacteria on the metal surface, for example Sulphur Reducing Bacteria, better known as SRBs, or MEMs, Metal Eating Microbes. Shown by > 5 Acids and alkalis ace beth eleewdWine H+ cl = hel/wat ou NADA yf Bi-metallc contact. Otherwise known as Execs OBehee od on da) Metals can be listed in order of nobility. A noble metal is one, which will not corrode, In descending order, the further down the list 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 called the Electro Motive forces series or 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 250c. Gavvanic MATERIAL KNOWN POTENTIAL AV. VALUES Graphit +025 v Titanium 0.0v Silver =O.1v Nickel 200 =0.15v Lead 20.2 v ‘Admiralty Brass =03¥ Copper =0.35¥ Tin 70.35¥ Mill Scale 70.4 Low Alloy Steel =0.7v Mild Steel <0.v + Aluminium Alloys =0.9V vw Zine ~1.0v ‘Magnesium: =16v Painting Inspection Grade 3/2. Rev 1 April 2004 Corrosion Copyright © 2003, TWI Ltd 13 WORLD CATRE FOR Twi MATERIALS JOINING TEoINGLOOY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 Jeft on the surface of steel sy accelerate the corrosion of the steel substrate. Paes ilscale is formed during the rolling operation of steel sections ¢.g. RSC, RSAC RSJ.” The oxides of iron form very quickly at temperatures in excess of 580c. The first oxide formed is FeO, iron oxide, the next is Fe;Os and last of all Fe:03, Common names in order are WIStTE, lagnetite and Haematite. These oxides are compressed during the rolling operation to produce blue millscale. The thickness of millscale varies from 25 to 100 um. Because millscale is only produced during rolling, when it has been removed by any surface preparation method, it can never ru) Feo = [won oxide $SP- plate - Ferrous — fegde —wi Scie fede - Fegog . z What is mill Scale, When Ruhore if OCourS § Painting Inspection Grade 3/2. Rev I April 2004 WORLD CENTRE FOR Corrosion 4 MATERIALS JOINING Copyright © 2003, TWI Lid TECHNOLOGY