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FUNDAMENTAL CAUSES

OF CORROSION AND ITS Module 2

CONTROL
OVERVIEW

Thermodynamics of Corrosion
Kinetics of electrodes
THERMODYNAMICS OF
CORROSION
NERNSTIAN CELL POTENTIALS

Spontaneous chemical
reactions release energy
All reactions can be
broken into two halves
Oxidation reactions which
release electrons.
Reduction Reactions which
Consume electrons
Instead of allowing the
two reactions to
happen in the same
place, we make a cell.
Electrons are forced
around a circuit.
STANDARD REDUCTION POTENTIALS

Each cell will contribute to the overall cell potential


(voltage).
This is the energy change of the process.
At the anode, electrons are pushed round the circuit.
At the cathode, electrons are pulled round the circuit.
Lists of cell potentials, as reduction values are published.
We can also use the Nernst equation to correct for changes in:
Concentration
Temperature
Pressure
Other ions in solution (activity)
The thermodynamic driving force for corrosion can be shown
in Pourbaix Diagrams
POURBAIX DIAGRAMS
INTRODUCTION

A potential (voltage) versus pH diagram is known as a


Pourbaix diagram
Named after Marcel Pourbaix 1904-1988
Shows equilibria stability as a function of E and pH
Boundaries are represented by lines.
Useful because corrosion is dependent on both the pH and the
voltage.
T YPES OF LINE

Horizontal: pH independent.
Ver tical: non redox reactions.
Sloping: dependant on E and pH.
Multiple: Depending on [metal ion].
Single: independent of [metal ion ].
REGIONS WHICH CAN BE IDENTIFIED

Immunity:
The metal exists as the solid metal, corrosion is impossible
Corrosion:
The metal exists as a soluble ion corrosion rates are expected to be
high.
Passivity:
The metal exists as a solid compound (usually an insoluble oxide).
The oxide acts as a barrier to the environment, preventing corrosion
of the underlying metal.
General Appearance of Eh pH Diagrams

High Valence High Valence


Cations Oxides (hydroxides)
Eh

Low Valence Low Valence


Cations Oxides (hydroxides)

Metal

0 7 14
pH
Iron Eh pH Diagram
1.5

Fe+3
1.0
0.769

Fe2O3
0.5
1.38

6.77
Fe+2
Eh

0.0
-0.185

-0.5
-0.586
Fe3O4 -0.613

Fe 8.47 -0.951
-1.0

-1.5
0 2 4 6 8 10 12 14
pH
Iron Eh pH Diagram
1.5

1.229

1.0 Aerated Solution


Fe+3

O2/H2O
0.5
0.402

Fe+2 Fe2O3
Eh

0.0
H+/H2

Deaerated Solution
-0.5 Fe3O4

-0.827
Fe
-1.0

-1.5
0 2 4 6 8 10 12 14
pH
NICKEL
ALUMINUM
TITANIUM
ZIRCONIUM
TANTALUM
ADVANTAGES/ DISADVANTAGES

Pourbaix diagrams show us the pH, E regions where corrosion


is impossible thermodynamically.
However:
Most diagrams are for pure substances
Room temperature
Engineering alloys are mixtures
Says nothing about corrosion rates
Pourbaix assumes that solid oxides are protective, not always the
case.
CORROSION 2
Electrode
FUNDAMENTALS Kinetics
RATE MEASUREMENT

Kinetics is the investigation of how fast a reaction proceeds -


vital in corrosion studies.
Methods used are:
Mass loss
Mass (g)= Current (A) x time (s) x Mwt
nF
n= no of electrons per mol of metal
Alternatively, Mwt/n = Equivalent weight, very useful when dealing
with alloys.
g=A x s x Eqwt
F
Mass loss per unit area :
Rate (g/cm 2 s) = i x Eqwt i= A/cm 2 , current
F density
Penetration Rate
A measure of thickness loss. Can be linked to either mass loss or
corrosion current.
It is more important to know the thickness loss than the mass loss as
it determines mechanical strength.
PENETRATION RATE FROM MASS LOSS
MEASUREMENTS

Rate = K x W
AxT xD
Where Rate Units K
K= constant mpy 3.45x10 6
W= weight loss (g) ipy 3.45x10 3
A = Area (cm 2 ) mmyr -1 8.74x10 4
T = Time (hours)
D = Density (g/cm 3 )
PENETRATION RATE FROM CURRENT
DENSIT Y

Rate = k x Eqwt x i
d
Where: Rate Units k
k = constant mpy 0.129
Eqwt = equivalent weight mm yr -1 0.00327
i = corrosion current density mm yr -1 3.27
(mAcm -2 )
d = density (g/cm 3 )
PENETRATION RATE LEVELS

What constitutes an acceptable penetration rate?


Depends upon the design life, but usually:
0-20 mpy : low corrosion rate
20-50 mpy: tolerable
50- 100 mpy high
>100 unacceptable rate
METHODS OF MEASURING THE CORROSION
RATE

Coupons (1 month to 1 week)


Gives mpy
Tafel plotting using potentiostat (1 hour)
Gives i corr
LPr Linear Polarization Resistance (5 mins): real time
monitoring.
Gives i corr
Electrochemical Resistance.
Electrochemical noise.
Electrochemical impedance spectroscopy.
ELECTRODE KINETICS

Rate of corrosion is determined from Evans Diagrams.


There are several parameters:
Cell Voltage anode, cathode (Nernst correction for T and [ ])
i o for the anodic reaction
i o for the cathodic reaction
Mixing efficiency.
Tafel slope, ba, bc
i o is a fundamental proper ty of metals
It is called the Exchange Current Density
EXCHANGE CURRENT DENSIT Y

At the atomic level, reactions tend to occur in stages.


Stage 1: adsorption onto the surface
Stage 2: bond breaking
Stage 3: bond formation
Stage 4: desorption
ECD is determined by the ease of bond breaking and
formation of adsorbed molecules occurring on the sur face.
Catalysts have high io, poisons have low io.
Imagine a treadmill. The runner stays in one place, but can
run at different speeds.
The runner is in equilibrium (not moving)
But the speed of the treadmill can change
This is the rate of exchange
DEPARTURE FROM EQUILIBRIUM

When Current begins to flow in a electrochemical cell two


processes occur:
Activation Polarisation.
Concentration Polarisation.
ACTIVATION POLARISATION

The flow of current changes the voltage. First identified by Tafel


(1905).
The change in voltage(DE= h) is called the Overvoltage or
Overpotential.
Rate of electron transfer determines the rate of corrosion.
Tafel equation:
h = ba log (i/i o )
ACTIVATION POLARISATION
FOR A CELL, BOTH REACTIONS
SUFFER FROM THIS EFFECT
CONCENTRATION POLARISATION

As current flows, reactants are consumed around the electrodes, and


corrosion products build up.
The current density is eventually limited by the rate at which
reactants can move (diffusion control) through the fluid.
Rate of mass transfer determines the rate of corrosion.
CONCENTRATION POLARISATION
SUMMARY

The energy of a chemical reactions can be used to give


electrons a driving force (voltage).
Chemical factors can change the amount of this force.
The voltage gives us the potential for change
(thermodynamics), but not rate of reaction.
Electrode Kinetics allow us to understand the rates of
corrosion, but the theory is not simple and a full treatment is
beyond this course.