Biodegradable Antifouling Coating

MPWT19-15293
Biodegradable Antifouling Coating
Mohammad Mizanur Rahman

Center of Research Excellence in Corrosion
King Fahd University of Petroleum and Minerals
Dhahran 31261
Saudi Arabia
ABSTRACT
Due to the regulations of toxic biocidal products in marine environments, the development of nontoxic
antifouling (AF) coatings has become required. The development of nontoxic antifouling formulations
implies the use of ingredients (such as: polymers, additives and pigments) that are devoid of toxicity
towards marine environments. In this regard, erodible coatings, based on biodegradable polymer, are
used to respond to this problem. Recently, polyurethane (PU) has been adopted into antifouling coating
due to its ability to migrate the certain functional groups which resist the attachment of fouling.
Biodegradation of PU can accelerate the erodible properties which ultimately improve the antifouling
properties. In this study, a series of biodegradable PU coatings was formulated by tuning biodegradable
polyol. The antifouling performance was evaluated after certain intervals.
Key words: Polyurethane, fouling, coating
INTRODUCTION
Marine biofouling is the undesirable settlement of macroorganisms (barnacles, mussels, hydroids, etc.)
and microorganisms (algae, bacteria, sponges, diatoms) on a immersed surfaces. Marine biofouling
has huge adverse effects on marine vessels as well as many offshore platforms and structures. Due to
the marine fouling adverse effect, the direct and indirect cost of maintenance of vessels and structures
is increasing every year. It is an urgent issue to mitigate marine fouling.1-3
Marine fouling is a natural process. Every immersed surface will usually be infested or covered by
foulers with given time. The fouling process is summarized in Figure 1. It’s impossible to avoid the
fouling process without any treatment. If fouling has begun, it’s also very difficult to stop or mitigate the
process. It is always highly recommended to start the mitigation process at a very early stage of the
immersion. The common practice is the use of coating (with or without biocide) which has antifouling
characteristics. The modern antifouling technology is based on primarily two methods; foul release
coating and self-polishing coating (SPC). The main mechanism of foul release coating is resisting the
surface from the attachment of foulers. A single biocide or a mixture of biocides can be used to make
the antifouling coating in SPC coating.3,4
Different polymeric materials play a vital role to mitigate the fouling in both ways.2-4 Polyurethane (PU)
has been considered by researchers to mitigate the fouling.5,6 In this study a series of biodegradable
PU coatings were synthesized by tuning polyol monomers. Polycaprolactone diol, which is
biodegradable, was used to synthesize PU coatings. The effect of the PCL content on antifouling
properties was evaluated.
Figure 1: Marine fouling formation.
EXPERIMENTAL PROCEDURE
Materials
Poly(tetramethyleneoxideglycol) and polycaprolactonediol (number-average molecular weight = 2000
g/mol) were vacuum-dried at 90 °C under a pressure of 1-2 mmHg for 3 hours prior to use. Triethylamine
(TEA), N-methyl-2-pyrrolidone (NMP), and 4,4’-dicyclohexylmethane diisocyanate (H12MDI) were used
after dehydration using 4-Å molecular sieves for 1 week. Eethylene diamine (EDA), 2, 2- dimethylol
propionic acid (DMPA) and dibutyltin dilaurate (DBTDL) were used as received.
Preparation of WBPU dispersion

All coating dispersions were prepared following a prepolymer process.6 The solid content of the
dispersion was fixed at 30 wt %. At first, the pre-polymer (NCO-terminated) was obtained by charging
dimethylol propionic acid, diisocyanate, and polyether polyol or polycaprolactone diol. A very small
amount of tin catalyst was added during the reaction of polyol and diisocyanate. 10 wt % methyl ethyl
ketone (MEK) was added to the pre-polymer to lower the viscosity of pre-polymer. To neutralize the
carboxyl group of prepolymer, triethylamine was added to the pre-polymer mixture. Distilled water was
added to the neutralized pre-polymer, which was followed by a chain extension by adding diamine.
Finally, the organic solvent was evaporated from the WBPU dispersion.
Preparation of the film
The films were prepared by pouring aqueous dispersions (10 g) onto a Teflon disc (diameter 7 cm)
followed by 48 hours of drying under ambient conditions. The films (typically ~0.5 mm thick) were also
dried at 60°C for 6 hours and vacuum dried at 80°C for 6 hours. The vacuum dried films were stored in a
desiccator at room temperature.
Mounting coatings onto polyvinychloride (PVC) sheet

The dispersion was mounted onto a PVC sheet with an applicator. The coated samples (200 μm wet
thickness) were dried at an ambient temperature.
Characterization
FTIR spectroscopy was used to identify the coating structure. The dispersion was coated on a
thalliumbromide/thalliumiodide crystal surface as a thin liquid film and dried for analysis. For each sample,
32 scans at a resolution of 4 cm-1 were collected at transmittance mode. An optical tensiometer was used
to analyze the water contact angle of the coatings. All the tested coatings were immersed in a real sea
environment for 30 days and photographs were taken to evaluate their antifouling performance.
RESULTS
All PU dispersions were prepared following the prepolymer process. In all cases, the disappearance of
NCO peak at 2170 cm-1 confirmed the reaction had been terminated; all monomer reacted - no unreacted
monomer was present in the dispersion. The identical peaks around 1710 cm-1 and 3430 cm-1 (for the C
O group and N H groups, respectively) for urethane/urea groups (see Figure 2) confirmed the
successful synthesis of PU dispersion. In addition, all spectra also showed other characteristic peaks at
2795, 1540 and 1110 cm-1.
PCL-based
coating
Transmittance (%)
PTMG-based
coating
4000 3000 2000 1000

-1
Wavenumber (cm )
Figure 2: FT-IR spectra of coating.
The water contact angle of the coatings is shown in Figure 3. The contact angle is a good technique to
evaluate the hydrophobicity of the coatings. The value of the contact angle decreased with the inclusion
of PCL. The value continued decreasing with increasing PCL content. It implies that the coating is more
hydrophilic with higher PCL content. The hydrophilicity, with the presence of PCL, can be attributed to
the hydrophilic nature of ester group in PCL.
80
60
Contact angle (°)

40
20
0 4.4 8. 13. 17.

2 PCL8 27 69
(mole%)
5
Figure 3: Water contact angle value of coating with different PCL content.
All the coated samples were immersed in a real sea environment. The antifouling performance was
examined by visual inspection after certain defined intervals. All the coatings were covered with marine
fouling (not shown). Different behavior was observed with biocide in the PCL based coating. In this case,
the coating was free from fouler attachment (see Figure 4). However, the coating with biocide in PTMG
based coating moderately resisted the fouler attachment. Though the biocide and monomer compositions
were similar, the PCL based coating may have eroded faster than the PTMG based coating due to its
biodegradable matter; as a result the PCL based coating may release the biocide continually and
properly. The ultimate result was improving the antifouling property.
Figure 4: Photograph of immersed coating.

CONCLUSIONS
A series of PU coatings were prepared using biodegradable polyol. The antifouling property was not
directly related to the biodegradable polyol. Using biocide in coating based on biodegradable polyol
showed excellent antifouling properties. Such PU coating might be a promising candidate in SPC
antifouling coating.
ACKNOWLEDGEMENTS
The authors would like to acknowledge the support provided by the Deanship of Scientific Research
(DSR) at King Fahd University of Petroleum and Minerals (KFUPM) for funding this work through project
No. SB171008.
REFERENCES
1. M.M. Rahman, H.H. Chun, H. Park, ‘‘Preparation and properties of waterborne polyurethane-silane:
A promising antifouling coating’’ Mac. Res. 19, (2011): p. 8.
2. M.M. Rahman, H.H. Chun, H. Park, ‘‘Preparation and properties of waterborne polyurethane-silane:
A promising antifouling coating’’ J. Coat. Technol. Res. 8, (2011): p. 389.
3. S. Verma, S. Mohanty, S. K. Nayak, ‘‘A review on protective polymeric coatings for marine
applications’’ J. Coat. Technol. Res. 16, (2019): p. 307.
4. S. Verma, S. Das, S. Mohanty, S. K. Nayak, ‘‘Development of multifunctional polydimethylsiloxane
(PDMS)-epoxy-zinc oxide nanocomposite coatings for marine applications’’ J. Coat. Technol. Res.
30, (2019): p. 2275.
5. D.K. Chattopadhyay, K.V.S.N. Raju, ‘‘Structural engineering of polyurethane coatings for high
performance applications’’ Prog. Polym. Sci. 32, (2007): p. 352.
6. M.M. Rahman, H.D. Kim, ‘‘Synthesis and characterization of waterborne polyurethane adhesives
containing different amount of ionic groups (I) ’’ J. Appl. Polym. Sci. 102, (2006): p. 5684.

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MPWT19-15293

Biodegradable Antifouling Coating

Mohammad Mizanur Rahman

Key words: Polyurethane, fouling, coating

Figure 1: Marine fouling formation.

Preparation of WBPU dispersion

Mounting coatings onto polyvinychloride (PVC) sheet

4000 3000 2000 1000

Figure 2: FT-IR spectra of coating.

Contact angle (°)

0 4.4 8. 13. 17.

Figure 4: Photograph of immersed coating.

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