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The Fundamentals of Asset Integrity Management

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COURSE C: THE FUNDAMENTALS OF CORROSION MANAGEMENT

Module 3: Effects of corrosion on materials


Why is it important to understand the environments that cause corrosion?

Corrosion is the interaction of a substance with its environment. A good understanding of corrosion therefore
requires an understanding of the environment.
Because corrosion happens when a metal and an environment combine together we need to understand the
environment and the types of environments to take into account.

What are the different types of corrosive environments?

These are the main types of corrosive environment to consider:


1. Atmospheric
2. Water
3. Acids
4. Hydrogen sulfide (sour)
5. Differential environment
6. Soil
7. Concrete
8. High Temperature

Atmospheric environments

Atmospheric environments can be further broken down into five types of atmosphere to consider:
1. Precipitation: Water falling from the sky (rain, sleet, fog, snow etc.)
2. Rural: Mostly an agricultural environment
3. Marine
4. Industrial
5. Biological effects that can also cause corrosion rates to change

How does precipitation affect corrosion?

In regards to precipitation and rainfall we are looking at the time of wetness. Whats important is how long the
metal is wet, not the amount of water that causes the corrosion.
The corrosion rate will be highest when the amount of Oxygen is highest.
Intermittent rain drizzle, a little rain shower, and another little rain shower increases corrosion rate because you
get an occasional wetting of the surface meaning a thin film of water. Oxygen penetrates through and you have
good corrosion of the metal underneath.
Corrosion happens where you have a Dew Point (formation of fog)

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If you have situations where youve got a lot of heavy rain e.g. Ireland, then you might not have such a high
corrosion rain because rain does not contain any salts and pure water does not conduct electricity. So if you have
pure water you have no corrosion. High rainfall washes away salt.

Will you see the same effects from frozen water?

An electrolyte consists of ions that move around. If youve got frozen water its not an electrolyte. So if youve got
wet insulation on your pipeline and its a chiller pipeline and the waters frozen youll have no problem with
corrosion.

Why do you still get corrosion in the dessert?

In the dessert you have very high corrosion rates if near the coast because you get a lot of humidity. When the
relative humidity rises above 70% (it still feels dry) any salt on the metal surface will pull water from the air and
produce a thin film of wet brine on the surface of the metal and that will be highly corrosive.
o Its saturated with salt so a very good conductor of electricity.
o A very thin film of water so oxygen from the air can travel through very quickly, reaches the surface of the
metal and causes rapid corrosion. Its the oxygen that causes corrosion not the water.

Why do you get a high corrosion rate in the Splash Zone?

In a Splash Zone you get an occasional wetting of the surface with salty water. The very thin layer of water means
the oxygen travels through it very quickly.

How can salt used on roads increase corrosion?

Salt used on roads causes contamination of the environment with chlorides e.g. A refinery in Holland installed a
stainless steel pipeline and buried it underground. Then decided to build a road along the line of the pipeline. When
winter came along salt was put down. Salt washed off road into the soil. Pipeline then suffers form chloride induced
stress corrosion cracking and fails.

How does dirt, dust, mud etc. increase corrosion?

Anything that will increase the time of wetness will increase corrosion. Any deposits on the surface of the metal that
are porous and can hold the water for longer dust, mud, bio-fouling, will all increase the time of wetness and will
increase the corrosion rate.
Washing your structures on a regular basis to keep dust down is an important part. If youve got enough dust/mud
then seeds/mosses/lichens and algae can start growing on the surface. Because theyre organic materials that need
water it increases the water content.

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Can the design of your structure affect corrosion rates?

Poorly designed structures with Poor design- narrow shaded gaps, no drainage, crevices etc. mean moisture from
fog can get in there but the sunshine cant get in and dry them out so you can end up with higher corrosion rates as
a consequence.
If youve got a design with shaded areas that are exposed, then humidity and fog can penetrate through the gaps.
When the sun comes out it takes a long time to dry them out. If theres no drainage or little crevices they can also
increase corrosion rates.

What affects corrosion in rural environments?

The environment we consider to be most benign is the rural environment. Theres very little in the way of pollution
These environments do not contain significant amounts of either salt or the products of combustion.
Biological decay can produce compounds such as Ammonia and Hydrogen Sulfide and they can cause increased rates
of corrosion.
Agrochemicals are quite nasty materials and they can accelerate corrosion rates.

Why do we see corrosion in marine environments?

Key thing here is the salt. Salt causes an increase in conductivity and also causes corrosion rates.
Salt can get blown around as a salty spray. When it dries out it leaves a crust of salt.
Salts can induce pitting in stainless steel. And can also cause cracking stress corrosion- not a pleasant form of
failure, usually catastrophic.
The splash zone has the highest corrosion rate in the marine environment. We dont have a huge corrosion problem
underneath the water. Above the water we dont have that big of a problem. The biggest corrosion happens in the
middle in what we call the splash zone which is just slightly above high tide, between low tide and high tide. As
waves splash up will splash a thin layer of water that will slowly dry and just as its about to dry another wave will
put another splash of water on top of it these thin films create rapid corrosion.
Splash zone corrosion is a major problem in the offshore oil and gas industry.
Both Offshore structures and coastal (within 1 mile) Can be defined as being offshore structures offshore rigs,
shipping also the coastal region up to within a mile of the sea.
Wet film thickness studies can be used to demonstrate the effects of the splash zone.
The diffusion of oxygen through the water depends very much on the thickness of the water.

What areas are considered to be industrial environments and how do they promote corrosion?

Any region where you have significant concentration of factories, which are producing smoke stacks.
Where they tend to have nitrogen oxides and sulphur dioxides these are acidic gases and they will dissolve in water
to form acids which will increase the rate of corrosion.
They also produce a lot of dust and smoke and they could produce deposits, which can increase the time of wetness.
The effect of e.g. a factory can be noticed up to 10 Km downwind.

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Effects of Water on Corrosion

Water doesnt cause corrosion but water is the electrolyte in the chemical reactions that allow corrosion to occur.
There are several properties of water which will affect the corrosion rate:
o Cathodic reactions
Electron consuming reactions in water are often the main driving force for the rate of corrosion.
Both Acidic and Neutral water can consume electrons.
Even neutral water if its got oxygen in it will consume electrons water plus four electrons
produces hydroxide ions. They can demand the electrons and drive the metal into solution.
o pH
pH means log [H+]. Little p is just a mathematical term meaning log of whatever comes next.
Neutral water has pH of 7 because its log base of hydrogen ion concentration.
Acid has a pH of 1. Alkalis have a pH of 14 and all the numbers in-between are on this spectrum.
H+ is one of the possible cathodic reactions which demand electrons.
As the hydrogen ion concentration increases pH decreases. A pH of 1 is a strong acid. A pH of 6 is a
weak acid. As the pH goes down the corrosion rate increases.
o Dissolved O2
Oxygen in water will consume electrons.
As the [O2] increases the electron demand increases, and the rate of corrosion increases.
This explains why splash zones, and thin wet films suffer the highest rate of corrosion.
o Dissolved solids
Dissolved solids increase the conductivity of water, increasing the corrosion rate. Salt is a good
example of a dissolved solid.
Dissolved solids can precipitate forming scale. The scale can be protective or non-protective.
o Suspended solids
Suspended solids floating around in suspension can increase corrosion rates by erosion corrosion
they may abrade surfaces.
Suspended solids can deposit (especially when flow velocity decreases) and they drop out of
suspension and fall onto the bottom of the pipeline, forming crevice corrosion.
o Temperature
In general an increase in temperature increases the rate of corrosion. This is a simple kinetics
process.
Increasing temperature can make Corrosion Resistant Alloys (CRA) corrode e.g. expensive high
Nickel alloys, have surprisingly low critical pitting temperatures (CPT). That means that the temp at
which the passive film will break down is quite low e.g. For 825 it can be as low as 35 degrees
Celsius. If youre operating in the North Sea your corrosion resistant alloys will give you good
service. If youre operating in the Gulf they wont work because the seawater is often above 35
degrees Celsius.
Increasing temperature decreases the passive film stability, a problem for Stainless Steel, Titanium
and Aluminium.
o Microbes

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Microbially Induced Corrosion (MIC) can be a major problem


Microbes live in the water and can cause all sorts of problems. Some microbes will consume the
oxygen from an environment producing stagnant conditions very quickly.
A good rule of thumb is that one cubic cm of active respiring bacteria have the same oxygen
demand as an African elephant.
Some bacteria only live in stagnant conditions. Sulphate reducing bacteria will produce acids and
hydrogen sulfide and they can cause all sorts of corrosion problems.
Manganese reducing bacteria precipitate manganese oxide onto the surface of the metal which will
make that piece of metal cathodic to the other piece of metal, increasing the rate of corrosion
Bacteria tend to produce bio-films on their surface and theyre very difficult to remove from it.
If youve got bacteria in your pipeline and you put some bleach down the pipeline to kill the bacteria
it will just run over the surface of the biofilm and the bacteria underneath will be unharmed you
have to scrape them off.
o Flowrate
Flowrates are a big problem. As flow rate increases the corrosion rates tends to increase.
Tempting to think that its good to have low flow rates. Which is true if you have Carbon Steel. But if
you replace Carbon Steel with Stainless Steel, you tend to find that low flow rates cause stagnant
conditions, which cause the passive film to be destroyed and the corrosion rate to increase.
Stainless steel actually wants good flow rate as long as its not so rigorous that it pushes it into the
erosion corrosion regime. Stainless steel does very well in flowing fluids.
The build up of corrosion products and the consumption of reactants can slow down the rate of
corrosion.
As flowrate increases, the better transport washes away corrosion products and brings more
reactants to the metal surface and corrosion rates increase.
However, low flowrates can also be a problem for passive film forming alloys, as well as
opportunities for differential aeration corrosion (under deposit corrosion, crevice corrosion to
occur).

Effects of Acids on Corrosion

There is a whole range of acids in industrial environments. They all cause intense amounts of corrosion in
metals.
Some examples of industrial acids are: Acetic, Sulphuric, Nitric, Hydrochloric
The high concentration of H+ means concentration polarisation does not occur. Some metals work well with
strong acids, whilst other metals do not.
Some metals work very well in dilute acids and fail in strong acid.
o Copper works well in low concentration of acid, but corrodes in strong acid.
o Carbon Steel performs very well in pure concentrated nitric acid, which is a strong oxidizing acid. But if
you dilute the acid and add water to it suddenly the passive film that forms on the metal will break
down and it will corrode rapidly.

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If youre going to deal with acids as a process stream then you need to make sure that you have specific metal
alloys that are known to work.

How does Hydrogen Sulfide effect corrosion?

Hydrogen sulfide is a nasty and very toxic gas. One lungful breathed in will kill a human being.
Hydrogen sulfide is extremely corrosive. It causes rapid uniform corrosion, thinning of metal as well as cracking of
metal.
Hydrogen sulfide will cause corrosion because it is an acidic gas but it will also produce iron sulphide as it produces
the acidic gas.
H2S decomposes on the metal surface to produce Hydrogen gas and Iron sulfide.
Iron sulphide is a strongly cathodic conductor and it will promote corrosion of the other bits of metal. Its also very
brittle and so it breaks off. This leads to quite rapid corrosion as a result.
Causes blistering and cracking of metals via mechanism known as Hydrogen Damage.
If you are dealing with any hydrogen sulfide environment then you use a standard called NAIS MR0175 or ISO15156,
which gives you everything you need to know about hydrogen sulphide.
Often if youre dealing with high hydrogen sulfide concentration you should get a professional in to give you advice.
Some of our new oil reservoirs are very sour and contain lots of hydrogen sulfide. As we move towards harder to
obtain oil reserves the first type of oil reserve were now considering are the sour ones. We used to find a sour
reservoir and leave it. Now were coming back to the sour reservoirs and theyre pretty nasty materials to deal with.

What is a Differential Environment and what is the impact on corrosion?

A differential environment is where youve got differences in concentration from one region to another e.g.
differences in oxygen concentration or temperature can affect corrosion rate.
The classic example is differential aeration. High [O2] regions are Cathodic - Since oxygen consumes electrons, it is
an important cathodic process. Any region that is high in oxygen will be a cathode. It occurs if the environment
surrounding a metal is different from one part of the metal to another.
Low [O2] regions are Anodic - If youve got two regions together, any region thats got a low concentration of oxygen
will be an anode
Corrosion happens when the local [O2] is lower than the surroundings: If the oxygen concentration changes the low
oxygen region is the one that corrodes e.g. mud, crevices, or in the flange joint.
Examples of differential environments are:
o Stagnant regions
o Under deposits
o In crevices
o Flange joints
Differences in temperature can result in corrosion, but the effect is quite small.
Sometimes you can have a problem with temperature differences e.g. If youve got a heat exchanger the hot region
will be anodic to the colder cathodic regions.

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How does soil affect corrosion?

Different soil has different properties. It is not uncommon in long pipelines to see corrosion in one area caused by
the different soil composition to another area 150m down the line.
Different soils have different corrosive properties e.g. Clay doesnt allow oxygen to go through. Clay soils are
stagnant, sandy soils are aerated.
Soil can contain microbes leading to increased corrosion - see coverage on microbes.
Above grade structures can affect buried structures (causing differential corrosion).
Steel in concrete is passive to steel in soil, therefore concrete should be brought above the grade.

Corrosion in concrete

Concrete is an electrolyte. The foundations of concrete structures should always be above the grade line.
Fresh new concrete does not corrode steel because its alkaline.
o Over time the alkalinity will drop away and if you get micro cracks and water gets in there or acidic gases
e.g. CO2, H2S, SO2.
o After an interval, the local environment is no longer alkaline, and the rebar corrodes.
Improper curing is a common cause of micro cracking.
Freeze thaw cycles widen the cracks.

How can you protect against high temperatures?

Exhaust stacks, exhaust pipes etc. have high temperatures. If the temp is high enough the corrosion product will
melt. If it melts it will crack and fall off and re-expose the metal to cause higher corrosion rates.
When youre looking at high temperature exhaust systems you use a very specialist alloy to protect against
corrosion.

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