Durability of materials

Degradation: reduction in performance of component during lifetime

fatigue

Mechanical processes Chemical processes

creep wear oxidation electrochemical corrosion

combinations and synergies

polymer degradation

Resources
Callister chapter 17 (6th edition) chapter 18 (5th edition) J.C. Scully: Fundamentals of corrosion (Pergamon Press, 1966 (1st edition), 1975 (2nd edition))

Origin of corrosion in metals

Metallic materials rarely found in nature extracted from ore e.g. Aluminium Al2O3 300 GJ/tonne Al ingot have to be

strong driving force for metal to return to its original state i.e. lose electrons / become oxidised
compound

Al

Al3+ + 3eaqueous ion

Ranking metals according to stability

noble metals

base metals

Gold Platinum Silver Copper Lead Tin Nickel Iron Zinc Aluminium Magnesium Sodium

(based on standard electrode potentials)

Dry corrosion / oxidation / tarnishing

Formation of oxide film at metal surface e.g. Aluminium (Al) Alumina (Al2O3) Not generally a problem at room temperature, because: reaction is slow film is protective i.e. separates reacting species

metal

air

Can be a problem at high temperatures, especially if film quality is poor i.e. it has cracks or pores, or is unstable

Oxidation: examples
Aluminium: oxide film is of high quality underlying metal protects

Magnesium: low-quality oxide film, with cracks and pores high oxidation rates Stainless steel: contains Cr, which forms protective and highly adherent Cr2O3 film Tungsten: oxide volatile above 800 C no protection

Electrochemical (wet) corrosion

Can simply occur due to water in atmosphere, but also promoted by: sea water presence of other materials (e.g. steel in concrete) bacteria etc etc

Electrochemical (wet) corrosion

Economic impact: ~3.5% of GDP in developed countries
component replacement

Direct losses

painting and other preventative measures use of expensive corrosionresistant materials

Indirect losses

plant shutdown loss of product e.g. in pipes loss of efficiency contamination of product

Electrochemical (wet) corrosion

Complex process Main focus when does it happen?

prevention measures

Electrochemical (wet) corrosion

Basic principles: Metals in aqueous solutions tend to form ions M M2+ + 2e-

e-

eM

M2+

2nd reaction mops up electrons

e-

eM2+

e.g. evolution of hydrogen: 2H+ +2e

_

H2
_

or, if oxygen is present: 2H2O + O2 + 4e 4OH

_

e-

eM2+

Corrosion cell
M eM2+ anodic reaction (oxidation)

econductive solution (electrolyte)

cathodic reaction (reduction)

Standard electrode potential

eeM
Voltage at equilibrium i.e.

M2+

M and

M2+ + 2e (oxidation reaction)

_

M2+ + 2e

M (reduction reaction)

occur at the same rate Standard electrode potential driving force for oxidation

Reactivity of metals
noble metals Metal Standard electrode potential +1.4 +1.2 +0.34 -0.44 -1.7 -2.3 -2.7 high reactivity low reactivity

Gold Platinum Copper Iron Aluminium Magnesium base metals Sodium

Standard electrode potential

eeH+ H+
Can also be defined for any cathodic reaction that might occur Voltage at equilibrium i.e. H2 and 2H+ + 2e (oxidation reaction)
_ _

H2

2H+ + 2e

H2 (reduction reaction)

occur at the same rate Standard electrode potential strength of cathodic reaction

Reactivity of metals
noble metals Metal Standard electrode potential +1.4 +1.2 +0.34 -0.44 -1.7 -2.3 -2.7 oxygen reduction hydrogen evolution

Gold Platinum Copper Iron Aluminium Magnesium base metals Sodium

Solid corrosion products

What happens to the metal ions? They can simply remain in solution or they can react with the electrolyte to form a solid product. This may take the form of a film, which may protect the passivation underlying metal

metal

electrolyte

e.g. stainless steel

Cr2O3 layer; aluminium

Corrosion types
Uniform corrosion Oxidation and reduction reactions occur randomly across whole surface. Corrosion process is predictable and unproblematic. Localised corrosion Oxidation reaction concentrated at one area of surface. Major problem, because component can fail without warning and even at low overall corrosion rates.

Crevice corrosion
Occurs in water when oxygen content varies across component surface e.g. in crevices around mechanical joints or under dirt.

Crevice corrosion (cont.)

Oxygen content in crevice is low only anodic reaction (dissolution of metal) can occur here. The electrons produced promotes cathodic are transferred to the remaining surface reaction

cathodic reaction

metal dissolution

cathodic reaction

Pitting corrosion
Similar to crevice corrosion. Arises from local breakdown in protective oxide film for aluminium, stainless steel _ Pitting promoted by presence of Cl ions. cathodic reaction metal dissolution problem

cathodic reaction

Galvanic corrosion
Occurs when dissimilar metals are in electrical contact e.g. steel screws in brass component, copper and steel tubing in radiator

Galvanic corrosion (cont.)

Oxidation reaction occurs at most reactive component, cathodic reaction at most stable component. Major problem if surface area of stable component (cathode) >> reactive component (anode).

metal dissolution

Fe _ e

Brass

cathodic reaction

Galvanic corrosion (cont.)

Oxidation reaction occurs at most reactive component, cathodic reaction at most stable component. Major problem if surface area of stable component (cathode) >> reactive component (anode). Avoid by electrically insulating dissimilar metals from one another.

Fe

Brass

Protecting against corrosion

Strategies: Isolate metal surface from electrolyte: Passivation, paint Inhibit anodic reaction: Cathodic protection, sacrificial protection Inhibit cathodic reaction: In closed systems e.g. boilers, minimise dissolved oxygen Reduce conductivity of electrolyte (in closed systems)

Cathodic protection
Aim is to bring potential below standard electrode potential _ prevent anodic reaction (M M2+ + 2e ) Connect to external dc power source Connect to more reactive metal (sacrificial anode)

steel pipe

coated Cu wire Mg anode

Polymer degradation
Behaviour highly specific to individual polymer General trends: Resistant to attack by acids, alkalis and salt water oxygen UV light heat ozone x-rays

partial dissolution / evaporation bond rupture (scission) cross-linking discoloration surface cracking embrittlement loss

Many polymers also tend to swell when exposed to liquids of mechanical properties