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LECTURE 11
Corrosion
Dec 31, 2013
CONTENTS
1. Introduction
2. Corrosion mechanism
3. Corrosion rates
4. Forms of corrosion
5. Controlling corrosion
CORROSION
Corrosion
INTRODUCTION
Classification of materials
Metals
Ceramics
Polymers
Composites
Corrosion
Leaching
Degradation
Deterioration of materials
DEFINITION
is a destructive and unintentional attack of a metal;
it is electrochemical and ordinarily begins at the surface.
ECONOMIC IMPACT
W.D. Callister, Materials Science and Engineering, An Introduction, John Wiley & Sons, New York etc., 1991, p.563.
Direct costs
Indirect costs
Table 1. Estimated direct annual costs of
corrosion in USA.
Year
1976
1982
2002
Corrosion
CORROSION MECHANISM
EXTRACTION
ORE
(metal oxides in minerals)
Fe2O3 + 3CO 2Fe + 3CO2
METALS
Corrosion
environment
AQUAEOUS
GASEOUS
AQUEOUS ELECTROLYTE
water in which ions are dissolved.
Corrosion
CORROSION MECHANISM
Fe Fe2+ + 2e
Cathode
Corrosion
CORROSION IN A GRAPEFRUIT
Cathode
Anode
Cu +
H+
H+
H+
Zn
Zn2+
2e-
reduction
2H 2e H2 (gas )
O2 4H 4e 2H2 O
H+
oxidation
H+
Acid
H+
H+
Corrosion
CORROSION MECHANISM
CORROSION OF ZINC IN ACID
Zn Zn 2 2e
2H 2e H2 (gas )
O2 4H 4e 2H2 O
O2 2H2 O 4e 4(OH)
Corrosion
Electrode Potentials
Cu2+ + Fe
Fe2+ + Cu
Corrosion
2H 2e H2 (gas )
Corrosion
H2(gas)
Mn+ H+
ions
H+
e-
2e-
25C
e-
nemetal, M
metal, M
ne-
e-
Platinum
e-
Mn+
ions
H+ 2eH+
Platinum
25C
o
Vmetal
0 (relative to Pt)
o
Vmetal
0 (relative to Pt)
Corrosion
Corrosion
more anodic
more cathodic
Corrosion
RT X
o
o
VNi VCd VNi VCd
ln
o
o
VNi
VCd
0.153
Cd
25C
Ni
1.0 M
1.0 M
Cd2+ solution Ni2+ solution
Cd
Ni
XM
YM
Cd2+ solution Ni2+ solution
nF
n = #eper unit
oxid/red
reaction
(=2 here)
F=
Faraday's
constant
=96,500
C/mol.
Corrosion
Corrosion
CORROSION RATES
CPR: The rate of material removal as a consequence of the chemical
action may be expressed as the corrosion penetration rate (CPR),or the
thickness loss of material per unit of time.
where W is the weight loss after exposure time t; and A represent the
density and exposed specimen area, respectively, and K is a constant 87.6
mm/yr or 534 mpy. W, ,A, and t are specified in units of milligrams, grams
per cubic centimeter, square centimeters, and hours.
CPR< 0.50 mm/yr -------Acceptable
Rate: Expression relating corrosion rate and current density
Corrosion
EXAMPLE
A thick steel sheet of area 100 in2 is exposed to air near the ocean. After
a one-year period it was found to experience a weight loss of 485 g due
to corrosion. To what rate of corrosion, in both mpy and mm/yr, does
this correspond?
This problem asks to calculate the CPR in both mpy and mm/yr for a thick steel
sheet of area 100 in.2 which experiences a weight loss of 485 g after one year.
Employment of CPR Equation leads to
KW
CPR =
A t
(87.6)(485 g) 10 3 mg / g
=
Self-help Problems:
= 0.952 mm/yr
Also
CPR =
= 37.4 mpy
Corrosion
Passivity
Material properties
Example with steel in
Metallurgical factors
nitric aciddilute
Passivity
solutions will cause rapid
Environment
attack, strong solutions
have little visible effect.
Metallurgical factors
Surface film can be
Chemical segregation
formed
Presence of multiple phases Some types of steel may
Inclusions
do this with rust
Cold Work
Aluminum does this
Non-uniform stresses
Corrosion
FORMS OF CORROSION
Stress corrosion
Stress & corrosion
Uniform Attack work together
Erosion-corrosion
Oxidation & reduction at crack tips.
Break down of passivating
occur uniformly over
layer by erosion (pipe
surface.
elbows).
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. 17.9, Callister 6e.
Pitting
Forms
of
corrosion
Galvanic
Downward propagation
of small pits & holes.
Fig. 17.8, Callister 6e.
(Fig. 17.8 from M.G.
Fontana, Corrosion
Engineering, 3rd ed.,
McGraw-Hill Book
Company, 1986.)
Corrosion
CONTROLLING CORROSION
Metal oxide
Metal (e.g., Al,
Self-protecting metals!
stainless steel)
Metal ions combine with O2 to form a thin, adhering oxide layer that
slows corrosion.
Corrosion
SUMMARY