CHAPTER 6

CORROSION & DEGRADATION OF MATERIALS

What is Corrosion?
Reaction of a metal with its environment Aqueous corrosion

reaction with water (usually containing dissolved ions) reaction with oxygen at high temperature

High temperature oxidation

High temperature corrosion

reaction with other gases

Examples of Corrosion

Rusting of steel

corrosion product (rust) is solid but not protective corrosion product is insoluble in water, so may be protective
high temperature oxidation

Reaction of aluminium with water

Burning of magnesium in air

Corrosion of Zinc in Acid

Acids and Bases

An acid is a substance that produces excess hydrogen ions (H+) when dissolved in water

examples are HCl, H2SO4

A base is a substance that produces excess hydroxyl ions (OH-) when dissolved in water

examples are NaOH, KOH

Corrosion of Zinc in Acid

Zinc dissolves with hydrogen evolution Zn + 2HCl ZnCl2 + H2 known as a base or active metal

Zinc

One atom zinc metal plusof two molecules hydrogen reacts toof form one molecule of molecule zinc chloride plus one of hydrogen gas chloride (hydrochloric goes to acid)

Corrosion of Platinum in Acid

Platinum does not react with acids Platinum is known as a noble metal

FORMS OF CORROSION Stress corrosion

Uniform Attack
Oxidation & reduction occur uniformly over surface. Stress & corrosion work together at crack tips.

Erosion-corrosion
Break down of passivating layer by erosion (pipe elbows).

Selective Leaching
Preferred corrosion of one element/constituent (e.g., Zn from brass (Cu-Zn)).

Pitting

Intergranular
Corrosion along grain boundaries, often where special phases exist.
g.b. prec. attacked zones

Forms of corrosion

Downward propagation of small pits & holes.

Galvanic
Dissimilar metals are physically joined. The more anodic one Corrodes Zn & Mg very anodic.

Crevice Between two

pieces of the same metal.
Rivet holes

UNIFORM ATTACK or GENERAL CORROSION

This is the most common form of corrosion. A chemical reaction (or electrochemical reaction) occurs over entire exposed surface (or large areas) more or less uniformly. Metal thins fails. Not usually serious and is typically predictable from simple tests (e.g., coupon or specimen immersion) Can be designed around by specifying an adequate CORROSION ALLOWANCE for the expected lifetime of the component.

Pitting corrosion
Pitting corrosion is the most destructive form of aluminium corrosion, developing at localised weak spots in the oxide barrier when contaminants (like the salts in sea air and inland dust, or in spray thrown up from asphalted surfaces) produce an active solution sufficient to destabilise the protective aluminium oxide film and attack the metal. The reaction commences localised pitting which continues to accelerate; the depth of the subsequent cavities may be greater than the width and the cavity may be concealed by the powdery corrosion products. Although they may not be readily visible, pits in the very thin sheet [~ 0.016 inch/0.4 mm] used in light aircraft stressed skins act as stress raisers/concentrators and can suddenly evolve into stress fractures.

Crevice or concentration cell corrosion

The process is similar to pitting corrosion except that it occurs in the very narrow gaps between faying surfaces where the solution concentrates by capillary or other action. Some moisture evaporates and the remaining solution trapped in the crevice becomes stagnant and increasingly corrosive. (Moisture deposited on metal will absorb carbondioxide from the atmosphere and form a mild carbonic acid which increases the electrolytic function). Crevice corrosion is often brought about by poor sealing/protection practices when applying/rinsing off acid etch cleaning solutions prior to painting. If dust containing salt is allowed to remain trapped in joints hygroscopic action will eventuate in a corrosion cell. Water staining found between bundled and stored aluminium sheets is a form of crevice corrosion.

Galvanic corrosion

When two dissimilar metals or alloys are in close contact in the presence of an electrolyte, a galvanic cell may be formed in which spontaneous electrochemical corrosion occurs. Oxidation occurs at the more active metal (the anode) and electrons flow from the anode to the less active metal (the cathode). The anodic metal corrodes but the cathodic metal may not; in a galvanic couple aluminium alloys are anodic to most other metals [see the following galvanic series table] so additional steps must taken to separate the two metals by using a corrosion inhibiting compound [CIC] for example.

Intergranular corrosion:
Attacks the grain boundaries within the metal structure when the chemical differences between grains and the grain boundaries react with each other in the presence of an electrolytic solution. Usually occurs in areas where end grain is exposed, rivet holes for example.

Stress corrosion cracking:

Occurs when high internal tensile stresses induced in the metal during manufacture are allowed to remain i.e. the metal is not properly stress relieved. A high permanent stress can also be introduced during structure assembly if any of the welding or fastening processes are incorrectly performed. If this residual stress condition or a stress condition introduced during normal operation exists in association with pitting or other corrosion multi-branched internal cracking may occur within the metal.

Connection of Platinum to Zinc

electrons

Zinc and platinum Zinc and platinum not current flows connected, no reaction and hydrogen is evolved on platinum on platinum

Zn

Pt

HCl
Zn 2HCl ZnCl 2H+ + 2e- H2 Zn + Zn2+ + 2e 2 + H2 metal + acid salt+ +electrons hydrogen hydrogen ions + electrons hydrogen gas metal metal ions

Connection of Platinum to Zinc

Zn + 2HCl ZnCl2 + H2 But we can separate metal dissolution and hydrogen evolution Zn Zn2+ + 2e-

2H+ + 2e- H2 These are known as electrochemical One of zinc metal reactions electrons in the metal oneatom zinc ion in two solution

Reactions that involve both chemical change and the transfer of charge

External Current Applied to Platinum in Acid

Hydrogen evolved on negative electrode 2H+ + 2e- H2 Oxygen evolved on positive electrode + 2H2O O2 + 4H+ + 4e-

Acid - chemical species Pt Pt that produces hydrogen ions in water

HCl

Overall reaction
2H2O 2H2 + O2

External Current Applied to Platinum A piece of metal

in the solution Hydrogen evolution at one electrode 2H+ + 2e- H2 (acids) or 2H2O + 2e- H2 + 2OH- (alkalis)

Oxygen evolution at the other electrode 2H2O O2 + 4H+ + 4e(acids) or 4OH- O2 + 2H2O + 4e(alkalis)

Faradays Law

Charge is related to mass of material reacted in and electrochemical reaction: 2H+ + 2e- H2
Two hydrogen ions To produce one molecule of hydrogen gas

React with two electrons

Faradays Constant
One mole of hydrogen ions (1 g) contains Avogadros number (6 1023) ions Hence electrons will react with each mole of hydrogen ions Charge on the electron is 1.6 10-19 C Hence one mole of ions requires 96500 C This is known as Faradays constant

Faradays Law
nFm Q M where Q charge (C) F Faraday' s constant (96500 C/mole) n number of electrons transferr ed m mass of metal oxidised (g) M atomic weight of metal (g/mole)

Electrodes
Electrodes are pieces of metal on which an electrochemical reaction is occurring An anode is an electrode on which an anodic or oxidation reaction is occurring A cathode is an electrode on which a cathodic or reduction reaction is occurring

Anodic Reactions
Examples

Zn Zn2+ + 2eFe Fe2+ + 2eAl Al3+ + 3eFe2+ Fe3+ + eH2 2H+ + 2e2H2O O2 + 4H+ evolution Oxidation reactions Produce electrons

zinc corrosion iron corrosion aluminium corrosion ferrous ion oxidation hydrogen oxidation + 4e- oxygen

Cathodic Reactions
Examples

O2 + 2H2O + 4e-4OH- oxygen reduction 2H2O + 2e- H2 + 2OH- hydrogen evolution Cu2+ + 2e- Cu Fe3+ + e- Fe2+
Reduction

copper plating ferric ion reduction

reactions Consume electrons

Metal Ion Hydrolysis

Note that metal ions may react with water (a hydrolysis reaction) e.g. Al3+ + 3H2O Al(OH)3 + 3H+ or 2Al3+ + 3H2O Al2O3 + 6H+

Note that in an electrochemical reaction, we have the same number of each atom on each side of the equation, and the same overall charge

Effect of Potential
Electrochemical reactions involve transfer of charge Hence, we expect that the voltage of the metal with respect to the solution will affect electrochemical reactions Voltage of metal with respect to solution is known as the electrochemical potential

Corrosion of zinc in acid

When zinc is placed in acid the metal will start to dissolve and hydrogen will start to be liberated according to the potential of the metal Consider the anodic zinc dissolution reaction Zn Zn2+ + 2e

How Fast will Corrosion Occur?

Corrosion kinetics

Concerned with the rates of corrosion reactions

Mixed potential theory:

The corrosion potential will be that potential at which the sum of all anodic (positive) and cathodic (negative) currents on the electrode is zero
The change in potential that is caused by the passage of a current

Polarization

Types of Polarization

Activation Polarization

The polarization necessary for the electrochemical reaction to go at the given rate Given by Tafels Law:

i E Eo b log io
E = potential at current i Eo = potential at current io b = Tafel slope

Concentration Polarization
Additional polarization caused by drop in concentration of a reactant at the electrode surface As concentration falls, more polarization is needed to make the current flow Eventually, no more current can flow because no more reactant can reach the metal, and a limiting current is reached

Concentration Polarization

Oxygen reduction is often affected by concentration polarization

Electrode Potential Rate of cathodic oxygen Rate of cathodic oxygen reduction without reduction with concentration polarization Limiting current density concentration polarization rate of reaction limited by availability of oxygen at the metal surface

log |current density|

Resistance Polarization
If there is a resistance between the anode and the cathode in a cell, then the current flowing through that resistance will cause a potential drop given by Ohms Law: V = IR This is important for paint films and for high resistance solutions

 Self-protecting metals!

CONTROLLING CORROSION
-- Metal ions combine with O to form a thin, adhering oxide layer that slows corrosion.
Metal oxide Metal (e.g., Al, stainless steel)

Reduce T (slows kinetics of oxidation and reduction) Add inhibitors

-- Slow oxidation/reduction reactions by removing reactants (e.g., remove O2 gas by reacting it w/an inhibitor). -- Slow oxidation reaction by attaching species to the surface (e.g., paint it!).

Cathodic (or sacrificial) protection

-- Attach a more anodic material to the one to be protected.
e.g., zinc-coated nail Zn 2+ e.g., Mg Anode

zinc

zinc

2e - 2e steel

steel pipe

e-

Cu wire Mg Mg 2+ anode Earth

SUMMARY
Corrosion occurs due to:
-- the natural tendency of metals to give up electrons. -- electrons are given up by an oxidation reaction. -- these electrons then used in a reduction reaction.

Metals with a more negative Standard Electrode Potential are more likely to corrode relative to other metals. The Galvanic Series ranks the reactivity of metals in seawater. Increasing T speeds up oxidation/reduction reactions. Corrosion may be controlled by:
-- using metals which form a protective oxide layer -- reducing T -- adding inhibitors -- painting -- using cathodic protection.