The University of Edinburgh Division of Engineering Session 2001-2002 Materials Science and Engineering

Corrosion of metals
Electrochemical theory of wet corrosion: fundamentals As with dry corrosion wet corrosion reactions are only possible if the free energy of the products of reaction is lower than the free energy of the reactants. This is the case however for the reaction of nearly all metals with water and oxygen to give metal hydroxides: M H2 Ol for example MOH2s (1)

for Mg: G 597 kJ/mol and for Cu: G 120 kJ/mol

In addition, and unfortunately, the rate of wet corrosion may often be very high compared with dry corrosion on the same metal at the same temperature. There are two underlying reasons for this:

the dipolar water molecule stabilizes the free (dissociated) metal ions in the metallic structure and water in contact with it can both conduct electric
current. solution;

This enables reaction 1 above to proceed through the coupling of two primary corrosion reactions: A: M M2 2e (2)

(Anode reaction: destroys metal, releases electrons, oxidation) 1 C : 2e H2 O O2 2 2OH (3)

(Cathode reaction: consumes electrons; electron sink reaction: reduction). Electrons liberated in the anode reaction A ow to the site of the cathode reaction C through the conducting metal. The movement of dissociated ions carries an equal ionic current in the water. The distances over which these currents ow can vary from microns to many metres. All wet corrosion processes can be analysed in terms of anodic and cathodic reactions. The anodic process is the direct cause of damage to metallic structures but both an anodic and a cathodic process must occur for a corrosion cell to be formed The corrosion of metals by reaction with air and water to form metal hydroxides as shown above is a very important wet corrosion process, especially in the construction industries. There are other corrosion reactions resulting from, for example, other cathode reactions (electron-consuming) 2e 2H 2e M2 or other anode reactions (electron releasing) M H2 O MO 2H 2e (6) H2 M (4) (5)

When a metal M is placed in pure water, some ions will immediately pass into solution: M2 2e

(7)

The build-up of negative charge on the metal and the build-up of metal ions in solution makes possible a back-reaction: M2 2e

(8)

and ultimately an equilibrium is established: M

M2 2e

(9)

At this stage, a steady potential difference now exists between metal and solution. The magnitude of this potential difference depends on the metal and composition of the solution. It is not possible to measure this potential difference for a single metal, but the potential difference (emf) between two metals dipping into a solution can be measured. Under well-dened conditions, this enables a single potential Em (relative to a common reference) to be assigned to every metal.

The Electrochemical Series The single electrode potential Em developed by a material M acting as an electrode depends on the constitution of the material and the composition of the solution with which it is in contact. The Electrochemical Series lists electrodes according to the standard single potential Em developed in contact with a 1 mol/L solution of the ion produced by the electrode reaction, at equilibrium (that is, no current owing), at 25 C. On this scale, the hydrogen electrode H2 2H + 2e , H2 pressure 1 atm) is given the arbitrary value zero. The recommended sign convention (Stockholm) is such that the more noble metals show increasingly positive potentials (eg Cu2 Cu E 0.34 V, not 0.34 V). Some older texts (especially American) use the opposite sign convention. Note that single potentials can be assigned to electrode reactions other than Mn M, including familar cathode reactions.

Nernst Equation Describes how Em varies with concentration of metal ions for the electrode Mn M. Em where b 0.059 V at 25 C. For the electrode O2 4OH E O2

b Em log c n

(10)

pO b EO2 log 4 2 4 cOH 3

(11)

Practical use of reference electrodes The hydrogen electrode is not a practical reference electrode for eld use. The copper/copper sulphate electrode is perhaps the most widely used. In sea water, the even simpler zinc electrode is often employed.

Polarisation In active corrosion cells, a net corrosion current ows at each electrode surface. At the anode, the electrode reaction (see note 4 above) is no longer in equilibrium. The rate of the forward reaction exceeds the rate of the back reaction: i f ib .
Potential

EM
i i0

Figure 1: Ideal polarisation curve for a metal surface in contact with water.

This net anodic current requires a shift of the electrode potential to a more positive value. This favours the forward reaction and disfavours the back reaction. A second surface acting as a cathode is cathodically polarised, as shown in Figure 2. Xn X ne 4, and Xn (12) 4OH .

Here for example X may stand for 2H2 O + O2 , with n 4

logi Current

EX

Ecorr EM

iM

iM i0 logi Current

Figure 2: Electrochemical cell working at a mixed corrosion potential Ecorr .

Potentialcurrent (Elog i) diagrams are known as polarisation diagrams or Tafel plots.

Simple calculations of corrosion rates The measured current and the corrosion rate are simply and directly related because 1 mol electrons has a total charge of 96500 C (coulombs). But 1 A s = 1 C (A current in amperes). Therefore, for example in the case of ferrous metals for which Fe Fe2 2e (13)

The corrosion of 1 mol Fe = 56 g = 0.056 kg Fe releases 2 mol electrons = 2 96500 C electric charge; therefore a current of 1 A corresponds to a corrosion rate of 0.056/(2 96500) kg/s iron. More useful units are g/year; or if density and surface area are know mm/y depth of penetration. Assumptions in the treatment: (1) The corrosion is uniform; (2) the entire current of the corrosion cell passes through the measuring instrument.

Potential

iX iX

Pourbaix diagram of iron These widely used diagrams show how corrosion behaviour depends on electrical potential E and pH. A simplied Pourbaix diagram for iron is shown here.

EFe/ V

pH

Passivity

EFe/ V
Active corrosion

Immunity

pH

Figure 3: Pourbaix diagram for iron, showing regions of active corrosion, passivity and immunity.

Types of corrosion cell

Dissimilar metals Differential aeration

Cathodic protection Widely used in the protection of marine structures, ships, underground structures (especially pipelines) and water lled structures. Under some circumstances used to protect reinforcing steel in concrete structures. Types of CP: impressed current; sacricial anode. Potentials (V) for cathodic protection relative to Cu CuSO4 reference electrode: Iron and steel Lead Copper and alloys Aluminium

0 85 to 0 95 0 6 0 5 to 0 66 0 95 to 1 2

Passivity Figs 1 and 2 showed the ideal anodic polarisation curve for metal dissolution M2 2e

(14)

In the presence of oxygen and other oxidising agents this curve for some metals extends only a certain distance before showing a sharp drop to lower current densities. When the anodic current density exceeds a critical value ic the metal

becomes passive or passivates. Passivity is caused by a chnage in the anodic reaction. The formation of free metal ions (reaction above) gives way to a reaction which forms an insoluble lm on the metal surface: M H2 O MOH2 2e 2H (15)

This anodic reaction proceeds more slowly because of the relatively high resistance of the lm. Note however that the current density does not drop to zero in the passive region a small residual anodic current ows and this repairs any damage to the passivation lm. The shape of the polarisation curve differs from one metal to another. The phenomenon of passivity is especially important for the corrosion behaviour of titanium (Ti), chromium (Cr) and stainless steels, aluminium (Al) and iron (Fe) and ferrous metals. The presence of aggressive anions, notably chloride, may cause severe pitting corrosion by attacking or preventing formation of a passive lm.

Corrosion of reinforcing steel in concrete The pH of the pore water in concrete is normally in the range 12-13 and thus steel is passive (see Pourbaix diagram for iron). Passivity may be destroyed by carbonation or by the presence of chloride ions. Carbonation is conned to the surface layer of concrete and steel is protected by providing adequate depth of cover. Methods of protection of steel in conditions where passivity is not achieved include cathodic protection, coating of steel and choking of oxygen. There is much current interest in the cathodic protection of marine structures.

Corrosion in the soil: microbial corrosion. Electrochemical corrosion can be assisted by bacteria. For example, corrosion of steel pipelines in waterlogged neutral ground containing little oxygen is often much more severe than might be expected. Cast iron pipes of 6 mm wall may perforate in less than ve years. Sulphate-reducing bacteria such as Desulphovibrio which ourish in oxygen-free conditions assist the corrosion of iron apparently by consuming hydrogen produced in the cathodic reaction e H H, thus 8

enhancing the rate of the cathodic reaction. The bacteria make use of the H to reduce sulphate (SO4 to sulphide (S ). The overall corrosion cell reaction is 8H 8e SO4 8H (16) (17)

8H

4H2 O
FeS

producing iron sulphide as the corrosion product. Fe2 S (18)

References. See Callister Ch 18. Supplementary reading. Fontana: Corrosion Engineering.

Revised 25 Apr 2002