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UMIST

Corrosion and Protection Centre

Module 0 Introduction to Corrosion

Module Notes - Corrosion Control

September 2003
This document is 2002 - 2003, the Corrosion and Protection Centre, UMIST.

All rights reserved


Corrosion Control
Learning outcomes at the end of the course you should be able to

Define the main components of a paint and their functions

State and use the four criteria necessary for CP to be successful

Explain the difference between sacrificial and impressed systems

Describe the three types of surface film formed by inhibitors, namely an adsorbed layer, a
passive film, a precipitated film.

Describe four factors that affect anodic inhibitor performance, namely, the inhibitor
concentration, pH, aggressive ion concentration, and the specific metal being inhibited.

Paints and Organic Coatings


A paint consists of a mixture of different materials each constituent possessing a specific
function.

1. The main constituent is known as the binder, a continuous polymeric phase which
is responsible for the cohesion of the dried film either by a physical polymer,
polymer interaction in the dry state or by further polymerisation during the drying
process, Further, the binder is the component in the paint which is responsible for
the adhesion of the paint to a substrate.
2. The second major constituent is the pigment, solid particles dispersed in the binder
which originally were designed to provide colour and opacity but with anti-
corrosive paints imparts to the final dried film a specific anti-corrosion function.
3. Extenders are solid particles whose main function is to lower the overall unit cost.
They may also provide mechanical reinforcement to the dried film, to adjust the
viscosity of the wet paint.
4. Solvents and thinners are low molecular weight highly volatile compounds that
make the liquid paint less viscous and evaporate during the drying process.
5. Plasticisers are non polymeric compounds and are sometimes added to improve the
flexibility of the final dried film.
6. Driers are salts of transition metals added to catalyse the autoxidation drying
reaction for air-drying systems.
7. A key feature of a paint coating is that it can be applied in a series of multiple
coats. Each layer will have a specific function, e.g. the layer next to the metal
surface may contain anti-corrosion pigments and is known as a primer. The layer
next to the environment is known as the top-coat, and may contain UV absorbing
pigments.

Cathodic protection
Cathodic protection is a useful and practical example of an electrochemical cell. An
example of the use of cathodic protection would be its use in the protection of
underground, high pressure gas pipelines made from steel. As well as a good quality

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coating, the corrosion control of such pipelines is also ensured by their being cathodically
protected. In practice, this involves connecting the pipeline to a source of electrons.
Current may be supplied spontaneously, as in a sacrificial cathodic protection system, or
the cell may be driven using a DC source in an Impressed current cathodic protection
system. In both cases, four areas are important.

1. The structure needing protection usually mild steel is one electrode, the cathode and
receives electrons.
2. The other electrode is an anode, and in the sacrificial system is a reactive metal,
alloys of zinc, aluminium and magnesium; in the impressed system is usually an inert
metal (or sometimes graphite). The electrochemical reaction at the anode generates
electrons.
3. The third feature is that there must be electron conduction between the two
electrodes.
4. There must be electrolyte contact between the two electrodes.

The electrode reactions in the sacrificial anode case are electrochemical oxidation of the
anode itself.
In the impressed current case, it is the electrochemical oxidation of the environment.

The sacrificial anode cathodic protection case may be thought of as a useful


case of galvanic corrosion.

Inhibitors and Water treatment

Definition of an Inhibitor
A corrosion inhibitor is a substance which, when added in small quantities to a normally
corrosive environment, reduces the corrosion rate of the metal, without significantly
changing the concentration of corrosive species.

It follows that the decision as to whether a substance is or is not an inhibitor may depend
on the nature of both the metal and the environment, and that substances that are
inhibitors in one environment for one metal may be ineffective, or even aggressive, if the
metal and/or the environment is changed.

Broadly, there are only two ways in which inhibitors can exert their action:

by forming an adsorbed layer on the metal surface, or,


by forming a three-dimensional film either a passive film or a precipitated film.

These are the basis of the classification of inhibitors as either interface or interphase, but
within each of these, particularly (b), there can be a variety of different mechanisms, and
some of the other classifications may be more useful. However, in general, inhibitors
used in acid solutions or in oxygen-free neutral solutions work by adsorption on the
surface whereas in aerated systems inhibition is a result of three-dimensional films.
These three dimensional films may be either passive films e.g. thin oxides on iron, or
thicker precipitated films formed from solution species.

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Classification of Inhibitors
Inhibitors can be classified in many ways, according to their mechanism of action, their
chemical structure, their chemical properties etc. Some of the classifications that have
been used are:

adsorption / film forming


anodic / cathodic
organic / inorganic
oxidising / non-oxidising
safe / dangerous

These classifications are not mutually exclusive and, to some extent, their usefulness
depends on the system.

In many cases it is convenient to classify inhibitors according to which electrode reaction


they affect and this is the basis of the anodic/cathodic classification. This classification
also, for aerated near-neutral solutions, divides inhibitors according to the mechanism by
which they act, and if this is known the effects of solution composition variables such as
chloride concentration can be predicted. Inhibitors that affect both processes are known
as mixed inhibitors.

Inhibitors that reduce the rate of the anodic reaction more than they reduce the rate of the
cathodic reaction will cause a rise in corrosion potential.

The mechanism of inhibition may be different in acidic and neutral solutions, and
different types of inhibitor are effective in these two environments, so these two cases
will be considered separately. Most attention will be given to the corrosion of iron and
steel, although the general principles apply to other metals.

Inhibitors for Acid Environments


In this case the corrosion reactions are metal dissolution with hydrogen evolution as the
cathodic reaction. These reactions occur in the absence of surface films of oxides or
corrosion products, because of their solubility in acid, and both reactions are under
activation control. Even a small reduction in the kinetics of either process will reduce the
corrosion rate.

Inhibitors for acid solutions usually function by adsorption on the metal surface, and
typically contain elements in Groups V or VI of the periodic table, e.g. N, P, O, S or As,
which possess lone pairs of electrons which can be donated to the metal to form a
chemical bond, a process known as chemisorption.

The adsorption of an inhibitor molecule or ion may depend on the other species present
in the solution. For example, cationic inhibitors may adsorb more strongly if there is also
anion adsorption, and for this reason many nitrogen-containing inhibitors are more
effective in hydrochloric acid (where chloride may adsorb) than in sulphuric acid. These
N-containing inhibitors include aliphatic amines (primary, secondary, tertiary and
quaternary), aromatic amines and heterocyclics.

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For sulphuric acid the common inhibitors are S-containing, such as thiourea and its
derivatives.

Inhibitors for Near-Neutral and Alkaline Environments


This section considers inhibitors that work in the presence of oxygen, since inhibitors for
oxygen-free near-neutral solutions, as may be found, for example, in oil production, are
of the type discussed above.

It is convenient here to consider anodic and cathodic inhibitors separately, since there are
essentially two ways of reducing the corrosion rate in these environments. For an actively
corroding steel surface the corrosion rate is under cathodic control, i.e. the rate is
determined by the transport of oxygen to the metal surface. The two ways of reducing
corrosion rate are

(a) to reduce the rate of this rate determining step, oxygen transport, by the
formation of a electronically non-conducting film on the metal surface
(cathodic inhibitors), or

(b) to cause the steel to form or retain a protective oxide film which acts as a
barrier to metal dissolution, so that the corrosion rate is now controlled by the
anodic process (anodic passivating inhibitors).

Anodic Inhibitors
These are effective because they maintain a passive oxide film on the metal surface. They
include oxidising inhibitors (chromate, nitrite etc) and non-oxidising ones (phosphate,
benzoate, borate, carbonate, hydroxide, molybdate etc). The classification as oxidising or
non-oxidising is based on whether dissolved oxygen is necessary for the maintenance of
a passive surface, and not necessarily on the intrinsic chemical properties of the inhibitor.

As regards the mechanism by which these inhibitors act, there are still several
hypotheses, but much of the available evidence is consistent with the effect of the
inhibitors being at defects in the oxide film. In the absence of inhibitors metal dissolution
would proceed and eventually the reduction of oxygen on the oxide surface would be
incapable of providing the required anodic current, reduction of the oxide film would
occur, and the metal would become active. The inhibitors prevent this process by
reducing the rate of metal dissolution at the defects, resulting in plugging of the defects
by iron compounds. Whilst this mechanism is still the subject of discussion, and the
above is a simplification, there are several properties of anodic passivating inhibitors that
are well established and of considerable practical importance.

In particular, the action of anodic inhibitors is very dependent on the inhibitor


concentration, the aggressive ion concentration, and the solution pH. In addition they are
sensitive to the nature of the metal and to the temperature.

If insufficient inhibitor is present there is little if any effect on corrosion rate, but above
the critical concentration the rate reduces essentially to zero. This sudden change occurs
because the uninhibited corrosion rate is controlled by the rate of oxygen transport to the
surface and small changes in the anodic kinetics do not affect the overall rate. With

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sufficient anodic inhibitor the anodic dissolution process becomes the rate-determining
step, and the corrosion rate falls.

The critical minimum concentration is dependent on the aggressive ion concentration,


and there is often a linear relationship between the logarithm of the aggressive ion and
inhibitive ion concentrations as shown below, with more inhibitor required as the
aggressive ion (e.g. chloride or sulphate) concentration increases. The minimum
concentration required for protection in distilled water is often around 10-3 M in distilled
water. For chromate about 100 ppm is required in distilled water but this increases to
about 1000 ppm in the presence of even 50 ppm chloride.

These inhibitors are also sensitive to pH, with a minimum pH below which they do not
work, although for many inhibitors this critical pH is well below those likely to be
encountered in their application.

Since anodic inhibitors influence the metal dissolution reaction they tend to be sensitive
to the nature of the metal. For example, benzoate is effective for steel, but not for cast
iron or zinc, and nitrite, while effective for a wide range of metals, accelerates the
corrosion of lead-tin solders.

Another feature of some anodic inhibitors which can give concern in practice is that if
they are present in insufficient amounts the may cause the corrosion to be localised
(pitting) without any reduction in the total amount of metal lost.

Cathodic Inhibitors
These are substances that reduce the rate of oxygen reduction at the metal surface by
precipitating on the surface a film that restricts the diffusion of oxygen to the metal.
Typical are the divalent metal cations, such as zinc, which will react with hydroxide
produced at the surface to give a zinc hydroxide precipitate. These are not sensitive to the
presence of aggressive ions, unless these in some way change the nature of the
precipitate, and even a small cathodic effect will lead to a reduction in corrosion rate,
unlike the anodic inhibitors.

Cathodic inhibitors have one major disadvantage over anodic inhibitors, but several
advantages. The disadvantage is that they do not prevent corrosion but merely reduce the
corrosion rate, but against this they are effective at much lower concentrations (typically
20-50 ppm), they are not greatly affected by the presence of aggressive ions and they are
effective on a wide range of metals, since they act by reaction with cathodically produced
hydroxide.

They, like anodic inhibitors, are sensitive to pH, but here this is not a sharp change from
protection to corrosion. The optimum pH is related to the solubility of the compound that
forms the protective surface film, and therefore depends on the inhibitor.

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Principles of Water Treatment
The aim of water treatment is not simply to reduce corrosion although this is part of the
requirements in most systems. The majority of areas where water treatments are carried
out involve the use of natural waters in heat transfer applications (cooling systems,
boilers etc.) and the maintenance of effective heat transfer is generally the major
consideration.

In such systems the problems to be overcome can be broadly divided into three
categories:

scaling, the formation of dense adherent deposits on the metal, particularly the
heat exchanger, surfaces causing less efficient cooling,

fouling, due to looser deposits of organic or inorganic origin, causing blockage of


pipes, pumps and filters and creating locally different environments under the
deposits, and

corrosion.

The three phenomena are interrelated and in some circumstances the optimum treatment
is a compromise between prevention of the various problems. For example, the presence
of fouling deposits can make corrosion worse due to differential aeration effects. Also,
the prevention of scale formation tends to increase corrosion rates, since the scales can
restrict oxygen access to the metal surface.

The relative importance of the various factors depends on the operating conditions of the
system, and on the composition of the water in the system.

Cooling Systems
These can be divided into the following types.

Once-through systems where the water is drawn in from the water source, flows through
the heat-exchanger and is then discarded to waste.

Open recirculating systems where after passage through the heat-exchanger the water is
cooled by passage down a cooling tower and then recirculated to the heat-exchanger.

Closed recirculating systems where the cooling water is cooled by passage through a
radiator before recirculation.

Open recirculating systems are commonly used for large installations, such as in power
generation, and when there is a limited supply of suitable water. These rely on
evaporation, via cooling towers, and so the circulating water becomes concentrated. To
prevent the build up of scale forming salts a portion of the water is discharged to waste
(blowdown) and the water topped up with fresh make-up water. Once-through systems
are also used in power generation especially for plants situated on coasts or the shores of
lakes. These require a plentiful supply of cooling water and since the water only passes
through the heat-exchanger once the cost of any treatment chemicals must be low.
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Against this, the capital cost of cooling towers is avoided. Closed recirculating systems
discharge heat to the atmosphere via a heat exchanger and evaporation of the water is
prevented, as is discharge of treatment chemicals to the environment.

Problems in Cooling Systems


Scaling
Due to the depositon of scales such as calcium carbonate. The main effect of scaling is a
reduction in heat transfer, although scaling of surfaces other than in heat exchangers can
reduce their corrosion rate.
Fouling
The origins of fouling deposits can be either inorganic or microbial. Inorganic deposits
can arise from:

sediments carried into the system with the make up water, such as silt,

reactions between the water and chemical additives, or

insoluble corrosion products

The range of organic fouling material includes slimes formed by bacteria, growths of iron
bacteria and massive algal growths.
Corrosion
Cooling systems are mostly aerated, although small areas may be anaerobic, and operate
at near neutral pH. As such the corrosion rate is largely influenced by the rate of oxygen
transport to the metal surfaces, and inhibitor treatments are based upon this corrosion
mechanism. The corrosion that occurs in locally anaerobic conditions is treated by
attempting to prevent such environments existing.

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