Absorption/Desorption
Characteristics of
Organic Tank
Lining Systems
By Trevor Parry
Scientific & Technical Services Ltd., Blaydon, UK
a fter more than 25
years of investigating coating fail-
ures in cargo tanks of chemical
tankers, it is clear that in many in-
stances the coatings failed even
though the ship’s operators strictly
followed the coating manufactur-
er’s guidelines for cargo compati-
bility.
The simple tests involving static
immersion of coated panels in car-
goes and visual examination of the
panels have limited value. There-
fore, a test programme was devel-
oped to compare the results of sim-
ple static immersion tests in single
cargoes with those of cyclic tests
involving repeated periods of im-
mersion and cleaning to simulate
typical voyages involving sequen-
tial cargo carriage.
The test programme evaluated
the coatings’ absorption/desorp-
tion characteristics with a range of
24 PCE December 1998
cargoes, since retention of cargo
within a coating can have a detri-
mental effect on the coating per-
formance and contaminate a sub-
sequent cargo by desorption.
This article deals with results of
the absorption/desorption charac-
teristics of a number of the tank
linings examined.
Absorption/Desorption Potential
Although the fact that organic
coatings absorb and desorb car-
goes is not new, only recently has
information on the subject been
published. Most of the work has
been done by a few researchers,
mainly in the employ of paint
manufacturers and often limited to
their own coating systems. Conse-
quently, many ship owners and
operators are unaware of the po-
tential for cargo retention in tank
linings until they are faced with
Copyright ©1998, Technology Publishing Company
 the problem. This frequently oc-
curs with high purity cargoes and
METHANOL
cargoes designated for the food EDC
chain, particularly those subjected STYRENE
to sophisticated modern techniques VAM
that enable content analysis down
to the level of parts per billion.
Although organic coatings con-
tain a degree of extractable materi-
al from solvents, additives, etc., it
is present in a defined quantity
and poses a limited risk of contam-
ination, since once the material
has been extracted—generally in
the early life of the coating—it is Fig. 1: Isocyanate-cured epoxy
no longer present.
The contamination potential of METHANOL
cargoes absorbed into a coating is EDC

far greater because STYRENE

• large quantities can be retained; VAM

• the amount retained after differ-

ent time periods is not well de-
fined;
• very variable absorption/desorp-
tion characteristics are found be-
tween different coating types and
within the same generic types of
coatings from different manufactur-
ers; and
• different rates of absorption/des- Fig. 2: Amine-cured epoxy

orption are found between differ-

ent cargoes. METHANOL

Factors such as coating thick- EDC

ness, temperature, and tank clean- STYRENE

ing also affect the potential for ab- VAM

sorption and desorption.

Test Programme
Seventeen coating systems of
three generic types—isocyanate-
cured epoxy, amine-cured epoxy,
and phenolic epoxy—were evaluat-
ed in the test programme.
The cargoes involved in the ab-
sorption/desorption work were Fig. 3: Phenolic epoxy

methanol, ethylene dichloride

(EDC), acetone, acrylonitrile
(ACN), caproic acid, methylene
chloride, trichloroethylene, distilled
water, ethyl acetate, ethylene glycol
monomethyl ether, methyl tertiary
butyl ether (MTBE), styrene
monomer, vinyl acetate monomer
(VAM), and gasoline.
The test method used was simi-
lar to one based on ASTM D570,
Standard Test Method for Water
Absorption of Plastics. It involved
immersing coated test panels into
the cargoes and then weighing the
panels to monitor the increase in
weight over a time period. After
constant weight was achieved, the
panels were allowed to naturally
desorb and the weight change was
monitored over another time period.
The following criteria were used.

Copyright ©1998, Technology Publishing Company PCE December 1998 25

 ISOCYANATE EPOXY

PHENOLIC EPOXY

AMINE EPOXY

25 C and 50% relative humidity.

Contributory factors that could
affect the absorption/desorption
rates, including temperature, hu-
midity, and simulated tank clean-
ing, were evaluated.

Results
Due to the very large amounts of
Fig. 4: Variation of coating types to EDC data produced in the study, the fo-
cus of this article is limited to only
four cargoes: methanol, EDC,
ISOCYANATE EPOXY
styrene monomer, and vinyl ac-
PHENOLIC EPOXY

Fig. 5: Variation of coating types to styrene
Fig. 6: Variation of coating types to VAM
• All coatings were applied to steel
panels blast cleaned to Sa 3 (white
metal).
• Coatings were applied to the
manufacturer’s recommended
thickness and cured to the manu-
facturer’s requirements.
AMINE EPOXY
ISOCYANATE EPOXY
PHENOLIC EPOXY
AMINE EPOXY
• Coatings were pre-extracted with
methanol to remove residual mate-
rial that could affect the test results
and then dried to a constant
weight to remove the methanol.
• The results described here are for
desorption into an atmosphere of
etate monomer. The results
demonstrate the variation in ab-
sorption/desorption rates for the
different cargoes; the variation that
occurs between coating types; and
the variation that occurs within the
same generic coating types pro-
duced by different manufacturers.
In Figures 1, 2, and 3, it can be
seen that irrespective of coating
type, EDC is absorbed to a far
greater degree than the other car-
goes and, except for styrene
monomer in amine-cured epoxy
and isocyanate-cured epoxy, the
initial absorption rate is rapid.
The initial desorption of all car-
goes is rapid, but in the case of
styrene monomer, it slows down
over a longer period of time with
generally more cargo being re-
tained in the coating at equilibri-
um, particularly in the case of iso-
cyanate-cured epoxy and phenolic
epoxy types.
With respect to EDC, Figure 4
shows that the isocyanate-cured
epoxy absorbed approximately
twice the amount of cargo as the
other coating types. However, the
release rates were rapid in all cas-
es, with approximately the same
amount of cargo being retained in
the coating at equilibrium.
Figure 5 demonstrates the large

26 PCE December 1998 Copyright ©1998, Technology Publishing Company

 COATING 1

COATING 2

COATING 3

variation among the coatings in

the absorption of styrene
monomer. The isocyanate epoxy
attained an initial equilibrium state
and then showed a further rapid
increase that did not attain equilib-
rium. The test was terminated at
6,000 hours to determine the des-
orption from that point. The initial
desorption initially occurred quick- Fig. 7: Variation within amine epoxies to EDC
ly, but after approximately 3,000
hours, 2.5–8% of styrene monomer COATING 1
remained in the coatings. COATING 2
The absorption characteristics of COATING 3
vinyl acetate monomer are shown
in Figure 6. The isocyanate epoxy
absorbed the greatest amount of
cargo at equilibrium. The initial
absorption and desorption rates
were rapid for all coating types,
but the percentage remaining at
equilibrium varied considerably,
with the isocyanate epoxy, having
absorbed the highest amount, re-
taining the least. Fig. 8: Variation within amine epoxies to styrene
The three amine-cured epoxy
coatings performed similarly with COATING 1
respect to initial absorption and COATING 2

desorption rates of EDC, but they COATING 3

showed a marked difference in the

maximum amounts absorbed and
retained at equilibrium (Fig. 7).
In Figure 8, very large variations
can be seen in the shape of the ab-
sorption/desorption curves for the
three amine-cured epoxies with re-
spect to styrene. The amount ab-
sorbed at equilibrium varied from
approximately 2.5–8.5%, and the
amount retained after desorption Fig. 9: Variation within amine epoxies to VAM

varied from approximately

1–5.5%. In coating 2, the desorp-
tion stage was initially rapid, with
approximately half of the cargo be-
ing desorbed in a short time peri-
od, after which the desorption
slowed dramatically. With coatings
1 and 3, however, the desorption
process was much slower and a
longer time period was required to
reach equilibrium.
Figure 9 shows the different
curves for three amine-cured
epoxy coatings with respect to
vinyl acetate monomer with the
significant difference being the
quantity of cargo absorbed at equi-
librium (8.5–14%) and remaining
after desorption (1.5–6%).
Four phenolic epoxy coatings are
shown in Figure 10 with respect to
EDC. Initial rapid absorption is

Copyright ©1998, Technology Publishing Company PCE December 1998 27

 COATING 10

COATING 11

COATING 12

COATING 13
coatings 11 and 13, which ab-
sorbed the greatest and least
amount of cargo at equilibrium, re-
tained a similar amount when des-
orption was complete.
Figure 11 shows a large variation
in the behaviour of the four pheno-
lic epoxy coatings in styrene
monomer. Coating 13, which ab-
Fig. 10: Variation within phenolic epoxies to EDC sorbed the lowest quantity of car-
go, retained the lowest quantity af-
ter desorption, whereas coating 12,
COATING 10
which absorbed the second highest
COATING 11
amount, retained almost 70% of
COATING 12
the absorbed cargo on completion
COATING 13
of the desorption phase.
Variations in the absorption/des-
orption of the four phenolic epoxy
coatings in vinyl acetate monomer
are shown in Figure 12. Three of
the coatings (10, 11, and 13) re-
tained approximately the same
amount after desorption at approxi-
mately 4% even though the
Fig. 11: Variation within phenolic epoxies to styrene amount absorbed varied consider-
ably, between 6.5 and 13%.
Although the rate of absorption
COATING 10
took different forms, the shape of
COATING 11
the desorption curves was similar.
COATING 12

Fig. 12: Variation within phenolic epoxies to VAM
demonstrated with coatings 10, 11,
and 12, and they also show a rapid
desorption of more than half the
absorbed cargo in a short time peri-
od before the process slows. Coat-
ing 13 has different absorption
characteristics—rapid for a compa-
COATING 13
rably short time period and subse-
quently reaching equilibrium more
slowly and gradually. The desorp-
tion is similarly rapid with approxi-
mately half of the absorbed cargo
being desorbed in a short time peri-
od. It is interesting to note that
Discussion
All the coatings that were exam-
ined absorbed and released the
cargoes to varying degrees and at
varying rates and confirmed in
general terms the previous work
undertaken by other researchers.
Although it is difficult to draw
conclusions from an extract of a
comprehensive test programme, it
can be seen that there was a large
variation in the characteristics of
the coatings of different types and
also a large variation within coat-
ings of the same generic type.
The amounts of cargoes ab-
sorbed at equilibrium varied con-
siderably, and major differences

28 PCE December 1998 Copyright ©1998, Technology Publishing Company

 were observed between the in-
dividual cargoes and the coat-
ings themselves.
The desorption phase was
initially rapid with most com-
binations of cargoes and coat-
ings, but it did not proceed to
zero in all but a few instances,
hence leaving residual cargo
within the coating system.
It must be noted that desorp-
tion into an atmosphere of 20 C
and 50% relative humidity can
provide a competing mecha-
nism whereby water vapour
from the atmosphere can ab-
sorb into the coating system. In
none of the illustrated results
was a weight gain found dur-
ing the desorption phase, and
analysis of paint flakes con-
firmed the presence of the cargo as
the major absorbed constituent.
The variable response to absorp-
tion and desorption of cargoes
within coatings of the same generic
type places the purchaser in a diffi-
cult position.
Take, for example, phenolic epoxy
materials where the purchaser must
choose based on published data,
and the principal information avail-
able is the paint manufacturer’s da-
ta sheets and cargo resistance lists.
Both the data sheets and cargo re-
sistance lists could, in effect, pro-
vide very similar information, and
to the purchaser there could appear
to be little or no difference in the
coating from a number of manufac-
turers. Figure 11, however, indicates
that the choice of coating 12 would
pose a much higher risk of retention
of styrene monomer with the subse-
quent higher risk of contamination
of a future cargo than, for example,
coating 13.
A similar situation exists with
Copyright ©1998, Technology Publishing Company
A cargo tank coating in good condition (top) and a test panel
showing coating breakdown in the form of blistering (bottom), 1.
which increases the tendency of the coating to absorb cargo
(Photos and figures courtesy of the author)
amine-cured epoxies where Figure
8 illustrates that coating 1 poses a
greater risk for potential cargo cont-
amination than coating 3.
In the case of EDC, which can re-
act with water to form acidic com-
ponents, paint manufacturers gen-
erally have a clause in their cargo
resistance lists to say that the cargo
should be completely removed from
the coating prior to tank cleaning,
loading an aqueous cargo, or other
contact with water. Figures 7 and
10 illustrate that some coating sys-
tems retain more EDC than others
at equilibrium and, hence, there is
a greater possibility of reaction with
water and breakdown of the coat-
ing system.
The amount of absorbed material
at equilibrium must be viewed in
each individual cargo and coating
combination because of the variable
lengths of time to reach equilibrium.
The amount of cargo absorbed into
the coating will depend on carriage
time, which is often considerably
PCE December 1998
less than the time taken to
reach the equilibrium absorp-
tion state. Hence, the amount of
retained cargo after discharge—
and that available for potential
cargo contamination—will be
influenced by the carriage time
of the cargo.
This article has only dealt
with a small amount of the da-
ta available from the test pro-
gramme. It is expected that fu-
ture works will include infor-
mation on other cargoes and
the effects of temperature and
tank cleaning.
References
O.B. Sorensen, “The Fac-
tors Influencing Ventilation and
Drying of Epoxy Coated Cargo
Tanks,” proceedings of Mari-Chem
89, Gastech Ltd. (ed.), 1989.
2. W. Woods, “Retention of
Chemicals by Tank Linings,”
F.O.S.F.A. International Symposium
on “Edible Oils—How Pure are
They?” 1989.
3. C.E.M. Van der Kolk, “OCL
Epoxy Tanklining—A New Contri-
bution to Operational Flexibility in
Chemical Cargo Transport,” pro-
ceedings of MariChem 89, 1989.
4. W. Woods, “Lining Up for the
Nineties,” Hazardous Cargo Bul-
letin, 1992.
5. W. Woods, “Tank Coatings—An
Absorbing Subject,” Ship Repair
and Marine Maintenance 94, New
Orleans, LA, USA, 1994.
6. O.B. Sorensen, “Marine Paints:
Coating Systems for Ballast and
Product Tanks,” Second Middle
East Conference on Technological
Developments in Coatings: Their
Application and Uses, Bahrain,
January 1995.
29