Technology update combating corrosion

Sandy Morrison, Member of SpecialChem Technical Expert Team

Introduction

Corrosion - that is to say, deterioration of metals rather than wood or plastics under exposure to
adverse environmental conditions - costs billions of dollars in terms of repairs, reducing the life
expectancy of constructions and occasionally resulting in serious accidents due to structural
failure. Surface coatings are not the only means by which corrosion can be prevented, but they
are certainly the most important, often the most cost-effective and sometimes the only
appropriate method.

Corrosion problems are normally associated with exterior exposure (and it is therefore necessary
to ensure coating systems will resist other environmental pressures such as wind and sunlight)
but extremely aggressive interior environments can also be found in industrial situations. A prime
example of this is a paper machine, on which different metal parts are exposed to various
combinations of water spray and splashes, high humidity, condensation, high temperatures and
attack by corrosive materials given off by the paper.

Waterbornes hold a relatively low share of the total market for anticorrosive coatings but there is
no doubt about their continuing progress. After some unpromising early experiments, they have
now advanced to the point at which they equal or even exceed the anticorrosive performance of
established solventborne systems and frequently offer faster drying.

By 2003, Airbus, one of the world's largest aircraft manufacturers, had converted all the coating
lines at its St Nazaire (France) factory to waterborne systems. Waterborne aerospace coatings
are also extensively used by other major manufacturers such as Boeing and Bombardier and
even by some military organisations.

It is difficult to put a figure on the value of this sector of the coatings market, since the use of the
coatings overlaps with other functions and definitions. As one rather incomplete measure, it can
be noted that corrosion inhibitors account for more than 10% of the $700 million US paint
additives market - and that figure does not include materials classed purely as pigments rather
than additives.

The causes of corrosion

What causes corrosion? Both moisture and oxygen must be present for it to occur. Thus, aircraft
which are to be taken out of service for extended periods may be stored in desert areas, where
the blazing sun and wide temperature variations are unkind to paintwork, but the low humidity
minimises corrosion. Even in other climates, it is sometimes possible to prevent corrosion in
enclosed spaces without painting, by controlling the atmosphere in the enclosed volume. These,
however, are hardly the service conditions encountered in common practice.

Corrosion arises from localised differences in the surface composition or structure of a metal.
These are sufficient to form minute electrical cells on the surface which, in the presence of
moisture, lead to localised current flows. Iron (for example) becomes ionised at the anode points,
and in the presence of water and oxygen (but not of water alone) is converted to hydrated iron
oxide, commonly known as rust. The presence of soluble salts does not cause this process, but
greatly increases the conductivity of water, and so speeds up corrosion.

Aluminium and some other metals are much more resistant to corrosion than iron and steel,
because the oxides formed in the initial stages of corrosion are insoluble in water and remain
tightly bound to the surface of the metal. This forms an ideal protective coating; but under
adverse conditions, particularly in the presence of salt, the oxide film breaks down and aluminium
corrodes rapidly.

Protective mechanisms

Coating steel with a firmly adhered material such as zinc which is more anodic than iron prevents
the corrosion process from occurring. While zinc inherently degrades less rapidly than steel,
painting retards the atmospheric attack on zinc so much that the durability of painted galvanised
steel exceeds the combined lifetimes of painted bare steel and unpainted galvanising by a factor
of 1.5 or more.

In some situations, galvanic protection may be employed by attaching blocks of zinc or other
metal at points (rather than in a continuous layer) to the steel and continuously passing an
electric current through the assembly, so that corrosion occurs only from the protective anode.
However, using this system to enhance the performance of a surface coating places the coating
itself under stress at thin points. Hydroxyl ions, moisture and hydrogen gas accumulate at
cathodic areas, creating both localised alkaline conditions and the potential for blistering.

While coatings which operate by a pure barrier effect will retard corrosion, it has been noted that,
to establish the effectiveness of the coating as a barrier in general terms (ie, assuming it is
bonded effectively to the surface) one should measure not simply its permeability to water and
oxygen but also to ions in solution (whose presence can be detected by a reduction in the
impedance of the coating). In addition, tests for potential leaching of components in the presence
of moisture, water uptake by the coating and DC current resistance through the thickness of the
coating are relevant measures of performance.1

The use of accelerated corrosion testing is (as with accelerated weathering) essential but not
entirely satisfactory. Many pigments owe their protective effects to their ability to undergo
reactions in the presence of corrosive salts. Accelerated saltspray tests will give favourable
results from pigments which react rapidly (and may therefore have a short working life) but may
give unrealistically poor results from coatings containing pigments such as zinc phosphate which
respond relatively slowly and are 'overwhelmed' by the test conditions but work effectively under
normal exposure conditions.

Resin systems

A wide range of binders is used in anticorrosive paints, and indeed it may be assumed that any
binder which is relatively inert and durable has applications in this area. A number of commonly
used binders are listed in the table below purely as examples, but this is far from being a
'complete' listing.

Waterborne,
Binder type Curing agents solventborne or 100%
solids
Acrylic copolymer Often physical drying only WB, SB
Water evaporation /reaction
Alkali silicate WB
with zinc
 Alkyd Metal soaps Normally SB
Chlorinated rubber Physical drying SB
Epoxy ester As alkyds SB
Ethyl silicate Reaction with zinc SB
Moisture cured PU Ambient moisture SB
Polysiloxane Self-crosslinking SB
Polyurea Isocyanate SB or 100%
Isocyanate, polyamide,
Two-pack epoxy WB, SB, 100%
ketimine or polyamine cure
Two-pack
Isocyanate SB or 100%
polyurethane

Table 1 : Examples of binders used in anticorrosive coatings

Understanding the nature of the coating can be critical to achieving good performance. Too high
a film build may cause solvent blistering or cure problems (and 'too high' can vary from 10-12 µm
for PVB etch primers to 500 µm or more for high-build epoxies). Additionally, while high humidity
can retard drying or cause coating failures in waterborne systems, systems such as single-pack
urethanes and ketimine-cured epoxies positively demand sufficient water in the air to achieve
curing.

Online coating systems

The majority of anticorrosive coating systems must be applied in situ - necessarily, since most of
the ships, aircraft and structures to be protected have design lifetimes far in excess of the life of
even the best factory-applied coatings. Nevertheless, this is an important market sector.

About 70-80% of coil-coated metal is used in structural applications as wall or roof cladding,
caravan or truck bodywork, in all of which high durability and corrosion protection are essential.

In automotive manufacture, cationic electrodeposition systems are essentially the standard form
of corrosion protection for vehicle bodies. Autodeposition coatings, which require no applied
current, are simpler to use and are widely applied in the production of automotive component
parts. Their principal limitation is that they must be applied to bare steel, since bonding is
achieved by a reaction with the substrate, whereas electrodeposition coatings are applied to steel
pretreated by conversion coatings or galvanising.

The latest range of autodeposition coatings have a very high level of saltspray and chipping
resistance, and can be used without overcoating where appearance is not critical. Both systems
are waterborne, using low levels of solvent, and current systems avoid the use of lead or
chromate pigments.
Radiation curing coatings have been evaluated by several researchers for anticorrosive
applications. In general terms, it may be said that, properly formulated, both liquid and powder
UV-curable coating systems offer good corrosion protection and resistance to weathering - but
there can be problems with limited flexibility leading to loss of adhesion.

Protective pigments

Zinc-rich coatings

Zinc-rich coatings incorporating very high levels of metallic zinc can under favourable
circumstances provide a maintenance-free coating lifetime of up to 25 years, comparable to or
exceeding the performance of galvanising. Indeed, one pipeline in Australia still has its original
coating, applied more than 50 years ago, in good condition with only localised repair work.

This kind of performance can only be achieved by using low levels of binder, yet establishing
maximum adhesion to the substrate. Inorganic paints using alkali-metal silicates (waterborne) or
ethyl silicate (solventborne) binders can perform extremely well in marine atmospheres, and have
no rivals where single-coat systems are required and aesthetics are unimportant, but the initial
drying conditions may be critical to achieving good performance and the highly alkaline system is
liable to cause problems when overcoating.
solution to form a hard coating and reactions with iron also occur, improving the bonding of the
coating to the substrate.

Organic zinc-rich coatings are preferred where the system is to be overcoated. Chlorinated
rubbers, polystyrene, moisture-curing urethanes and alkyds have all been used as binders, but
the most commonly used systems today are based on epoxy resins.

Barrier pigments

Many pigments operate mainly by offering "passive protection", enhancing the barrier effect of the
coating. Mica, aluminium, glass flake and micaceous iron oxide (MIO) are all widely used. Their
effectiveness depends on the fact that they have a lamellar, flake form and will normally align
themselves more or less parallel to the surface of the coating. This reduces water and ionic
permeability by forcing ions or water molecules to take an indirect path from surface to substrate
(see figure). Talc, usually classed as an "extender" rather than a primary pigment, is also
commonly found in anticorrosive paints, because it is both highly inert and has a lamellar form.

Figure 1: Lamellar extender (Top) showing barrier effect reducing

moisture penetration, with near spherical particles (below) for comparison.

MIO is a highly effective anticorrosive pigment which has been used in coatings for more than
100 years. In volume terms, MIO accounts for only 1% of the world's demand for iron oxides -
about 15 000 tonnes per year - but prices for the lamellar grades which give the best performance
are relatively high for a natural pigment, at around $300 per tonne. There is currently a trend to
blend this material with non-lamellar MIO which can be readily obtained for a tenth of the price.

Although micronised grades have been introduced to allow the material to be used in thinner
coatings, demand is relatively static, due to competition from glass flake in high-build coatings,
the introduction of more effective lower-build coatings based on more advanced binders, and a
trend towards the construction of bridges in concrete rather than steel.

Of the other common barrier pigments, mica is almost totally inert chemically and is resistant to
high temperatures. Aluminium flake is sensitive to moisture and alkaline conditions. Stainless
steel flake finds some applications, but is relatively expensive. Glass flake is popular in high-build
coatings for heavy-duty applications.
Primary grinding by the manufacturer of lamellar pigment is usually aimed at producing the
thinnest flakes possible, but subsequent grinding during paint manufacture may break down the
platelets, and then as the particle size is reduced, the effectiveness decreases as the 'labyrinth'
effect is reduced.

The bonding between pigment particles and resin is critical to achieving an effective barrier. It will
be affected by surface treatment and the choice of dispersing surfactant - and not necessarily in
ways that might be expected. Improving the bond creates an impermeable layer around the
particles and so effectively enlarges the volume occupied by the filler. While this reduces the
permeability of the coating, it is also liable to increase internal stresses and in that way reduce
adhesion to the substrate, increasing the risk of coating failure.

Active protection pigments

Various forms of lead and chromate pigments have traditionally been used to provide effective
corrosion protection, but current legislation greatly restricts their use. With their departure, zinc
phosphate has established a strong position as an active pigment in anticorrosive primers. It is
considered to have three protective mechanisms:

• formation of a protective anodic film;

• phosphate ion donation to the substrate;
• formation of anticorrosive complexes with certain binders.

While zinc phosphate has proved effective in real-world situations, as already noted, it is often
found to perform poorly in accelerated humidity or saltspray tests. It appears that the material is
not able to leach and react rapidly enough to respond to such severe environments, but under
practical conditions its response to corrosive attack is perfectly adequate. Thus, when suppliers of
proprietary modified zinc phosphate pigments claim superior performance for their products, one
must ask whether the results obtained in accelerated tests will be reflected in improved
performance in practice!
Zinc phosphate modifications include, for example, aluminium zinc phosphate, zinc molybdate
phosphate and zinc silicophosphate hydrate.

Some of the difficulties that can occur in evaluating active pigments are illustrated by tests on zinc
polyphosphate. This was prepared by reaction between sodium tripolyphosphate and zinc nitrate.
The resulting pigment (which incorporated a small amount of residual sodium) was found to
perform effectively at low additions in alkyd paints, but less effectively in epoxy paints. It is
suggested that there may be, on the one hand, synergistic reactions between the zinc and alkyd
resins, and on the other, a degree of incompatibility between the pigment and the epoxy resin
system.2

Again, zinc oxide can be added in small quantities along with other actives, but must be used with
care as it has the effect of increasing the crosslink density of alkyd and other binders, increasing
their hardness but also making the system more brittle. An additional protective effect in topcoats
results from its UV absorption properties.

Calcium-exchanged silica represents a different approach to corrosion protection. This type of

pigment has a small particle size, low density and contains about 6% calcium by weight. It is
manufactured by an ion-exchange reaction on silica gel particles. Its protective action is believed
to be an ion-exchange process, in which corrosive salts penetrating the coating are immobilised
on the silica substrate while both calcium and silica ions are released and migrate towards the
substrate, (though this mechanism has been disputed). The pigment has the unusual property of
releasing its inhibiting components only in response to corrosive attack, thus minimising losses by
leaching, and appears to be at least as effective as zinc phosphate.

Because of its low density and high active surface area, it is generally considered that the amount
required in a formulation corresponds to the volume, rather than the weight, of zinc pigment
replaced. It appears to combine well with other types of protective pigments, but it should be
noted that it is highly alkaline, and therefore problems may occur with acid-bearing binder
systems.

While most corrosion inhibitors are solids, a number of liquid materials may be combined with
them. Many are amine salts of some form, others are organic acids, and consideration therefore
has to be given to potential reactions with the binder system or pigments.
Permutations and combinations

A number of elements and compounds may be considered to exert some protective effect against
corrosion, and this has led to the evolution of a wide range of pigments which turn out, on
examination, to feature the same relatively small range of protective materials in different
combinations. Some further examples (necessarily incomplete) may be briefly mentioned:

• Molybdates are effective but expensive, and so usually found in the form of compounds
that incorporate other anticorrosive elements such as zinc molybdate, calcium zinc
molybdate and zinc molybdate phosphate.
• Aluminium tripolyphosphate (also available in forms modified with zinc ions or silicate) -
the tripolyphosphate ion is able to chelate iron ions, in addition to the protective effect of
the phosphate itself.
• Silicates may be found in the form of combinations such as calcium borosilicate, calcium
barium phosphosilicate, calcium strontium zinc phosphosilicate, strontium
phosphosilicate, barium phosphosilicate.
• An oxyaminophosphate salt of magnesium is offered commercially, though it is
recommended only for use in solvent-borne primers. With a relatively low specific gravity
of 2.2, it can be used at a lower weight addition than zinc-based pigments.3

Conductive polymers

Inherently conductive polymers, of which the most widely known is polyaniline, are a truly modern
development, and among their many applications they have been found to have a dual
anticorrosive effect:

• a catalytic reaction with steel produces a thin, dense layer of Fe2O3 oxide, which has a
barrier effect similar to that of the Al2O3 layer that forms naturally on aluminium;
• a cathodic protection mechanism which is similar to that offered by zinc.

Thus, the polyaniline must be in direct contact with the metallic substrate in order to be effective.
It has been shown to work well as a thin film pretreatment under other anticorrosive paints, and
has been commercialised in the form of primers which are claimed to outperform zinc-rich primers
when overcoated with epoxies, being able to protect the surface even when coating damage
extends to a 2mm wide scratch.4
It has been further claimed in a patent that this level of protection can be enhanced by
incorporating sacrificial anodic metal or metal alloy particles along with inherently conductive
polymers such as polyaniline. In this way both barrier and anodic protection systems are applied
in a single coating.5

Beauty is only skin deep

Much of the effort (and pigment) that is put into an anticorrosive paint essentially has the function
of trying to maximise protection of damaged areas of the coating, and in that sense, much of it is
not required. Then, too, in any protective reaction between pigment and corrosive salts it is the
surface of the pigment rather than the entire particle which is involved. Core-shell materials with
an inert core have been shown to be an effective way of reducing the quantity of biocide needed
to provide protection in antifouling paints. Is it then possible to develop coatings which will have
an extended lifetime and make more efficient use of anticorrosive pigments which are often
expensive? A number of approaches are under investigation.

For example, one commercially available composite pigment comprises 80% ferric oxide with a
surface coating of zinc phosphate. It is recommended as a zinc phosphate replacement for
anticorrosive primers and fillers.6

A dual-purpose opacifying and anticorrosion pigment has been produced by coating titanium
dioxide first with an anticorrosive layer then with an organic treatment to improve dispersibility. It
is claimed that the composite pigment not only provides excellent protection in (for example) coil
coating primers but in artificial weathering tests, gave better gloss retention and less chalking
than standard titanium dioxide.7

One evident problem with two-phase materials such as these is that excessive grinding will
destroy their effectiveness.

Physician, heal thyself

The inspiration for some novel systems has been derived from work on 'self-healing' plastic
composites. It is well-established that plastics (and coatings) can be toughened by incorporating
discrete particles of material that is more flexible than the base resin. If correctly bound, these
have the effect of absorbing and diffusing localised stresses. In the first development of self-
healing systems, urea formaldehyde microcapsules and fine catalyst particles were incorporated
into a thermoset system. When a crack started to form, rupture of the microcapsules released
liquid dicyclopentadiene which was then polymerised by the catalyst and filled the crack. The
material was shown to be able to regain up to 75% of its original toughness, even after the
formation of a major crack.8

This principle has been shown to work in coatings, but there are some practical difficulties, in that
microcapsules which are brittle enough to rupture when the coating is damaged are also liable to
fracture during spraying (the most common method of applying anticorrosive coatings). They may
also reduce the adhesion of a primer to the substrate. Even so, microcapsules containing
anticorrosive liquids and/or oxidative binders have been shown to improve the corrosion
resistance of epoxy coatings9 . At least one patent claims the use of microcapsules which release
their liquid contents when an area of coating is damaged.10 The contents may be formulated to
strengthen the coating, increase the level of anticorrosives present or have other functions such
as making the existence of minor damage more obvious.
Paints that cry out for help

Looking further ahead, paints that change their appearance in areas where corrosion has
commenced have been studied as a possible means of detecting early coating failure. One type
is based on the inclusion of a pH indicator which changes its appearance when corrosion causes
a localised increase in acidity or alkalinity. Common laboratory indicator dyes were used in initial
research, but it is thought that practical systems are more likely to incorporate compounds whose
fluorescence is affected by pH.

Engineers at Ohio State University, USA, are developing a paint which not only controls corrosion
but can indicate when repainting is required. The pigment in the new paint contains tiny particles
of clay that capture the chemicals causing corrosion. It then releases just the appropriate amount
of a cerium-based anticorrosive when it is needed. Rudolph Buchheit, professor of materials
science and engineering has described the paint as working 'kind of like high-tech kitty litter'.

The pigment absorbs chloride and releases cerium (and potentially other corrosion inhibitors) to
form a protective film over cracks in the paint. In accelerated tests, it has given protection similar
to that offered by chromate-containing coatings. X-ray diffraction can then be used to measure
how much cerium has been released and how much is left in the paint - an indicator of whether a
piece of metal would need to be repainted.11

Both of these developments are, some years from practical implementation, but their potential
benefits in terms of reducing the cost of repainting and the risk of coating failure are obvious.

References

1.D J Mills, Surf Coat Intl A, 2004/A08 pp 352-358

2.M Deyá et al, Surf Coat Intl B, 2003/B1 pp 79-85
3.Pigmentan E data sheet
4.B Wessling, Chemistry in Britain, March 2001 pp 40-42
5.USP 5 976 419
6.Jacor Fe-1 data sheet
7.T Rentschler, A Claßen, Europ Coat Jnl 9/2002 pp22, 24-27
8.Nature, 2001 19 pp 794-797
9.A Kumar, L D Stephenson, Coatings World, June 2004 pp 24-26, 28-33
10.EP 1 153 988
11.Paint Insider, 24 Aug 2004