CHEM ENG 3029_7055

Materials Science and Engineering

 Lecture 7

Kinetics, Polarisation and Diffusion of Corrosion

 Lecture Structure
Lecture 7 (Kinetics, Polarisation and Diffusion of Corrosion) is
divided into the following sections:
• L7.1 – Kinetics of Corrosion
– Understanding Kinetics of Corrosion
– Free Energy and Corrosion Current
– Electrical Double Layer
– Faraday's Law of Electrolysis
– Corrosion Rate
• L7.2 – Polarisation
– Non-equilibrium Conditions
– Equilibrium Conditions
– Activation Energy for Anodic and Cathodic Reactions
– Butler-Volmer Equation
– Tafel Equation
• L7.3 – Diffusion and Double Layer
– Kinetics vs Diffusion
– Diffusion as Controlling Factor of Corrosion

Reference Book: W. D. Callister and D. G. Rethwisch, Materials Science and Engineering: An Introduction, John
Willey & Sons ISBN: 9781119321590

Complementary Reference Book: P. A. Schweitzer, Fundamentals Of Corrosion: Mechanisms, Causes, and

Preventative Methods, CRC Press ISBN: 9781420067705
 Lecture Structure
• L7.1 – Kinetics of Corrosion
– Understanding Kinetics of Corrosion
– Free Energy and Corrosion Current
– Electrical Double Layer
– Faraday's Law of Electrolysis
– Corrosion Rate
L7.1 – Kinetics of Corrosion
o Learning Objectives

✓ Fundamentals of corrosion kinetics (how fast things

corrode)

✓ How current density of corrosion is related with free

energy and the Faraday’s law of electrolysis

✓ Establishment of corrosion rate

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L7.1 – Kinetics of Corrosion
• Understanding Kinetics of Corrosion
So far we have just seen tendency to corrode
– Need to understand the relationship between
• Potential and Current (and Current Density)
– Consider 2 pieces of the same metal with different surface area
corroding in separate cells at a rate of 10 electrons/second
– Which piece does corrode fastest (i.e., losses most thickness)?

2 mm2 20 mm2

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L7.1 – Kinetics of Corrosion

• Understanding Kinetics of Corrosion

– The smaller because it loses more electrons per unit surface area
• Corrosion of the smaller piece will be 10 times worse (if z = 1)
• Current density i (A/m2)
• Absolute current I (A)

– Use only electron flow (current density) NOT conventional

current
• ia – Anodic current density
• ic – Cathodic current density
20 mm2
2 mm2

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L7.1 – Kinetics of Corrosion
• Free Energy and Corrosion Current
Consider pure copper in pure water: Cu Cu2+ + 2 e-
ic

ia

ia > ic ia = ic = i0
e flow

Initial Condition Equilibrium

(after some corrosion)
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L7.1 – Kinetics of Corrosion
• Free Energy and Corrosion Current
Corrosion of a single piece of metal in water (e.g., pure
copper in ultra-pure water)
– Single piece of metal can act as:
• Cathode, anode and electrical connection
– Why?
• Micro-variations in the structure
• Environmental differences over the surface
– The tendency for copper to corrode decreases as the
current increases (i.e., voltage/potential E drops)
• Hence ΔG decreases – Faraday’s law ΔG = (-zF)E
• At equilibrium ΔG = 0 and for a divalent metal:

M M2+ + 2e- (ia →; ic ←)

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L7.1 – Kinetics of Corrosion
• Electrical Double Layer
Current does flow but it cannot be measured
– Exchange current (io)
• Gives a non-homogeneous layer of electrons
• Double layer
– Compact layer or Helmholtz Layer
– Outer more diffuse layer or Gouy-Chapman Layer

Exponential change in potential

Linear change in potential

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L7.1 – Kinetics of Corrosion
• Faraday’s Law of Electrolysis
– Non-equilibrium conditions
– Constitution of double layer will change to establish a
continuous flow of electrons
– Faraday’s law of electrolysis
– Q = zFM where Q = charge created by ionisation of M mols of
material
– Differentiating with time:
dQ/dt = zF dM/dt rate of flow of charge is current (I) (i = I/A)
so
dM/Adt = J (flux of substance) and therefore i = zFJ

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L7.1 – Kinetics of Corrosion
• Corrosion Rate
– Non-equilibrium conditions
– Hence
Current Density = Corrosion Rate
– However A·m–2 is not very useful for engineers so we use:
– mm/year (mm/y)
– milli-inches/year (mils) – USA
– milligram/decimeter2/day (mdd)
– Can be dangerous for crack and pitting corrosion
– Owing to local rapid penetration of surface (renders an average rate that
might be useless in some scenarios)

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