國立清華大學材料科學工程學系

111 下學期課程

Materials Science and Engineering

II

Corrosion I

An-Chou Yeh/Andrew
葉安洲

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Corrosion
The deterioration of materials due to reactions with their environments is the currently
accepted broad definition of corrosion. From a practical standpoint, the term material
refers to those substances used in the construction of machines, process equipment,
and other manufactured products. These materials include metals, polymers, and
ceramics.
Rate of corrosion depends upon temperature and concentration of reactants and
products. Metals have free electrons that setup electrochemical cells (galvanic cell)
within their structure. Metals have tendency to go back to low energy state by
corroding. Ceramics and polymers suffer corrosion by direct chemical attack, not
electrochemical attack.

Refining-Corrosion cycles

 Why study corrosion?

There are four main reasons to study corrosion. Three of these reasons are based on
societal issues regarding (i) human life and safety, (ii) the cost of corrosion, and (iii)
conservation of materials. The fourth reason is that corrosion is inherently a difficult
phenomenon to understand, and its study is in itself a challenging and interesting
pursuit.

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 Electrochemical Corrosion of Metals
Lets take an example of placing a piece of zinc into a baker of HCl acid:
What is happening is that Zinc corrodes in the acid,
while ZnCl2 and H2 are produced.
Chemical reaction: Zn + 2HCl ZnCl2 + H2
or
Ionic form reaction: Zn + 2H+ Zn2+ + H2
Actually, this reaction consists of two half reactions:
Oxidation half cell reaction: Zn Zn2+ + 2e
Reduction half cell reaction: 2H+ + 2e H2

• Oxidation reaction: Metals form ions at local anode. i.e. electrons are
produced., metals form cations
• Reduction reaction: Metal is reduced in local charge at local cathode. i.e.
electrons are consumed.
• Oxidation and reduction takes place at same rate to prevent build-up of electric
charge in the metal.

Every metal has a different tendency to corrode, and one method for comparing the
tendency is to compare their half cell oxidation potential or half cell reduction
potential to that of a standard hydrogen-hydrogen-ion half cell potential. The
following is the setup:

• Oxidation/Reduction half cell potentials are compared with standard hydrogen

ion half cell (1 M, 25C) potential.

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 • Voltage of metal is directly measured against hydrogen half cell electrode. For
example: the potential of the hydrogen half cell reaction is assigned to “0”,
then the zinc half cell reaction is measured directly to be -0.763V. So, zinc is
more anodic to hydrogen:
Anodic reaction: Zn Zn2+ + 2e
Cathodic reaction: 2H+ + 2e H2
• If the metal is more cathodic to hydrogen:

• Anodic to hydrogen: More tendency to corrode

 Examples: Fe (0.440 V), Na (2.714 V)
• Cathodic to hydrogen: Less tendency to corrode
 Examples: Au (1.498 V), Cu (0.337 V)

E is the electrode potential

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 Galvanic Cells
Since most metallic corrosion involves electrochemical reactions, it is important to
understand the principle of the electrochemical cell, i.e. galvanic cell. Let’s consider
the followings:
Macroscopic Galvanic Cells with 1M Electrolyte
Consider two dissimilar metal electrodes immersed in solution of their own ions.
Electrode that has more negative oxidation potential will be oxidized. For example,
Zn-Cu:

oxidation reduction

Half cell reactions are

Zn2+ + 2e Zn E = 0.763 V
2+
Cu + 2e  Cu E = + 0.337 V
The overall electrochemical potential (electromotive force/emf) of the cell = Ecathod -
Eanode = Ecell = 1.100 V
Zn + Cu2+ Zn2+ + Cu Ecell = 1.100 V
(emf: electromotive force = the overall electrochemical potential of the cell)

Galvanic Cells With Electrolytes not 1M

• If the concentration of electrolyte surrounding anode is less than 1 M, driving
force for corrosion is greater.
• There will be more negative emf half cell reaction
M  Mn+ + ne

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 • Nernst Equation:
0.0592
E  Eo  log Cion
n
E = Net emf of half cell
E = Standard emf of half cell
n = Number of electrons transferred
Cion = Molar concentration of ions.

Cathode reaction: EC= -0.288 V,

emf of the cell = -0.288 – (-0.793) = 0.505 V

Galvanic Cells With Acid or Alkaline Electrolytes with no Metal Ions

• Consider iron and copper electrodes in acidic electrolyte.
• Since standard electrode potential of Fe to oxidize is
–0.44 V, compared to 0.337 V of copper,
Fe Fe2+ + 2e
• Since there are no copper ions to reduce
2H+ + 2e H2
• If electrolyte contains oxidizing agent (acid solution)
O2 + 4H+ + 4e 2H2O
• If electrolyte is neutral or basic (alkaline solution),
O2 + 2H2O + 4e 4OH

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Microscopic Galvanic Cell Corrosion of Single Electrode
• When single electrode is immersed in an electrolyte, microscopic cathodes and
anodes are formed due to structural irregularities.
• Oxidation reaction occurs at local anode and reduction reaction at local
cathode.

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 Zinc in HCl Iron in oxygenated water
(a) Anodic reaction: Zn Zn2+ + 2e
(a) Cathodic reaction: 2H+ + 2e H2

(b) Anodic reaction:

(b) Cathodic reaction:

2Fe + 2H2O + O2 2Fe2+ + 4OH 2Fe(OH)2 precipitate

2Fe(OH)2 + H2O + ½O2  2Fe(OH)3 red rust

Concentration of Galvanic Cells

• If a concentration cell is created by immersing 2 electrodes in electrolytes of
different concentrations of same ion, electrode in dilute electrolyte will be
anode.
• Example: 2 Fe electrodes immersed in electrolytes of 0.001M and 0.01 M
Fe 2+ electrolyte.
E Fe2+ = E + 0.0296 log Cion

for 0.001M E Fe2+ = 0.44V + 0.0296 log 0.001 = 0.529 V

for 0.01M E Fe2+ = 0.44V + 0.0296 log 0.01 = 0.499 V
• Since –0.529 V is more negative than –0.499 V, electrode in 0.001 M solution
is anode and gets corroded.

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Oxygen Concentration Cells
• If two electrodes are immersed in electrolytes of different oxygen
concentrations, electrode in low-oxygen content electrolyte is anode.
• Example: Two iron electrodes, one in low oxygen concentration water
and another in high oxygen concentration water.
Anode: Fe  Fe2+ + 2e
Cathode: O2 + 2H2O + 4e  4OH
• Since cathode reaction requires O2 and electrons, high concentration oxygen
is cathode.

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Microscopic Galvanic Cells:
Due to difference in composition and microstructures, these metallurgical factors can
influence the corrosion behaviors of metals and alloys.
• <Grain – Grain boundary Electrochemical cells>:
In most cases, grain boundaries are more anodic and hence get corroded by
electrochemical attack. Grain boundaries are usually at higher energy, i.e. planer
defect. Solute segregation might cause grain boundaries to become more
cathodic in some situations.

• <Multiple Phase Electrochemical Cells>:

In multiple alloys, one phase can be more anodic than another. Corrosion rates
are higher in multiphase alloys than in single phase alloys.
Example: In pearlite gray cast iron, graphite flake is cathodic than surrounding
pearlite matrix, so anodic pearlite corrodes
For Steel, in martensitic condition (single phase) after quenching from austenitic
condition, has better corrosion resistance.

• <Impurity Galvanic Cells>: Impurities in metals leads to precipitation of

intermetallic phases and hence forms anodic and cathodic regions leading to
corrosion.

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 Corrosion Rates
ItM iAtM
Faraday’s equation: W 
nF nF

W = weight of metal (g), corroded or electroplated in an aqueous solution in time t,

seconds.
I = current flow, A; i = current density, A/cm2
M = atomic mass of metal, g/mol
n = number of atoms/electron produced or consumed
F = Faraday’s constant 96,500 C/mol; A = area, cm2
• Corrosion rate is expressed as weight loss per unit area per unit time or loss in
depth per unit time.

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Corrosion Reaction and Polarization
• When a metal corrodes, the potentials of local cathode and anode are not at
equilibrium. Polarization can occur: Displacement of electrode potential
from their equilibrium values to some intermediate value and creation of net
current flow.
• Point A : equilibrium potential and current density of Zn
• Point B : equilibrium potential and current density of H
• Point C : Intermediate point

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 • Activation polarization: Electrochemical reactions that are controlled by a
slow step in a reaction sequence. There is critical activation energy to
surmount energy barrier associated with slowest step.

• Concentration polarization: Associate with electrochemical reaction and

controlled by diffusion of ions. Example: Reduction rate of H+ ions at surface
is controlled by diffusion of H+ ions into metal surface. Stirring and raising
temperature can decrease the concentration effect.

Passivation
• Passivation is loss of chemical reactivity in presence of an environmental
condition.
 Formation of surface layer of reaction products that inhibit further
reaction.

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• Oxide film theory: Passive film is always a diffusion barrier of reaction
products.
• Adsorption theory: Passive metals are covered by chemisorbed films of
oxygen.
• Polarization curve shows how the potential of a metal varies with current
density.
• As the electrode potential is made more positive, the metal behaves as an
active metal. When potential reaches Epp (primary passive potential) current
density decreases and hence the corrosion rate. Further increase in potential
makes metal active again. Transpassive (過鈍化 )

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The Galvanic Series
• Many metals do not behave as galvanic cells due to passive films.
• Galvanic series gives the cathodic, anodic relationship between the metals.
• In flowing seawater, Zinc is more active than Aluminum.
• Series is determined experimentally for every corrosive environment.

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