Material Science and Engineering

School of Chemical and Bio Engineering

LECTURE 11

Corrosion
Dec 31, 2013
CONTENTS
1. Introduction
2. Corrosion mechanism
3. Corrosion rates
4. Forms of corrosion
5. Controlling corrosion

CORROSION

Why does corrosion occur?

What metals are most likely to corrode?
How do temperature and environment affect
corrosion rate?
How do we suppress 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

Billion (109) USD

70
126
276

Figure 1. Golden Gate Bridge, San Francisco.

http://en.wikipedia.org/wiki/Golden_Gate_Bridge

GOLDEN GATE, San Francisco

Due to corrosion original lead paint was replaced by zinc-silicate and acrylic topcoat.
It took 30 years to complete the project.
Currently 38 painters and 17 ironworkers continually work on protection and
replacement of corroded parts.

Corrosion

CORROSION MECHANISM
EXTRACTION
ORE
(metal oxides in minerals)
Fe2O3 + 3CO 2Fe + 3CO2

METALS

2Al2O3 + 3C 4Al + 3CO2

CORROSION

Corrosion is an elctrochemical process thus,

it is a chemical reaction in which there is
transfer of electrons from one chemical
species to another.

Corrosion
environment

AQUAEOUS
GASEOUS

AQUEOUS ELECTROLYTE
water in which ions are dissolved.

Figure 3. A simple electrochemical cell.

Corrosion

CORROSION MECHANISM

Corrosion of steel under a drop of water

4Fe + 6H2O + 3O2 4Fe(OH)3

gives ferric hydroxide

2Fe(OH)3 Fe2O3 3H2O

gives iron oxide (rust) and water

H2O + O2 + 2e 2OH
Anode

Fe Fe2+ + 2e

Cathode

Fe2+ + 2OH Fe(OH)2

Basic rusting or corrosion requirements

1.
2.
3.
4.
5.

The metal is oxidized at the anode of an electrolytic cell

Some ions are reduced at the cathode
There is a potential or voltage difference between the anode and cathode
An electrolyte (fluid) must be present
The electrical path must be completed

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

Two reactions are necessary:

Oxidation reaction:
Reduction reaction:

Zn Zn 2 2e

2H 2e H2 (gas )

Other reduction reactions:

In an acid solution

O2 4H 4e 2H2 O

In a neutral or base solution

O2 2H2 O 4e 4(OH)

Corrosion

Electrode Potentials

Cu2+ + Fe

Fe2+ + Cu

Corrosion

The standard hydrogen electrode consists of

an inert platinum electrode in a 1 M
solution of H+ ions, saturated with hydrogen
gas that is bubbled through the solution at a
pressure of 1 atm and a temperature of 25 oC.

2H 2e H2 (gas )

Corrosion

STANDARD HYDROGEN (EMF) TEST

Two outcomes:

H2(gas)
Mn+ H+
ions
H+

e-

2e-

25C

e-

nemetal, M

metal, M

ne-

e-

Platinum

e-

-Metal sample mass

Mn+
ions

H+ 2eH+

Platinum

-Metal sample mass

25C

1M Mn+ soln 1M H+ soln

1M Mn+ soln 1M H+ soln

--Metal is the anode (-)

--Metal is the cathode (+)

o
Vmetal
0 (relative to Pt)

o
Vmetal
0 (relative to Pt)

Standard Electrode Potential

Corrosion

Corrosion

STANDARD EMF SERIES

Metal with smaller
EMF series
o
o
Vmetal
Vmetal
corrodes.
metal
Ex: Cd-Ni cell
Au
+1.420 V
Cu
+0.340
+
Pb
- 0.126
Sn
- 0.136
Ni
- 0.250
o
DV =
Co
- 0.277
0.153V
Cd
- 0.403
Cd
Ni
25C
Fe
- 0.440
Cr
- 0.744
Zn
- 0.763
1.0 M
1.0 M
Al
- 1.662
Cd2+ solution Ni2+ solution
Mg
- 2.262
Na
- 2.714
Data based on Table
K
- 2.924 17.1, Callister 6e.

more anodic

more cathodic

Corrosion

EFFECT OF SOLUTION CONCENTRATION

AND TEMPERATURE
Ex: Cd-Ni cell with
standard 1M solutions

RT X
o
o
VNi VCd VNi VCd
ln

o
o
VNi
VCd
0.153

Cd

25C

Ex: Cd-Ni cell with

non-standard solutions
Nernst Equation

Ni

1.0 M
1.0 M
Cd2+ solution Ni2+ solution

Cd

Ni

XM
YM
Cd2+ solution Ni2+ solution

Reduce VNi - VCd by

--increasing X
--decreasing Y

nF

n = #eper unit
oxid/red
reaction
(=2 here)
F=
Faraday's
constant
=96,500
C/mol.

Corrosion

THE GALVANIC SERIES

A more realistic and

practical ranking that
represents the relative
reactivities of a number
of metals and commercial
alloys in seawater.

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

where, again,n is the number of electrons associated with the ionization of

each metal atom, and f is 96,500 C/mol.

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
=

7.9 g / cm 3 100 in.2 (2.54 cm / in.)2 (24 h / day )(365

day / yr)(1 yr)

Self-help Problems:
= 0.952 mm/yr
Also
CPR =

(534)( 485 g )103 mg / g

CPR =
7.9 g / cm 3 100in.2 (24h / day )(365day / yr )(1 yr )

= 37.4 mpy

Corrosion

FACTORS AFFECTING 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.)

Crevice Between two

Dissimilar metals are
pieces of the same metal.
physically joined. The
Rivet holes
more anodic one
Corrodes. Zn & Mg
very anodic.
Fig. 17.6, Callister 6e. (Fig. 17.6 is
courtesy LaQue Center for Corrosion
Technology, Inc.)

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.

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

SUMMARY

Corrosion occurs due to:

-the natural tendency of metals to give up electrons.
-electrons are given up by an oxidation reaction.
-these electrons then are part of a reduction reaction.
Metals with a more negative Standard Electrode
Potential are more likely to corrode relative to
other metals.
The Galvanic Series ranks the reactivity of metals in
seawater.
Increasing T speeds up oxidation/reduction reactions.
Corrosion may be controlled by:
- using metals which form
a protective oxide layer
- reducing T
- adding inhibitors
- painting
-using cathodic protection.