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Durability of materials

Degradation: reduction in performance of component


during lifetime
fatigue
creep

Mechanical processes

wear

Chemical processes

oxidation
electrochemical
corrosion

polymer
degradation

combinations
and
synergies

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  have to be
extracted from ore
e.g. Aluminium
Al2O3

300 GJ/tonne

Al ingot

 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  protects
underlying metal
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 800C  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-

e-

M2+

2nd reaction mops


up electrons

e-

eM2+

e.g. evolution of hydrogen:


_

2H+ +2e

H2

or, if oxygen is present:


_

2H2O + O2 + 4e

e-

eM2+

4OH

Corrosion cell
M
e-

M2+

anodic reaction (oxidation)

econductive solution
(electrolyte)

cathodic reaction (reduction)

Standard electrode potential


e-

M2+

e-

Voltage at equilibrium i.e.


_

M2+ + 2e (oxidation reaction)

M2+ + 2e

M (reduction reaction)

Standard electrode potential


driving force for oxidation

occur at the same rate

and

Reactivity of metals
noble metals

base metals

Metal

Standard
electrode
potential

Gold

+1.4

Platinum

+1.2

Copper

+0.34

Iron

-0.44

Aluminium

-1.7

Magnesium

-2.3

Sodium

-2.7

low reactivity

high reactivity

Standard electrode potential


H+
H+

Voltage at equilibrium i.e.


H2

2H+ + 2e (oxidation reaction)

and
_

2H+ + 2e

H2 (reduction reaction)

Standard electrode potential


strength of cathodic reaction

occur at the same rate

H2

ee-

Can also be defined for any cathodic


reaction that might occur

Reactivity of metals
noble metals

base metals

Metal

Standard
electrode
potential

Gold

+1.4

Platinum

+1.2

Copper

+0.34

Iron

-0.44

Aluminium

-1.7

Magnesium

-2.3

Sodium

-2.7

oxygen reduction
hydrogen evolution

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
underlying metal  passivation

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

Many polymers also tend to swell when exposed to liquids


of mechanical properties

loss