The Fundamentals of Asset Integrity Management

Online Training Series Course Summary

COURSE C: THE FUNDAMENTALS OF CORROSION MANAGEMENT

Module 2: The fundamental causes of corrosion and how it can be controlled

The Thermodynamics of Corrosion

Nernstian Cell Potentials

The Nernst cell potential. Spontaneous chemical reactions release energy. All reactions that happen in chemistry can
be broken up into two half reactions. There can be a process where oxidation occurs in which electrons are released
and a reduction process where electrons are consumed.
When you put a piece of metal in acid and watch it fizz youre seeing the two half reactions taking place in the same
place. If youre clever you can break it up so the two half reactions happen in a different place.
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

Of these potentials. Each of these half cells can be chopped up into a half cell where reduction or oxidation happens.
We can think of corrosion as being the energy associated with electrons being produced and the energy associated
with electrons being consumed.
That is the combination of pushing electrons around the circuit and pulling electrons around the circuit. That push
and the pull can work together and the sum of both is the total 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 list all of these half cells according to the voltage relative to a hydrogen electrode. Can list them as values of
voltages that gives us our standard voltage.
Nernst worked out that you can convert your standard cell voltages to correct for:
o Concentration
o Temperature
o Pressure
o Other ions in solution (activity)
The thermodynamic driving force for corrosion can be shown in Pourbaix Diagrams.
This gives us a voltage that voltage is the EMF electro motive force - that is driving corrosion. Measured in vaults.
The voltage by itself doesnt tell us everything we need to know about corrosion. We also need to take into account
pH. Acidity or alkalinity also affects corrosion not just voltage.
Voltage and pH both effect the rate of corrosion

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What are Pourbaix diagrams and why are they useful?

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
The thermodynamic driving force for corrosion can be shown in Pourbaix Diagrams.
Pourbaix diagrams take into account both the voltage and the pH of the process.
Useful because corrosion is dependent on both the pH and the voltage.
Pourbaix diagrams help us to identify ways of protecting against corrosion.
pH is a measure of the hydrogen ion concentration or acidity of a solution.
Shows equilibria stability as a function of E and pH.
Boundaries represented by lines give us different regions which can be identified:
o Immunity - The metal exists as the solid metal, corrosion is impossible
o Active corrosion where the metal is stable as the soluble ion in solution corrosion rates expected to be
high
o Passivity Corrosion product is insoluble and therefore is protecting the underlying metal

General appearance of Eh-pH diagrams

Generally a Pourbaix diagram is a box with the metal on the bottom and on the left hand side metal ions in solution.
As you rise up the table you get higher and higher voltages and also more and more oxidizing environment. Right
hand side tend to have oxides and hydroxides.

What are the advantages and disadvantages of Pourbaix diagrams?

Pourbaix diagrams show us the pH, E regions where corrosion is impossible thermodynamically.
However:
o Most diagrams are for pure substances
o Room temperature rarely run them at room temp
o Engineering alloys are mixtures
Says nothing about corrosion rates.
Pourbaix assumes that solid oxides are protective, not always the case.
Thermodynamics says what is and what isnt possible but nothing about how fast it happens.
Pourbaix tables assume that any solid oxide is protective we know that iron corrodes underneath rust
Take them with a pinch of salt theyre a good starting point

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The Fundamentals of Asset Integrity Management
Online Training Series Course Summary

Corrosion Electrode Kinetics

Kinetics is the investigation of how fast a reaction proceeds (rates of reaction) - vital in corrosion studies.
We can measure mass loss to give us a starting point in measuring a rate of reaction.
We can also look at equivalent weight. We have engineering tables of the equivalent weight of different alloys.
Corrosion is something that happens on the surface of metals so if we want to compare samples we talk about the
specific current where we measure the current per square centimetre.
That gives a rate of corrosion in grams per square cm per second, which is not actually used in corrosion because its
a horrible sounding unit.
You want to know the consequences to the engineering strength of the corrosion i.e. how the metal is getting
thinner penetration rate.
Thickness loss will correlate directly with loss in engineering strength, this is much more useful to us.
Penetration rate can be measured in two different ways:
1. You can measure it from mass loss.
2. Can also measure it from the current.
Penetration rates vary enormously.

What constitutes an acceptable penetration rate?

This depends upon the design life, but usually:

o 0-20 mpy: low corrosion rate
o 20-50 mpy: tolerable
o 50- 100 mpy high
o >100 unacceptable rate
100 mpy over 10 years is one inch. Very few pipe wall thicknesses are more than an inch thick. Your pipe will only
last 7.5 years and then will need replacing.

How do we measure this corrosion rate?

Coupons a coupon is a little piece of metal that is the same metal as your structure:
o Clean it weigh it immerse it in your environment and measure weight loss. Giving you mils per year.
o Can even inject coupons into a live pressurized pipeline.
o It takes one week > one month to get result.
o Problem with coupons is that its the average corrosion over the past month, so if you have a varying
environment it wont tell you whats caused the corrosion.
Tafal using a machine called a potentiostat, gives you a corrosion rate in about an hour.
LPr Linear Polarization Resistance gives you a corrosion rate in 5 mins and that can give you real time monitoring.
Can also use Electrochemical Resistance, Electrochemical noise and Electrochemical impedance spectroscopy.

THIS IS A CONFIDENTIAL SUMMARY OF THE CONTENTS OF AN ONLINE TRAINING COURSE FOUND AT WWW.OILANDGASFUNDAMENTALS.COM.
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The Fundamentals of Asset Integrity Management
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What is Electrode Kinetics?

Electrode Kinetics allows us to understand the rates of corrosion, but the theory is not simple and a full
treatment is beyond this course.
We look at how corrosion rate is changed using an Evans diagram.

What is io?

It is called the Exchange Current Density (ECD).

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
io is the speed at which the treadmill runs, and it varies between metals.
io is a fundamental property of metals.
At the atomic level, reactions tend to occur in stages:
1. Stage 1: adsorption onto the surface
2. Stage 2: bond breaking
3. Stage 3: bond formation
4. Stage 4: desorption
ECD is determined by the ease of bond breaking and formation of adsorbed molecules occurring on the surface.

What happens when we depart from equilibrium?

In corrosion current flows. A change in voltage is called polarization.

When Current begins to flow in a electrochemical cell two processes occur:
o Activation Polarisation:
The flow of current changes the voltage. First identified by Tafel (1905).
Tafel equation: h = ba log (i/io)
Rate of electron transfer determines the rate of corrosion.
If you artificially force the voltage down then cathodic reactions occur. If you force the voltage up the
system responds by releasing electrons to consume the positive charge = corrosion, anodic polarisation.
For a cell, both reactions suffer from this effect.
Evans diagram helps you calculate what the corrosion rate will be.
o Concentration Polarisation:
Were dealing with Heterogeneous processes where the metal has to come into contact with liquids
and the reactants and the products travel through the liquid.
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.
Diffusion can slow down the rate of corrosion because it stops hydrogen ions from moving. You end up
with a limiting current that prevents further corrosion.

THIS IS A CONFIDENTIAL SUMMARY OF THE CONTENTS OF AN ONLINE TRAINING COURSE FOUND AT WWW.OILANDGASFUNDAMENTALS.COM.
IT IS FOR THE REVIEW OF COURSE PARTICIPANTS ONLY AND IS NOT FOR DISSEMINATION COPYRIGHT RESTRICTIONS APPLY