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Biofouling: The Journal of Bioadhesion and Biofilm

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Silicone fouling-release coatings: effects of the

molecular weight of poly(dimethylsiloxane) and
tetraethyl orthosilicate on the magnitude of
pseudobarnacle adhesion strength
a a a
Azadeh Kaffashi , Ali Jannesari & Zahra Ranjbar
a
Institute for Color Science and Technology , Tehran , 16765-654 , Iran
Published online: 16 Jul 2012.

To cite this article: Azadeh Kaffashi , Ali Jannesari & Zahra Ranjbar (2012) Silicone fouling-release coatings: effects of
the molecular weight of poly(dimethylsiloxane) and tetraethyl orthosilicate on the magnitude of pseudobarnacle adhesion
strength, Biofouling: The Journal of Bioadhesion and Biofilm Research, 28:7, 729-741, DOI: 10.1080/08927014.2012.702342

To link to this article: http://dx.doi.org/10.1080/08927014.2012.702342

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 Biofouling
Vol. 28, No. 7, August 2012, 729–741

Silicone fouling-release coatings: effects of the molecular weight of poly(dimethylsiloxane) and

tetraethyl orthosilicate on the magnitude of pseudobarnacle adhesion strength
Azadeh Kaffashi, Ali Jannesari* and Zahra Ranjbar
Institute for Color Science and Technology, Tehran 16765-654, Iran
(Received 17 February 2012; final version received 9 June 2012)

A series of poly(dimethyl siloxane) (PDMS)/silica nanocomposites were synthesized utilizing a sol gel method. The
samples were evaluated using pseudobarnacle adhesion and tensile strength tests. The effects of the molecular weight
of the PDMS and the size and structure of the silica domains on biofouling release and the mechanical behavior of
the PDMS/silica materials were investigated. Three different molecular weights (18,000, 49,000 and 79,000 g mol71)
of hydroxyl-terminated PDMS (HT-PDMS) were used to prepare the nanocomposites with three different weight
ratios (1:1, 3:1 and 5:1) of HT-PDMS to tetraethyl orthosilicate (TEOS). TEOS served as a crosslinker to form
PDMS networks and as a precursor to form silica domains. Two different variants of TEOS with regard to its degree
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of polymerization (n) (monomeric type: n ffi 1 and oligomeric type: n ffi 5) were used for in situ formation of silica
particles via the sol-gel process. The mechanical properties of the composites were characterized using stress–strain
isotherms. All the mechanical properties evaluated (Young’s modulus, tensile strength, energy required for rupture,
elongation at break) improved with increases in the molecular weight of the HT-PDMS and the silica content. The
pseudobarnacle adhesion test was used to examine the fouling- release (FR) properties of coatings applied on
aluminum plates. The rupture energy and tensile strength increased substantially when oligomeric TEOS was
employed in the PDMS/silica composites. Scanning electron microscopy (SEM) was used to investigate the structure
of the silica domains. It was found that the use of oligomeric TEOS in higher molecular weight PDMS samples with
higher PDMS/TEOS weight ratios led to low pseudobarnacle adhesion strengths of *0.3 MPa, which is in the range
of commercial FR coatings.
Keywords: biofouling release; poly(dimethylsiloxane)/silica nanocomposites; pseudobarnacle adhesion; stress–strain
isotherms, fouling-release coatings

Introduction Initially, both silicones and fluoropolymers were

Biofouling is ubiquitous in the marine environment.
This fouling that clings to the hulls of ships results
in increased operational and maintenance costs by
increasing the fuel consumption and frequency of
dry-docking operations (Callow 1990; Townsin 2003;
Yebra et al. 2004; Schultz et al. 2011). Toxic
antifouling paints containing copper, tin and other
biocides have been applied to ships to combat fouling
(Rascio 2000; Thomas and Brooks 2010) until the use
of tin-based paints was banned by environmental
organizations (Champ 2000; Dafforn et al. 2011). This
legislation led to the development of fouling-release
(FR) coatings as an alternative nontoxic technology
(Brady et al. 1987; Brady 1994, 1997, 2000; Adkins
et al. 1996). Although organisms can attach to these
coatings, they are removed by either mechanical or
forceful water movement, which is caused by the
motion of the vessel (Swain and Schultz 1996;
Kavanagh et al. 2005).
identified as FR surfaces because both polymers
exhibit low critical surface tension and this character
is considered crucial for foul releasing ability (Baier
and Meyer 1992; Callow and Fletcher 1994). Baier and
Depalma (1971) studied the relationship between the
critical surface tension of the polymer surface and the
relative amount of bioadhesion. The results were
shown as the ‘‘Baier curve.’’ An important feature of
this curve is that the minimum in bioadhesion does not
occur at the lowest critical surface energy. The mini-
mum of the Baier curve is attributed to poly(dimethyl-
siloxane), which has a very low elastic modulus
(0.002 GPa). Later, it was found that the FR behavior
of polymers depends not only on the surface energy
but also upon mechanical properties such as the elastic
modulus (Brady and Singer 2000; Singer and Kohl
2000; Brady 2001). Because of this, silicone polymers
outperformed fluoropolymers (Brady 1999). Further-
more, fluoropolymers are porous, thus they allow

*Corresponding author. Email: ajannesari@icrc.ac.ir

ISSN 0892-7014 print/ISSN 1029-2454 online

Ó 2012 Taylor & Francis
http://dx.doi.org/10.1080/08927014.2012.702342
http://www.tandfonline.com
 730 A. Kaffashi et al.
fouling organisms to establish a mechanical interlock.
The superior properties of silicones also have been
attributed to the low glass transition temperature of
silicones that is reflected in their molecular mobility
(Bausch and Tonge 1996; Brady 1997). Interfacial
slippage and friction also play a role in enhancement of
the release properties of silicones compared to
fluoropolymers (Newby et al. 1995; Newby and
Chaudhury 1997).
Commercially available FR coatings are based
on silicone elastomers formed from polymerized
dimethylsiloxanes (PDMS) (Yebra et al. 2004). Poly
(dimethylsiloxane) elastomers are inherently weak
materials and exhibit very poor mechanical properties
(Dewimillea et al. 2005). Therefore, they may not be
durable enough to survive on a ship’s hull. Because of
their poor mechanical strength, there is a great need to
improve the mechanical properties of PDMS-based
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FR coatings. Griffith (1995) introduced a duplex
silicone coating that is considerably tougher than a
single layer coating. A silicone duplex or bi-layer
elastomeric coating consists of a low-modulus silicone
top layer bonded to a substratum by the use of a stiffer
silicone bond coat, which is blended with copolymers
such as butyl acrylate styrene (Kohl and Bolstes 2001).
Although the bond coat is responsible for bonding to a
substratum and providing mechanical strength, many
attempts have been made to enhance the mechanical
properties of the silicone top coat. Some studies (Yuan
and Mark 1999; Mirabedini 2008; Fang et al. 2010;
Rath et al. 2010) have been carried out to alleviate
the durability problems of PDMS-based coatings.
Due to the good mechanical properties of the cured
epoxy resin materials, Rath et al. (2010) employed
epoxy resin to modify PDMS-based FR coatings. They
investigated the effect of modulus and surface energy
on pseudobarnacle and macrofouling behavior. But
pseudobarnacle tests revealed that the release force
increased significantly by using epoxy. Incorporation
of polyurea segments to the PDMS backbone is ano-
ther way for reinforcing PDMS (Fang et al. 2010).
The extent of phase separation with the extensively
hard domains created an interconnected network that
imparted mechanical rigidity.
In addition to blending PDMS with other poly-
mers, some studies (Mark 1996, 1999; Dewimillea et al.
2005; Paul and Mark 2010) have shown that incor-
poration of filler particles (usually silica) into the soft
matrix has a profound effect on mechanical properties.
Silica can be used for reinforcing PDMS in two ways.
In the first conventional method, particulate silica
particles are blended into the PDMS before cross-
linking (Sun and Mark 1989). However, this type of
ex situ blending process is difficult, time consuming
and energy intensive (Yuan and Mark 1999). An
alternative technique, which was used for the study
reported here, is a sol–gel method that was introduced
by Mark et al. (1984). In this method, hydroxyl-
terminated PDMS chains are blended with enough
tetraethyl orthosilicate to simultaneously end-link the
PDMS chains and produce the silica particles (Mark
et al. 1984; Dewimillea et al.2005; Alexandru et al.
2009). Mark et al. (1984) investigated the mechanical
properties of such in situ networks and showed that
increasing the silica content generated in situ leads to
an increased elastic modulus, but there is a tradeoff
between FR properties and mechanical durability.
Although the best mechanical performance has been
seen with harder coatings, the best FR properties are
obtained with softer materials (Stein et al. 2003a,
2003b; Perera 2004; Mirabedini et al. 2008).
With FR coatings, the most important point that
must be considered is that increasing the elastic
modulus may have deleterious effect on the FR
property. Finding a solution to this problem is one
of the greatest challenges faced by scientists today.
Therefore, there is a great need to adopt a new
approach to this challenge. All strategies mentioned
above for reinforcing PDMS adversely affect FR
behavior. This paper makes the suggestion of using
oligomeric (instead of monomeric) ethyl silicate
in order to have good mechanical durability, in
addition to acceptable FR. The present investigation
extends the studies referred to by employing oligo-
meric ethyl silicate (partially hydrolyzed ethyl silicate),
as well as the monomeric form, and 3 different molecular
weights of hydroxyl-terminated PDMS (low, moderate,
and high molecular weights). The mechanical properties
of the PDMS/silica nanocomposites were examined by
analyzing the tensile strength, elongation at break,
Young’s modulus, and the energy required for rupture.
In addition, scanning electron microscopy was employed
to study the structure of the silica domains generated in
situ. FR was measured by the pseudobarnacle adhesion
test to determine the effect of oligomeric ethyl silicate on
the FR coatings.
Materials and methods
Materials
Hydroxyl-terminated PDMS with number average
molecular weight of 18, 49 and 79 (6103 g mol71)
were obtained from Bluestar Silicones (France). Either
TES 28 (a monomeric TEOS) or TES 40 (a partially
hydrolyzed form TEOS), were used as the crosslinking
agent for the formation of the PDMS network and also
as the precursor for the in situ formation of silica.
TEOS materials were obtained from Wacker Corpora-
tion (Germany). The catalyst, dibutyltindiacetate
(DBTDA) and xylene were purchased from Merck
 Biofouling 731

(Germany). All of these chemicals were used as
received without further purification.
Sample preparation
According to Scheme 1, a series of PDMS/silica nano-
composites was prepared from three different molecular
weights of HT-PDMS (18, 49 and 79 (6103 g mol71))
and two TEOS materials for the end-linking of HT-
PDMS and the forming of silica domains. The cross-
linking agent was mixed with HT-PDMS in three
weight ratios (1:1, 1:3 and 1:5). Table 1 presents the
information on the prepared PDMS/silica nanocom-
posites. Sample designations indicate the form of
TEOS used (TES 28 or TES 40), the PDMS/TEOS
weight ratio (1, 3, or 5), and the PDMS molecular
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weight (18, 49, or 79 6 103 g mol71); eg 28-1-18
designates TES 28, a 1:1 PDMS/TEOS weight
ratio, and an initial PDMS molecular weight of
18,000 g mol71.
In the general procedure, TEOS and HT-PDMS
were mixed together and then 40 wt% xylene was
added to the mixture. The resulting mixture was stirred
for 20 min at room temperature until it became
homogeneous. Then, 1% (w/w) of catalyst (DBTDA),
based upon the total weight of the composition, was
added to the mixture. Afterwards, the mixture was
poured into rectangular Teflon molds (10064061 mm)
to prepare free films with film thickness of less than
1 mm. For pseudobarnacle adhesion measurements, a
part of each mixture was applied on sanded and
degreased aluminum plates (1506100 mm) by a manual
film applicator. The thickness of dry films on the
aluminum plates was 175 (+25) mm.

The curing reaction was allowed to proceed at

room temperature and 50% relative humidity for
3 days. The water required for the hydrolysis of the
TEOS was generally absorbed from the humidity in the
air. Finally, the film was vacuum-dried to constant
weight in order to remove the byproduct C2H5OH and
unreacted TEOS.

Scheme 1. The investigating parameters for studying the
mechanical properties and FR behavior of PDMS/silica
nanocomposites.
Characterization techniques
Mechanical properties
The stress–strain isotherms were obtained using a
Santam tester. Modulus, tensile strength, elongation
and rupture energy were derived from these isotherms.
Samples of dimensions 10064061 mm were pulled to

Table 1. Synthesis information and composition of the nanocomposites.

Molecular weight
of PDMS Weight ratio % Silica precipitated
Sample (61073 g mol71) PDMS/TEOS Type of TEOS calculated theoretically
28-1-18 18 1:1 TES 28 20.14
40-1-18 18 1:1 TES 40 29.63
28-3-18 18 3:1 TES 28 8.27
40-3-18 18 3:1 TES 40 13.99
28-5-18 18 5:1 TES 28 5.15
40-5-18 18 5:1 TES 40 9.04
28-1-49 49 1:1 TES 28 20.23
40-1-49 49 1:1 TES 40 29.85
28-3-49 49 3:1 TES 28 8.38
40-3-49 49 3:1 TES 40 14.19
28-5-49 49 5:1 TES 28 5.26
40-5-49 49 5:1 TES 40 9.33
28-1-79 79 1:1 TES 28 20.24
40-1-79 79 1:1 TES 40 29.90
28-3-79 79 3:1 TES 28 8.43
40-3-79 79 3:1 TES 40 14.25
28-5-79 79 5:1 TES 28 5.28
40-5-79 79 5:1 TES 40 9.44
 732 A. Kaffashi et al.
rupture at a rate of 50 mm min71 using the procedure
defined by ASTM Standard D 412 (2006). Eighteen
different samples were prepared for tensile testing
(Table 1). The values reported for elastic modulus,
tensile strength, elongation and rupture energy are the
average of five replicates of each of the 18 samples.
Scanning electron microscopy (SEM)
The SEM images of fractured surfaces of PDMS/silica
films were obtained using a LEO 1455VP instrument.
Pseudobarnacle adhesion test
Pseudobarnacle adhesion measurements were per-
formed on samples using ASTM D5618 (2011).
Wooden studs of known diameter were glued (epoxy
adhesive) to the surface of coatings on the aluminum
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plates. The adhesive was allowed to harden for 3 days
under ambient condition before testing. After that, the
shear force required for removing each stud was
measured using a force gauge. The force gauge was
mounted on a surface, as can be seen in Figure 1; the
coated plates were moved parallel to the force gauge.
The velocity of the moving plate has no effect on
pseudobarnacle adhesion strength (Stein et al. 2003a).
Results and discussion
Mechanical properties
In order to determine the effect of incorporating
oligomeric TEOS (TES 40) as a crosslinking agent on
reinforcement of PDMS elastomers, the mechanical
properties of PDMS/silica nanocomposites prepared
using different molecular weights of PDMS and
PDMS/TEOS weight ratios were investigated and
compared to the mechanical properties of samples
prepared with the monomeric TEOS (TES 28). The
average values for 5 replicates of each sample are given
in Table 2. Figures 2 and 3, respectively, show the
elastic modulus and tensile strength of the in situ silica-
Figure 1. The pseudobarnacle adhesion test.
filled PDMS samples. According to the data, the
increase in the silica content lead to an increase in
modulus, which results from the inclusion of rigid
particles in the soft matrix. This trend can be seen in all
samples of three different molecular weights of PDMS
without considering the type of TEOS. The results
show that samples prepared with the oligomeric TEOS
were stiffer than those synthesized by monomeric
TEOS in three different molecular weights of PDMS.
This would be attributed to difference in the weight
percentages of silica precipitated in the both oligomeric
and monomeric TEOS cured samples. TES 40 (the
oligomeric type) is an ethyl silicate providing approxi-
mately 41wt% of silicon dioxide (silica) upon complete
hydrolysis whereas TES 28 (the monomeric type)
contains 28.5wt% silica after being completely
hydrolyzed.
With respect to the weight ratio of PDMS to
TEOS, in the monomeric TEOS-cured samples, the
silica content ranged from 5% to 20%; while in the
oligomeric samples, it ranged between 9% and 29%
(Table 1). Although the oligomeric TEOS-cured
composites had higher moduli than the monomeric
samples, some of them (such as 40-5-79, 40-3-79, 40-5-
49 and 40-5-18) had elastic moduli of *2 MPa, which
is an acceptable value for the FR coatings. As already
mentioned, the low elastic modulus of the PDMS had a
profound effect on decreasing the bioadhesion
strength. The samples with suitable low elastic moduli,
prepared by the oligomeric TEOS, should be enough
on a ship’s hull to provide mechanical durability and
FR.
The tensile strength values of the samples are
shown in Figure 3. The important point to make is that
the oligomeric TEOS had two completely different
effects on tensile strength in high- and low-molecular
weights PDMS. As can be seen in Figure 3, the
incorporation of oligomeric TEOS at different weight
ratios of PDMS to TEOS lead to improvement in the
tensile strength values with PDMS having molecular
weights of 49,000 g mol71 and 79,000 g mol71.
 Biofouling 733

Table 2. Mechanical properties of the nanocomposites. However, the oligomeric TEOS-cured samples pre-
Tensile Rupture pared with PDMS having a molecular weight of
Modulus strength Elongation energy 18,000 g mol71 showed lower tensile strengths than
Sample (MPa) (MPa) (%) (6103 J mm73) the monomeric-cured samples. These results emphasize
the effect of the molecular weight of PDMS on the
28-1-18 4.45 0.2 4.69 5.55
40-1-18 25.72 0.18 0.26 0.89 mechanical properties of oligomeric TEOS-cured
28-3-18 1.77 0.48 27.58 78.06 samples.
40-3-18 5.99 0.208 3.48 4.05 The elongation and rupture energy values of
28-5-18 1.03 0.25 24.4 34.62 PDMS/silica samples prepared by the oligomeric
40-5-18 2.3 0.21 9.37 5.66
28-1-49 7.28 0.53 7.53 25.23 TEOS are given in Table 3. As can be seen, with
40-1-49 5.88 0.92 15.19 101.09 increasing molecular weight of PDMS, the elongation
28-3-49 0.81 0.37 45.94 123.69 and rupture energy values of the samples increased.
40-3-49 5.70 0.57 10.42 38.39 This trend can be seen in the all three PDMS/TEOS
28-5-49 0.74 0.19 34.34 49.41
40-5-49 2.12 0.63 33.21 89.09 weight ratios (1:1, 3:1 and 5:1). Moreover, very low
28-1-79 2.39 0.87 36.28 197.6 elongation and rupture energy values for the oligo-
40-1-79 3.75 0.71 19.13 106.82 meric TEOS-cured samples prepared with PDMS
28-3-79 0.73 0.289 39.98 80.57
40-3-79 2.56 0.78 31.16 165.85
having a molecular weight of 18,000 g mol71 demon-
28-5-79 0.47 0.201 41.83 51.37 strate that the oligomeric TEOS made these samples
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40-5-79 1.205 0.54 45.06 147.55 brittle. However, the samples based on PDMS with a
molecular weight of 79,000 g mol71 had higher

Figure 2. The effect of silica content and TEOS type on the elastic modulus of PDMS/silica nanocomposites with molecular
weights of (a) 18,000, (b) 49,000 and (c) 79,000 g mol71.
 734 A. Kaffashi et al.
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Figure 3. The effect of oligomeric TEOS on the tensile strength of PDMS/silica nanocomposites with molecular weights of (a)
18,000, (b) 49,000 and (c) 79,000 g mol71.

Table 3. The effect of the molecular weight of PDMS on PDMS/silica composites, samples 40-1-49 and 40-1-79
elongation and rupture energy values of samples prepared showed an unusual behavior. The stress–strain iso-
using TES 40 in three different PDMS/TEOS weight ratios.
therms of these samples show an anomalous decrease
Rupture energy in the modulus at higher stress values. However,
Sample Elongation % (6103 J mm73) sample 40-1-18 showed normal behavior and ruptured
40-1-18 0.26 0.89 at very low stress.
40-1-49 15.19 101.09 The differences observed in mechanical behavior
40-1-79 19.13 106.82 of the oligomeric TEOS-cured composites encouraged
40-3-18 3.48 4.05 probing more deeply into the effects of the mole-
40-3-49 10.42 38.39
40-3-79 31.16 165.85 cular weight of PDMS. This different mechanical
40-5-18 9.37 5.66 behavior of the samples prepared by low and high
40-5-49 33.21 89.09 molecular weight PDMS would probably be due to
40-5-79 45.06 147.55 the difference in the nature of the network and the
cross linking density. Schematic structural models of
the oligomeric TEOS-cured samples with low and
rupture energies and would be tougher compared to high molecular weights of PDMS are proposed in
the other samples. Figure 5. In the networks having a low molecular
On the other hand, analysis of the stress–strain weight, oligomeric TES 40 can lead to network
isotherms revealed another interesting effect of oligo- rupture because of the low elasticity and poor
meric TEOS on the mechanical behavior of PDMS/ mechanical strength of the samples. But at the higher
silica composites. As seen in Figure 4, among all molecular weight, the networks can resist rupturing
 Biofouling 735
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Figure 4. The stress–strain isotherm of PDMS/silica samples prepared with PDMS having molecular weights of (a) 18,000, (b)
49,000 and (c) 79,000 g mol71.

Figure 5. Schematic structural models of the oligomeric TEOS based networks with (a) a low molecular weight of PDMS and
(b) a high molecular weight of PDMS.
 736 A. Kaffashi et al.
because of high elasticity; meanwhile, as the stress
increases there is a corresponding decrease in the
elastic modulus.
At the weight ratio of PDMS/TEOS of 1:1 (high
silica content), if oligomeric TEOS is used to
crosslink PDMS with high molecular weight, hetero-
geneity in the samples is enhanced. This hetero-
geneity is caused by the phase separation of the
micron-sized rigid silica networks and the PDMS
elastomer network. Under low applied stress and low
strain, the mechanical behavior of oligomeric TEOS-
cured PDMS elastomers are dominated by the silica
domains as hard inclusions in a soft matrix. With
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Figure 6. Two elastic zones observed for the oligomeric TEOS cured samples, (a) 40-1-49 and (b) 40-1-79. The inset images
show the samples after tension at the first elastic zone.
increasing stress/strain and interruption of the silica
domains, the elastomeric network of PDMS will
control the mechanical behavior of composites. The
samples 40-1-49 and 40-1-79 at the first elastic zone
show high modulus values of 18.17 MPa and 14.19
MPa, respectively. As can be seen in Figure 6a and
6b, at the first elastic zone, cracks appeared on these
two samples, indicating the role played by the silica
domains. With applied stress, the micron-sized silica
domains are broken. It is interesting that the
transition zone for both samples occurred at a stress
range between 0.33 MPa and 0.57 MPa. At the
second elastic zone, samples 40-1-49 and 40-1-79
 Biofouling 737

showed low modulus values of 2.94 MPa and 1.07
MPa, respectively (Figure 6a and 6b).
Scanning electron microscopy
SEM was used to investigate the structure of the silica
domains in order to explain the different properties of
samples based on the oligomeric tetraethyl orthosili-
cate. Figures 7 and 8 show SEM images of the com-
posites prepared by monomeric and oligomeric TEOS,
respectively.
PDMS/silica nanocomposites have a very complex
morphology extending from several nanometers to
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hundreds of microns (Schaefer et al. 2000, 2002;
Schaefer and Mark 2001). SEM was used to identify
the large-scale structure of the silica domains. It can be
seen that silica domains in the oligomeric TEOS-cured
sample (Figure 8) were larger than those of the
monomeric-cured sample (Figure 7). In Figure 7b,
the silica domains generated by monomeric TEOS are
not easily visible at the scale of 200nm. However, in
Figure 8b, those generated by oligomeric TEOS can be
seen to be 41 mm in size. The different large-scale
structure of the silica domains in monomeric and
oligomeric TEOS-cured samples apparently led to
different mechanical behaviors. The phase separation

Figure 7. SEM images of a fractured surface of sample 28-1-49. Scale bar: (a) 20 mm, (b) 200 nm.

Figure 8. SEM images of fractured surface of sample 40-1-49. Scale bar: (a) 10 mm, (b) 3 mm.
 738 A. Kaffashi et al.
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Figure 9. The effect of silica content and TEOS type on the pseudobarnacle adhesion strength of PDMS/silica nanocomposites
with molecular weights of (a) 18,000, (b) 49,000 and (c) 79000 g mol71.
of micron-sized silica domains and PDMS chains,
which occurred in the 40-1-49 sample, would be a
reason for the unusual stress–strain behavior of the
oligomeric TEOS-cured samples with high molecular
weight PDMS.
Pseudobarnacle adhesion measurements
In order to quantify the potential effect of oligomeric
TEOS on organismal detachment strength, the pseu-
dobarnacle adhesion strengths of PDMS/silica nano-
composites were measured. The pseudobarnacle
adhesion values were obtained rather than barnacle
adhesion values in order to decrease the standard error
and experimental time in measurements. Swain et al.
(1997) showed that, over large ranges in fouling
adhesion, an excellent correlation existed between
pseudobarnacle adhesion strength and barnacle adhe-
sion strength for silicone coatings.
The pseudobarnacle adhesion values of the
samples prepared with PDMS having molecular
weight of 18,000 g mol71 increased using the oligo-
meric TEOS (Figure 9). According to Figure 9a, the
stress required to remove studs glued on sample 28-3-
18 was much lower (ie 0.008 MPa) than sample 40-3-
18 (ie 0.68 MPa). Moreover, with an increased load of
oligomeric TEOS (ie a decreased PDMS/TEOS
weight ratio), pseudobarnacle adhesion strength
increased. The pseudobarnacle adhesion strengths of
the nanocomposites prepared with PDMS having
molecular weights of 49 and 796103 g mol71 also
increased by employing the oligomeric TEOS in
comparison with monomeric TEOS. In addition, as
can be seen in Figure 9b and 9c, both the monomeric
and oligomeric TEOS cured samples showed an
increasing trend in adhesion strength with the increas-
ing silica loading. By changing the weight ratio of
PDMS/TEOS from 5:1 to 1:1, the corresponding
adhesion values increased 300% and 135%, respec-
tively, for the monomeric and oligomeric TEOS-
cured samples prepared with PDMS having molecular
weight of 49,000 g mol71.

As already mentioned, the low elastic modulus of
silicone coatings is known as an important factor that
contributes to their efficacy as FR surfaces. Tradition-
ally, FR behavior has been associated with low surface
energy (Callow and Fletcher 1994). However, a more
complete model of FR behavior requires the fracture
mechanics approach, as demonstrated by Kendall
(1971) who showed that the release behavior of
elastomers depends not only on the surface energy,
but also upon mechanical properties such as the
modulus of elasticity and, for coatings, the thickness.
The pseudobarnacle adhesion values were plotted vs
elastic modulus for all prepared PDMS/silica nano-
composites (Figure 10). The force needed to remove
pseudobarnacles was shown to increase as the elastic
modulus increased. As the data indicate, the pseudo-
barnacle adhesion strength and the elastic modulus
correlated with an R-squared value of 0.94. Because
Downloaded by [77.175.35.198] at 14:42 05 August 2014
the thickness of the specimens was essentially the
same for all coatings, the less than ideal value of the
least square may be due to differences in surface
properties.
Because of an inverse correlation between FR
performance and mechanical properties, it is necessary
to consider the optimum properties to achieve efficient
FR coating with the highest durability. Therefore, in
order to study the effect of type and the amount of
TEOS on FR coatings, the pseudobarnacle adhesion
strength must be considered as well as the mechanical
properties. It has been shown that the rupture energy
and the tensile strength have been improved substan-
tially by employing the oligomeric TEOS in the
composites prepared with PDMS having molecular
weights of 49 and 796103 g mol71. But the adhesion
values of oligomeric TEOS-based samples are gener-
ally higher than the monomeric TEOS-based samples
because of higher elastic modulus. However, some of
the oligomeric TEOS-cured samples such as 40-5-79,
40-3-79, 40-3-49 and 40-5-49 have pseudobarnacle
adhesion values of *0.3 MPa which is in the range of
Figure 10. The pseudobarnacle adhesion strength as a
function of elastic modulus.
Biofouling 739
commercial FR coatings. As a consequence, the
oligomeric TEOS can be used as a crosslinking and
filling agent in PDMS-based FR coatings to improve
mechanical durability, besides having acceptable FR
performance.
Conclusions
The mechanical properties, morphology and FR
properties of PDMS/silica nanocomposites were in-
vestigated. Regardless of the molecular weight of the
PDMS, the moduli of both monomeric and oligomeric
TEOS-based samples increased with increasing silica
loading. In all, the samples prepared using oligomeric
TEOS had higher moduli than the samples prepared
with monomeric TEOS. In addition, the incorpora-
tion of oligomeric TEOS showed two completely
different effects on the mechanical behavior of the
nanocomposites in high and low molecular weight
PDMS. It was seen that the rupture energies and the
tensile strengths of the oligomeric TEOS-cured sam-
ples prepared with PDMS having molecular weights of
49 and 796103 g mol71, was substantially improved
(increased). According to SEM images, the different
large scale structure of silica domains in the mono-
meric and oligomeric TEOS-cured samples may con-
tribute to the different mechanical behaviors.
According to the pseudobarnacle adhesion mea-
surements, the adhesion strength of studs glued on
the oligomeric TEOS-cured samples was generally
higher than that of the adhesion to monomeric-cured
samples because of the higher elastic moduli of the
former. However, some of the oligomeric TEOS-
cured samples such as 40-5-79, 40-3-79, 40-3-49 and
40-5-49 showed an acceptable pseudobarnacle adhe-
sion value of *0.3 MPa. As a consequence, the
oligomeric tetraethyl orthosilicate can be considered
as a crosslinking and filling agent in PDMS-based
FR coatings.
Acknowledgements
The authors would like to acknowledge with gratitude the
PARS PAMCHAL CHEMICAL CO. who kindly supported
this work financially.
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