Chapter 2

REVIEW OF RELATED LITERATURES

Biofouling and its Effects
Biofouling is simply the attachment of an organism or organisms to a surface in contact
with water for a period of time. That explanation sounds fairly straightforward, but there are
several organisms that cause biofouling, many different types of surfaces affected by it, and, due
to the work of scientists, engineers and others, scores of solutions to the problem. Even this
definition greatly simplifies what really occurs.
Biofouling occurs worldwide in various industries, from offshore oil and gas industries in
China and the Indian Ocean, to fishing equipment in the Caspian Sea, to cooling systems in the
Chesapeake Bay. One of the most common biofouling sites is on the hulls of ships, where
barnacles are often found. The most obvious problem of growth on a ship is the eventual
corrosion of the hull, leading to the ship's deterioration. Even before corrosion occurs, if left
unattended, organic growth can increase the roughness of the hull, thereby decreasing its
maneuverability and increasing drag (Roland et al., 2003). This domino effect continues when
the ship's fuel consumption increases, in some cases by 30% (Younqlood et al., 2003). This in
turn has economic and environmental consequences, as increased fuel consumption leads to
increased output of greenhouse gases (Anderson et al., 2002). Economic losses are tremendous,
as fuel accounts for up to 50% of marine transportation costs (Roland et al., 2003).
Biofouling is everywhere. Parts of a ship other than the hull are affected as well: heat
exchangers, water-cooling pipes, propellers, even the ballast water. Heating and cooling systems
biofouling might also be found in power stations or factories. Just like a clogged drain in your
kitchen or bathroom, buildup of matter inside cooling system pipes decreases performance
(Roland et al., 2003). Again, fouling causes a domino effect. Equipment must be cleaned

frequently, at times with harsh chemicals, and the obstruction of piping can lead to a shutdown of
plants and economic losses (De Rincon et al., 2001).
The problem is more serious in tropical waters. Cold waters have a low prevalence of
biofouling, perhaps because of the physiology of the organisms responsible (Panchal et al.,
1984). It is not only barnacles that create difficulties, and as we've seen, it's not just on ships'
hulls; moreover, the old method of scraping barnacles is not the only solution.
Types of Biofouling
Microfouling
Microfouling is a type of biofouling in which microscopic organisms including bacteria
and diatoms and the slimy substances that they produce. Biofouling comprised of only
microfouling is commonly referred to as slime layer otherwise known as biofilm (IMO, 2011).
Macrofouling
Macrofouling is a type of biofouling in which means large, distinct multicellular
organisms visible to the human eye such as barnacles, mussels, tubeworms, or fronds of algae
(IMO, 2011).
Biofilm and its Relevance to Biofouling
Biofouling is not as simple a process as it sounds. Organisms do not usually simply suck
onto a substrate like a suction cup. The complex process often begins with the production of a
biofilm. A biofilm is a film made of bacteria, such as Thiobacilli or other microorganisms that
forms on a material when conditions are right (Gehrke et al., 2003). Nutrient availability is an
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important factor; bacteria require dissolved organic carbon, humic substances and uronic acid for
optimum biofilm growth (Griebe et al., 2000). Biofilms do not have to contain living material;
they may instead contain such once living material as dead bacteria and/or secretions. Bacteria
are not the only organisms that can create this initial site of attachment (sometimes called the
slime layer); diatoms, seaweed, and their secretions are also culprits.
Treatments Against Biofouling
There are several treatments used against biofouling, these are the patented antifouling
agents, antifouling agents based on natural products and applications of polymer-metal
nanocomposites.
Patents on Antifouling Agents
Patents such as: WO2014177638 (Weber et al., 2014), WO2014175246 (Yamamoto et
al., 2014), WO2014171321 (Fukami et al., 2014), WO2014158398 (Yeganeh et al., 2014),
EP2781567 (Niimoto et al., 2014), WO2014126643 (Liao et al., 2014), WO2014120095 (Zhu et
al., 2014) and EP2749583 (Chen et al., 2014) uses antifouling coatings and substrates made from
modified polymers such as polysiloxanes and polysilicones; while patents WO2014169342
(Ginic-Markovic et al., 2013) and US20140299538 (Gleason et al., 2014) uses antifouling
membranes for water treatment facilities and patent US20140296371 (Kappock et al., 2014) uses
a metal salt called copper pyrithione synthesized from zinc pyrithione and an undisclosed copper
compound. And lastly, the patent US20140275391 (Walls et al., 2014) invented additives for
antifouling paints that improves the antifouling behavior of antifouling coatings.
Natural Products as Antifouling Agents

Natural products are also studied as antifouling agents. Organic extracts from some
epibiont-free Colombian Caribbean Sea sponges (Agelas tabulata, Myrmekioderma gyroderma,
Oceanapia peltata, Aplysina lacunosa, Neopetrosia sp.) and a sea-cucumber (Holoturia
glaberrima) are made into paints and shown significant reduction of biofilm formation after 45
and 90 days (Avecedo et al., 2013) as well as bioactive metabolites from seagrasses Syringodium
isoetifolium and Cymodocea serrulata shown complete inhibition from limpet (Patella vulgate)
attachment and 50% inhibiton from mussel Perna indica. The active metabolites were
characterized using gas chromatography coupled with mass spectroscopy (GC-MS) and keyed
out that fatty acids (C16 to C24) were the major components which responsible for the
antifouling properties of the candidate seagrasses. (P. Iyapparaj, Peranandam Revathi, et al.,
2014).
Polymer-Metal Nanocomposites
Another strategy to combat biofouling is to use metal nanoparticle coated polymer
nanocomposites. These are made from embedding the metal nanoparticle on a polymer substrate
or matrix. Several nanocomposites from various matrices have been made. These polymer
matrices are polysulfones, sol gels, poly(vinyl pyrrolidone), and ion exchange resins. The
commonly used metal nanoparticles in making polymer-metal nanocomposites are silver and
copper due to their antimicrobial and antifouling properties.

Metals Commonly Used in Anti-Biofouling

Copper
Copper; a Group 11 transition metal like silver and gold has potent antibacterial
properties and has been able to kill bacteria, fungi and viruses. The potency of the copper is
attributed to the elements ability to disrupt various critical functions of the bacteria/microbe to
survive survive (Dick et al., 1985), alter the structural integrity of proteins and enzymes of
microbes (Thurman et al., 1989) and in case of viruses, copper can also form radicals that
inactivate viruses (Kurawara et al., 1986) and (Vasudevachari et al., 1982).
Silver
A commonly utilized metal in antifouling is silver. Silver interrupts the bacteria cells
ability to form the chemical bonds essential to its survival. These bonds produce the cells
physical structure so when bacteria meets silver it literally falls apart. For this reason, silver
enforced bandages are especially in demand. Bandages with silver ions prevent bacterial growth
and speed healing time, making them especially valuable for treating burn and wound victims.
Substrates Used in Making Metal-Polymer Nanocomposites
Polysulfone
A family of sulfur-containing thermoplastics, closely related to polyethersulfone (PES).
The structure of the polysulfones is aromatic groups, generally with more than one benzene ring,
joined by a sulfone group. Generally, polysulfone is a high cost, rigid, amorphous material with
low moisture absorption. Reinforcement improves toughness and further enhances dimensional
stability, but turns materials opaque. In addition, polysulfones are characterized by high strength,
very high surface-temperature limits, low creep, good electrical characteristics, transparency,
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self-extinguishing ability, and resistance to greases, many solvents, and chemicals. Polysufones
may be processed by extrusion, injection molding, and blow molding.
A study about metal-polymer nanocomposites is by using Polyethersulfone (PES)
ultrafiltration membranes blending with halloysite nanotubes-chitosan-Ag nanoparticles (HNTsCSAg) for the effective biofouling control (Chen et al., 2013). The SEM results indicated that
addition of HNTs-CSAg did not affect the microstructure of the PES membranes. The AFM
results showed that the surface of the hybrid membrane became smooth. In addition, the hybrid
membranes were shown to be more hydrophilic, with a higher pure water flux, as high as 375.6
L/(m2 h), which was about 233.0% higher than that of the pure PES membrane. The antifouling
test revealed that the hybrid membranes modified by HNTs-CSAg had a good antifouling
performance. Moreover, the antibacterial test indicated that the hybrid membrane had a good
antibacterial activity, and the antibacterial rates against E. coli and S. aureus were about 94.0%
and 92.6%, respectively.
Next study about metal-polymer nanocomposites using polysulfone is by using silvernanoparticle attached thin film composite membranes using covalent bonding to E. coli growth
(J. Yin et al., 2013). The nanocomposite is made by mixing and incubating the silver
nanoparticles made from PVP40 solution and thin film composite made from polysulfone and
SH-terminated polysulfone thin-film composite. Scanning electron microscopy (SEM), energy
dispersive X-ray spectroscopy (EDS) and cross-sectional transmission electron microscopy
(TEM) studies all showed the immobilization of AgNPs. Compared with the pristine TFC
membrane, thiol-terminated membrane (TFCSH) and AgNPs grafted membrane (TFC-S
AgNPs) both showed a higher water flux with slightly lower salt rejection. At a constant
transmenbrane pressure of 300 psi, the water permeability of TFCSH, TFC-SAgNPs, and
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control TFC membranes was 70.60.5, 69.40.3, and 49.81.7 L/m2h, respectively, while NaCl
rejection was 93.40.1%, 93.60.2%, and 95.90.6%, respectively. NaCl rejection is regarded as
the chloride ion decreases the anti-fouling effects of silver nanoparticles. TFC-SAgNPs had an
improved antibacterial ability to inhibit E. coli growth. The silver leaching from the TFC-S
AgNPs membrane surfaces was minimal, as tested by both batch and flow-through methods. The
study concludes that the silver nanoparticles could be grafted into a polysulfone TFC using
covalent bonding to improve the TFCs antifouling effects.
PES membrane characteristics were changed by the addition of Se or Cu nanoparticles
(Akar et al., 2014) to the polymer solution with hydrophobic interaction between the membrane
surface and foulants such as protein and activated sludge suspension. Contact angle
measurements and protein rejection studies indicated that the significant increment in surface
hydrophilicity as well as protein rejection were obtained by Cu nanoparticles blended
membranes. The result of the both protein separation and activated sludge filtration studies
showed that all Se or Cu nanoparticles blended PES membranes had good antifouling properties
with high-rejection rate, compared to neat PES membranes. Especially, 0.05 Se/PES and Cu/PES
membranes had better antifouling performance.
The next study about copper metal-polymer nanocomposites using PES (polysulfone)
membrane is by using selenium and copper nanoparticles- doped PES membrane (N. Akar et al.,
2013). Selenium nanoparticles were prepared by the reduction of aqueous sodium selenite
solution with glucose solution and the Se nanoparticles size distribution was in the range around
150175 nm. However, copper nanoparticles were prepared by sonochemical reduction of copper
(II) hydrazine carboxylate complex in an aqueous medium and the size of copper nanoparticles
was about 90105 nm.
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Within the 1418 wt% polymer concentration, the 18% PES was found as the optimum
concentration. Also, the optimum solvent evaporation time was found to be 0 s, within the 0
90 s. The nanoparticle concentrations in the casting solution increased from 0.002 to 0.050
Se/PES or Cu/PES, distilled water permeability decreased from 121 to 58 L/(m2 h bar) and from
249 to 69 L/(m2 h bar) for Se-entrapped PES and Cu-entrapped PES membranes, respectively.
Sol Gels
A sol gel is a colloidal suspension of tiny particles in a liquid medium which undergoes
hydrolysis and condensation polymerization to form a gel. Sol gels are used in antifouling
coatings due to their chemical inertness and offering environmental protection on exposed
surfaces such as boat hulls (TWI, 2014).
One study on using nanocomposites made from solgels is by using the period IV metal
nanoparticle doped sol gels (Chapman et al., 2010). Chlorides of scandium, titanium, vanadium,
chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium and selenium were
reduced into metallic forms using sodium borohydride and polyvinylpyrrolidone solution and
then doped into a tetraethoxysilane/3-aminopropyltriethoxysilane sol-gel. After preparation, the
doped solgels were tested for the physical and anti-fouling effects.
Results showed that The spectra of V, Cr, Mn, Ni and Ge all have two or more bands,
suggesting that a different shape is being detected. Whereas Sc, Fe, Co, Cu, Zn, Ga and Se have
one succinct broad or sharp peak. According to Mie's theory only a single SPR band is expected
in the absorption spectra of spherical nanoparticles, whereas anisotropic particles give rise to
multiple SPR bands depending completely on the shape , as witnessed in Sc, Fe, Co, Ni, Ga and
Se. Therefore the number of SPR bands increases the symmetry of the nanoparticle decreases.
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UVvis is an adequate tool for initial analysis of MNPs and has shown in this work that the
production of MNPs has occurred; this was further confirmed by clarification methods below.
According to particle size analysis, the biofouling control of the nanoparticle is also
dictated by the nanoparticles shape and maximum absorption (Pal et al., 2007). The sol-gel is
characterized by using SEM. The mean thickness of the sol-gel used to dope nanoparticles is 92
micrometers. According to surface energy analysis, MNP-doped solgels show more
hydrophilicity compared to the undoped solgel blank. Therefore we propose that the MNP is
changing the surface energy across the doped solgels. It is suggested by Sharma et al. that water
spreading occurs in solgels with MNP introduced due to the metal conferring hydrophilicity to
the doping matrix; this property is exhibited in the MNP-doped solgels. From the biomass
analysis of the MNP-doped sol-gels, it is clear that the MNP-doped solgels give better response
to inhibition of biofouling in this instance biomass, in the case of this 7-day study, showing upto
50% better response compared to the undoped solgel. Ga, Ge and Se all show promising levels
of biomass inhibition with Ga showing upto 125% better biomass resistance compared to the
solgel blank.
The results show that Ga MNP-doped solgels have given signification of better
biofouling resistance to microorganisms compared to any of the other MNP-doped solgels. This
is observed as nearly 500% better inhibition to microorganism attachment compared to the sol
gel blank. Cr, Mn, Ge and Se all gave similar results and proved to be effective at resisting
microbial attachment up to 200% better than the undoped coating.
It is apparent that some MNPs show superior antifouling response to others but all still
performed, in some cases 150% better than the solgel blank. In this work gallium MNPs are
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first reported using the polyol reduction method. In addition this preliminary study illustrates the
capacity for their use in antifouling materials and applications. Gallium is known to be Ferromimicking, which means that iron-dependent bacterial strains are able to uptake Ga as if it were
Fe. The MIC (Minimum inhibitory concentration) of Ga and Ge MNPs, illustrates that Ga has
better response in resisting pure culture E. coli than Ge.
Poly(vinyl pyrrolidone)
Polyvinylpyrrolidone (PVP), also called Polyvidone, is a water-soluble polymer made
from the monomer N-vinylpyrrolidone. PVP is soluble in water and other polar solvents. When
dry it is a light flaky powder, which readily absorbs up to 40% of its weight in atmospheric
water. In solution, it has excellent wetting properties and readily forms films. This makes it good
as a coating or an additive to coatings (Haaf et al., 1985). Poly(vinyl pyrrolidone) is often used
as an additive to antifouling coatings because it improves the antifouling effects of the
nanocomposite (Chen et al., 2012), (Yuan et al., 2014).
One study on using poly(vinyl pyrrolidone) as a substrate is by impregnating the polymer
with silver nanoparticles (Zodrow et al., 2009). Using the synthesized metal-polymer
nanocomposites, it is shown that the nanocomposite is able to inhibit the biofilm formation and
also kill the bacteria Pseudomonas mendocina and E. coli. The mechanism behind this is the Ag+
ion released from the nanocomposite membrane. However, addition of 3.0 mg/l cysteine inhibits
the antifouling effects of the silver nanoparticle as it binds to silver thus, allowing the bacteria to
grow again. Similarly, when 27 mg/l cysteine is added, the bacteria is inactivated to 60% instead.
Also, the nanocomposite is able to remove up to 50.25 PFU/mL of poliovirus. The reason
behind this is the silver nanoparticles is able to adsorb the virus by decreasing the magnitude of
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negative charge on the suface of the nanoparticle; and also the release of Ag + from the nAg
nanocomposite.
However, the drawbacks of this study is that the nanocomposite is rapidly releases the
nAg particle, thus hastening its depletion and the silver resistances of some bacterial strains. The
options to remediate this problem is to encapsulate the nanoparticle in a polymer an then
covalently binding it to membrane polymers or encapsulating in a substance that is degraded by
bacteria so that it releases in a constant rate.(Loher et al., 2008) Also the presence of ions and
substance such as chlorides, phosphates, sulphides and thiols decrease the potency of silver ions
and can reverse (like cysteine) the damage done to the bacteria. The antifouling activity of the
silver nanoparticles is increases with the increasing pH and temperature.
Ion Exchange Resins
Ion exchange resins, any of a wide variety of organic compounds synthetically
polymerized and containing positively or negatively charged sites that can attract an ion of
opposite charge from a surrounding solution. The resins commonly consist of a styrenedivinylbenzene copolymer (high molecular weight substance), although other compositions, such
as methacrylic aciddivinylbenzene and phenol-formaldehyde polymers, are also employed. The
electrically charged groups are commonly sulfonic or carboxylic acid salts or quaternary
ammonium salts. Polymers containing acid groups are classified as acid, or cation, exchangers
because they exchange positively charged ions, such as hydrogen ions and metal ions; those
containing ammonium groups are considered basic, or anion, exchangers because they exchange
negatively charged ions, usually hydroxide ions or halide ions (Encyclopedia Britannica, 2014).

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The usage of ion exchange resins as substrate for metal nanoparticles with antifouling
properties because it reduces agglomeration, increases the antimicrobial activity (Bankura et al.,
2012), (Cho et al., 2005), (Li et al., 2008), providing greater bioavailability (Yee et al., 2014)
and providing low cost of producing the nanocomposite suitable for industrial scale (Yee et al.,
2014).
In the study of (Yee et al., 2014), they have developed a metal-polymer nanocomposites
using silver nanoparticles with narrow size distributions made from reducing silver nitrate using
sodium borohydride. The templating matrix used is Dowex protonated copolymer ion
exchange resin microbeads. The silver is introduced into the microbeads using an ion-exchange
process with silver nitrate. And then followed by chemical reduction by sodium borohydride to
form metallic Ag on the surface of the resin microbead. Using SEM, it reveals that the Ag
nanoparticles are uniformly distributed with diameters 20 and 60 nm on the surface of the
microbeads. Using UV-VIS spectroscopy, it indicates that the maxmum detection (using suface
plasmon resonance) of Ag nanoparticles absorbed into the surface of the microbead is at 406 to
422 nm. Also, the thermal stability of the nanocompostie is increased from 130 to 323 degrees
Celsius, compared to 300 degrees for the copolymer microbead. There is a significant biofilm
inhibiton by Halomonas pacifica at 76%, and according to results, the nanocomposite is
biocompatible and non-toxic to human lung cell fibroblast, and also non-toxic to target
microorgansims such as Isochrysis sp. and Dunanenlia tertiolecta .
Next study on using ion exchange resin as a substrate is using copper nanoparticle-coated
poly(styrene-co-sulfonic acid) nanocomposite. (Zhang et al., 2014) synthesized using
microspheres using only commonly found apparatus such as centrifuge and environmentally
friendly reducing agent such as glucose which is applicable to industrial scale. Results showed
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that the distribution of copper nanoparticle in the microsphere is evenly distributed and coated
using the glucose and sulfonating agents in preparation of the microspheres, XRD indicates that
the copper nanoparticles has crystalline planes of Cu crystal, respectively, which corresponded to
the typical peaks of the face centered cubic Cu and also had narrow size distribution. Also XPS
indicates that the nanocomposite had the content of Cu nanoparticles on the surface of PS could
be estimated to be about 4.3%. In addition, the aromatic p-electrons of the resin also interacted
with the atoms of metal surface layer, which greatly increased the stability of the nano- particles
in the hybrid materials. In addition, the nanocomposite is able to kill the E. coli and S. aureus at
1g/l of nanocomposite due to to the fact that Cu nanoparticles with positive charge could easily
react with Gram negative E. coli and S. aureus due to the electrostatic attraction. Based on the
XPS analysis, there existed two forms of the Cu in PS, and the Cu/PS-3 could dissolve in water
slowly and release Cu2+, which made it easier to interact with the bacteria. Therefore, it could
cause structural change of the outer membrane of the bacteria, further resulting in cell
degenerating.

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