TBT FREE ANTIFOULINGS

AND FOUL RELEASE

SYSTEMS
TBT Free
Antifoulings
and
Foul Release
Systems (2002)
Professor Colin D Anderson
International Marine Coatings and Visiting
Professor, Department of Marine Sciences,
University of Newcastle upon Tyne, UK.
TBT Free Antifoulings and
Foul Release Systems
Prof. Colin D Anderson

International Marine Coatings and Visiting Professor, Department of Marine Sciences,

University of Newcastle upon Tyne, UK.

Summary
When choosing TBT free antifoulings there are two principal technology options to consider: Biocidal or Foul
Release.
Biocidal: Biocidal antifoulings depend for their effectiveness on both the biocide itself and the technology
used to control the biocide release, or leaching rate. Copper is the main biocide used in TBT free antifoulings,
together with rapidly degrading boosting biocides which do not bio-accumulate in the marine environment.
The release of the biocides is typically controlled using one of three technologies:
1. Rosin based: These antifoulings can have either low or high quantities of Rosin. The products with a low
level of Rosin are hard and are referred to as Contact Leaching antifoulings. They are mechanically tough,
have no polishing characteristics and commonly have a maximum in service lifetime of 24 months
(depending on in service conditions and specification applied). The high Rosin products are softer, dissolve
slowly in seawater over time and are referred to as Controlled Depletion Polymer (CDP) antifoulings. These
products have in service lifetimes of up to 36 months on the vertical sides and up to 60 months on the flat
bottom (depending on in service conditions and specification applied). International’s CDP antifouling is
Interspeed® 340 (Interspeed® 640 and Interclene® 245 NA in North America). Both the Contact Leaching
and CDP products show declining (approximately exponential) biocide release rates with time.
2. Self-Polishing Copolymer (SPC): These antifoulings use an acrylic copolymer, which undergoes hydrolysis
or ion exchange in seawater to effect biocide release. International’s TBT free SPC antifoulings are
Intersmooth® 360/365 Ecoloflex SPC for coastal vessels, and Intersmooth® 460/465 Ecoloflex SPC for
deep sea ships. These products demonstrate controlled biocide release rates, and have a proven 60 months
in service track record.
3. Hybrid SPC/CDP: These are antifoulings based upon a combination of the CDP and SPC technologies
outlined previously. International’s Hybrid SPC/Rosin CDP product of this type is Interswift® 655. This
antifouling has a price and performance profile midway between that of Intersmooth® Ecoloflex SPC and
Interspeed® 340 (CDP).
Foul Release: Foul Release is the name given to technology which does not use biocides to control fouling
but relies on a “non-stick” principle to minimise fouling adhesion to the surface. Most Foul Release products
currently available are based on silicone technology. International’s products of this type are Intersleek® 425
(for high speed coastal vessels operating above 30 knots), and Intersleek® 700 (for deep sea, high activity
scheduled ships with speeds greater than 15 knots).

With the exception of Papers written exclusively by International Marine Coatings, the Papers presented do not necessarily reflect the
opinion of International Marine Coatings and, whilst every effort has been made to ensure that the information in this publication is
accurate, International Marine Coatings makes no representation or warranty, expressed or implied, as to the accuracy, completeness
or correctness of such information. Please note that the information does not necessarily stand on its own and is not intended to be
relied upon in specific circumstances. To the extent permitted by law, International Marine Coatings accepts no responsibility
whatsoever for any loss, damage or other liability arising from any use of this publication or reliance upon the information which it
contains.

© Akzo Nobel, 2003

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 TBT Free Antifouling Technology
Introduction
Controlling the growth of marine fouling on underwater hulls without the use of the Tributyltin (TBT) biocide
is achieved in one of two main ways. The first, and more common approach, is to use combinations of
alternative, non TBT biocides. These are finely dispersed in the antifouling binder system and then released
from the surface of the coating once it is immersed in sea water. Biocidal antifoulings are generally
differentiated from each other by the mechanisms (technology types) used to effect this biocide release.
These mechanisms are outlined in the first part of this paper.
The second and more novel approach to fouling control is to make the surface “non-stick”, and prevent
fouling attachment without the use of biocides. Antifoulings of this type are known as Foul Release coatings
and are described in the second part of this paper.
Biocidal Antifoulings
There are two key factors in the successful development of a biocidal antifouling:
• The efficacy or efficiency of the biocide, or biocide combination
• The delivery mechanism of the biocide or biocide combination
1. Biocide Efficacy
Arising, no doubt, from the measure of success achieved with the historical use of copper as underwater hull
sheathing, copper compounds were the first biocides developed for the large scale industrial production of
antifouling paints, and they are still extensively used in TBT free antifoulings today. The most commonly used
copper compounds are cuprous oxide (Cu2O), which is red, cuprous thiocyanate (CuSCN), which is a pale
cream colour (used for making brightly coloured TBT free antifoulings) and metallic copper, either in the
traditional sheet form or as a powder.
Copper by itself is, however, limited in its effectiveness. Copper tends to work well against animal (shell)
fouling, but algal (weed) fouling is more resistant to it. As a result, over the years, antifouling chemists have
spent much time and effort searching for additional biocides which can be added to the copper to boost its
performance. These biocides are referred to as “boosting biocides”.
The key characteristics of a successful boosting biocide are:
• Very low seawater solubility (ideally less than 10ppm) so that it is not released too quickly from the
antifouling paint film once immersed.
• No human or eco-toxicity problems
• Appropriate price
As a result of the outstanding fouling control performance of the organotin compounds such as TBTO
(Tributyltin Oxide) and TBTF (Tributyltin Fluoride), which were first used as boosting biocides in the 1960’s,
research to find suitable alternatives in the 1970’s and 1980’s was largely unsuccessful. The reason for this
was because it proved very difficult to better the biocidal effectiveness and comparatively low cost of the
organotins.
The demise of the organotins in the 1990’s could perhaps have led to more boosting biocides becoming
available, but this period also coincided with a very large increase in the cost, and quantity, of regulatory data
required for the registration of new boosting biocides for antifoulings. For suppliers, the relatively small size
of the global antifouling market makes it difficult to recoup the very high cost of developing and registering
new antifouling boosting biocides. As an example, it can now cost in excess of US$ 4 million to undertake
all the necessary human and environmental toxicity testing required for the registration of a new antifouling
biocide. Not surprisingly, therefore, there have been very few new boosting biocides introduced to replace
the organotins. Those that are now available are generally more specific against particular types of fouling
organisms and require careful formulation to achieve optimum biocide synergy and antifouling performance.
Research and development in antifouling coatings has focussed primarily on maximising the efficiency and
delivery mechanisms of the biocides that are available. This involves studies on both the synergies between
the biocides, to get the maximum efficiency from the minimum quantities, and detailed work on the best
mechanism to control the release of biocides, to maximise coating lifetimes (vessel in service periods).

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2. Biocide Release Mechanisms
The standard method for measuring biocide release is the Leaching Rate. This is defined as the quantity of
biocide released from a given surface area in a given time, expressed as µg/cm2/day. The release mechanism
itself depends on the technology of the coating system employed. There are three main technologies:
• Rosin based
• Self-Polishing Copolymer (SPC)
• Hybrid SPC/CDP

2.1. Rosin based: Rosin, or chemical derivatives of Rosin, allow seawater to penetrate the paint film, and as
it does so, it dissolves the biocides contained therein thus allowing their release by a diffusion process. This
results in an “exponential” leaching rate, with an excessive release in the early days of immersion which falls
quite rapidly, eventually to a level which is too low to prevent fouling. A typical exponential leaching rate
graph is shown in Figure 1 below:
Figure 1: Exponential Leaching Rate
Copper Leaching (µgCu/cm2/day

Days from start of test

Rosin comes from trees and is also widely used in the adhesives industry. It has a complex chemical make-
up, which varies depending upon where the trees are grown from which it is extracted. The major constituent
of Rosin is Abietic Acid, which is slightly soluble in seawater (pH ~8.2), and it is this slight solubility which
makes it suitable for use in antifouling coatings. Purification of Rosin, to improve its solubility, can be carried
out in a number of ways, such as hydrogenation or esterification.
Rosin by itself is not a film forming material and it has to have other film forming or binder components added
(referred to as resins and plasticizers) to give films of good mechanical strength. However these added
components are generally insoluble in seawater and their use has to be limited or biocide leaching will be
impaired. A careful balance is needed between the amount of Rosin required to provide sufficient biocide
release and the quantity of the other film forming components used to make the coating tough and durable.
As the Rosin content increases the binder system becomes softer and more soluble in seawater whereas a
low Rosin content makes the binder system virtually insoluble and hard. Antifoulings which are softer and
more soluble are known as “Controlled Depletion Polymer” (CDP) or Soluble Matrix antifoulings, whereas
the hard types are known as Insoluble Matrix or “Contact Leaching” antifoulings.

2.1.1. Contact Leaching Antifoulings

In the 1960’s attempts were made to increase the lifetime of antifoulings by increasing their biocide content.

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 Such highly filled coatings required increased quantities of the film forming resin and plasticizer components
for film integrity, at the expense of the Rosin, so making these coatings hard and almost insoluble in
seawater. They became known as Contact Leaching antifoulings since the biocide particles were all in close
contact with each other.
The toughness of these paints means that there is essentially no dissolution or decrease of the paint film
thickness over time, and, as more and more biocide is leached out, a thick depleted layer develops at the
surface, which is referred to as the “Leached Layer”. As this layer increases in size, the diffusion of biocides
from the depth of the film slows down meaning that few products of this type have life times in excess of 24
months (depending on in service conditions and specification applied).

2.1.2. Controlled Depletion Polymer (CDP) antifoulings

Until the 1930’s almost all antifouling paints were of the Controlled Depletion Polymer type, which at that time
were referred to as “Soluble Matrix”. In the late 1940’s major improvements came about with the advent of
a wide range of new industrial film forming materials such as the synthetic petroleum based resins. As
chemical companies developed these new resins they were used to upgrade and improve Soluble Matrix
antifoulings, giving them increased film integrity and toughness. Continual improvement has resulted in the
Controlled Depletion Polymer (CDP) antifoulings available today.
Most Marine paint companies market their own versions of CDP antifoulings, and use a wide variety of
nomenclatures to describe them. Typical of these are “Eroding”, “Ablative”, “Polishing”, “Hydration”, “Ion
Exchange”, ”Hydrolysable Activated” and “Self-Polishing”. The common feature in all of these products is
the high proportion (>50%) of Rosin, or Rosin derivatives, in the binder component. The main biocide used
in CDP antifoulings is copper oxide, together with boosting biocides.
Although in theory these paints can dissolve or polish away fully over time, this does not happen in practice
since the surface becomes increasingly less soluble due to the build up of insoluble copper salts and other
inert species (such as the Rosin impurities and the insoluble film forming binder). This results in the
development of a thick leached layer through which the biocides have to diffuse to the surface, and this limits
the lifetime of CDP antifoulings to a maximum of 36 months between dry dockings, on the vertical sides
(depending on in service conditions and specification applied). On the flat bottom, where the fouling
challenge is less severe, in service periods can be extended up to 60 months (depending on in service
conditions and specification applied).
The cross section of a typical CDP antifouling is shown in Figure 2 below, after 90 days dynamic rotation in
seawater. The leached layer at the surface where the copper and boosting biocides have leached out is
approximately 55µm thick.
Figure 2: Cross section through a CDP antifouling

Leached Layer
(55µm)

Unleached
Antifouling

International’s CDP antifouling is Interspeed® 340 (Interspeed® 640 and Interclene® 245 NA in North
America).

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2.2. Self-Polishing Copolymer (SPC)
These antifoulings release the biocides by a hydrolysis or ion exchange reaction of an acrylic polymer with
seawater. This reaction only occurs near the surface, and, unlike the Rosin systems, seawater penetration
into the bulk of the film is prevented by the hydrophobic nature of the polymer system. The fact that the
solubility of the polymer binder is confined to the surface layer only gives a greatly increased control of
release of the biocides since the leached layer of SPC systems is always thin).
Figure 3 below shows the leaching rate graph for a typical TBT free SPC system, compared to that of a Rosin
based CDP system. The initial leaching rate of the SPC is much lower than that of the CDP system, and then
a “steady state” constant leaching rate is achieved as the surface reaction continues. This steady state
continues for as long as antifouling paint film remains. These characteristics make SPC systems far more
efficient as antifoulings than the Rosin based CDP types.
Figure 3: TBT free SPC vs CDP Leaching Rates
Copper Leaching (µgCu/cm2/day

Days from start of test

The first TBT free SPC system was introduced in 1990, based on Copper Acrylate technology, using a
patented copolymer system which mimics the reaction of the TBT acrylate SPC copolymers in seawater, as
shown below:
TBT Acrylate: Polymer- COO – Sn(Bu)3 ⇔ Polymer- COO¯ + Sn(Bu)3+
Copper Acrylate: Polymer- COO – Cu-R ⇔ Polymer- COO¯ + Cu - R+
This seawater reaction gives the Copper Acrylate system exactly the same controlled mechanism for biocide
release as the previous TBT SPC antifoulings. Thus Copper Acrylate SPC systems have all the benefits
previously associated with the TBT SPC systems, as follows:
• High levels of fouling control
• Leached layer control
• Controlled polishing rate and biocide release
• Self-smoothing
• Extended in service periods of up to 60 months (depending on in service conditions and specification
applied)
• Tough and durable films; ideal for use at the new construction stage
Since 1990, International Marine Coatings and our Japanese partner Nippon Paint Marine Coatings (NPMC)
have introduced a number of TBT free SPC systems based on Copper Acrylate technology, under the
Ecoloflex brand name:

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 For Coastal vessels: Intersmooth® 360 (or 365) Ecoloflex SPC products
For Deep Sea vessels: Intersmooth® 460 (or 465) Ecoloflex SPC products
The thin Leached Layer of a typical Intersmooth® Ecoloflex SPC antifouling is shown in Figure 4, after 15
months static immersion:
Figure 4: Cross section through an Intersmooth® Ecoloflex SPC antifouling

Leached Layer
(15µm)

Unleached
Antifouling

Anticorrosive

The large particles observable in the cross section of Intersmooth® Ecoloflex SPC above are cuprous
oxide. This is the main biocide used in this antifouling, together with Zinc Pyrithione, a non-persistent, rapidly
degradable boosting biocide which does not bio-accumulate in the marine environment.
To date over 6,000 Ecoloflex vessel applications have been carried out. The product performance on these
ships compared to that of the previous biggest selling TBT SPC antifouling has been monitored through
International’s Dataplan system, and the results of this are shown in Figure 5 below:
Figure 5: Relative Antifouling Performance

This in service data proves that the Ecoloflex products work as well as the TBT SPC antifoulings which they
have replaced, for up to 60 months. Both the TBT SPC and TBT free SPC antifouling types are also shown
to be far superior to the Rosin based (CDP) products.

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Further information on the Track Record and performance of the Intersmooth® Ecoloflex SPC products
(including the 60 month in service results) can be found via the website www.intersmoothecoloflexSPC.com.

2.3. Hybrid SPC/CDP systems

This relatively new antifouling type is a blend of a hydrolysable TBT free SPC technology (Copper Acrylate
SPC) with the Rosin based CDP technology. By carefully combining these two technologies to form a
“hybrid”, it is possible to produce an antifouling which has the CDP features of surface tolerance and
attractive volume solids, together with the SPC benefits of polishing rate control, control of biocide release
and reduced leached layer size. The addition of a hydrolysable polymer (such as Copper Acrylate) to Rosin
to form this new type of hybrid antifouling has been patented (International Patent Publication Number WO
00/43640), and performance has been enhanced by the use of a Pyrithione boosting biocide.
The typical leaching rate of Interswift® 655 is shown in Figure 6 below:
Figure 6: Interswift® 655 Leaching Rate
Copper Leaching (µg/cm2/day

Days from start of test

Figure 7 below shows the cross section of a typical Hybrid SPC/CDP antifouling, after 90 days dynamic
rotation in seawater:
Figure 7: Cross section through a Hybrid SPC/CDP antifouling

Leached Layer
(25µm)

Unleached
Antifouling

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 International’s Hybrid SPC/CDP system is Interswift® 655 which has the following features and benefits:

Features Benefits
TBT free Freedom from TBT restrictions and associated
waste disposal costs.
Controlled polishing rate and biocide release Tailored specification design with optimum dry
film thickness
Contains Copper Acrylate SPC Improved leached layer control (cf CDP products)
Vertical Sides: Up to 36 mo. in service* Flexibility in dry dock interval
Flat Bottom: Up to 60 mo. in service*
* depending on in service conditions and
specification applied
Surface tolerant Freedom to apply over existing antifoulings in
good condition (consult International Marine
Coatings for suitability)
Attractive volume solids Control of solvent emissions
Good mechanical properties More durable films in comparison to CDP
antifoulings

In terms of performance and price this Hybrid SPC/CDP antifouling (Interswift® 655) is midway between the
SPC (Intersmooth® Ecoloflex SPC) and CDP (Interspeed® 340) technologies.

Performance Price
SPC
(Intersmooth®
Ecoloflex SPC)

Hybrid
(Interswift® 655)

Rosin based CDP

(Interspeed® 340)

3. Foul Release
From an environmental perspective, the ultimate approach to fouling control is one which does not rely on
the release of biocides to achieve its effect. A plethora of ideas on how this can be achieved have been
proposed over the years, and numerous patents have appeared, but only the Foul Release or low adherence
systems have been commercialised successfully to date.
The concept of low adherence to deter fouling was first considered in the 19th century but it was not until
the discovery of the fouling control properties of silicones that commercial systems started to appear. These
have been improved and refined over time and the majority of Foul Release systems currently available are
silicone materials, based on polydimethylsiloxane (PDMS). The only other chemistry types to be considered
to any great extent have been fluorinated polymers, but these have not been commercialised to any great
extent.

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Low surface energy is one key characteristic of these systems, and is achieved since PDMS is a molecule
with an extremely flexible backbone. This allows the polymer chain to readily adopt the lowest surface energy
configuration. Other important characteristics of these systems are coating thickness, elastic modulus and
smoothness. The latter has always been known to be important since fouling species prefer rough surfaces
to settle on, an effect which is known as the thigmotactic nature of fouling settlement. Foul Release silicone
coatings are very smooth with a completely different surface texture to that of SPC antifoulings. Whereas
SPC antifoulings have a “closed texture” with frequent peaks and troughs akin to a steep mountain range
(Figure 8 below), the Foul Release systems have a long wavelength “open texture” surface, similar to well
rounded hills and shallow valleys (Figure 9 below):
Figure 8: Surface Profile of a TBT free SPC surface, freshly sprayed

Figure 9: Surface Profile of a Foul Release surface, freshly sprayed

International Marine Coatings has two Foul Release products, Intersleek® 425 for high speed coastal
vessels which operate at speeds in excess of 30 knots, and Intersleek® 700 for deep sea high activity
scheduled ships. Both Intersleek products have now been well proven over in service periods in excess of
60 months. Performance and Track Record details of the deep sea scheduled ships can be found on
www.intersleek700.com.
Despite their attractive environmental profile, the market penetration of Foul Release coatings has so far been
limited. In part this is due to the increased initial cost of installation, but is also due to the fact that the majority
of the world’s fleet (Tankers and Bulk Carriers) does not operate at high enough speeds, and does not have
sufficient activity, for the current Foul Release coatings to perform at their best.

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 Notes

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Notes

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 Notes

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