CORROSION &

DEGRADATION OF METALS
 CORROSION

Figure 1 is a view of the failure origin showing severe areas of surface

corrosion. The corrosive environment is the typical salt/water mixture
resulting from the deicing of roads during the winter.
DEFINITION OF CORROSION

“Slow and progressive destruction of a metal

brought about by the action of an external
agent and various causes of a mechanical
nature.
Corrosive Environments
pH
(Remember! pH 0 to 7: acidic, pH 7 to 14: alkaline)
• Lower pH
 Higher the amount of free acid present
 more corrosive the solution

Aggressive species
• Aggressive species are corrosive materials that can penetrate and brake down
protective surface films or modify the shape of the cathodic polarization curve.
• Ex: chloride ion, sulphur ion

Oxidizing species
• Oxidizing species exhibit mild to severe effects on corrosiveness. Oxidizing
species depolarize corrosion reactions.
To forms of metal deterioration can be
stated:

DIRECT OXIDATION:
Where the metal’s atoms combine with the aggressive
substance:
2Fe +O2 ------2FeO.
ELECTROCHEMICAL CORROSION
• For metals, corrosion process is an electrochemical process
where metal will loose electron(s)
M → Mn+ + ne- oxidation
Fe → Fe2+ + 2e- or Al → Al3+ + 3e-
• The side which oxidation occur anode
• Electron(s) generated from the metal (during oxidation) must
be transferred to form a chemical species.
• Process of gaining electron(s) reduction
2H+ + 2e- → H2
• Reduction occurs at
cathode
 Oxidation:
Zn → Zn2+ + 2e-

Acid solution

Reduction
2H+ + 2e- → H2 (gas)
 Standard EMF Series
more cathodic Au •EMF series is gathered by
Cu
coupling a standard half cell
Pb
of a metal to standard
Sn
hydrogen electrode
Ni
•EMF series give corrosion
Co
Cd
tendencies of metals
Fe
•Those on top …………………>
Cr difficult to oxidise
Zn •Those on bottom …………....>
Al easy to be oxidised
Mg
Na
more anodic
K
 FORMS OF CORROSION
• Uniform Attack
Oxidation & reduction
occur uniformly over
surface.
• Selective Leaching
Preferred corrosion of
one element/constituent
(e.g., Zn from brass (Cu-Zn)).
• Intergranular
Corrosion along
grain boundaries,
often where special
phases exist.
g.b.
prec.
attacked
zones
Fig. 17.18, Callister 7e.
• Stress corrosion
Stress & corrosion
work together • Erosion-corrosion
at crack tips. Break down of passivating
layer by erosion (pipe
elbows).
• Pitting
Forms Downward propagation
of small pits & holes.
of Fig. 17.17, Callister 7e.
corrosion (Fig. 17.17 from M.G.
Fontana, Corrosion
Engineering, 3rd ed.,
McGraw-Hill Book
Company, 1986.)
• Galvanic
Dissimilar metals are
• Crevice Between two
pieces of the same metal.
physically joined. The
Rivet holes
more anodic one
corrodes.
Fig. 17.15, Callister 7e. (Fig. 17.15 is
courtesy LaQue Center for Corrosion
Technology, Inc.)
 Erosion-corrosion
• Erosion corrosion: acceleration in rate of
corrosion due to relative motion between
corrosive fluid & surface
• Found mostly in piping; especially at bends,
elbows or abrupt change in pipe diameter
where fluids become turbulence or fluid
change direction suddenly
Pitting corrosion
• Localized corrosion attack
• Small pits/holes form
• Oxidation occurs within the pits itself
• A pit must form from detects like
scratches or slight variation in
combination
• Undetected and sudden unexpected
failure
 Crevice corrosion

• Corrosion occurs because of different in

concentration electrolyte around metal parts
• Occurs under valve, washers, insulation
material, fastener heads, surface deposits,
coatings, threads, lap joints & clamps
 Galvanic corrosion
• Two metals or alloys having
different compositions are
electrically coupled while exposed
to an electrolyte
• Electrochemical reaction leads to
corrosion of metal
GALVANIC CORROSION
• 2 dissimilar metal electrodes immersed
in solution of their own ions.
• Electrode that has more negative
oxidation potential will be oxidized.

Zn → Zn2+
oxidized

Cu2+ → Cu
reduced
GALVANIC SERIES
ranks of the reactivity of metals/alloys in seawater
Platinum
Gold
Graphite • Galvanic series gives
Titanium the cathodic, anodic
Silver relationship between
316 Stainless Steel metals
Nickel (passive) – E.g in seawater, Zinc is
Copper more active than
Nickel (active) aluminum
Tin
Lead • Series is determined
316 Stainless Steel experimentally for
Iron / Steel every corrosive
Aluminum alloys environment
Cadmium
Zinc
Magnesium
 Intergranular corrosion

• Corrosion occurs along grain boundaries for

alloys in specific conditions
• Specimen disintegrates along the grain
boundaries and result in failure
Corrosion Prevention – Materials
Selections & Design

• Choose a right metal once the working environment

has been detected. Use less active metal (galvanic
series and EMF)
• Avoid dissimilar metals that can cause galvanic
corrosion
• Provide allowance for corrosion of thickness
• Allow complete drainage
• Make sure parts can be replaced
• Weld rather than rivet
 Corrosion Prevention – Environment
Metal oxide
• Self-protecting metals! Metal (e.g., Al,
-- Metal ions combine with O stainless steel)
to form a thin, adhering oxide layer that slows corrosion.
• Change the environment e.g. lowering the fluid
temperature, pressure, concentration and velocity
- 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.
Corrosion Prevention – Anticorrosion
Treatments
METAL coatings:
• via ELECTROLYSIS: Protective films of metal using the coating as the anode
and the part being coated as the cathode, employing sulphates or cyanides as
an electrolyte. The substance is broken down by applying an electrical voltage
over a controlled period at a controlled current, giving us the desired layer.
Steel parts should be covered with 3-4 alternating layers of Cu, Ni, Cr.
– NICKEL PLATING.
– CHROME PLATING.
– COPPER PLATING.

• via IMMERSION IN MOLTEN METAL: Immersing the piece in a bath of

molten protective metal.
– GALVANISING. Pipes/tubes.
– TINNING. Tinplate.
• via METALLISING: Using a legalising spray gun to coat the piece in
molten metal.
– Zn,P, Al, Stainless steel.

• via CASE HARDENING: Methods in which the piece to be coated is

covered in powdered Zn and Naphthalene / Cr, alumina / Aluminium / Si ,
heated up to set temperature for a specific time to create a coating on the
piece.
– SHERARDIZING.
– CHROMIZING.
– CALORIZING.
– SILICATION.

• via PLATING: Superimposing plates of metal on one or both sides of the

metal to be protected..
– Cu, brass, Ni, Cupro-nickel, Stainless steel.
NON METALLIC:
• inorganic:
– Enamel.
– Via thermo chemical treatment.
PHOSPHATING (immersing the steel pieces in an aqueous solution
of metal phosphate at 100ºC).
ANODISING (forcing aluminium to oxidise electrolytic ally in order
to strengthen the layer of oxide, giving it greater protection),
BLUING (treatment applied to steels to protect them against
oxidation, producing a dark protective layer of magnetite. Heated up
to 200ºC and then tempered in oil).
• organic:
– Paints.

CATHODIC PROTECTION:
Steel pipes using Mg or Zn. Ships propellers which are made of Cu using
electrodes made of Zn & Mg.