NewAntiFoulingCoatingsBasedonConductivePolymers

Sze C. Yang, Richard Brown, Thomas Ramotowski, Wayne Tucker,

Lucie Maranda, Ryan Chena, Mae Shen

University of Rhode Island

October 2009

URITC PROJECT NO. 0001032

PREPARED FOR
UNIVERSITY OF RHODE ISLAND
TRANSPORTATION CENTER

DISCLAIMER
This report, prepared in cooperation with the University of Rhode Island
Transportation Center, does not constitute a standard, specification, or
regulation. The contents of this report reflect the views of the author(s) who
is (are) responsible for the facts and the accuracy of the data presented
herein. This document is disseminated under the sponsorship of the
Department of Transportation, University Transportation Centers Program,
in the interest of information exchange. The U.S. Government assumes no
liability for the contents or use thereof.

New Anti Fouling Coating Based on Conductive Polymers

Sze C. Yanga, Richard Brownb, Thomas Ramotowskic, Wayne Tuckerc, Lucie Marandad,
Ryan Chena, Mae Shena
a. University of Rhode Island, Chemistry Department, Kingston, RI
b. University of Rhode Island, Chemical Engineering Department, Kingston, RI
c. Naval Undersea Warfare Center, Newport, RI
d. University of Rhode Island, Graduate School of Oceanography, Narragansett, RI
Final Report to the URI Transportation Center for Project 1032
Introduction
Within the marine environment, any surface in contact with seawater suffers
from bio-fouling by marine organisms. When these organisms, such as algae and
barnacles, attach to the hull of a ship performance of the vessel is compromised.
Fouling on hulls increases fuel costs significantly, creates extra wear on engine
components due to extra power to move ships and can ultimately cause engine failure if
water intakes for cooling become blocked. Increased maintenance costs also occur as a
result of fouling as ships need to be dry docked more frequently for cleaning.
There are also unintended ecological effects when a bio-fouled ship moves
between ports. Fouling will transport non-indigenous species around. Greater
environmental inspections are required to detect any issues as soon as possible. This
requires more personnel, equipment and specific training.
Traditional antifouling paints were designed to release toxins from the surface of
the paint to prevent micro-organisms attaching to the surface1. The toxicity of the
released chemical species has been found to be damaging to the marine ecology and
poses problems for the environment. The previously banned tributyltin (TBT)
antifoulant was found to be extremely harmful to the environment. The current
commercial antifouling paint which contain large amounts (50% by weight) of copper
based antifoulants, is also harmful to the environment.
In this research, we explored the possibility for an alternative method for
reducing biofouling. We used an electronically conductive polymer as an additive to the
commercial paints such as polyurethane and epoxy. We set out to examine if the
additive is helpful for reducing fouling.

Our proposal was motivated by the empirical data reported in the literature.
Medical researchers had found an unusually strong effect on cell growth in the presence
of a conducting polymer film2,3,4. Cell growth was reported to be either strongly
suppressed or promoted depending upon environemental circumstances. In addition,
Wang et al reported an antifouling effect observed on paints containing single-strand
polyaniline5. Previous researchers had reported a retardation in fouling by one to two
months relative to the same paint without polyaniline. These empirical results are
intriguing because it could be the first coated surface that prevents the attachment of
marine organisms without the release of any chemical agent.
For conducting polymer based antifouling paint5, the authors indicated that the
antifouling effect slowly decreased after immersion for one month. Their study
indicated that the decrease of effectiveness correlated with loss of electronic
conductivity of polyaniline. The reason for the loss of electronic conductivity is
dissolution of an anionic dopant (toluene sulfonate) in water. When the anionic dopant
is lost, the positive charge carrier on the polyaniline backbone becomes energetically
unfavorable and the conducting polymer is converted into the non-conductive form.
In this study we use a double-strand conducting polymer synthesized at URI6,7 to
replace the single-strand conducting polymer used in the previous study by Wang et al.
The purpose is to extend the duration of effectiveness of conducting polymers. The
double-strand polymer is a side-by-side complex of a conducting polymer with a
polymeric dopant and is shown schematically in figure1. Since the dopant is an integral
part of the conducting polymer, it is not susceptible to the problem of loss by
dissolution. An additional advantage is that the double-strand conducting polymer is
much easier to blend with paint compared with the single-strand conducting polymer
used by the previous researchers.

Figure 1 A schematic of the URI double-strand conducting polymer.

Synthesis of double-strand polyaniline

Double-strand polyaniline was synthesized by a template-guided synthesis8. A
typical small scale synthesis is described in the following: 0.25g Poly(acrylic acid)
powder (PAA) (M.W. 450,000, from Aldrich) was used as the template and was stirred
with 20 ml distilled water until all the powder was dissolved. Then 0.323 g aniline was
added into the PAA solution and was stirred for 24 hours to form PAA:An adduct. Next,
5 ml 1 M sulfuric acid was added into the PAA:An solution and was stirred for one hour
to acidify the adduct. At the end of this time, 5 ml 0.69 M ammonium persulfate
solution (0.79 g (NH4)2S2O8 dissolved in 5 ml distilled water) was added ito the solution
and stirred for more than four hours. At this stage the product has a dark green color.
To obtain the final product this PAA:PAN complex was purified with a dialysis membrane
(35,000 M.W., Spectrum), first in hydrochloric acid then in distilled water.
Synthesis of organic/inorganic composite as a conducting polymer pigments for
paints.
A conducting polymer based pigment was previously developed at URI in
collaboration with Wayne Pigment Corporation.9 This conducting polymer pigment was
investigated as a non-chromate anticorrosive pigment for coatings on aluminum alloys.
In the present research work this type of pigment was used as an additive to epoxy or
polyurethane paints for its ease in blending with commercial paints, not because of the
need for its corrosion inhibition properties. The pigment was produced in a physical
adsorption process. An aqueous solution of the double-strand conducting polymer was
mixed with a slurry of inorganic pigments, such as SrHPO4, WO3, or CeO2. When the
condition of the mixture is properly adjusted, the organic conductive polymer
spontaneously and quantitatively adsorbs onto the inorganic pigment to form an
organic/inorganic composite suitable as a pigment for paints.
Figure 2 shows the adsorption of PAA:PAN on SrHPO4 particles, 1.00 g of SrHPO 4
particles were mixed with 250 ml of 0.1528 g/l unpurified PAA:PAN solution then stirred
for two minutes. After stirring, when all the particles settled, the upper solution was
totally clear and the particles were green in color, which indicates that all the doublestrand polyaniline was adsorbed onto the SrHPO4 particles.
By mechanically suspending inorganic particles in an aqueous solution of doublestrand polyaniline, a core-shell structure for the composite is expected with the polymer
coated on inorganic particles. Microscopic study, figure 3, shows that all the composites
have a uniform size within the range of 10 micrometer, while a bi-refringent

phenomenon9 under cross polarizer shows that the particles are really a composite
instead of a single amorphous polymer.

Mix

Figure 2. Physical adsorption of PAA:PAN on SrHPO 4 particles. In the left image,

PAA:PAN solution(green with white SrHPO4 powder, and right image, particles settled
and clear upper solution.

(a)

(b)

Figure 3. (a) Microscope image of the micron size (10 m) SrHPO 4/ds-PAN composite
particles; (b) Bi-refringence phenomenon of the particles.

Paints containing conducting polymers as an additive.

The conducting polymer organic/inorganic composite was blended at 5% by
weight into a commercial polyurethane. The mixture is applied as a coating on glass or
onto procured polyurethane boards. The coatings show green color when the
conducting polymer is polyaniline. The coatings show a black color when polypyrrole
was used as the organic component of the composite.
In other tests, the conducting polymer pigments were blended at 1% to 5% by
weight into commercial epoxy resins. The paint was used to coat substrates of glass,
aluminum and steel.

Fig. 4 Conducting polymer containing pigments.

Laboratory Evaluation of the conducting polymer coatings
Conducting polymer antifouling paint is not toxic to marine micro organisms.
In this section, laboratory experiments demonstrate that the conducting polymer
based antifouling paint is environmentally friendly. It is different from commercial
copper based antifouling paint, which leaches out chemicals that are toxic to algae and
marine micro-organisms. The experiments described in the followings showed that
although the conducting polymer paint inhibits the growth of algae directly on its
surface, it does not stop the growth of algae at the nearby surfaces. In contrast, the
commercial copper based antifouling paint not only inhibited the growth of algae on the
copper paint surface, but it also killed the algae in the surrounding sea water, and the
surrounding non-coated surfaces.
Experimental details:
Laboratory storage of algae containing sea water:
Diatom and green algae from the Narragansett Bay sea water was collected and
incubated. The sea water was stored in a 20 gallon fish tank indoors with a moderate
level of exposure to sun light. The stored sea water was supplemented with daily
addition of low concentration mineral (ferric nitrate) and sodium phosphate nutrients.
The stored sea water in the fish tank showed moderate and controlled growth of algae.
Experimental design:
A small quantity of the algae containing sea water was transferred to three
incubator bottles which were sterilized prior to the experiment. Figure 5 shows the
three bottles employed for the investigation. Bottle A serves as a control. It contains
the algae in sea water with a small amount of sand and stone pebbles from the beach at

the URI Graduate School Oceanography pier on Narragansett Bay in Rhode Island.
Bottle B contains a paint chip of 5% conducting polymer in commercial epoxy paint, in
the same sea water as Bottle A. Bottle C contains a paint chip of commercial copper
based antifouling marine paint in the initially the same sea water as that in Bottle A.
All three bottles were placed on a laboratory bench that receives relatively
uniform and indirect sun light. The same amount of low concentration nutrient
(mineral phosphate and nitrate) was fed to all bottles daily during weekdays. Figure 5
shows that there were observable differences after two weeks of the comparative test.
The green color from the algae in the salt water in Bottles A and B is maintained at
nearly the same intensity during the test period. There are about the same amount of
algae attachment and growth at the inside walls of Bottles A and B. In contrast, the
green color of the initially algae infested water in Bottle C disappeared within the first
week of the test. A closer examination showed that there was no algae attached to the
walls.

Figure 5. The conductive polymer containing paint (middle incubator flask) inhibits
fouling on the paint surface without decimating the algae activity on the surfaces of the
uncoated wall of the incubatior flask.
From this study, the toxicity of the presently used copper based antifouling paint
is clear. It rapidly kills all the algae that tries to attach to the paint surface, but it is also
toxic to algae in the near vicinity. To that extent it is non selective, it is toxic to all alge
independent of location as long as it is close to the paint. The conductive polymer

containing paint on the other hand appears to be non toxic to algae that is not in direct
contact with it. Because no algae appeared to settle on the paint, it cannot be
determined whether it is toxic on contact or just that the conductive polymer has some
mechansim by which the polymer does not want to settle on the surface.
Laboratory tests for conducting polymer as additive in urethane
In this part of study, seawater was collected from Narragansett Bay, filtered with
a coarse mesh screen to remove any large particles and used as the test environment.
Conducting polymer painted glass slides immersed in the seawater tank were employed
for an initial study of submerged surfaces.
Before 30 gallon tanks were filled with the Narragansettt Bay filtered seawater,
sand and pebbles with visible algae growth on the surface were used to line the bottom
of clean tanks. An aerator was used to pump room air through the seawater. The tanks
were placed on a laboratory bench that receives indirect sun light. Small quantities of
nutrients (dilute sodium nitrate and phosphate solutions) were added periodically. All
tanks maintained a steady growth of algae. The side walls and the bottom of the tank
show accumulation of green algae coatings. A rack holding about 15 to 20 paint coated
slides were submerged in the algae containing seawater. Figure 6 shows an example of
an experiment at the initial stage of the test.

Figure 6. Initial stage of the laboratory test. A rack of test samples in an algaecontaining seawater in a laboratory glass tank. The bottom of the tank is lined with
pebbles from the Narragansett Bay.

Figures 7a and 7b show an example of coated glass slides exposed in the algaecontaining seawater for 4 weeks. It can be seen that both the bare glass and the
polyurethane coated glass (in the middle) are infested with bio-fouling. The sample
with the same polyurethane coating with 5% conducting polymer (dark colored samples)
are relatively free from the adhesion of algae. Figure 7b shows a close up of the three
samples and the control in a different illumination.

Figure 7a. Photo of coated glass slides exposed in algae-containing laboratory tank for 4
weeks.

Figure 7b. A close-up photo of the test panels in figure 7a.

The same set of samples were photographed after 90 days of exposure in the
laboratory seawater. Figure 8 shows that algae has begun to coat the conducting
polymer containing polyurethane and the control samples.

Figure 8. The samples and controls from figure 7b after 90 days of exposure to algaecontaining laboratory seawater. The area with conducting polymer paint has less fouling
than the uncoated area (top) and the control sample of uncoated glass on the left hand
side of the image.
Field test in Narrangansett Bay, Rhode Island
In order to assess the antifouling properties of the conducting polymer coated
polyurethane panels in a marine environment, a series of field tests in collaboration
with Mr. Thomas Ramotowski and Dr. Wayne Tucker of NUWC, Newport were
performed. The objective was to compare the effectiveness for inhibiting biofouling of a
conducting polymer coated non-toxic paint with the commercial copper based
antifouling paints. A set of test panels were prepared in Aug. 2006 for immersion in
Narragansett Bay, Rhode Island, which is a nutrient-rich body of water. A recent
technical report10 published by the Narragansett Bay National Estuarine Research
Center analyzed the recent and historical data of the nutrients.

Figure 9. Conducting polymer pigmented polyurethane coating on polyurenthane test

panels with dimension of 12x12x1 before the field test.
A typical test panel after coating is shown in figure 9. The four holes, one in each
corner, allowed these individual panels to be spaced out on tubes and to make a kite
for immersion. Several samples could then be tested on a single kite and the
environment would be similar for all the individual panels on the test kite. The panels
were in a horizontal position when immersed.

Figure 10. Test panels (1 ft x 1 ft) mounted on box kite type support structure.

A typical kite of test samples is shown in figure 10 just prior to immersion. These
test panels were immersed 6 within the low-tide level at the side of a NUWC test site at
the Narragansett Bay of Rhode Island , figure 11. One set of tests started in Aug. 2006.
Another set of tests started in the spring of 2007.

Figure 11. Immersion of test panels at about 6 below the low-tide level, suspended
besides a dock area at NUWC test site in Narragansett Bay, RI.
These test panels were periodically pulled to the pier for photograph taking and
examination. Figure 12 shows a photograph of a box kite test assembly pulled out of
the Narragansett Bay during Aug. 2008 after 3 weeks of immersion. The front panel is a
coating with 5% conducting polymer pigment. The back panel is the same polyurethane
coating without conducting polymer pigment. It can be seen that the control panel has
much heavier bio-fouling comparing with that of the conducting polymer pigmented
panel. It can also be seen that the type of marine organisms attached to these two
panels are visually different. This impression was verified in panels examined by marine
biologists. This and other test results show that the conducting polymer pigmented
coatings can delay the bio-fouling in the field condition for about 1 month.
The field test results are consistent with the laboratory seawater tests described
in the previous section. The conducting polymer pigmented paints can delay the biofouling but they eventually overcame by bio-fouling. Although this is an interesting
finding for a non-toxic antifouling paint, it is not competitive with the commercial
copper based antifouling paint. Figure 13 shows a set of test panels photographed after
2 months of field test. The front panel is a conducting polymer pigmented coating. The
back panel is a commercial copper based antifouling paint. The conducting polymer
pigmented coating is heavily fouled by the end of the second month, but the copper
based paint in the back is still relatively free from fouling.

Figure 12. A photograph of test panels after 3-weeks of immersion in seawater. The
front panel is a conducting polymer pigmented coating. The back panel is a control
panel.
Figure 14 show the conducting polymer pigmented test panels after immersion
of about 6 months. At this point, there is no visual difference between the conducting
polymer pigmented panel and the control panel. It was noted that the initial surface
morphology (within the first 1 months) of marine organism growth on the paints with
conducting polymer additives was different from that of the control panels, see for
example figure 12. It appears that the conductive polymer was selective in allowing
deposition.

Figure 13. Test panels immersed for 2 months. Front: conducting polymer pigmented
polyurethane coating. Back: Commercial copper based antifouling paint.

Figure 14. Test panels immersed for 6 months.

Conclusions:
A pigment was synthesized that consisted of a composite material of an
organic polyaniline electronic conducting polymer with an inorganic core. These
pigments were used to blend into commercial polyurethane and epoxy paints. These
paints were then coated on glass, metal and polyurethane substrates for tests of their
antifouling properties in the laboratory seawater tanks and in the field.
Laboratory tests in seawater comparing conductive polymer containing paint
to copper containing antifouling paints showed that the conducting polymer based paint
does not release toxic chemicals unlike the copper containing paint which was toxic to
the surrounding environment.
Another laboratory test was performed to verify that the conducting polymer
has antifouling property. The 5% conducting polymer paints showed resistance to
biofouling relative to that of the control sample in a time window of 1 month before
both samples were fouled with algae growth.
Field tests of 12x12x1 coated panels were performed by immersion of test
panels in Narragansett Bay during the period of Nov. 2007 to June 2008. The field tests
showed that there is a moderate delay of fouling of 3 weeks to 1 month compared with
control panels with the same commercial paint without the conducting polymer
additive. The conducting polymers eventually fouled. Although the conducting polymer

is a non-toxic antifoulants, the antifouling resistance faded faster than the control
panels containing copper paints. With a relative short period of antifouling activity of 1
month, it was concluded that the present formulation is not yet a viable replacement for
copper based antifouling paint.
In the field studies, it was noted that the initial surface morphology (within the
first 1 months) of marine organism growth on the paints with conducting polymer
additives was different from that of the control panels. From these limited number of
observations it can be speculated that the conducting polymer inhibits adhesion for
certain species of marine organism, but not all the species. The adhesion of the noninhibited species then form a bio-mass coated surface that facilitates further growth of
marine organisms and the eventual fouling. This leads to a recommendation on a
further study to validate this speculation. If validated, an understanding of the
mechanism for the physiological effect may be useful for further development of a
viable conducting polymer based antifouling paint.

References:
1.

M. E. Callow and J. A. Callow, Marine biofouling: a sticky problem, Biologist 49, 1

(2002)
2.

J.Y. Wong, et al., Electrically conducting polymers can non-invasively control the shape
and growth of mammalian cells, Proc. Nat. Acad. Sci., 91, 1994, pp. 3201-3204.

3.

B.E. Schmidt, et al., Stimulation of neurite outgrowth using an electrically conductive

polymer, Proc. Nat. Acad. Sci., 94, 1997, pp. 8948-8953.

4.

A. Kotwal, et al., Electrical stimulation alters protein adsorption and nerve cell
interactions with electrically conducting biomaterials, Biomaterials, 22, 2001, pp. 10551064.

5.

Wang, X.-H.; Li, J.; Zhang, J.-Y.; Sun, Z.-C.; Yu, L.; Jing, X.-B.; Wang, F.-.S.; Sun, Z.-X.;
Ye, Z.-J. Polyaniline as marine antifouling and corrosion-prevention agent. Synthetic
Metals (1999), 102(1-3), 1377-1380.

6.

L. Sun, H. Liu, R. Clark, S. C. Yang, Sun, Double-Strand Polyaniline, Syn Met 85, 67
(1997)

7.

J.-M. Liu and S. C. Yang, "Novel Colloidal Polyaniline Fibrils Made by Template Guided
Chemical Polymrization", J. Chem. Soc., Chem. Comm., 1529 (1991).

8.

L. Sun, S. C. Yang, J.-M. Liu, "Template-Guided Synthesis of Conducting Polymers:

Molecular Complex of Polyaniline and Polyelectrolyte.", American Chemical Society,
Polymer Preprints, 33, 379 (1992).

9.

Conductive Polymer-Inorganic Hybrid composites, John Sinko, Sze C. Yang,

U.S. Patent 7125925 B2, Oct. 24, 2006.

10.

Leanna Heffner, Nutrients in Mid-Narragansett Bay: A Spatial Comparison of Recent

and Historical Data Narragansett Bay Research Reserve, Technical Report, Jan., 2009,
http://www.nbnerr.org/.

AN ANALYSIS OF THE RELATIONSHIP BETWEEN ALGAE GROWTH RATES AND

THE TEXTURE OF THE ASSOCIATED MEDIUM.

Patrick Fullera, David Keacha and Richard Brownb

a. Bishop Hendricken High School, Warwick, RI.

b. University of Rhode Island, Chemical Engineering Department, Kingston, RI
Final report to the URI Transportation Center for Project 1032
Introduction

Marine biologists have empirically observed a distinct variation in algae growth

rates on different types of shells. A proposed theory for this anomaly is that the texture
of a seashell may inhibit or promote algae growth. This theory may be applied to the
hulls of seafaring vessels. Many ships, especially cargo vessels, constantly have to deal
with algae growth on their hulls. Present solutions to this problem are few, and include
simply accelerating to wash off the algae on the hull. However, algae adheres to the
hulls of the ships, costing many companies millions of dollars in operating, maintenance
and failures. Assuming the aforementioned theory is valid, it logically follows that that a
properly textured hull could be resistant or immune to sea algae growth. If one could
devise a more precise correlation between algae growth and the texture of the growth
medium, the results could be applied to create algae-resistant textured hulls.
In order to test the validity of the theory relating shell texture to algae growth,
images were taken different types of shells. In this study, none of the shells had algae
growth on them, so it was hoped to find a surface feature that would be consistent
between the shells and lead to a non-fouling surface texture. A scanning electron
microscope (SEM) was used to image the surface features of shells at 250, 500, 1000,
2000, and 4000 times standard magnification. Twelve different types of shells, collected
from different areas on the east coast, were examined. The varying SEM magnifications
permitted observation of regularities and irregularities in shell texture, with the aim of
the ability to categorizing shells based on texture.

Results
Although characteristics between the 12 seashells were distinct and different from each
other, there seemed to be some notable similarities. All of the shells observed can be
grouped into one of three categories. The few shells contained in category one had long
grooves, much like canyons, that ran parallel to each other. Henceforth, these will be
referred to as refer to as the canyon group.

Figure 1.1 Shell 6 at 250 magnification

The texture of shell 6, figure 1.1, was smooth to the touch. When imaged in
the SEM, one could make out small linear ridges. The scale of these ridges was on the
order of one to two microns in width.

Figure 1.2 Shell 3 at 100 magnification

These concave grooves were the foundation of microscopic islands which

scattered themselves across the surface of shell 6.A second shell with the canyon
configuration is shown in figure 1.2. The features in this case are quite coarse, on the
scale of tens of microns in width and uneven in comparison to the earlier shell in figure
1.1.
The next category is slightly broader. The shells in group two appeared to have
no canyons of any kind. For the shells in this category a consistent surface roughness
apparent, figure 2.1 and figure 2.2. This was roughness raised above the surface.

Figure 2.1 Shell 10 at 1000 magnification

Figure 2.2 Shell 5 at 500 magnification

For this second category of shell, the surfaces are always uneven. Unlike the
canyon group, there is really no easy smooth place for algae to settle on the surface.
The scale of the roughness was of the order of 5 to 10 microns.
The third category of shells was actually a combination of two other surfaces.
Rather than a surface roughness, these shells had flat surfaces with depressions like
craters in the surface and these were part of a coarser ridge type structure, figure 3.1.

Figure 3.1 Shell 23 at 1000 magnification

This distinct combination was most prominent on shell 23, figure 3.2. In
addition to craters and flat areas contained within ridges cracks were present on this
surface shown by the white area in the micrograph where gold coating used to provide
conductivity to the shell did not penetrate down into the cracks.

Figure 3.2 Shell 8 at 100 magnification

A slightly smoother surface but with overall the same characteristics is shown
in figure 3.2. For this shell the ridges were not as sharp and the background surface was
not as rough. For the shells of this category, there were large smooth area where algae
would be able to settle.
There was one particular specimen that did not fall into any of the three
categories. However, it should be noted that this was not a shell but a plaster of Paris
mold of a shell. Needles were present on the surface and it is suspected that this is from
the calcium based crystals and does not reflect the shell surface but the surface of
plaster of Paris. This materials therefore should not be used to copy the surface of shells
to mimic them.

Figure 4.1 Shell sculpture at 1000 magnification

Conclusion

There did not seem to be one overriding feature of the shells surface that
pointed to an control of the fouling behavior. Shells had coarse ridges in quite large
scales down to microscopic features that would probably be disruptive to marine
growth such as algae. However the large ridge or canyon structures have rather large
flat areas, by comparison, which would allow easy settlement of algae and adhesion to
the surface. It would then appear that there may be other factors, such as a biological
agent on the surface that may control adhesion of algae. It would appear from this study
that surface texture is not a method to pursue for algae growth suppression.

21