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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))
strong driving force for metal to return to its original state i.e. lose electrons / become oxidised
compound
Al
base metals
Gold Platinum Silver Copper Lead Tin Nickel Iron Zinc Aluminium Magnesium Sodium
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
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
Direct losses
Indirect losses
plant shutdown loss of product e.g. in pipes loss of efficiency contamination of product
prevention measures
e-
eM
M2+
e-
eM2+
H2
_
e-
eM2+
Corrosion cell
M eM2+ anodic reaction (oxidation)
M2+
M and
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
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
metal
electrolyte
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.
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
metal dissolution
Fe _ e
Brass
cathodic reaction
Fe
Brass
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
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