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The role of tank coatings in cargo contamination

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INSIGHT 152, 1998
01 DEC 1998

By David R. Jones, Oil & Chemical Dept., CWA Consultants Ltd, London

The modern trend towards locating refineries and integrated petrochemical complexes near
to the sites of crude oil and gas production has led increasingly to the shipment of ‘value
added’ refined petroleum products and petrochemicals on board ocean carriers. Formerly,
Tank
the crude oil itself would have been carried in uncoated or part coated VLCCs for refining at
coatings
destination. Now, however, tanker shipowners are under increasing pressure to carry an
in
even greater variety of cargoes at purity levels driven ever higher by competitive receivers
excellent
with exacting quality expectations.
condition.
It is true to say that many chemical tanker owners have invested heavily in costly ships with either all or
a high percentage of cargo tanks fabricated from stainless steel. In general, stainless steel is
considered to be the ideal material of construction, being non-corrosive and easy to clean. However,
not all cargoes can be carried in stainless steel tanks. Many vessels employed in the chemical and
petroleum product trade have cargo tanks fabricated from mild steel coated with a paint system which
serves to prevent corrosion of the steel and to protect the cargo from contamination by contact with
the steel. Cargo tank coatings systems can be broadly categorised into two main groups:

(1) Inorganic coatings – zinc silicates and ethyl zinc silicate types;

(2) Organic coatings – Epoxy and modified Epoxy systems.

Over the years inorganic zinc-rich coatings have proved themselves to be durable tanklinings in a
variety of service applications. The paint itself consists of a single layer, typically of 100 micron
thickness, comprising of inorganic silicates (or ethyl silicate) pigmented with a high percentage of
elemental zinc powder. Usually the elemental zinc content is greater than 90 per cent of the paint film
by weight. Complex curing reactions bind the zinc particles in an inorganic silicate matrix which
chemically adheres the coating to the steel substrate. The result is a paint system with outstanding
mechanical strength.

The paint film is porous in nature, in that the cargo can physically penetrate into the interstices formed
between the zinc particles and the complex silicate matrix binder. The porosity of these paint systems
has two consequences. On the good side, very volatile solvent-like cargoes are able to be rapidly and
virtually completely removed from the coating by evaporation/ventilation upon completion of
discharge. Thus the potential risk of contamination of the subsequent cargo is virtually non-existent as
no residues remain behind within the coating. On the other hand, the same cannot be said for heavier
oil-like (residual) cargoes (e.g., lube oils), which cannot be removed by evaporation/ventilation. The
presence of these substances within the pores of the coating presents the vessel’s crew with a tank
cleaning problem and the risk of contamination of the next cargo is considerably increased especially if
the next cargo is a ‘good’ solvent (e.g., motor gasoline or benzene, etc.).

In general the life expectancy of these coatings is proportional to their thickness. This is because
corrosion protection is afforded to the steel substrate by virtue of a sacrificial cathodic mechanism
whereby the zinc content of the coating ultimately becomes depleted.

A major disadvantage of inorganic zinc coatings of this type is their inability to resist cargoes in
anything other than a narrow ‘neutral’ range of acidity/alkalinity. Thus strong acids and alkalies,
vegetable oils and solvents prone to hydrolysis (reaction with water to produce acids) cannot be
carried in cargo tanks lined with this type of paint. For many shipowners this places an unacceptable
restraint on their trading activities and for this reason they elect to have some or all of the cargo tanks
of their vessel coated with organic paint systems.

Organic epoxy paint coatings comprise of a ‘family’ of products each having slightly different
properties. It is not the intention of this article to discuss in detail each epoxy type. Suffice it to say that
epoxy paints consist of an organic resin system which, when mixed with a hardener, forms a coating
film that produces a three-dimensional cross-linked array of chemical bonds between the resin
molecules. When fully cured, this film offers corrosion protection to the steel substrate by virtue of
forming a barrier between the cargo and the steel.

The differing epoxy types, e.g., pure epoxy, phenolic epoxy, isocyanate epoxy, etc., form cross-linkages
to different degrees resulting in increased resistance to a greater range of cargoes as the extent of
cross-linking increases.

Typically, organic coatings are applied in several layers (three coats each of approximately 100 micron
thickness), to a steel substrate pre-prepared to a high standard (Sa2½) using blasting techniques.
Temperature and humidity control of cargo tank atmospheres are usually necessary during application
of the coating as is attention to post-cure conditions.

In contrast to inorganic zinc paints, epoxy systems are resistant to strong acids and alkalies and do not,
in general, absorb significant quantities of oil-like (residual) substances. Such substances merely stay
on the surface of the paint where they can be removed by conventional cleaning methods. Organic
coatings do, however, absorb significant quantities of solvent-like cargoes into the paint film and
subsequently desorb (release) these solvent residues following discharge of the cargo. It is this
property of absorption and desorption of cargo residues to and from organic coatings that has
resulted in numerous cargo contamination incidents.

It has been known for many years that organic coatings absorb and desorb cargoes and the
mathematics of this behaviour has been described in the scientific literature1. Generally, absorption of
a substance into a paint film proceeds at an initially rapid (linear) rate and then falls to zero when the
paint film becomes saturated. In an analogous way, desorption is initially rapid and eventually ‘tails-off’
to a level that does not necessarily represent a situation where all of the absorbed substance is
removed from the paint film but a state, nonetheless, where no more is desorbed. This is shown
diagramatically in figure 1 below.

Figure 1

It can be seen that in the above example the quantity of absorbed cargo rapidly reaches a maximum
within three days but thereafter stays approximately at that level for the duration of the laden passage.
Following discharge (day 14) desorption occurs at a rapid rate until after four days there is no
significant further loss of the retained species.

It is emphasised that different epoxy types (i.e., pure, phenolic epoxy, etc.) absorb and desorb to
differing extents (see figure 2 on the following page), and indeed considerable variation is known to
exist between similar generic types of epoxy paint produced by the various paint manufacturers.

1 Fujita H, Adv. Polym. Sci, 3, 1 (1961).

In general it can be said that cargoes having small molecular structures are able to penetrate organic
coatings to a greater extent than those cargoes with larger molecules, thus methanol is known to be a
very penetrative cargo and is widely acknowledged within the industry as being one of the most
‘aggressive’ cargoes that can be carried in organic coated tanks. Absorption/desorption characteristics
for each cargo will differ.

Figure 2

Figure 3

A typical example is provided in figure 3 above. It is re-emphasised that the absorption/desorption

characteristics of each manufacturer’s product also differs markedly in extent. This phenomenon has
been described in greater detail in a recently published technical paper2 and the reader is directed to
this publication and to the individual manufacturer of tank coatings to obtain the specific absorption
characteristics for any given cargo in the paint system of interest. The diagrams provided in this article
are notional only to illustrate the underlying principles and are not meant for reference.

The rate of absorption and desorption is critically influenced not only by the thickness of the paint film
but also by temperature. Absorption and desorption rates are increased as temperature is raised. Thus
it is in owners’ interests to carry cargo at the lowest practical temperature (to lessen absorption) and to
increase the air/steel temperature of their cargo tanks following completion of discharge of any cargo
in order to maximise the rate of desorption. It is also known that water greatly influences the rate of
absorption/desorption, some paint systems having a considerably lower rate of sorption when
saturated with water. This effect has a direct bearing on the type of tank cleaning which should be
carried out after discharge.

It can be appreciated that certain cargoes cannot be entirely eradicated from some paint systems in a
reasonable time between discharge of one cargo and the lifting of the next. These retained residues
subsequently contaminate the next cargo by the mechanism of continued desorption and can
sometimes be found to contaminate second, third and even later subsequent cargoes. This is
especially true for highly odiforous cargoes such as acrylates and styrene monomer where even sub-
ppm contaminations can, in the first instance, be readily detected by simple odour evaluation tests. In a
recent incident, styrene monomer has been shown to be the contaminant in a vegetable oil cargo
despite being the third last cargo. Whilst the concentration of styrene monomer was not great (0.3 – 0.9
ppm wt) modern instrumental analytical techniques are more than capable of detecting such trace
concentrations and such detection is sufficient to give rise to a claim. Vegetable oil cargoes are
especially susceptible to contamination due to the fact that they are often carried at elevated
temperatures (+35°C) which considerably increase the rate of desorbing contaminant.

2 Parry T, The Absorption/Desorption Characteristics of Organic Tanklining Systems. Proc PCE 98, 1st to
3rd April 1998, pp 251 - 261.

Faced with a conflicting interest between trading economics and the possibility of contamination of the
cargo, what can a prudent owner do to reduce the risk of contamination incidents?

– Coating choice is crucial. The absorption/desorption characteristics of the paint systems currently
available to owners differ significantly. Some paints (the best) absorb lesser quantities of cargo than
similarly specified products from rival paint companies and desorb more completely. Selection of such
coating systems significantly reduces the risk of contamination. In future, paint manufacturers will
formulate coatings that will outperform even the best of those available today.

– Allow coatings to desorb for as long as possible. The rate of desorption is greatly increased by raising
the temperature of the coating within the tank. It is not necessary to continuously ventilate the tank, this
has been shown to be ineffective3.

– Avoid the stowage of ‘sensitive’ cargoes such as refined foodstuffs, potable ethanol, methanol,
ethylene glycol, isopropanol, etc., in tanks where ‘incompatible’ cargoes have been stowed as first,
second and, if possible, third/fourth last.

If unfavourable stowage is unavoidable, charterers should be fully advised of the contamination

potential and an indemnity sought.

3 Sorensen O.B, "The Factors Influencing Ventilation and Drying of Epoxy Coated Cargo Tanks" Proc.
Marichem 89, Session 8, Paper 8.7.

Gard News is published quarterly by Assuranceforeningen Gard, Arendal Norway.

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