CORROSION OF METALS Corrosion is metal dissolution: metal atoms break away from the metal surface and enter

the aqueous solution as a metal ion leaving electrons behind. An energy barrier must be overcome for this. The metal is said to be oxidised as it loses electrons.

The polar water molecules surround the positively charged metal ion thus providing it with an electronic environment as close as possible to that of an atom at the metal surface. Metal dissolution results in separation of +ve and ve charges at the metal/solution interface resulting in the formation of an electric field known as the Hermholtz double layer (HDL). Equilibrium is reached when the HDL opposes further movement of ions from the metal to the solution. This is dynamic equilibrium: the number of metal atoms leaving the surface as an ion is equal to the number of ions going back into the metal surface.

Matom Mion + eFeatures of HDL: Characteristic of each metal/solution combination: different electric fields are produced for metals when placed in different solutions e.g. distilled water, salt water. Cannot be measured directly: the distance over which the potential is created is very small thus cannot be measured with a digital voltmeter. Can only be measured against a second arbitrarily selected system. The electrode potential EM for a given metal/solution is measured against the standard hydrogen electrode (the reference electrode) at equilibrium. Under standard conditions (of temperature and concentration), the HDL voltage/electrode potential is defined as EMO.

The platinum electrode is used because it is unreactive (inert) and provides a surface onto which H2 molecules are absorbed resulting in the formation of a HDL between H2 and H+ ions. Some electrode potentials are shown in the electrochemical series table next page and the key concepts are: Enables us to predict whether a metal will tend to corrode in a given chemical environment. The lower the EM, the greater the driving force for corrosion. The value of EM tells us nothing about the rate of corrosion i.e. how fast it occurs. EM is a true equilibrium potential i.e. the potential at which the number of metal atoms leaving the surface as an ion is equal to the number of ions going back into the metal surface. Recall Year 13 chemistry if confused, for a reaction to be spontaneous Eocell must be positive: Eocell = Eoreduction - Eooxidation Eooxidation = electrode potential for metal shown in table below.

Electrode System (M/M+) Electrode potential EMO (volts) 3+ Au/Au 1.42 Pt/Pt 1.20 O2/OH0.80 Ag/Ag+ 0.79 2+ Cu/Cu 0.34 H2/H+ 0.00 Pb/Pb2+ -0.13 Sn/Sn2+ -0.14 Ni/Ni2+ -0.25 Cd/Cd2+ -0.40 Fe/Fe2+ -0.44 3+ Cr/Cr -0.74 Zn/Zn2+ -0.76 Al/Al3+ -1.66 2+ Mg/Mg -2.36 Na/Na+ -2.71 As we go down the table, metals become more base and reactive. As we move up the table, metals have increasing inertness and nobility. In other words, the more negative the electrode potential, the metal is more likely to lose electrons i.e. become oxidised to form a cation. This means a greater driving force for corrosion. The polarisation diagram Polarisation is a shift in electrode potential of an electrode from the equilibrium potential due to current flow through its surface. This current could be anodic due to oxidation of metal or cathodic due to reduction of metal ions. Polarisation takes place by connecting two electrodes with different electrode potentials together. When the electrode potential changes from the equilibrium value, it is said to be polarised. A metal can act as cathode or anode depending whether its polarised positively or negatively with respect to its equilibrium potential, EM. Positive polarisation: metal loses electrons (oxidation) i.e. metal dissolution occurs which is an anodic behaviour thus electrode potential increases from equilibrium. Negative polarisation: metal ions gain electrons (reduction) i.e. metal deposition occurs which is a cathodic behaviour thus electrode potential decreases from equilibrium.

Shape of polarisation curves At dynamic equilibrium the number of metal atoms leaving the surface as an ion is equal to the number of ions going back into the metal surface. The rate of this equal and opposite flow of charged species (i.e. current) will depend on the height of the energy barrier. The current at equilibrium expressed per unit area is called exchange current density, io. ia = anodic current ib = cathodic current

At equilibrium ia = ic = io. The net current will be zero. A large io indicates a large ionic flow in both directions at equilibrium. Therefore any polarisation of the electrode from its equilibrium value will result in a large net current flow in one direction. The diagram below shows a corrosion couple/cell or electrochemical cell. Two electrodes, M/M+ (more base) and X/X- (more noble) are connected together. Corrosion involves electron transfer. Electrode M is polarised positively by X. Electrode X is polarised negatively by M.

Thus for spontaneous corrosion to occur, there must be: An anode: where electrons are produced via oxidation metal dissolution occurs. A cathode: where electrons are consumed via reduction no metal is lost here. An electron path for electrons to travel from anode to cathode. An electrolytic solution that can conduct electrical currents through movement of ions. Positive and negative ions are present in equal amounts. Positive ions tend to migrate towards cathodic areas while negative ions tend to migrate towards anodic areas. These maintain the balance of charges in each electrode so that electrons continue to flow. The two most common cathodic reactions that support anodic dissolution of metals are the hydrogen ion reduction reaction and the oxygen gas reduction reaction. 1. Metallic corrosion involving H+ ion reduction reaction Metals produce hydrogen gas from acids. The electrode potential for metals must be lower than the electrode potential of H2/H+ for corrosion reaction to occur. Reduction reaction: 2H+ + 2e- H2 Oxidation reaction: 2M 2M+ + 2eThe more base the metal the greater the driving force for the reduction reaction. The exchange current density, io for the H+ ion reduction reaction on a given metal will determine the rate of H2 evolution and thus the rate of corrosion of the metal. Two metals with very similar EMs may have widely different corrosion rates in the same acid solution. Metal H2/H+ Pb/Pb2+ Zn/Zn2+ Sn/Sn2+ Fe/Fe2+ EM (volts) 0.00 -0.13 -0.76 -0.14 -0.44 Io (amps/cm2) 10-13 10-11 10-10 10-6

The importance of io is illustrated in the examples below.

Example 1: Pure Zn dissolves very slowly in acid even though it has the most negative electrode potential i.e. strongly basic whereas Zn with Fe impurities dissolves more rapidly.

The hydrogen ion reduction reaction takes place more easily at Fe sites than the Zn sites. This is because the value of io for the H+ ion reduction reaction on Fe is higher as compared to Zn. Example 2: corrosion rates for Pb and Sn.

Although Pb and Sn have similar EM values, io values differ significantly. Thus Pb corrodes more slowly than Sn. Eocell gives no information about the rate of corrosion, it is used to predict whether or not a reaction is spontaneous. The greater the Eocell, the greater the driving force for corrosion OR the lower the EM, (the more base the metal), the greater the driving force for the corrosion. io is what determines the rate of corrosion. The larger the io at equilibrium, the larger the current flow to the cathode after polarisation. Thus rate of corrosion increases. 2. Corrosion of metals involving the oxygen gas reduction reaction Occurs in neutral or alkaline solutions where there is limited supply of H+ ions. In moist and well aerated conditions, EO2/OH- = +0.8V. This means there is a high driving force for the reduction of O2 to support metal corrosion. However, the exchange current density, io for the oxygen gas reduction on most metals is quite slow due to the presence of a chemically stable oxide layer. This makes it more difficult for metal atoms to leave the metal surface and go into the solution as an ion i.e. a high energy barrier has to be overcome. Therefore corrosion rates due to oxygen reduction are usually low and fairly similar to H+ ion reduction reaction. Reduction reaction: O2 + 2H2O + 4e- 4OHOxidation reaction: 4M 4M+ + 4e-

The oxygen concentration cell

Oxygen rich regions tend to become cathodic sites where O2 reduction occurs. Oxygen starved regions tend to become anodic sites where metal dissolution occurs. This is known as differential aeration corrosion. Some examples of corrosion of steel structures caused by differential aeration:

The area over which corrosion occurs I = current i = current/unit area In any corrosion process, the same current must flow at anode and cathode sites: Ia = Ic Cathodic and anodic sites microscopically close on the metal surface results in uniform corrosion: Ia = Ic and ia = ic.

Note: ia = Ia / Aa where Aa is anodic area. ic = Ic / Ac where Ac cathodic area. Cathodic current: is the flow of electrons from the electrode surface to a species in solution. e.g. O2 + 2H2O + 4e- 4OHElectrons flow to oxygen in solution from the Fe electrode surface. Anodic current: is the flow of electrons into the electrode from a species in solution. e.g. 2Fe 2Fe2+ + 4eElectrons flow from the Fe2+ solution into the Fe electrode. The electrons must be equal i.e. Ia = Ic. Recall the oxygen concentration cell diagram. Small breaks in the oxide layer that cover the steel surface. The oxide layer can conduct electrons but do not allow passage of Fe2+ ions: Ia = Ic and ia >> ic. An intense localised corrosion due to a large cathodic area but small anodic area is called pitting corrosion. This is dangerous as it can lead to stress concentrations when a tensile stress is applied i.e. less material to support load.

Dissimilar metals in contact and the area principle When different metals are in electrical contact in a potentially corrosive environment, two distinct types of corrosion related responses can occur. Galvanic attack: the corrosion rate of a small area of the more base metal (e.g. Zn) is greatly increased when in electrical contact with a large area of the more noble metal (e.g. Fe). Reason: the small area, base metal is positively polarised by the large area, noble metal, which corrodes at its own rate (i.e. base metal becomes more anodic), thus causing it to corrode faster than if it was alone in the same corrosive environment. EO2/OH- = +0.80V EFe/Fe++ = -0.44V EZn/Zn++ = -0.76V Eocell = -0.44 0.76 = +0.32 Zn corrodes.

Galvanic or sacrificial protection: the small area of the more noble metal (e.g. Fe) is protected by the slow corrosion of the large area of the more base metal (e.g. Zn). Reason: small area, noble metal is polarised below its equilibrium potential by the large area, base metal thus preventing it from corroding. Eocell = -0.760 0.44 = -0.32 Fe does not corrode.

If confused, think of galvanised steel, which is an example of galvanic protection.

Faradays Equation This used to calculate: The rate of metal loss in a corrosion process. The rate of metal deposition in an electroplating process. m = (ItM) / (nF) Where: m = mass lost or deposited in grams I = current in amps t = time in seconds M = atomic mass of metal in grams per mol n = number of electrons/atoms exchanged in the process (valency) (e.g. for the anodic reaction Zn Zn2+ + 2e- n=2) F = Faradays number (96,500C/mol or amp.sec/mol) Methods of preventing corrosion Cathodic Protection: involves polarising the metal below the equilibrium potential to prevent the anodic reaction from taking place e.g. galvanised steel. Two methods are used: 1. Sacrificial anode method: involves connecting a galvanic anode with a more negative electrode potential to the metal. Polarization of the protected metal is caused by the electron flow
from the anode to the metal. The galvanic anode will corrode until eventually it must be replaced.

2.

Impressed current method: involves connecting the negative pole of DC source to the metal while the positive pole is connected to the anode such as platinum and graphite. Since the driving voltage is provided by the DC source there is no need for the anode to be more active than the structure to be protected.

Generally a protective coating is applied to the structure therefore only breaks in coating need to be cathodic protected. This reduces the amount of cathodic current required and hence the cost to achieve corrosion protection. Anodic protection: involves polarising the metal above its equilibrium potential into its passive region where metal dissolution rates are low due to a passive oxide layer. In a moist oxygen rich environment, it can be seen from the electrochemical series table that Cr and Al have a high driving force for corrosion. Yet Cr and Al are used because of their corrosion resistance because both chromium oxide and aluminium oxide form as a strong, stable and coherent layer with the metal lattice below. These oxides also reform rapidly when damaged and act as a barrier to further metal dissolution i.e. the oxides form a passive protective layer of film. The property of coherence arises because aluminium atoms in the {111} FCC planes of the Al lattice match perfectly with the positions of the Al atoms in the basal plane of the HCP Al2O3 layer, thus enhancing the bonds between the metal and oxide. Polarisation curve for a metal that forms a passive layer

Anodizing of aluminium This involves anodic polarisation to achieve a thick coherent layer of Al2O3 layer that protects the underlying metal. The amount of porosity of the oxide layer can also be controlled and foreign atoms can be allowed to diffuse into structure to obtain different decorative colours. However, corrosion protection by reliance on passive film development is dangerous because breaks in film can lead to intense localised corrosion at the anodic sites. Stainless steels (S/S) S/S require more than 12% Cr to maintain C2O3 film to provide passive film protection. A common composition is: Fe + 18%Cr + 8%Ni also called 18:8 stainless steel. Ni allows FCC austenite to be retained at room temperature thus improving ductility for manufacturing process. Ni does not contribute to corrosion resistance. S/Ss are vulnerable to sensitization. If the S/S is held in the temperature range 500-800oC for too long during either heating or cooling, the Cr will combine with carbon to form CrC (chromium carbide) precipitates at the austenite grain boundaries.

Slowly cooled through 800-500oC Normal S/S with 12% Cr Sensitized S/S with Cr depleted zone at grain boundaries (GBs)

CrC forms at GBs as these are high energy regions. CrC formation leads to a Cr depleted zone at the GB. The Cr level falls below 12% at the GB, making it anodic with respect to a much larger area of the remaining grain that is not depleted of Cr. Hence we get intense localised corrosion at the GBs. Sensitization is encountered when S/Ss are welded corrosion occurs where material has been welded due to depleted Cr. (Corrosion occurs because you stay at a higher temperature for a longer time which allows time for atoms to diffuse and form CrC precipitates). This is referred to as weldy decay. Methods of preventing sensitization in stainless steels Heat treat at high temperature after welding to re-dissolve CrC and then cool quickly. Rapid cooling means there is insufficient time for CrC precipitates to form via diffusion. Add strong carbide formers to scavenge carbon atoms e.g. Ti, Nb. This means there are no carbon atoms to form CrC precipitate. Reduce carbon content of steel to less than 0.03%. Increase Cr content. Even if CrC forms, there are sufficient Cr atoms to provide passive film protection. Combining corrosion and stress There are 3 important mechanisms: Stress corrosion cracking Cracking due to combined effect of a tensile stress and a corrosive environment. This mechanism can operate at stress levels less than 10% of the metals yield stress. Cracking starts at notches created by corrosion at grain boundaries. Grain boundaries are sites of intense corrosion because interatomic bonds are strained. This means GBs are high energy regions and atoms are easily removed. Hence, GBs are anodic with respect to the rest of the grain.

Stress concentration at the tip of the notch also means interatomic bonds are strained. The atoms have high energy and hence easily removed. Hence, the notch tip is more anodic with respect to the rest of the lattice. Corrosion rate is therefore high at the crack tip. Another factor that would increase corrosion rate at the crack tip is low O2 supply. Normally ductile metals often fail in brittle manner as a result of stress corrosion cracking e.g. brass, 18:8 S/S (both FCC) in the presence of chloride ions. Reason 1: Cl- weaken interatomic bonds in the Fe lattice thereby making it easier for cracks to propagate through the lattice under stress. Reason 2: Cl- also break down the passive protection layer resulting in intense localised corrosion in these same regions. Stress corrosion cracking is common in metals that passivate. Think of the two regions on the anodic passivation curve where the protective film is especially vulnerable: the transpressive region and the region where the film spreads. S/Ss can be protected from chloride ion attack by addition of 2% molybdenum (Mo). Mo improves the stability of the passive oxide layer in the presence of Cl- ions. Hydrogen embrittlement A corrosion related failure (in steels, titanium alloys and BCC steels) which involves the formation of hydrogen gas in the atomic structure of the metal. This builds up high gas pressures sufficient to break bonds in the lattice, thus making the metal susceptible to brittle fracture. It occurs in corrosive acid environments where the hydrogen ion reduction reaction can take place and involves the initial production of nascent (atomic) hydrogen. 2H+ + 2e- H2 H2 H + H It occurs during thermal processing of steels when contaminant water molecules, ammonia and hydrogen dissociate to produce H atoms. H2 H + H H2O H + H + O NH3 H + H + N The hydrogen atoms can diffuse rapidly through the BCC lattice of the ferrite phase in steels and build up at trap sites e.g. dislocations, GBs, precipitates, vacancies. The hydrogen atoms recombine to form molecular hydrogen gas, building high pressures. H + H H2 Cavitation corrosion Corrosion caused by the formation and implosion of gas bubbles on the metal surface thereby destroying the passive protective layer. Where water flows at high velocity, the pressure is lower and water vapour bubbles form. When these bubbles move to an area of low water velocity, the pressure is higher and the gas bubbles collapse. This creates a shock wave which can destroy the passive protective layer.

Pressure drop

Local boiling

Pressure increase

Bubble collapses

Generates shock wave

Generates 300-400MPa pressure

Breaks passive film layer

Exposes fresh metal

Renewed corrosion

New passive film growth etc.