Understanding Corrosion Inhibitive Pigments

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Understanding Corrosion Inhibitive Pigments

July 3, 2014 by Ron Lewarchik

The annual cost of steel corrosion is estimated to be over $400 billion in the United States and $2
trillion globally. Corrosion is a process where the metal can be degraded by electrochemical
and/or chemical processes. This article will discuss the use of lead- and chrome-free corrosion
inhibitive pigments in coatings where corrosion is primarily from electrochemical processes.
Accordingly, the correct use of corrosion inhibitive pigments can be of enormous economic value.
Metals desire to be in their most thermodynamically stable state, which, in simplified terms, is the
naturally occurring state of matter in its lowest energy state. Metals ordinarily exist naturally as
oxides (e.g. iron oxide, aluminum oxide, zinc oxide, because oxides represent their lowest energy
state. Corrosion is an electrochemical deterioration of a metal due to the reaction with its
environment to transform the metal into its lowest energy state. Oxidation occurs at the anode
(positive electrode) and reduction occurs at the cathode (negative electrode). Corrosion is
normally accelerated by the presence of water, oxygen and salts (particularly of strong acids).
For example in the case of steel:

Corrosion inhibitive pigments can deter

corrosion by multiple mechanisms. However,
all of these mechanisms have the ability to
disrupt the electrochemical corrosion reaction
in common.

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Understanding Corrosion Inhibitive Pigments

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Cathodic inhibition inhibits corrosion by impeding the flow of electrons at the cathode, whereas
anodic inhibition inhibits corrosion by impeding the flow of electrons at the anode. The following is
the standard MF series of metals with the more inert or cathodic metals toward the top and the
more anodic or active metals toward the bottom:

Accordingly, in the above MF series, n is more active than Fe.

hen a zinc rich primer is

applied over steel, zinc will oxidize preferentially to steel and thus prevent the underlying steel
from oxidizing. In this scenario, n is anodic (more readily oxidized) to steel and therefore protects
steel from oxidation. Thus, steel is protected from corrosion by cathodic inhibition, as well as by
the barrier that the zinc-rich primer provides.

hen choosing a corrosion inhibitive pigment,

several factors must be considered.

nvironmental factors that influence the rate of corrosion include moisture, pH of the moisture,
wet and dry cycles, soluble salts, temperature and time.
For example, moisture, soluble salts, higher temperatures and longer exposure times all normally
exacerbate corrosion in coated metal films.

ith these issues in mind, the evaluation criteria and

test methods must be carefully contemplated before selecting corrosion inhibitive pigments.
The comparative corrosion resistance of coatings will vary dramatically depending on the test
environment: atural exposure and exposure conditions, salt spray (

humidity/

salt and

always moist), acidic salt spray, prohesion cyclic corrosion (wet and dry cycle with 0.04
ammonium sulfate and 0.0

salt, electrochemical impedance spectroscopy, salt soak or other.

Most experts agree that accelerated tests are not always a good indication of how the coated
metal will perform in the real world.

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Additional considerations are the metal type (e.g. steel, aluminum, galvanized), pretreatment and
cleanliness of the surface. If the metal surface is not properly cleaned and prepared, the coating
will lack ade uate adhesion and premature failure will result.
Furthermore, the type of coating in which the pigments will be used affects the selection of
appropriate corrosion inhibitive pigments. Considerations include whether the coating is
solventborne, waterborne, powder, air dry or baked, and if the film will be cross-linked or
thermoplastic. ou should also consider the coating s resin type and pigment volume
concentration.
Corrosion inhibitive or passivating pigments promote the formation of a barrier layer over anodic
areas, thus passivating the surface. To be effective, these pigments have a minimum solubility. If
the solubility is too high, the pigment will leach out of the coating too rapidly- reducing the time
that the pigment is available to inhibit corrosion. If the coating film is more open (e.g. air dry latex),
water permeation is higher and thus the corrosion inhibitive pigment will be depleted more rapidly.
To function properly, the coating must permit the diffusion of some water to dissolve the pigment.
Accordingly, blister formation may result under humid conditions as the pigment dissolves. Higher
Tg (glass transition temperature) and higher crosslink density binders are known to improve blister
resistance.
Another prime consideration in the selection of a corrosion inhibitive pigment is the pH ( U). For
example, a pigment with a high pH may have a deleterious effect on the cure of acid catalyzed
systems. Conversely, a pigment with a low pH may adversely affect the stability of waterborne
systems.
The vast ma ority of corrosion inhibitive pigments are comprised of the combination of metal ions
(cations) derived from: zinc, strontium, chromium, lead, molybdenum, aluminum, calcium or
barium and anions, such as those derived from phosphorous (orthophosphoric and
polyphosphoric acids), chromic acid and boric acid. Although chromate and lead, containing
passivating pigments, are very effective in inhibiting corrosion, their use is very limited due to a
variety of environmental and toxicological regulations.
Suppliers of Corrosion Inhibitive Pigments Include:
uckman
race
Halox ( U)
Heubach ( U)

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ichent
ubiola ( U)
S C ( U)
The views, opinions and technical analyses presented here are those of the author, and are not
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Filed Under: Paint

Coatings

About Ron Lewarchik

Ronald J. Lewarchik brings 40 years of paint and coatings industry
expertise to his role as a contributing author with the Prospector
nowledge Center. As a contributing writer, Ron pens articles on
topics relevant to formulators in the coatings industry. He also
serves as a consultant for the Prospector materials search engine,
advising on issues related to optimization and organization materials within the database.
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