INCORPORATION OF LESS TOXIC ANTIFOULING COMPOUNDS INTO SILICONE COATINGS TO STUDY THEIR RELEASE BEHAVIORS A Dissertation Presented to The Graduate Faculty of The University of Akron In Partial Fulfillment of the Requirement for the Degree Doctor of Philosophy Abdulhadi Abdullah Al-Juhni August, 2006
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order of: benzoic acid > capsaicin > sodium benzoate > tannic acid. The solvent-assisted
blending technique was adequate for the cases of sodium benzoate and tannic acid
whereas it was not suitable for benzoic acid and capsaicin. Sodium benzoate/Sylgard®
184 coating was then selected as the model system to obtain the miscibility-release
relationship. The preparation conditions were found to have important effects on the
morphological structure and final distribution of sodium benzoate in silicone, hence the
leaching. The minimum average aggregate size obtained was ~ 3 µm, which had resulted
in the lowest value for the steady leaching rate of ~ 0.1 µg/cm2/day. Empirical
correlations were obtained between the aggregate size as well as the matrix loading of sodium benzoate and the leaching rate. It was found that increasing the aggregate size
had a sharp effect on the increase of the leaching rate, whereas increasing the matrix
loading (up to 5 wt. %) had a mild effect on the leaching rate. The current study did
show that the solvent-assisted blending technique can be an efficient approach for
constructing the miscibility-release correlations.
Both thermodynamic analysis and experimental observations showed that sodium
benzoate has limited solubility in the Sylgard® 184 coating. This, combined with the
mass transfer analysis of the leaching, led us to confirm that the release mechanism of the
monolithic sodium benzoate/silicone coatings generated via the solvent-assisted blending
technique is mainly by the diffusion of the compound through water-filled pores and
constricted channels within the matrix, not through the continuum of the polymer phase.
4.3.2 Modification of the Flory-Huggins theory to include electrostaticcontribution and concentration-dependent interaction parameters…..………………………………………………………...86
4.3.3 Comparison between the theoretical miscibility trends and the
V. RESULTS AND DISCUSSION FOR BENZOIC ACID AND CAPSAICIN-BASED COATINGS…............................................................................................144
5.1 Effects of the compounds on coating’s properties…………...……………….144
5.1.1 Effect of benzoic acid…………………………….............................144
5.1.2 Effect of capsaicin…………………………………………………...147
5.2 Miscibility of the compounds in silicones…….……………………………....150
5.2.1 Miscibility of benzoic acid…………………………..........................150
5.2.2 Miscibility of capsaicin……………………………………………...154
3.1 The compositions of the two types of silicones (RTV11 and Sylgard® 184) usedin the current study. All percentage shown here are in mass basis …….…............48
3.2 The actual combinations of (antifoulant/solvent/polymer) mixtures used in thecurrent study to incorporate the antifoulant into the bulk of the polymer matrix by the solvent-blending technique…………………………………………………49
3.3 The detailed concentrations for NaB/ Sylgard®184 samples prepared at differentconditions. All concentration shown here are in mass basis. (Abbreviation: W:water, A: acetone, S: solvent (i.e. water + acetone), P: silicone polymer base)…..51
3.4 The detailed compositions for the samples that were subjected to leachingexperiments in the current study. All concentration shown here are in mass basis. (Abbreviation: W: water, A: acetone, S: solvent, P: silicone polymer base, NaB: sodium benzoate, BA: benzoic acid, TA: tannic acid)………………..55
4.1 Static water contact angles of NaB-entrapped RTV11 films. The (solvent: polymer) ratio and the (water: acetone) ratio were respectively (20: 80) and(50: 50) by mass……………………………………………………………….......69
4.2 Aggregate size distribution of 1 wt.% of sodium benzoate inside the(99 wt.%) bulk of Sylgard® 184 matrix, for samples prepared at differentwater/acetone ( W/A) mass ratios. The solvent/polymer ratio was fixed at20/80 by mass……………………………………………………………………...76
4.3 Aggregate size distribution of 1 wt.% of sodium benzoate inside the(99 wt.%) bulk of Sylgard® 184 matrix, for samples prepared at differentsolvent/polymer (S/P) mass ratios. The water/acetone ratio was fixed at50/50 by mass……………………………………………………………………...80
4.4 Aggregate size distribution of sodium benzoate inside the bulk of Sylgard® 184 matrix, for samples prepared at different NaB matrix loading(wt% NaB in the matrix). The water/acetone ratio was fixed at 50/50 by mass.The solvent/polymer ratio was fixed at 20/80 by mass……………………………82
4.5 Physical parameters of relevance importance to the miscibility of NaB/PDMS.V and δ are the molar volume and the solubility parameter of the material,respectively. δ12 is the difference in solubility parameters between the materialand PDMS. χ 12 is the interaction parameter between the material and PDMS*…..84
4.6 Data analysis for the results shown in Figure 4.21. The apparent diffusioncoefficient (DA) for NaB/Sylgard® system was obtained by fitting the experimentalleaching data to equation 4.17. The solvent/polymer ratio was 20/80, which wasfixed for all samples. (Abbreviation: W: water, A: acetone).……………………132
5.1 Static water contact angles of BA-entrapped Sylgard® coatings compared tothat of the controlled BA-free SylgardTM coatings. The (solvent: polymer)ratio was (20: 80) by mass………………………………………………..............146
5.2 Static water contact angles of BA-entrapped RTV11 coatings compared tothat of the controlled BA-free RTV11 coatings. The (solvent: polymer) ratio
was (20: 80) by mass……………………………………………………………..1465.3 Elastic modulus of BA-entrapped Sylgard®184 films. The (solvent: polymer)
ratio was (20: 80) by mass………………………………………………………..146
5.4 Elastic modulus of capsaicin-entrapped RTV11 films. The (solvent: polymer)ratio was (20: 80) by mass………………………………………………………..149
5.5 Physical parameters of relevance importance to the miscibility of BA/PDMS.V and δ are the molar volume and the solubility parameter of the material,respectively. δ12 is the difference in solubility parameters between the materialand PDMS.
χ 12is the interaction parameter between the material and PDMS*…153
5.6 Physical parameters of relevance importance to the miscibility of capsaicin/PDMS. V and δ are the molar volume and the solubility parameter of thematerial, respectively. δ12 is the difference in solubility parameters betweenthe material and PDMS. χ 12 is the interaction parameter between the materialand PDMS*………………………………………………………………………156
6.1 Physical parameters of relevance importance to the miscibility of tannicacid/PDMS system. δ is the solubility parameter of the material. δ12 isthe difference in solubility parameters between the material and PDMS.χ 12 is the interaction parameter between the material and PDMS………………..175
3.1 A schematic diagrams for the sample preparation steps used for incorporatingSodium benzoate into the silicone polymer coating……………………………….50
3.2 A simplified sketch for the contact angle concept. (a) the static contact angle:a liquid drop being in equilibrium with a solid substrate in air. γLV, γSV and γSL
are respectively the surface energies at the liquid/vapor, solid/vapor, and solid/liquid interfaces, and θ is the equilibrium (static) contact angle. (b) theadvancing contact angle (θa). (c) the receding contact angle (θa)………………....58
3.3 A simplified sketch for the set-up of the JKR apparatus…………………………..62
4.1 Water contact angles of NaB-entrapped Sylgard®184 films (advancing:,receding:, and static:). The (solvent: polymer) ratio and the (water: acetone)ratio were respectively (20: 80) and (50: 50) by mass, which were fixed at allconcentrations. Error for each data point (average over 12 measurements) is presented by the vertical line………………………………………………………68
4.2 Elastic modulus variations of NaB - entrapped Sylgard® 184 coating. The(solvent: polymer) ratio and the (water: acetone) ratio were respectively(20: 80) and (50: 50) by mass, which were fixed at all concentrations.Error for each data point (average over 6 measurements) is presented by thevertical line………………………………………………………………………...72
4.3 Optical microscope (bright field) images (570 µm x 480 µm) of the bulk morphology of 1 wt % NaB/Sylgard® 184 matrix, prepared at differentwater/acetone ratios, keeping the solvent/polymer ratio fixed at 20/80.(a) 20/80 water/acetone; (b) 30/70 water/acetone; (c) 50/50 water/acetone;(d) 80/20 water/acetone; (e) 90/10 water/acetone; (f) 100% water. All thevalues are based on weight………………………………………………………...75
4.4 Guidelines chart for preparing NaB-incorporated Sylgard® 184 coatings atdifferent set of conditions. The saturation line “ — ” represents the maximumsolubility of NaB in water (0.555 g NaB per 1 g of water). Above this line, NaBis not soluble in the mixed solvent (water + acetone), and hence the bulk entrapment method will not be feasible at this particular set of conditions.
(Abbreviations: S: solvent; P: polymer). All values are in mass basis…………...77
4.5 Optical microscope (bright field) images (570 µm x 480 µm) of the bulk morphology of 1 wt % NaB/Sylgard® 184 matrix, prepared at differentsolvent/polymer ratios, keeping the water/acetone ratio fixed at 50/50. (a) 10/90solvent/polymer; (b) 20/80 solvent/polymer; (c) 30/70 solvent/polymer;(d) 40/60 solvent/polymer; (e) 50/50 solvent/polymer. All the values are basedon weight…………………………………………………………………………..79
4.6 Optical microscope (bright field) images (570 µm x 480 µm) of the bulk morphology of NaB/ Sylgard® 184 matrix of different NaB concentrations,
keeping the solvent/polymer ratio and the water/acetone ratio fixed at 20/80and 50/50, respectively. (a) 0.5 wt% NaB/ Sylgard® 184; (b) 1 wt% NaB/Sylgard® 184; (c) 2 wt% NaB/ Sylgard® 184; (d) 3 wt% NaB/ Sylgard® 184;(e) 4 wt% NaB/ Sylgard® 184; (f) 5 wt% NaB/ Sylgard® 184; All the valuesare based on weight………………………………………………………………..81
4.7 The miscibility trends for NaB/acetone/water/PDMS mixtures, for all possibleconditions, as predicted by the original Flory-Huggins (FH) model (equation 4.2).(a) Effect of the water/acetone (W/A) ratio; parameters fixed: 1 wt% NaB/polymer.(b) Effect of the NaB matrix loading; parameters fixed: 50/50 water/acetone. Allthe values shown in the legends are based on weight……………………………..87
4.8 The miscibility trends for NaB/acetone/water/PDMS mixtures for all possibleconditions, as predicted by the new model (equation 4.9). (a) Effect of thewater/acetone (W/A) ratio; parameters fixed: 1 wt% NaB/polymer. (b) Effect of the NaB matrix loading; parameters fixed: 50/50 water/acetone. All the valuesshown in the legends are based on weight………………………………………...94
4.9 The free energy of mixing (Gmix/nkT) for NaB/acetone/water/PDMS mixtures prepared at different conditions, as predicted by two models: the Flory-Huggins(F-H) model (equation 4.2), and the new model (equation 4.9). (a) Effect of thewater/acetone ratio, parameters fixed: 20/80 solvent/polymer and 1 wt%
NaB/polymer. (b) Effect of the solvent/polymer ratio, parameters fixed: 50/50water/acetone and 1 wt% NaB/polymer. (c) Effect of NaB matrix loading, parameters fixed: 50/50 water/acetone and 20/80 solvent/polymer. The solventis defined here as water + acetone + NaB. All the values are based on weight.The preparation conditions described here correspond to the actual conditionsfor the morphology experiments performed in the current study. The insert ineach plot represent the corresponding experimental morphology trend ………….96
4.10 Cumulative leaching (Q) of NaB from Sylgard® 184 matrix immersed in water.The samples were prepared at different water/acetone ratios, keeping the other conditions unchanged (20/80 solvent/polymer, and 1 wt% NaB/matrix). Allthe values are based on weight. Solid lines are for showing the trends.(Abbreviations: W: water; A: acetone). Error for each data point (average
over 2 batches) is presented by the vertical line………………………………….101
4.11 Cumulative leaching (Q) of NaB from Sylgard® 184 matrix immersed in water.The samples were prepared at different solvent/polymer ratios, keeping the other conditions unchanged (50/50 water/acetone, and 1 wt% NaB/matrix). All thevalues are based on weight. (Abbreviations: S: solvent; P: polymer). Error for each data point (average over 2 batches) is presented by the vertical line….........103
4.12 Cumulative leaching (Q) of NaB from Sylgard® 184 matrix immersed in water.The samples were prepared at different wt% NaB/matrix, keeping the other conditions unchanged (50/50 water/acetone, and 20/80 solvent/polymer). All
the values are based on weight. Error for each data point (average over 2 batches) is presented by the vertical line…………………………………………104
4.13 Cumulative leaching of NaB from its incorporated silicone coating:Sylgard® 184 () or RTV11 (▲). The common solvent used was 50/50water/acetone by weight. The initial concentration of NaB in both coatingswas kept constant at 1 wt%., and the solvent/polymer ratios was kept constantat 20/80 by weight for both combinations………………………………………..106
4.14 Empirical correlations for the leaching rate of NaB from Sylgard® 184.(a) Effect of the aggregate size (d, the arithmetic mean size), parameter fixed:1 wt% NaB/matrix. (b) Effect of the NaB matrix loading, parameter fixed:d ~ 3 - 4 µm. The insert in (b) is for enlarging the scale of the y-axis. The symbols(■) and (O) represent the initial and the steady leaching rates, respectively….....110
4.15 Cumulative leaching (Q) of NaB from Sylgard® 184 matrix immersed in water.The samples were prepared at the base case conditions ((1 wt% NaB/Sylgard® 184; 50/50 water/acetone; and 20/80 solvent/polymer)), and the leaching weremeasured at three different conditions: under constant stirring (□), replacing water daily (∆), and at static conditions (O). Error for each data point (average over 3 batches) is presented by the vertical line…………………………………………113
4.16 A simplified sketch (not to scale) for the mass release of antifouling compoundsfrom polymer paint (water-insoluble matrix). In this case, the compound issoluble in the matrix and is initially loaded in excess of its solubility limit inthe matrix. The dissolved zone means that the compound is already absorbed by the polymer phase…………………………………………………………......115
4.17 A simplified sketch (not to scale) for the leaching of antifouling compoundsfrom polymer paint (water-insoluble matrix). In this case, the compound isinsoluble in the matrix. (Figure re-drawn from Caprari et al . (1990), withslight modification)………………………………………………………………116
4.18 A simplified sketch (not to scale) of a polymer coating incorporated with AFcompound, and immersed in water. The purpose of the sketch is to show themeaning of the axial distance x that was used in equation 4.12………………….117
4.19 Parametric sensitivity analysis for the general mass transfer model (equation 4.19).The dimensionless surface concentration (Ψ|ζ=0 = C/CO |x=0) is plotted againstthe dimensionless time (τ = DA t / L2), for different values of the dimensionless parameter Bm (Bm = k L / DA). The trends were generated by solving equation4.19 numerically………………………………………………………………….122
4.20 Simplified sketch (not to scale) for the possible leaching mechanisms of NaB from
Sylgard
®
184 coating: (a) Perfect packing of the particles; (b) Complete ruptures of the thin membranes; (c) The existence of initial porosity of the matrix, which ismainly composed of constricted narrowed channels. The first column representsthe coatings initially before immersion, the second column after some time t1 > 0,and the third column after some time t2 > t1………………..…………………….126
4.21 Fitting of the cumulative leaching data for NaB/Sylgard® 184 coatings to thesimplified mass transfer model (equation 4.17). (a) Samples were prepared atdifferent NaB matrix loading, keeping the water/acetone ratio and thesolvent/polymer ratio fixed at 50/50 and 20/80, respectively. (b) Samples were prepared at different water/acetone (W/A) ratios, keeping the NaB matrix loadingand the solvent/polymer ratio fixed at 1 wt% NaB/matrix and 20/80 ratio,respectively. Points are experimental data and solid lines are linear fitting of themodel.…………………………………………………………………………….132
4.22 Optical microscope images of the bacterial attachment study for NaB-Sylgard® 184 coating. (a, c) 1 wt% sodium benzoate-blended Sylgard® 184.(b, d) control Sylgard® 184. The coatings were immersed in water containing Lake Erie bacteria for 2 weeks (a, b) and 4 weeks (c, d). Image size is(285 µm x 215 µm)……………………………………………….........................139
4.23 Antibacterial performance of 1 wt% NaB-incorporated Sylgard® 184 coatings,compared to control SylgardTM 184 samples. The % reduction was defined as[(1-A/B) 100), where A and B refer to the area coverage of NaB-containingcoatings and NaB-free coatings, respectively……………………………………140
4.24 Optical microscopic (reflection bright field) images of bacterial attachment oncontrolled RTV11 coatings after the coatings were immersed in water containing Lake Erie bacteria for 28 days. (a) Half of the coatings surfaces were physicallycleaned by scotch tape, and overall pictures [image size: (2850 x 2150) µm] weretaken showing the cleaned area (right side of picture a) and the un-cleaned area (left
side of picture a). Pictures (b) and (c) are the magnifications [image size: (285 x215) µm] of the two area indicated in picture (a).………………………………..141
5.1 Water contact angles of capsaicin-entrapped RTV11 films (advancing:,receding:, and static:). The (solvent: polymer) ratio was (20: 80) by mass,which was fixed at all concentrations. Error for each data point (average over 12 measurements) is presented by the vertical line………………………………148
5.2 Optical microscope (bright field) images of resulting BA distribution in the bulk of Sylgard® 184 matrix when different solvent were used to mix BA withSylgard® 184: (a) toluene, (b) acetone, (c) acetonitrile, and (d) ether. The
concentration of BA in the matrix was fixed at 1 wt%, and the (solvent: polymer)ratio was fixed at (20: 80) by mass. The image size is 2850 µm x 2400 µmfor (a), and 1140 µm x 960 µm for (b)-(d)………………… ……………………151
5.3 Optical microscope (transmission bright field) image of resulting capsaicindistribution in the bulk of Sylgard® 184 base material. Toluene was used asthe common solvent. The concentration of capsaicin in the matrix was 1 wt%,and the (solvent: polymer) ratio was (20: 80) by mass. The image size is(570 x 480) µm…………………………………………………………………...155
5.4 Cumulative leaching of BA from its incorporated silicone coating: Sylgard® 184
(open symbols) or RTV11 (filled symbols). The common solvent used for BA/silicones were acetone (squares) and Toluene (circle). The initial concentrationof BA in all coatings was kept constant at 1 wt%., and the solvent/polymer ratioswere kept constant at 20/80 by weight for all combinations………………….….158
5.5 Capsaicin cumulative mass per area (Q, in µg/cm2) released from 1 wt %capsaicin-incorporated RTV11 sheet (total mass and surface area of the sheetwere respectively 6.55 g and 114 cm2), plotted against time of immersion in DIwater. Toluene was used as the common solvent to mix capsaicin with RTV11,and the (solvent: polymer) ratio was (20: 80) by mass……………………...…...160
5.6 Effect of the mixing order on the capsaicin cumulative leaching from 1 wt %capsaicin-incorporated RTV11 sheet (total mass and surface area of the sheet wererespectively 1.64 g and 38 cm2). Ethanol was used as the common solvent, and the(solvent: polymer) ratio was kept constant at (20: 80) by mass. The open squarescorrespond to the conditions of mixing capsaicin/ethanol solution with the RTV11 base and drying off the solvent before adding the catalyst. The filled squarescorrespond to the same conditions of the open square data, except that thecapsaicin/ethanol solution was mixed after adding the catalyst………………….162
5.7 Effect of water immersion time on the wettability of RTV11 films in terms of thestatic contact angles taken for RTV11 immersed in Lake Erie (Δ) and deionizedwater (▲). The advancing (□) and receding () contact angles taken for RTV11immersed in deionized water are also presented. Error for each data point (averageover 12 measurements) is presented by the vertical line………………………....165
5.8 Surface topographic images of Capsaicn-RTV11 coatings. (a) as-preparedcontrolled RTV11 film, surface roughness: 6.7 nm; (b) as-prepared RTV11 filmcontaining 1 wt % capsaicin, surface roughness: 12.3 nm; (c) controlled RTV11film after 14 days of immersion in DI water, surface roughness: 10.5 nm; (d)RTV11 film containing 1 wt% capsaicin after 14 days of immersion in DI water,surface roughness: 88.0 nm. The images (scan size: 80 µm x 80 µm; z-scale: 400nm) were generated using scanning probe microscopy with the non-contact mode ata scan rate of 0.20 Hz……………………………………………………………166
5.9 Effect of water type and immersion time on the elastic modulus of RTV11 films
immersed in different types of water samples (sterilized Lake Erie water:Δ,enriched Lake Erie water: ○, and sterilized Lake Erie water with 20 ppm capsaicin:□). Error for each data point (average over 6 measurements) is presented by thevertical line……………………………………………………………………….168
5.10 Optical microscopic (reflection bright field) images of bacterial attachment for capsaicn-RTV11 coatings. (a) 1 wt% Capsaicin/RTV11, (b) control RTV11. Thecoatings were immersed in water containing Lake Erie bacteria for 14 days. Thesize for both images is (285 x 215) µm…………………………..........................170
6.1 Static water contact angles of TA-entrapped silicone films compared to that of
the controlled TA-free silicones. The concentration of TA in the matrix was fixedat 1 wt% for both combinations. The (solvent: polymer) ratio was fixed at (20: 80) by mass (acetone was the solvent for both combinations). Error for each data point(average over 12 measurements) is presented by the vertical line………….........172
6.2 Optical microscope (transmission bright field) image of resulting TA distributionin the bulk of Sylgard® 184 matrix: (a) 1 wt% TA/Polymer; (b) 4 wt%TA/Polymer. Acetone was used as the common solvent, and the solvent/polymer ratio was 20/80 by mass. The image size is (570 x 480) µm……………………174
6.3 Cumulative leaching of TA from its incorporated silicone coating: Sylgard®
184 () or RTV11 (▲). The common solvent used was acetone for bothcombinations. The initial concentration of TA in both coatings was kept constantat 1 wt%., and the solvent/polymer ratio was kept constant at 20/80 by weightfor both combinations. Error for each data point (average over 2 batches) is presented by the vertical line……………………………………………………..177
firmly attached, bacteria start to generate extracellular polymeric substances (EPS),
which connect the cells in between each others as well as connecting to the surface. The
cells plus EPS is what we called the “biofilm”. Finally, the biomass continues to grow,
with some large macro fouling organisms attach to, while other cells detach from the
film. The first step, conditioning films adsorption, is very fast and occurs within hours of
immersion, whereas the later step, production of EPS, is very slow and needs weeks or
perhaps months to complete.
Antifouling paints have long been the most effective method to prevent biofouling, where biocides or heavy metal compounds such as TBTO (Tributyltin oxide)
are released from the coatings and inhibit organism’s attachment. TBT compounds are
the most effective compounds for biofouling prevention. Unfortunately, they are also the
most toxic compounds against non-target marine organisms (Axiak et. al., 2000;
Haslbeck et. al., 1996). As a result, the International Maritime Organization (IMO)
banned the application of TBT compounds on 2003, and the entire removal of TBT
coatings by year 2008 will be required worldwide (Champ, 2000).
Recognizing the harmful effects and the already-started bans for TBT compounds,
considerable efforts are being committed worldwide to find new non-toxic or less-toxic
antifouling alternatives. Possibilities which have been considered include dissolution of
adhesive substance by various enzymes, biogenic agents, smart polymer coatings,
polymer coatings with defined surface-microstructures (Jelvestam et. al , 2003), foul-
2001, Ponasik et. al. 1998), and less-toxic and commercially available preservatives,
pesticides, drugs, and insecticides.
Upon the use of the less toxic antifouling compounds, the selection of a less toxic
antifouling compound is the first step toward biofouling control. The next important step
is to control its release from the coating. Control-release technologies that were
originally developed for drug-release are expected to be useful for controlling the release
of antifouling compounds. Three drug-release technologies are widely used: membrane-
reservoir, microencapsulation, and monolithic coatings (Figure 1.1). In a membrane-reservoir device, the active compound is highly concentrated into a middle layer of the
polymer coating, which is surrounded by a second layer of another polymer coating. In
microencapsulation, the active compound is encapsulated into microcapsules, which are
distributed in a polymer coating made of a material differed from that of the capsules. In
a monolithic coating, the active compound is distributed within the layer of the polymer
coating. Depending on the solubility and loading of the compound in the monolithic
coating, the compound can be molecularly dissolved in the polymer phase or it can be
uniformly dispersed as a separate droplet phase (as shown in Figure 1.1c). The
monolithic coating technology is the most widely used due to its simplicity. Several
experimental approaches exist to prepare monolithic coatings; the solvent casting
technique and the compressing molding technique (Fan and Singh, 1989) are two
common ones. In the current study, monolithic coatings prepared using a solvent-assisted
Many non-toxic or less-toxic antifouling (AF) compounds have been identified in
the literature. Some of these compounds are directly blended with different polymer
coatings and tested for biofouling prevention. Although direct blending is a simple
method, in most cases, the release rate of AF compound will be very fast and hence the
service life of the coating will be very short. Different methods have been suggested in
literature to extend the service life of the coating, either by chemically attaching the
compound to the coating surface or by employing sophisticated controlled releasetechniques such as the micro-encapsulation method or the membrane reservoir method.
However, these methods are highly complicated and, in some cases, are challenging for
certain compounds. In the current study, we are proposing a simple experimental
approach (dissolving the compound in a solvent or in a blend of solvents and then
homogenizing the solution with the polymer) to generate monolithic coatings that are
expected to result in the desired slow-controlled release of the AF compound. This
experimental approach is termed as the “solvent-assisted blending technique”. For the
current study, a systematic combination of the compound/solvents/polymer will be
carried out, and a systematic evaluation of the miscibility and leaching behavior of the
compound from the coatings will be conducted. The main focus of the current study is to
obtain the relationship between the miscibility of the compounds in the coating matrix
and their leaching in water, for the purpose of controlling the release rate and maintaining
the antifouling performance of the coatings for their long term service.
(c) Perform a mass transfer modeling on the leaching to explain the
experimental data and propose a suitable leaching mechanism of the
monolithic sodium benzoate/silicone coating generated using the solvent-
assisted blending method.
1.4 Dissertation outline
The outline of the dissertation is as follow. In chapter 2, the dissertation starts with
providing backgrounds and literature review about various issues of relevance to thecurrent study, including biofouling and its control, foul-release coatings and less toxic
antifoulants, antifoulant-coating miscibility, and antifoulant leaching modeling. The
experimental approach is described in chapter 3. The results and discussion for sodium
benzoate-based coatings are presented in chapter 4. The results and discussion for
benzoic acid and capsaicin-based coatings are presented in chapter 5, and the results and
discussion for tannic acid-based coatings are presented in chapter 6. Finally, in chapter 7,
the dissertation concludes with summarizing the key results and providing
forces are further classified into long-range and short-range interactions (Dankert et al .
1986). The long-range interactions are nonspecific interactions, which are effective when
the distance between the bacterium and the substrate is greater than 150 nm. Short-range
interactions become effective when the distance between the bacterium and the substrate
is less than 5 nm. These short-range interactions include chemical bonds (such as
hydrogen bonding), ionic and dipole interactions, and hydrophobic interactions (An and
Friedman, 1998; Gottenbos et al ., 2002). The short-interactions forces from phase 1
provide the suitable ground for the second phase of adhesion to occur, where here
molecular reactions between specific bacterial surface structure and substratum surface become predominant. The active sites of the bacterium surface that are responsible for
firm adhesions are those polymeric surface structures that contain adhesins as parts of
their structures, which include capsules, fimbriae (or pili), and fibrillae. At the
irreversible stage of adhesion, bacteria start to produce slime extracellular polymeric
substances (EPS), which are exopolymers composed of mainly polysaccharides. EPS can
be regarded as external adhesives that connect the bacteria between each others as well as
connecting the bacteria to the substrate.
2.2 Biofouling controls
Biofouling has caused serious problems to the maritime industry including
enormous economic loss due to considerable increase in ship’s fuel consumption and
maintenance costs, and damages and harmful effects resulted from biocorrosion of the
immersed infrastructures. Consequently, the prevention or minimization of biofouling is
the condensation cured PDMS, such as RTV11. This subsection reviews some of the
recent works done for investigating silicone coatings as a nontoxic alternative for marine
biofouling control.
Wynne et al . (2000) evaluated two types of PDMS coatings (RTV11, and an in-
house unfilled hydrosilation cured PDMS). They evaluated the surface hydrophobicity
and roughness of the coatings, and the mass loss of the coatings upon immersion in
water. They found that the hydrosilation cured PDMS was fairly stable in water; with the
mass loss was less than 0.2 % after 50 days of immersion. RTV11, on the other hand,was not stable in water, with a mass loss of about 0.8 % after 50 days of immersion.
However, the bulk moduli of the two coatings in water were not evaluated. The two
coatings were also evaluated for barnacle adhesion. The barnacle adhesion strength to
the hydrosilation cured PDMS and to the RTV11 coatings were found to be about 0.5 and
0.78 kg/cm2, respectively. In another publication of the same research group (Bullock et
al ., 1999), the surface properties of RTV11 (with different catalyst concentration) were
investigated in more details, and a mechanism for the mass loss of RTV11 in water was
proposed.
Arce et al. (2003) performed a comparative study for the microelastic properties
of RTV11 and Intersleesk TM elastomers (Intersleek TM is the trade name of a PDMS-based
coating, which is already of being used as a foul release coating in some vessels). The
measurements were done by using AFM and other techniques, which gave valuable
information about the local structural and mechanical properties of the as-prepared
coatings. However, the behavior of the coatings in water and their antifouling
performance were not evaluated.
The nature and failure mechanism of bioadhesive bonding between barnacles
and two types of PDMS coatings (RTV11 and RTV1556) were investigated by Berglin
and Gatenholm (1999). Analysis of the fracture surfaces indicated that the failure
mechanism was a cohesive failure within the PDMS coatings. As a control, they
compared their results with PMMA coatings, and they found that the failure mechanism
of PMMA coatings was more complex than the failure mechanism of PDMS coatings.Also, the surface energies of the coatings were calculated from contact angles data, and
the values were 23.3 mJ/m2 and 22.4 mJ/m2 for RTV11 and RTV1556 coatings,
respectively.
Edwards et al . (1994) evaluated the hydrophobicity and antifouling performance
of some room-temperature-vulcanizing PDMS and polydimethyldiphenylsiloxane
(PDMDPS) coatings. The authors selected these two classes of silicones to relate their
hydrophobicity to their antifouling performances. PDMDPS showed higher
hydrophobicity (contact angle ~ 123) and better antifouling performance than PDMS
(contact angle ~ 112). Incorporation of silicone oils into the coatings was also
investigated in the range of 0 — 20 %. It was concluded that silicone oil had only a
significant positive effect for enhancing the antifouling performance if its concentration
was sufficiently high (between 10 to 20 %), and the enhancement here was speculated to
Estarllich et al . (2000) studied the change in surface properties of some PDMS
coatings (RTV11, RTV160, and RTV655) and flourosilicones as a function of immersion
time in different types of water. Bacteria and microalgae attachment tests were also
performed, where it was found that the early attachment was least on RTV11 and greatest
on flourosilicones.
Barnacle release mechanism for two silicone coatings (a single layer coating consists
of Sylgard® 184, and a duplex coatings consist of RTV11 as a top coat and Silgan ® J-501
as the bond coat) were studied by Singer et al . (2000). The results suggested that thecoatings with lower modulus and thicker thickness had a better foul release performance.
This was confirmed by the theoretical fracture-mechanical analysis of Brady and co-
authors (Brady and Singer, 2000; Brady, 2001).
The two classes of foul release coatings (fluorinated and silicone coatings) have
shown to be partially effective and both have advantages and limitations. Brady and
Aronson (2003) synthesized a new foul release coating that combined the best features of
the two classes of materials. After optimizing the preparation conditions, the new
material (an elastomeric fluorinated polyurethane coating) was found to be effective as
foul release coating with the desired surface and mechanical properties. It should be
noticed that this new product is a polyurethane-based coating, not a silicone-based
coating.
Stein et al. (2002) evaluated systematically model silicone coatings (both
condensation-cured and hydrosilylation-cured types) with controlled molecular
The structure of any NPA is usually complex with many functional groups, and
usually difficult to be commercialized. Efforts are being made to examine simplified
structures of a lot of NPAs for antifouling activity and then synthesizing them. The
resulted synthesized compound, no longer now called NPAs, could have potentials as
antifoulants, antibacterial drugs, and food-preservatives. Based on this strategy, different
analogues compounds have been identified, synthesized, and tested for antifouling
activity. The synthesized compounds with proved antifouling activity and much less
toxicity (compared to heavy metal compounds) include benzoic acid, nicotinic acid,
picolinic acid, 2-furyl-n-pentyl ketone, 3-acetyl-2,5-dimethyl furan, and their derivatives(Stupak et. al ., 2003; Clare, 1996; Sundberg et. al ., 1997; Railkin, 2004). Again, most
evaluations are concerned with the biological side, and a detailed study on the
compatibility, miscibility, leaching and material properties of the antifoulant/polymer
systems is still lacking.
Understanding the mechanism of action for the antifouling compounds is
necessary. For toxic compounds such as TBT and heavy metals, the mechanism of action
is acute toxicity, which results simply in killing the attached microorganisms. For less or
nontoxic compounds, the identification and experimental validation of the mode of action
is rather complicated (Railkin, 2004). In general, two antifouling mechanisms are
suggested for the effectiveness of the non-toxic compounds: repellency and chemical
anti-adhesive (Sundberg et. al ., 1997, Railkin, 2004). As emphasized by Railkin (2004),
the following exact definition should be applied to assign the non-toxic repellency
mechanism for a certain antifouling compound: “Repellents are cues inducing a negative
motor response, taxis, or kinesis in organisms at a certain stage of development, which
causes them to move away from the source of these cues” (Railkin, 2004). This precise
definition differentiates the true repellent property (a non-toxic mode of action) from
other toxic properties of the antifouling material. For this definition to be applied, special
experimental behavioral tests should be performed. For example, the repellent effect can
be evaluated using the special test developed by Railkin (1995), where here chemotactic
chambers made of Plexiglas and measuring 36 x 40 x 80 mm can be used, with each
chamber consists of 3 sections, separated by 0.92-micro nucleopore filters. The
microorganism is placed in the middle section; the antifoulant solution is filled in oneside and a reference solution (e.g. sea water) is filled in the other side. However, in most
studies, the true repellent function of various natural and synthetic antifoulants is
hypothetically assumed rather than experimentally verified (Railkin, 2004). Among a
few studies that followed the standard behavioral tests, benzoic acid and tannic acid were
proved to have a true repellent mechanism as a non-toxic mode of action. (Mitchell and
Kirchman, 1984; Railkin et. al ., 1993; Railkin, 1995, Railkin and Dobretsov, 1994). In
addition to the repellency mechanism, the non-toxic antifouling compounds can also
exhibit the chemical anti-adhesive mechanism, where molecules of the antifouling
compound exist freely in water and act as catalytic inhibitors for the biochemical
reactions involved in cell adhesion. The word “chemical” is used here to distinguish this
mechanism from the physical anti-adhesive mechanism, which usually refers to the easy-
release silicone coatings. The chemical anti-adhesive mechanism, a terminology used by
Railkin (2004), appears to be the same as described by Sundberg and his co-workers
(1997) but in different terminology: “the blocking of the attachment sites mechanism”,
where Sundberg et al . (1997) hypothesized that the molecules of the compound exist
freely in water could bind to the attachment sites on the microorganism cell wall and thus
prevent cell adhesion. Again, special experimental behavioral tests should be performed
in order to confirm the chemical anti-adhesive mechanism, such as the standard tests
developed by Ina et. al . (1989) or Hellio et. al . (2000). Among a few studies that applied
these controlled tests, benzoic acid was also proved to have chemical anti-adhesive
properties (Railkin et. al ., 1993; Railkin, 1995, Railkin and Dobretsov, 1994).
Among the environmentally benign NPAs, capsaicin, a stable monocliniccrystalline alkaloid extracted from chili peppers, is being considered as a potential.
Capsaicin, or 8-methyl-N-vanillyl-6-nonenamide, and its analogues have been used as
active ingredients in medicinal products, and are found to be effective in inhibiting
deactivates the enzymes that control acetic acid metabolism and oxidative
phosphorilation in yeast and bacteria. In a recent review on antibacterial mechanisms
(Chapman, 2003), benzoic acid is believed to act by interfering with the ability of the cell
membrane to maintain a suitable pH level, which consequently leads to acidification of
the cell interior and widespread disruption of the metabolism process (Eklund, 1985). As
mentioned before (Railkin, 2004), the mode of action of benzoic acid has been identified
experimentally by standard behavioral tests, where benzoic acid is proved to exhibit both
non-toxic modes of actions (repellency and chemical anti-adhesive). This finding
highlights the possibility of benzoic acid to be effective against broad spectra of microand macro fouling species. In addition, field studies had shown that benzoic acid when
added to vinyl-rosin coating was effective in inhibiting different species of both micro
and macro foulers (Railkin, 1995), making it a very attractive non-toxic or less toxic
antifouling candidate. However, due to the extremely fast leaching of the compound, the
effectiveness of the coating with benzoic acid incorporated was only for a short period of
time (1 month). Therefore, for further utilization of benzoic acid, understanding the
causes of the fast leaching is essential and seeking techniques to incorporate benzoic acid
into a coating to control its leaching is also important.
The salt form of benzoic acid, such as sodium benzoate (NaB) is even more
environmentally benign as compared to benzoic acid. Static biological assays have also
proved that NaB showed a narcotic (non-toxic) effect on the investigated microorganisms
(Vetere et. al ., 1999). In addition to sodium benzoate, other different benzoic acid salts
(calcium benzoate and aluminum benzoate) have also been tested by biological assays,
Most of the above models are based on the Flory-Huggins theory. The Flory-
Huggins theory was originally derived to describe the miscibility of polymer-solvent and
polymer-polymer mixtures (Flory, 1953). Although still widely used due to its
simplicity, it is now well-known that the Flory-Huggins theory has many limitations,
which make its prediction weak for many situations. One weakness of the Flory-
Huggins theory came from the original cubic lattice model that was used to derive the
mixing functions (entropy and enthalpy of mixing) of a solvent (or a polymer) with
another polymer. According to the Flory-Huggins theory, for a binary solvent-polymer
system, the lattice is subdivided into n number of sites, each site is filled by either asolvent molecule or a segment of polymer chain (the polymer chain is divided into N
number of segments, each segment is assigned to be equivalent in length to the size of the
solvent molecule). Similarly, for a binary polymer-polymer system, each site is filled by
either a segment of the chain of the first polymer or a segment of the chain of the second
polymer. In other words, no sites are allowed to be empty because the polymers are
assumed to be simple incompressible fluids and hence there is no volume change upon
mixing, which is not a true assumption for a polymeric material due to its huge size. The
weakness of the Flory- Huggins theory can be further understood by elaborating more on
the binary interaction parameter, χ 12. According to the Flory-Huggins theory, χ 12 is
always greater than zero, a smaller χ 12 indicates a higher chance that the binary solvent-
polymer system would be miscible, and a value of χ 12 < 0.5 is the Flory-Huggins criterion
for a solvent/polymer system to be completely miscible. However, it is now believed that
χ 12 is qualitatively described in the following more general form:
for controlled drug release delivery systems, and most of these models are empirical or
semi-empirical. A review of this modeling effort is the subject of section 2.4.3.
The mass release mechanism of an antifoulant from a polymer matrix immersed
in water depends largely on the solubility of the antifoulant in the matrix. If it has a high
solubility, the release primarily follows a diffusion-dissolution mechanism, which takes
place in the continuum of the polymer phase. If the solubility is very low, the mechanism
is controlled by the channeling/pores formation, where the pores and channels are formed
progressively due to water diffusion within the aggregate phase and/or at the polymer/aggregate interface and dissolution of the particles and generation of more
empty space (voids), and therefore the media of diffusion here is water that fills the
pores, not the continuum of the polymer phase. If the solubility is intermediate, both
mechanisms contribute to the overall release and the medium of diffusion are both in the
polymer phase and the water-filled pores phase.
Sections 2.4.1 and 2.4.2 review the mathematical modeling efforts published for
the case of very high and very low antifoulant/polymer miscibility, respectively. For
both sections 2.4.1 and 2.4.2, the review of the modeling efforts is strictly referred to the
situations where the following conditions are always satisfied: the polymer matrix is
monolithic; the polymer matrix is neither soluble nor swell-able in water; and the active
compound is initially loaded in the matrix at a concentration in excess of its solubility
limit in the matrix. Also, unless specified, the geometry of the matrix is always in
frequently used by antifouling paints researchers) is always referred to the antifouling
compound.
Insoluble matrix coatings are those that do not erode over time in water, and
sometimes called continuous contact or contact leaching coatings, because of the leaching
mechanism involved. Marson (1969) was the first who mathematically modeled the
antifoulant leaching from insoluble matrix paints. In order to come up with his model, he
postulated the following leaching mechanism, with an assumption that the antifoulant
particles (Cu2O in his study) were spherical of equal size and uniformly distributed inmulti layers in the matrix (a rubber resin in his study). First, when the coating is initially
immersed in water, the pigment particles at the surface layer of the film dissolve forming
a saturated solution of the pigment at the pigment/leachate interface. Then, the saturated
solution diffuses outward through the diffusion layer in contact with the coating surface.
When a particle dissolves in seawater to reveal the thin binder membrane separating it
from the un-dissolved particles, water diffuses into the thin membrane and dissolves
some of the un-dissolved particles. Consequently, the resulting osmotic pressure ruptures
the membrane and the pores become interconnected. After many simplifications, Marson
was able to come up with a simple analytical equation that shows the dependency of the
leaching rate on the parameters of the coating and of the leaching media:
F = B υ / [1 + Cd/P) (2.35)
where F is the leaching rate, B and C are constants, υ is the pigment volume fraction, d is
the thickness of the matrix, and P is the fraction of interconnected holes that depends on υ
where a is the radius of the cylinder. By fitting the leaching data to the above equation,
they calculated the diffusion coefficient, D, to be 1.7 x 10 -14 and 3.8 x 10-13 cm2/s at 20
wt% and 35 wt% loading, respectively. However, the model that they selected was
strictly derived by Crank for a special case when the compound is initially loaded in the
matrix at a concentration well below the compound/matrix solubility, thus the compound
is always molecularly dissolved in the polymer phase. However, in their work, Vasishtha
et al . (1995) did not justify if the solubility of Sea Nine 211 in VYHH is greater than 35wt%, in order to use the Crank equation. In fact, it is very rare to have an antifouling
compound with such a high solubility in the matrix.
Table 3.1 The compositions of the two types of silicones (RTV11 and Sylgard® 184)used in the current study. All percentage shown here are in mass basis.
Component RTV11 Sylgard® 184
Polymer base OH-PDMS (66.4 %) * Vinyl-PDMS (90.9 %)
Curing agent ES40 (1.6 %) * SiH-PDMS (9.1 %)
Inorganic Filler CaCO3 (32 %) * -
Catalyst DBT (0.5 %) ** Pt (included in the curing agent)
* comes in one part (part 1).
** per 99.5 % of part 1
Aldrich, the molecular weight is specified as 1700 g/mol. It has a melting point of 210 0
C. It is highly soluble in water (1 g/ 0.35 ml water) and also has good solubility in some
organic solvents such as acetone and ethanol.
The organic solvents used in the current study (toluene, acetone, acetonitrile,
ethanol and ether) were purchased from VWR and used as received. Microscopic glass
slides (pre-cleaned, size: 25 x 75 x 1 mm) were obtained from VWR and used as
received.
3.2 Sample preparation
The antifoulants (capsaicin, benzoic acid, sodium benzoate, and tannic acid) were
incorporated into two polymeric silicone coatings (Sylgard® 184 and RTV11) by the
Table 3.2 The actual combinations of (antifoulant/solvent/polymer) mixtures used inthe current study to incorporate the antifoulant into the bulk of the polymer matrix by thesolvent-blending technique.
Antifoulant Silicone matrix Solvents
Sodium benzoateSylgard®184,
RTV11water/acetone blends
(different ratios)
Benzoic acidSylgard®184,
RTV11
Acetone,toluene,
acetonitrile,
ether
Capsaicin RTV11Toluene,Ethanol
Tannic acidSylgard®184,
RTV11Acetone
solvent-blending technique. Briefly, in order to obtain homogeneous antifoulant/silicone
blending by the solvent-blending method, the antifoulant was first dissolved in a solvent
or blend of solvents, and then the solution was homogenized with the polymer base, then
the curing agent was added to the mixture after drying off the solvent used. Table 3.2
summarizes the actual combinations of materials (antifoulant/solvent/matrix mixtures)
For incorporating sodium benzoate (NaB) into silicones, the following procedure
was followed, which is shown schematically in Figure 3.1, and the detailed
concentrations of the samples prepared are summarized in Table 3.3. NaB is much more
inorganic in nature than the other antifoulants, and consequently has low solubility in
organic solvents. On the other side, it has a high solubility in water (0.555 g of NaB per
1 g of water). Therefore, it was first dissolved in de-ionized water at a certain
concentration (the exact concentration is shown in Table 3.3). Next, a water-miscible
organic solvent, acetone, was added to the aqueous phase at a certain water/acetone mass
ratio (the exact ratio is shown in Table 3.3) while maintaining the complete solubility of NaB in the mixed-solvent. Then, the NaB/(water + acetone) solution was homogenized
Figure 3.1 A schematic diagrams for the sample preparation steps used for incorporating sodium benzoate into the silicone polymer coating.
Table 3.3 The detailed concentrations for NaB/ Sylgard®184 samples prepared atdifferent conditions. All concentration shown here are in mass basis. (Abbreviation: W:
Table 3.4 The detailed compositions for the samples that were subjected to leachingexperiments in the current study. All concentration shown here are in mass basis.(Abbreviation: W: water, A: acetone, S: solvent, P: silicone polymer base, NaB: sodium benzoate, BA: benzoic acid, TA: tannic acid).
in Figure 3.2a). Therefore, the Young’s equation relates the contact angle to the surface
energy of the substrate. Experimentally, the contact angles can be measured by applying
the sessile drop method where both dynamic and static contact angles can be measured.
For dynamic angles, the advancing and receding angles are achieved by the addition and
removal, respectively, of water from the drops formed on the coating surface, whereas for
static angles the water drop is placed on the coating surface and let to equilibrate without
external force (as shown in Figure 3.2b).
Figure 3.2 A simplified sketch for the contact angle concept. (a) the static contactangle: a liquid drop being in equilibrium with a solid substrate in air. γLV, γSV and γSL
are respectively the surface energies at the liquid/vapor, solid/vapor, and solid/liquidinterfaces, and θ is the equilibrium (static) contact angle. (b) the advancing contact angle(θa). (c) the receding contact angle (θa).
In the current study, the contact angle technique was applied to evaluate the
surface wettability of the coatings. Deionized water was the probe liquid, and both
dynamic and static contact angles were measured via the sessile drop method. Images of
the drops were captured using the Dazzle DVC (Digital Video Creator) and its software,
and data were processed using the Scion Image Software.
It should be noticed that both advancing and receding contact angles slightly
depend on the rate of fluid injection (for advancing) and removal (for receding). For
advancing angle, it slightly increases as the rate of injection increases. For recedingangle, it slightly decreases as the rate of removal increases. Therefore, for our
experiments, the rate of injection was gradually increased at three rates and the
corresponding advancing contact angles were measured and averaged all together.
Similarly, the rate of removal was gradually decreased at three rates and the
corresponding receding contact angles were measured and averaged all together.
3.4.2 The stress - strain technique
The stress – strain technique is a common and widely used technique for
measuring the elastic modulus of most types of materials, including both soft and hard
materials. According to this method, the elastic modulus (E) is defined as ratio of the
stress applied on a sample over the strain resulted in the shape of the sample.
Experimentally, the stress is usually varied at a certain range, and at each time the
elongation in the sample length is measured. Strain is defined as [(L ─ L0)/L0)], where L
and L0 are the initial length and the elongated length of the sample, respectively. Stress is
defined as [mg/(w x t)], where m is the mass of the load used, g is the acceleration of
gravity, w and t are respectively the width and thickness of the sample. Hence, E is
obtained as the slope of the linear plot of stress v.s strain data.
For the current study, the stress – strain technique was applied to measure the
elastic modulus of antifoulant-blended RTV11 coatings, due to their opaque nature. A
small rectangular sheet (length ~ 25 mm, width ~ 6 mm, and thickness ~ 1 mm) of
coating was vertically hung in air, its elongation under a particular weight was measuredfrom the magnified images captured using the goniometer video system and the Dazzle
DVC and its software. Stress was varied gradually up to ~ 0.13 MPa.
3.4.3 The JKR technique
The JKR technique is a specialized technique for measuring the elastic modulus
of soft materials. It is also a direct quantative method for measuring their surface
energies. Its name came on behalf of the three scientists (Johnson-Kendall-Roberts)
whose originally established the theoretical framework for this method in 1971 (Johnson
et al., 1971), and sometimes called contact mechanics technique. The detailed theory
behind the JKR technique can be found elsewhere (Chaudhury and Whitesides, 1991;
Johnson et al., 1971). Briefly, a soft elastic lens is brought into contact with an elastic
surface, and the deformation of the contact zone (normally a circular area) under a certain
load can be related to the elastic modulus of the system, thus the modulus of the coating.
In the current study, the JKR method was used to measure the elastic modulus of
Sylgard® 184 coatings and antifoulant-incorporated Sylgard® 184 coatings. The modulus
of antifoulant-incorporated Sylgard®184 coatings could also be measured via the
stress-strain technique. However, the JKR technique was selected here because of the
extensive usage of the JKR technique for evaluating the properties of Sylgard®184, a
highly transparent coating, and the values measured in this study could be compared to
the reported values. The elastic modulus of control Sylgard®184 coating was also
measured by the stress-strain method to compare between the accuracy of the two
methods. For the JKR method, the procedures developed by Chaudhury and Whitesides(1991) were followed in the current study. Briefly, as shown schematically in figure 3.3,
the radii of contact areas for 8 to 10 different compression loads were measured,
and the contact radius vs. load was plotted to extrapolate the modulus of the system
from the slope of the plot. With the known modulus of the lens and assuming the
materials were perfect elastic, the modulus of the coating was deduced from the modulus
of the system.
3.4.4 Optical Microscopy
Optical microscopy is a quick nondestructive tool for providing useful
information about the overall morphology – in two dimensions – of the sample surface.
The principle behind it is that it employs a visible light. Because optical microscope
requires a visible light source, it has a limitation that it can not scan very small area of
less than tens of microns, therefore localized morphology information in nanometer scale
In the current study, variations in the morphology of the AF compounds-
incorporated silicone films were observed using an optical microscope (Model IX-70,
Olympus) having video and still image capturing capabilities.
3.4.5 Scanning Probe Microscopy
Scanning probe microscopy (SPM) involves several types, such as scanning
tunneling microscopy (STM), atomic force microscopy (AFM), lateral force microscopy
(LFM), and magnetic force microscopy (MFM). The basic components of SPM are thelaser diode, the piezoelectric scanner, the cantilever and tip probe, and the position
sensitive photo detector. The tip is usually made of silicon or silicon nitrile. AFM was
the technique used in the current study. In AFM, a force probe is applied, which detects
the van der Waals interaction force between the probe tip and the surface, to scan over
the surface of a sample. AFM has the advantages over the optical microscopy technique
is that it can provide quantitative information about the localized surface topography of
the samples both in two dimensions and three dimensions, and it can also provide
quantative information about the surface roughness (Magonov and Reneker, 1997). The
resolution of AFM is very high, close to the atomic level, where a surface area of as small
as 1µm x 1µm can be scanned with a high image quality. However, opposite to optical
microscopy technique, AFM has a limitation that it is not suitable for scanning large
surface area (e.g. > 100µm x 100µm) to provide overall morphology of the sample
surface. AFM is commonly operated in either a contact mode (where repulsive force is
used) or a non-contact mode (where attractive force is used). The non-contact mode is
generally preferred because it usually gives better resolution than the contact mode.
In the current study, the details of the coating surface were examined with the
non-contact mode AFM (Metrology 2000, Molecular Imaging), where a Si3 N4 cantilever
with a spring constant of 21 – 78 N/m was used. All the AFM images presented in this
study have a scan size of 80 µm x 80 µm and obtained with a scan rate of 0.20 Hz.
3.4.6 High Performance Liquid Chromatography (HPLC)
HPLC is a popular method of analysis. It has many applications such as
separation, identification, purification, and quantification of various compounds. The
basic components of the HPLC set-up are the solvent reservoir (where the mobile phase
comes from), the pump, the injection port (where the samples are injected into the mobile
phase), the column (where the stationary phase is placed), the detector, and the waste
reservoir. The basic principle behind HPLC is that certain compounds have different
migration rates given a particular column and mobile phase. Thus, the chromatographer
can separate compounds from each other, and the degree of separation is mostly
determined by the selection of the mobile phase and the stationary phase. The mobile
phase is the solvent being continually applied to the column, and acts as a carrier for thesample solution. As a sample solution flows through the column with the mobile phase,
the components of that solution migrate and separate according to the non-covalent
interactions of the compound and the mobile phase with the stationary phase. For
example, those samples which have stronger interactions with the stationary phase than
with the mobile phase will elute from the column slower and therefore will have a longer
retention time, whereas the reverse is also true (Schoeff and Williams, 1993).
In the current study, HPLC technique was employed to determine the unknown
bulk concentrations of capsaicin in water, as part of the leaching experiment. The
solutions of unknown capsaicin concentrations were subjected to HPLC analysis (Model
LC-10AT from Shimadzu with the symmetry C-18L column from Walters) using a
mixture of acetonitrile + DI water (50:50 vol/vol) with a pH value of 2.1 as the mobile phase. 10 µL of the solution was injected into the column and flown at a constant rate of
1 ml/min. In order to obtain the calibration curve, a set of standard solutions with
concentrations in the range of 13 – 5000 ppm of the purchased capsaicin were prepared
RESULTS AND DISSCUSSION FOR SODIUM BENZOATE-BASED COATINGS
In this chapter, the results obtained for sodium benzoates (NaB) - incorporated
silicone coatings are presented and discussed. The effect of incorporating the compound
on the surface and bulk properties of the coatings is presented in section 4.1. The effectof varying the preparation conditions on the bulk morphology/miscibility of NaB-based
coatings is discussed in section 4.2. Theoretical thermodynamic analysis for the
miscibility study is presented in section 4.3. The effect of varying the preparation
conditions on leaching of the compound in water is presented in section 4.4. Theoretical
mass transfer analysis for the leaching study is presented in section 4.5. The antibacterial
performance for the NaB-incorporated coating is presented in section 4.6.
4.1 Effect of sodium benzoate on surface and bulk properties of silicones
Sodium benzoate (NaB) was incorporated into two types of silicones (Sylgard®
184 and RTV11). For Sylgard® 184 coating, the concentration of NaB in the matrix was
varied from 0 to 5 wt%. For RTV11 coating, only one concentration was prepared (1
wt% NaB in the matrix). For all of the samples prepared, it was observed that the NaB-
blended coatings were cured similarly as the NaB-free coatings alone. Further examining
the effect of incorporated compound on the surface and bulk properties of the silicone
coatings qualitatively confirmed this observation, as to be discussed in sections 4.1.1 and
4.1.2.
4.1.1 Effect on wettability
The wettability of the coatings was investigated in terms of measuring the water
contact angles. Sylgard® 184 coatings of various amounts of NaB (0 - 2 wt %) were
subjected to contact angle measurements, and the results are shown in Figure 4.1. For control samples of NaB - free Sylgard® 184 coatings, the advancing, static, and receding
contact angles were measured to be 110°, 106° and 80°, respectively. As seen in Figure
4.1, the incorporation of NaB in Sylgard® 184 (up to 2 wt. %) had little effect on the
wettability of Sylgard® 184 coating. This could suggest that most of NaB molecules
were entrapped inside the bulk of Sylgard® 184 rather than aggregated to the surface.
Otherwise, the contact angle was expected to decrease considerably due to the fact that
NaB has much higher surface energy than silicones (the surface energy for different types
of silicones is in the range of 20 - 24 mJ/m2), and the contact angle hysteresis (difference
between the advancing and receding angles) should increase due to the in-homogeneity of
aggregates if presented on the surface.
In addition, the contact angles of NaB-free RTV11 coating and 1 wt%
NaB/RTV11 coating were also measured, and the results are shown in Table 4.1. For
control samples of NaB - free RTV11 coatings, the static contact angle was 101°,
Figure 4.1 Water contact angles of NaB-entrapped Sylgard®184 films (advancing: ,receding: , and static: ). The (solvent: polymer) ratio and the (water: acetone) ratiowere respectively (20: 80) and (50: 50) by mass, which were fixed at all concentrations.Error for each data point (average over 12 measurements) is presented by the verticalline.
Table 4.1 Static water contact angles of NaB-entrapped RTV11 films. The (solvent: polymer) ratio and the (water: acetone) ratio were respectively (20: 80) and (50: 50) bymass.
Coating Static Contact angles
Control RTV11 101.2 ± 0.5
1 wt% NaB/RTV11 100.7 ± 0.7
and maintained around this value for the 1 wt% NaB-blended RTV11 coating. The
indifferent contact angle values of 1 wt% NaB-blended RTV11 as those of pure RTV11
could give us the indication that most of NaB molecules were entrapped inside the bulk
of RTV11 rather than aggregated to the surface for the same reasoning mentioned above
for NaB- Sylgard® 184. To summarize, the indifferent contact angle values of NaB
blended coatings as those of pure silicone is the first indication that the NaB-blended
silicone coatings could be cured.
It could be of interest also to notice here the slight difference in the wettability of
pure (i.e. NaB-free) Sylgard® 184 and pure RTV11 coatings. By comparing the static
contact angle data for control samples of NaB-free coatings, it could be suggested thatSylgard® 184 silicone has slightly a higher hydrophobicity than RTV11 silicone. The
same conclusion could be drawn from the surface energy data for the two matrices, as
follow. From literature, the surface energy of RTV11 is 23.3 mJ/m2 (Berglin and
Gatenholm, 1999), which is slightly higher than the surface energy of Sylgard® 184
silicone (~ 20 mJ/m2).
Another interesting observation is the effect of the curing temperature on the
contact angle hysteresis for the two matrices. During the initial stage of trying different
schemes to prepare the samples, it was observed that the curing temperature had a strong
effect on the contact angles hysteresis for Sylgard® 184 coating but had no effect on the
contact angles hysteresis for RTV11 coatings. Both control samples of RTV11 and
Sylgard
®
184 were cured at two temperatures: 25° C and at 100° C. For RTV11, thetemperature had no effect on the advancing (103 °) and receding (95°) contact angles.
For Sylgard® 184, however, the advancing contact angle was about 110° at both
temperatures while the receding contact angle increased significantly from about 80° at
the lower temperature to about 95° at the higher temperature. In other words, for
Sylgard® 184, the contact angle hysteresis decreased from 30° at the lower curing
temperature to 15° at the higher curing temperature. Although it is not intended in the
current study to explore this effect in details, it could be anticipated that there were more
un-cross linked chains aggregated on the surface of Sylgard® 184 at the lower
temperature compared to the higher temperature, which would result in increasing the
contact angle hysteresis. For the purpose of enhancing the antifouling performance of the
silicone coating by means of minimizing its contact angle hysteresis, it might be better
technically to process Sylgard® 184 at higher temperatures, although this might not be an
easy task practically. However, for the current study henceforth, all the results associated
with Sylgard® 184 were corresponding to samples cured at room temperature.
The elastic modulus of a coating is a good measure of its bulk properties. Thus,
Sylgard® 184 coatings of various amounts of NaB (0 - 2 wt %) were subjected to elastic
modulus measurements, and the results are shown in Figure 4.2. For control NaB-free
Sylgard® 184 coating, the elastic modulus was 0.95 MPa, which was in agreement with
the literature value reported (Eddington et. al ., 2003). As shown in Figure 4.2, after
incorporating NaB into Sylgard® 184, it was observed that the elastic modulus increased
slightly from those of control value. This slight variation of the modulus could beattributed to the final distribution and aggregate size of the compound inside the bulk of
the matrix. As to be seen in the next section, sodium benzoate has a uniform distribution
with small aggregate size about 3 µm. Consequently, Sodium benzoate could behave
here as a fine reinforced filler that resulted in increasing the elastic modulus.
Nevertheless, the elastic modulus measurements for the above systems indicated that the
low content of NaB was insignificant in affecting the bulk properties of the silicone
coatings. Also, it confirmed that NaB had little effect on the curing behaviors of
Sylgard® 184 coatings, as the bulk modulus was expected to drop significantly for the
uncured, liquid like coating. To summarize, the incorporation of NaB into Sylgard® 184
coatings did not considerably affect the surface and bulk properties of the Sylgard® 184
coatings, suggesting that the foul-release property of Sylgard® 184 likely be retained.
Figure 4.2 Elastic modulus variations of NaB - entrapped Sylgard® 184 coating. The(solvent: polymer) ratio and the (water: acetone) ratio were respectively (20: 80) and (50:50) by mass, which were fixed at all concentrations. Error for each data point (averageover 6 measurements) is presented by the vertical line.
Figure 4.3 Optical microscope (bright field) images (570 µm x 480 µm) of the bulk morphology of 1 wt % NaB/Sylgard® 184 matrix, prepared at different water/acetoneratios, keeping the solvent/polymer ratio fixed at 20/80. (a) 20/80 water/acetone; (b)30/70 water/acetone; (c) 50/50 water/acetone; (d) 80/20 water/acetone; (e) 90/10water/acetone; (f) 100% water. All the values are based on weight.
Based on this fact, the limiting acetone/water ratios for different sets of conditions are
calculated and presented in Figure 4.4, which serves as a practical guide for preparing the
samples.
0.0
0.5
1.0
1.5
2.0
0% 20% 40% 60% 80% 100%
water/(water + acetone) mass %
m
a s s N a B / m a s s
w a t e r
1 wt% NaB/P; 20/80 S/P
saturation line
5 wt% NaB/P; 20/80 S/P
7 wt% NaB/P; 20/80 S/P
Figure 4.4 Guidelines chart for preparing NaB-incorporated Sylgard® 184 coatings at
different set of conditions. The saturation line “ — ” represents the maximum solubilityof NaB in water (0.555 g NaB per 1 g of water). Above this line, NaB is not soluble inthe mixed solvent (water + acetone), and hence the bulk entrapment method will not befeasible at this particular set of conditions. (Abbreviations: S: solvent; P: polymer). Allvalues are in mass basis.
Figure 4.5 Optical microscope (bright field) images (570 µm x 480 µm) of the bulk morphology of 1 wt % NaB/Sylgard® 184 matrix, prepared at different solvent/polymer ratios, keeping the water/acetone ratio fixed at 50/50. (a) 10/90 solvent/polymer; (b)20/80 solvent/polymer; (c) 30/70 solvent/polymer; (d) 40/60 solvent/polymer; (e) 50/50solvent/polymer. All the values are based on weight.
Table 4.3 Aggregate size distribution of 1 wt.% of sodium benzoate inside the (99wt.%) bulk of Sylgard® 184 matrix, for samples prepared at different solvent/polymer (S/P) mass ratios. The water/acetone ratio was fixed at 50/50 by mass.
* The number outside the parenthesis is the average aggregate size evaluated in that particular size range. The number inside the parenthesis is the percentage of number of aggregate at that particular size range to the total number of aggregates.** The arithmetic mean size is defined by summing the sizes of all aggregates anddividing by the total number of aggregates.*** The quadratic mean size is defied as: (∑ di
2 ni/ntot)1/2 , where di and ni are,
respectively, the average size and the number of aggregates at that particular size range,and ntot is the total number of aggregates.
Figure 4.6 Optical microscope (bright field) images (570 µm x 480 µm) of the bulk morphology of NaB/ Sylgard® 184 matrix of different NaB concentrations, keeping the
solvent/polymer ratio and the water/acetone ratio fixed at 20/80 and 50/50, respectively.(a) 0.5 wt% NaB/ Sylgard® 184; (b) 1 wt% NaB/ Sylgard® 184; (c) 2 wt% NaB/ Sylgard®
184; (d) 3 wt% NaB/ Sylgard® 184; (e) 4 wt% NaB/ Sylgard® 184; (f) 5 wt% NaB/Sylgard® 184; All the values are based on weight.
Table 4.4 Aggregate size distribution of sodium benzoate inside the bulk of Sylgard®
184 matrix, for samples prepared at different NaB matrix loading (wt% NaB in thematrix). The water/acetone ratio was fixed at 50/50 by mass. The solvent/polymer ratiowas fixed at 20/80 by mass.
* The number outside the parenthesis is the average aggregate size evaluated in that particular size range. The number inside the parenthesis is the percentage of number of aggregate at that particular size range to the total number of aggregates.** The arithmetic mean size is defined by summing the sizes of all aggregates anddividing by the total number of aggregates.*** The quadratic mean size is defied as: (∑ di
2 ni/ntot)1/2 , where di and ni are,
respectively, the average size and the number of aggregates at that particular size range,
Table 4.5 Physical parameters of relevance importance to the miscibility of NaB/PDMS. V and δ are the molar volume and the solubility parameter of the material,respectively. δ12 is the difference in solubility parameters between the material andPDMS. χ 12 is the interaction parameter between the material and PDMS*.
MaterialV
(cm3/mol)
δ (MPa)
½
∆δ12 (MPa)
½ χ 12 Boilingpoint
(oC)
Water 18.2 47.9 a 33.0 8.000 100
Acetone 74.0 20.3 a 5.4 0.871 56
NaB 100.1 35.8 b 20.9 17.648 -
a, b Values obtained from (Rodriguez, 1989) and (Bustamante et. al., 2000), respectively* For PDMS, the literature value of its solubility parameter (14.9 MPa½, from: Rodriguez, 1989) was used
The interaction parameter calculated by equation 4.1 provides a rough prediction for
the miscibility of the mixture. However, the effect of composition of the mixture is not
explicitly accounted for by this method. In a more general form, the miscibility of the
mixture can be predicted by calculating the free energy of mixing (∆Gmix) for the system
at all compositions. As thermodynamics states, the system becomes more heterogeneous
as ∆Gmix increases, and becomes spontaneously homogeneous when ∆Gmix is less than
zero. NaB/water/acetone/PDMS is a quaternary system. According to the “Flory-
Huggins” theory, the free energy of mixing for a quaternary system is given by ((Flory,
Figure 4.7 The miscibility trends for NaB/acetone/water/PDMS mixtures, for all possible conditions, as predicted by the original Flory-Huggins (FH) model (equation4.2). (a) Effect of the water/acetone (W/A) ratio; parameters fixed: 1 wt% NaB/polymer.(b) Effect of the NaB matrix loading; parameters fixed: 50/50 water/acetone. All thevalues shown in the legends are based on weight.
where χ ij, d accounts for the dispersion interactions, χ ij, fv accounts for the interactions
resulted from the free volume effect, and χ ij, sp accounts for the specific interactions such
as acid-base interactions or H-bonding. However, the “Flory-Huggins” theory only
considers the dispersion interactions and totally neglects the other two types of
interactions, which might result in errors in estimating the values of χ ij and consequently
some errors could result in the value of ∆Gmix. For example, neglecting the free volume
effect is based upon the assumption that there is no volume change upon mixing, which is
rarely satisfied for mixing large macromolecules with solvents or additives of much
smaller size. Specific interactions could exist in our system and affect the value of thefree energy of mixing. One specific interaction that could be identified here is the
electrostatic interactions, because our system is in fact containing electrolyte solution
(NaB, which dissociates into salt ions in water). Other specific interactions are the polar
interactions for water/acetone and NaB/water. Another source of error is the assumption
that the interaction parameters are not functions of concentrations. All these factors
together could affect the miscibility prediction. In the current subsection, we are
modifying the Flory-Huggins thermodynamic model (equation 4.2) to include
electrostatic contribution term to the total free energy and concentration-dependent
interaction parameters.
The NaB aqueous solution is an electrolyte solution. Thus, when mixed with
polymers, specific interaction like electrostatic interaction will exist that could change the
phase behavior of the mixture. In this section, we present a simple lattice thermodynamic
model that accounts for this electrostatic interaction. The model was originally
where Φsalt is the volume fraction of the salt, and zM and zX are, respectively, the valences
of the cation and anion. In the above model (equation 4.6-4.8), several assumptions are
employed. The polymer is assumed to be neutral. The ternary system is assumed to be
incompressible. It is also assumed that the salt is completely dissociated into ions.
In the following, we extend the above model (equation 4.6-4.8) to our quaternary
system consisting of water (1), acetone (2), NaB (3), and PDMS (4). The complete
equation is:
∆Gmix / nkT = Φ1 (W/1000) [— A (4 I / b) ln (1 + b I1/2)]
+ Φ1 ln Φ1 + (Φ2 / R 21) ln Φ2 + (Φ3 / R 31) ln Φ3 + (Φ4 / R 41) ln Φ4
+ Φ1 Φ2 χ 12
* + Φ1 Φ3 χ 13 + Φ1 Φ4 χ 14 + (Φ2 / R 21) Φ3 χ 23
+ (Φ2 / R 21) Φ4 χ 24* + (Φ3 / R 31) Φ4 χ 34 (4.9)
Another new feature of the new model (equation 4.9) is the introduction of the
concentration-dependent interaction parameters for water-acetone pair, χ 12*, and acetone-
PDMS pair, χ 24*. These two parameters are obtained from the literature for experimental
data collected specifically for these two particular systems. Therefore, they are expected
to give better values than the values predicted by equation (4.1). The reason why
specifically the above pairs (water/acetone, and acetone/PDMS) are consideredconcentration-dependent is because acetone is highly miscible in water and acetone has
some miscibility in PDMS. On the other hand, the interaction parameter for water-
PDMS system (χ 14) is considered constant and calculated by equation (4.1). This is
To criticize the validity of equation (4.1) for acetone-PDMS system and acetone-
water system, the following can be mentioned. The experimental value for acetone-
PDMS interaction parameter is in the range of 1.3 to 1.9 ((Singh et. al, 1998), indicating
that acetone is not a good solvent for PDMS. To verify this experimentally, we did a
simple experiment of dissolving a small amount of PDMS in acetone (1 wt%
PDMS/acetone mixture), and it had been observed that the mixture was not miscible even
after two days of continuous stirring. However, the prediction of the interaction
parameter by equation (4.1) gives a value of 0.87, which is lower than the measured
value, mainly because of the reason described by equation (4.5). Similarly, theexperimental value for the water-acetone interaction parameter is in the range of 1 to 2
(Yilmaz and McHugh, 1986), whereas it is 5.5 when predicted by equation (4.1). Again,
this predicted value was higher than the measured value, since water and acetone are
highly miscible with each other, and the reason for the disagreement is also as described
by equation (4.5). Therefore, it is always better, whenever possible, to use experimental
values for the interaction parameters.
In summary, it should be noticed that the new model (equation 4.9) as well as the
conventional Flory-Huggins model (equation 4.2) contain no adjustable parameters. Two
of the binary interactions, χ 12* and χ 24
*, are concentration-dependents and obtained form
empirical correlations, and the others are concentration-independent and calculated byequation (4.1). In summary, in equation (4.9), the first term of the right hand side is the
electrostatic contribution term (which is always negative). The remaining terms are
Flory-Huggins terms but with two concentration-dependent interaction parameters (χ 12*
and χ 12*). The second to the fifth terms of the right-hand side are the entropic terms
(always negative), and the sixth to the eleventh terms are the enthalpic terms (always
positive). Therefore, compared to equation (4.2), the free energy of mixing could be
negative if the favorable electrostatic term is high enough to overcome the unfavorable
enthalpic terms.
Equation (4.9) is evaluated for our particular system and compared to the results
obtained by the conventional Flory-Huggins model (equation 4.2), and the results are
shown in Figure 4.8. Compared to the trends obtained by equation (4.2), the change inthe trends is observed, but does not change the earlier conclusions that the mixtures are
immiscible because the free energy of mixing is positive at all the conditions. This is
expected because the unfavorable enthalpic interaction between water and PDMS is too
large to be compensated by the favorable electrostatic interaction. The observed
difference between the trends obtained by the new model and the Flory-Huggins model is
due mainly to the effect of introducing the concentration-dependent interaction
parameters, χ 12* and χ 24
* , and not because of the introduction of the electrostatic term.
Nevertheless, the new model (equation 4.9) is useful because it isolates most of the
possible interactions existing in the system and thus gives us practical guidelines to tailor
the system. For example, we could slightly modify the polymer from being strongly
hydrophobic to be partially hydrophobic. In this case, the unfavorable enthalpic terms
will be reduced and the system will be more miscible.
Figure 4.8 The miscibility trends for NaB/acetone/water/PDMS mixtures for all possible conditions, as predicted by the new model (equation 4.9). (a) Effect of thewater/acetone (W/A) ratio; parameters fixed: 1 wt% NaB/polymer. (b) Effect of the NaBmatrix loading; parameters fixed: 50/50 water/acetone. All the values shown in thelegends are based on weight
4.3.3 Comparison between the theoretical miscibility trends and the experimentalmorphology trends
In this subsection, we are making comparison between the experimental
morphology trends (aggregate size of NaB as function of preparation conditions) and the
theoretical miscibility trends (Gmix as function of preparation conditions), in an attempts
to explain the role of thermodynamics on the aggregate size and also to compare between
accuracy of the Flory-Huggins model and the new model. To do this, Gmix calculated
by both models is plotted as function of one preparation parameter, keeping the other
parameters fixed. At the same time, the insert in the same plot shows the experimentallymeasured aggregate size as a function of this preparation parameter. The results are
shown in Figure 4.9. As can be seen from Figure 4.9, both models do capture
qualitatively most of the important effects of the preparation conditions on the aggregate
size of NaB in PDMS. In addition, both models correctly predict that NaB matrix
loading has no strong effect on the aggregate size, as long as NaB is soluble in the mixed
solvent. To compare between the accuracy of the two models, the following can be
mentioned. Experimentally, the aggregate size increased strongly as the solvent/polymer
ratio increased from 20/80 to 30/70, but after the ratio of 30/70 the increase was little
(8.7, 10.4, and 10.5 µm for samples prepared at 30/70, 40/60, and 50/50 solvent/polymer
ratio, respectively). The trend for Gmix calculated by the new model in this
solvent/polymer ratios range is more similar to the experimental morphology trend than
the trend of Gmix calculated by the Flory- Huggins model (see Figure 4.9b). Therefore,
the new model is shown to be more accurate than the Flory-Huggins model.
Figure 4.9 The free energy of mixing (Gmix/nkT) for NaB/acetone/water/PDMSmixtures prepared at different conditions, as predicted by two models: the Flory-Huggins
(F-H) model (equation 4.2), and the new model (equation 4.9). (a) Effect of thewater/acetone ratio, parameters fixed: 20/80 solvent/polymer and 1 wt% NaB/polymer.(b) Effect of the solvent/polymer ratio, parameters fixed: 50/50 water/acetone and 1 wt% NaB/polymer. All the values are based on weight. The preparation conditions describedhere correspond to the actual conditions for the morphology experiments performed inthe current study. The insert in each plot represents the corresponding experimentalmorphology trend.
Figure 4.9 The free energy of mixing (Gmix/nkT) for NaB/acetone/water/PDMSmixtures prepared at different conditions, as predicted by two models: the Flory-Huggins(F-H) model (equation 4.2), and the new model (equation 4.9). (c) Effect of NaB matrixloading, parameters fixed: 50/50 water/acetone and 20/80 solvent/polymer. The solvent isdefined here as water + acetone + NaB. All the values are based on weight. The preparation conditions described here correspond to the actual conditions for themorphology experiments performed in the current study. The insert in each plotrepresents the corresponding experimental morphology trend. (continued)
However, both the Flory-Huggins model and the new model could not explain
two experimental observations. First, the aggregate size at the smallest experimental
solvent/polymer ratio used (10/90) was 6.9 µm, which was larger than the corresponding
aggregate size (4.0 µm) at 20/80 solvent/polymer. However, Gmix at the (10/90) ratio is
lower than Gmix at the (20/80) solvent/polymer ratio. Second, experimentally, the
water/acetone ratio in the range of 20/80 to 50/50 water/acetone did not affect
considerably the aggregate size (the aggregate size was in the range 3-4 µm), but it
affected the aggregate size sharply after the ratio of 80/20 water/acetone (the aggregate
size was 15.6 for samples prepared with 90/10 water/acetone ratio). However,
theoretically, Gmix increases almost linearly as the water/acetone ratio increases. The
reasons will be discussed in the next paragraph. Before that, it should be noticed that the
comparison made in Figure 4.9 between the experimental morphology curves and the
theoretical miscibility curves is qualitative because the y-axis is not the same. Our
objective here is to prove that as Gmix for any set of preparation conditions increases,the aggregate size increases, which were true for most of the sets of the preparation
conditions.
The difference between the predictions and the above two observations could be
explained as follow. The values of ∆Gmix shown in Figure 4.9 and predicted by equations
(4.2) and (4.9) are the description for a situation of thermodynamic mixing of an isolated
system. That is, the NaB/water/acetone/PDMS system is placed inside a closed vial that
is perfectly insulated, the mixture is well-mixed, and then the mixing is stopped and
enough time is allowed for the system to equilibrate. ∆Gmix shown in Figure 4.9 is,
hence, of what is described above. Under the situation described above, the total
composition of the entire system is presumably the same, in other words, water and
acetone do not evaporate in this isolated system. However, this was not the case for our
NaB/PDMS morphology experiments. That is, in the process of incorporating NaB into
PDMS by the solvent blending technique and during the process of heating and drying
the system, the composition of the system was continually changing due to evaporation of
water and acetone because the system here was open to the environment. This resulted in
the nucleation and growth of new solid phase (solid NaB particles) as the solvent became
more concentrated, until the solvent was completely dried off. This dynamic drying step
would strongly affect the final morphology of the NaB/PDMS composites, but equation
4.2 and equation 4.9 do not consider such a dynamic effect. In order to account for this
dynamic effect, a mass transfer model has to be combined with the thermodynamic
model. The mass transfer model would need to account for the phase change
(vaporization) of acetone and water, and to account for the phase change (solidification)
of NaB, whereas PDMS can be considered as an inert material (i.e. no phase change for PDMS) at all time. As more water vaporizing, the NaB volume fraction will be closer to
its solubility limit in water, and hence start to precipitate out. Once precipitation occurs,
the unfavorable enthalpic terms (in equations 4.2 and 4.9) will increase and the favorable
entropic terms (in equations 4.2 and 4.9) will decrease, both will result in the
enhancement the phase separation of the system. It has been shown that when mixing
solid particles with solvent and polymer, the entropy-driven phase separation is possible
even for athermal (i.e. zero χ ij) system (Schaink and Smith, 1996). Since water and
acetone are not good solvents for PDMS, the system can not form a homogeneous phase.
Instead, a two phase or even a multi-phase system is expected, and the development for a
multi-phase transport phenomena model for this system and combining it with the
thermodynamic model is too complicated and beyond the scope of the current study.
Nevertheless, the rough prediction based on the thermodynamic models presented
here did qualitatively describe most of the features of our system, and still useful as a
preliminary guide for selecting the components of the quaternary system.
The NaB molecules incorporated into the coatings should leach out in order for
them to antifoul. Therefore, the NaB-entrapped silicone coatings were subjected to
leaching studies in static cells. The effects of different preparation conditions on the
leaching behaviors are presented in the following subsections. The parameters varied
were: solvent composition (acetone/water ratio), solvent/polymer ratio, wt% NaB in the
matrix, and type of the matrix. We selected the base case conditions to be: 50/50
water/acetone ratio, 20/80 solvent/polymer ratio, 1 wt% sodium benzoate in the matrix,and Sylgard® 184 as the base-case matrix. Thus, when varying any one parameter, the
other parameters were fixed at the base case conditions.
4.4.1 Effect of composition of the mixed solvent
NaB-incorporated Sylgard® 184 samples prepared at different water/acetone
ratios, whose bulk morphology are shown in Figure 4.3, were subjected to leaching
evaluations, and the results are shown in Figure 4.10. For all these samples, the
solvent/polymer ratio was fixed at 20/80, and the wt. % NaB in the coating was fixed at 1
wt. %. As shown in Figure 4.10, the general trend, regardless water/acetone ratio used,
was observed. Sodium benzoate leached out in two stages, a first fast stage occurred in
the initial few days and followed with a second steady stage having a much slower rate.
This leaching behavior is not unique to the sodium benzoate/Sylgard® 184 coating. In
Figure 4.10 Cumulative leaching (Q) of NaB from Sylgard® 184 matrix immersed inwater. The samples were prepared at different water/acetone ratios, keeping the other conditions unchanged (20/80 solvent/polymer, and 1 wt% NaB/matrix). All the valuesare based on weight. Solid lines are for showing the trends. (Abbreviations: W: water;A: acetone). Error for each data point (average over 2 batches) is presented by thevertical line.
Figure 4.11 Cumulative leaching (Q) of NaB from Sylgard® 184 matrix immersed inwater. The samples were prepared at different solvent/polymer ratios, keeping the other conditions unchanged (50/50 water/acetone, and 1 wt% NaB/matrix). All the values are based on weight. (Abbreviations: S: solvent; P: polymer). Error for each data point(average over 2 batches) is presented by the vertical line.
Figure 4.12 Cumulative leaching (Q) of NaB from Sylgard® 184 matrix immersed inwater. The samples were prepared at different wt% NaB/matrix, keeping the other conditions unchanged (50/50 water/acetone, and 20/80 solvent/polymer). All the valuesare based on weight. Error for each data point (average over 2 batches) is presented bythe vertical line.
Figure 4.13 Cumulative leaching of NaB from its incorporated silicone coating:Sylgard® 184 ( ) or RTV11 (▲). The common solvent used was 50/50 water/acetone byweight. The initial concentration of NaB in both coatings was kept constant at 1 wt%.,
and the solvent/polymer ratios was kept constant at 20/80 by weight for bothcombinations.
Therefore, the effect of changing the matrix type on NaB leaching was clearly
observed, where the leaching of NaB from RTV11 was higher than that from Sylgard®
184. This could be attributed to the following reasons. First, partial degradation and
erosion of the RTV11 matrix in water, which were confirmed experimentally by Bullock
et. al. (1999) and Brady (2000), could be contributing and facilitating the leaching.
Wynne et al . (2000) evaluated two types of PDMS coatings (RTV11, and an in-house
unfilled hydrosilation cured PDMS), and they found that the hydrosilation cured PDMS
was very stable in water, whereas RTV11 was not stable in water with a mass loss of
about 0.8 % after 30 days of immersion. This mass loss from RTV11 was attributed tothe leaching of the RTV11 filler (RTV11 has a high content of inorganic fillers including
CaCO3 (32 wt.%)), and was also attributed to the continuous loss of small amounts of
RTV11 constituents, such as Me2SiO, other than CaCO3 (Bullock et. al., 1999). Second,
as mentioned before, RTV11 has a high content of inorganic fillers including CaCO 3 (32
wt. %), which has a pore volume of 0.1 ─ 0.8 cm3/g (Wypych, 1999). At this high filler
content, filler agglomeration, which is a result of incomplete dispersion or flocculation, is
highly possible, which could lead to “voids” in-between the filler particles and at the
filler/polymer interface (Wel and Adaned, 1999). Thus, these voids allow water
molecules to seep into the silicone matrix more easily through these empty spaces and
carry the dissolved antifoulants molecules with them as they leave the coating. Third, the
reported solubility of water in PDMS is 7000 ppm and 700 ppm for filled and unfilled
silicone, respectively (Banerjee et al ., 1997), which implies that the water uptake of
RTV11 is higher than that of Sylgard® 18 matrix. The finding of the current study on the
effect of the matrix type on NaB leaching was supported by the leaching results obtained
Figure 4.14 Empirical correlations for the leaching rate of NaB from Sylgard® 184.(a) Effect of the aggregate size (d, the arithmetic mean size), parameter fixed: 1 wt% NaB/matrix. (b) Effect of the NaB matrix loading, parameter fixed: d ~ 3 - 4 µm. Theinsert in (b) is for enlarging the scale of the y-axis. The symbols (■) and (O) representthe initial and the steady leaching rates, respectively.
samples corresponded to static conditions, water replacement conditions, and continuous
stirring conditions, respectively. Based on the mass balance analysis, about 5.1 %, 5.4 %,
and 5.9 % of the NaB original mass had leached out after 19 days of immersion for
samples corresponded to static conditions, water replacement conditions, and continuous
stirring conditions, respectively.
A final note is made here about the experimental method used to evaluate the
leaching of NaB. The amount of NaB leached out into the solution was determined via
conductivity measurements. The conductivity meter used in the leaching experiments isof high precision and accuracy. It gives readings in two digits, and its accuracy is
specified by the manufacturer as ± 0.4%, and it has the ability to detect as small as 0.1
ppm of dissolved matters. For example, for one of the NaB/Sylgard® 184 samples
prepared at the base-case conditions, the concentration of NaB in solution was 0.83 ppm,
6.59 ppm, and 10.01 ppm after 1 hr, 1 day, and 1 week of immersion, respectively. The
change in concentrations here was higher than the range of the error of the equipment.
Therefore, we believe that the increase in conductivity of the solution is because of the
real change of NaB concentration in solution, which is resulted from leaching of NaB
Figure 4.15 Cumulative leaching (Q) of NaB from Sylgard® 184 matrix immersed inwater. The samples were prepared at the base case conditions ((1 wt% NaB/Sylgard® 184; 50/50 water/acetone; and 20/80 solvent/polymer)), and the leaching were measuredat three different conditions: under constant stirring (□), replacing water daily (∆) , and atstatic conditions (O). Error for each data point (average over 3 batches) is presented by
The previous subsection (section 4.4.5) provides two empirical correlations for
the effect of NaB aggregate size and NaB matrix loading on the leaching rates. Here, we
are trying to provide more fundamental mass transfer analysis for the leaching process.
The antifoulant release mechanism can be classified according to the solubility of the
compound in the polymer phase. As shown in Figure 4.16, if it has a high solubility andinitially loaded in excess of its solubility limit, the release primarily follows a diffusion-
dissolution mechanism, which takes place in the continuum of the polymer phase
(Cardarelli, 1980; Fan and Sigh, 1989). On the other hand, as shown in Figure 4.17, if
the solubility is very low, the media of dissolution and diffusion is water that fills the
porosity of the matrix, not the continuum of the polymer phase (Cardarelli, 1980; Fan and
Sigh, 1989). Since NaB is not soluble in silicones (the χ 12 value for sodium
benzoate/PDMS is 17.6), most likely the release is by the porosity formation mechanism.
In this case, the release process can be described mathematically based on the basics of
diffusion in porous media as follow. The concentration, C, of the compound in the water-
filled pores at time t and axial distance x can be described by (see Figure 4.18):
(∂C / ∂t) = DA (∂2 C / ∂x2) (4.12)
where DA is the apparent diffusion coefficient of the compound in the water-filled pores,
Figure 4.16 A simplified sketch (not to scale) for the mass release of antifoulingcompounds from polymer paint (water-insoluble matrix). In this case, the compound issoluble in the matrix and is initially loaded in excess of its solubility limit in the matrix.The dissolved zone means that the compound is already absorbed by the polymer phase.
Figure 4.17 A simplified sketch (not to scale) for the leaching of antifoulingcompounds from polymer paint (water-insoluble matrix). In this case, the compound isinsoluble in the matrix. (Figure re-drawn from Caprari et al . (1990), with slightmodification).
Figure 4.18 A simplified sketch (not to scale) of a polymer coating incorporated withAF compound, and immersed in water. The purpose of the sketch is to show themeaning of the axial distance x that was used in equation 4.12
where D is the molecular diffusion coefficient of the compound in water, and ε and θ are,
respectively, the porosity and tortuosity of the matrix. The porosity here is the initial
porosity of the matrix (generated by the preparation conditions) plus the empty spaces
generated progressively with time when the compound is released out. The tortuosity is
the deviation of the diffusion path from ideality, where for ideal case the diffusion path is
straight and hence θ is equal to unity, whereas for nonideal case θ is greater than one (Fan
and Sigh, 1989; Welty et al., 1984). In other words, the tortuosity is a measure thatdescribes how much the diffusion path is zigzagging. The initial and boundary
conditions associated with equation (4.12) are:
C = CO at t = 0, all x (4.14a)
DA (∂C / ∂x) = k (C — C b), at x = 0 (4.14b)
(∂C / ∂x) = 0, at x = L (4.14c)
where CO is the initial concentration of the compound in the matrix, L is the thickness of
the matrix, C b is the bulk concentration of the compound in the water bath, x=0 is the
coating surface -water bath interface, and k is the external mass transfer coeffieicent
(which is associated with the convective bulk flow). For simplicity, C b can be assumed
zero at all time, and then equation (4.14b) is replaced by:
were 8 ppm and 23 ppm, respectively. These concentrations are close enough to zero to
justify the first assumption. Second, our system was not continually and perfectly stirred,
but at each time of measurement the water bath was gently stirred to get an average bulk
concentration. This gentle stirring could be enough to satisfy the second assumption.
The difference between perfect stirring and gentle stirring is elaborated more on the next
paragraph.
Equations (4.15) is a general form whereas equation (4.16) is a special form, both
of them are boundary conditions for the same system of equations. Equation (4.15) isapplicable for any degree of stirring whereas equation (4.16) is originally assumed for
perfect stirring. It is of interest to examine mathematically the difference between the
two situations. To do so, the PDE with the general boundary condition (equation 4.15)
has to be solved, and then the situations can be identified where the general boundary
condition (equation 4.15) can be reduced to the special boundary condition (equation
4.16). This procedure is called “model sensitivity analysis or model parametric study”,
and we apply it here for our system as follow. Equations (4.13) to (4.15) are rewritten in
dimensionless forms by defining the following dimensionless variables:
ζ= x / L; Ψ = C / CO; τ = t DA / L2 (4.18)
Hence, the PDE with its boundary conditions in normalized form are:
where the dimensionless parameter Bm is the Biot number for mass transfer, and defined
as: (Bm = k L / DA ). Equations (4.19a) to (4.19d) are difficult to solve analytically.
Therefore, we solved it numerically by Orthogonal Collocation technique. Details about
the theory and application of the Orthogonal Collocation technique can be found
elsewhere (Ruthven, 1984; Rice and Do, 1994), and for solving the problem a computer
program in MATLAB was written (the program is shown in the appendix). Thesimulations are performed here for all range of Bm, from a very small value (almost zero)
to a very large value (almost infinity). These two limits have physical meanings. If Bm
goes to infinity (i.e. k L >> DA), it means that the mass transfer process is diffusion-
limited and there is large bulk convection due to high bulk velocity, and hence there will
be no boundary layer at the surface at all because of having perfect mixing or because
that the coated object (e.g. a moving ship) is moving with very high speed, and
consequently the surface concentration is equal to zero [i.e. the problem is reduced to the
special case of equation (4.16)]. If Bm goes to zero ((i.e. k L << DA), it means that the
mass transfer process is bulk convection-limited and the coated object and the water bath
are perfectly stagnant and there is a strong boundary layer established, and in this case the
surface concentration is high. This physical meaning is understood more clearly with
referring to the simulations trends shown in Figure 4.19. In Figure 4.19, the normalized
surface concentration is plotted as a function of the normalized time, for different values
of the normalized parameter Bm. As can be seen in the figure, the surface concentration
Figure 4.19 Parametric sensitivity analysis for the general mass transfer model (equation4.19). The dimensionless surface concentration (Ψ|ζ=0 = C/CO |x=0) is plotted against thedimensionless time (τ = DA t / L2), for different values of the dimensionless parameter Bm (Bm = k L / DA). The trends were generated by solving equation 4.19 numerically.
becomes close to zero when the value of Bm is greater than 100, which implies that the
applicability of equation (4.16) could be valid if Bm is greater than 100.
Bm is a function of k, the external mass transfer coefficient. In standard tests
available in the literature (Court and Vries, 1973), k is determined experimentally by
connecting the coated object to a motor thus the object is rotating with different velocity
(this is to simulate a ship moving with different speeds), and hence k can be calculated by
correlating with the angular velocity. We do not have this kind of setup and therefore we
do not know the exact value of k and Bm for our particular system, but for our experimental setup where we have gentle stirring at each time of leaching measurement,
we assume that this gentle mixing is enough for Bm to be greater than 100 and therefore
the validity of equation (4.17) is assumed. The estimation for the value of Bm for our
particular experimental setup is elaborated more on the next paragraph.
The value of Bm for our particular NaB system is estimated as follow. The external
mass transfer coefficient, k, can be estimated by the correlation (Welty et al., 1984;
Skelland, 1985):
Sh = k l / D = 0.664 (Re)1/2 (Sc)1/3 (4.20)
where Sh, Re, and Sc are the Sherwood number, Reynolds number, and Schmidt number,
will be shown that the apparent diffusion coefficient, DA, is in the order of 10-11 cm2/s
(see Table 4.6). Thus, from the relation Bm = k L / DA, with L ~ 1 mm and DA ~ 10-11
cm2/s, a value of about 600 for Bm is obtained. As demonstrated in Figure 4.19, this
value for Bm is high enough for the surface concentration to be close to zero and hence
the validity of equation 4.17 could be justified. This estimated high value for Bm is not
because the bulk velocity is high, but because the parameter (ε/θ) is very small, as to be
discussed more on the next paragraph.
In order to understand the physical meaning of the porosity that we are talkingabout and its relation to the aggregate size and the matrix loading, we need to elaborate
more on the leaching mechanism. During the immersion of NaB-incorporated Sylgard®
184 coatings, there is more than one possible mechanism for the compound to release.
First, in the most ideal case, the aggregates are spherical and uniformly distributed
throughout the matrix, and perfectly packed such that the particles are smoothly touching
each others (Figure 4.20a). In this case, a sharp boundary (Caprari et al . (1990) between
the dissolved zone and the un-dissolved zone of the matrix will be established during
immersion, and the location of this boundary is moving inward into the matrix as
immersion time proceeds. The second possibility is that all the particles are not touching
each other initially (Figure 4.20b). In this case, a sharp boundary between the dissolved
zone and the un-dissolved zone will not be observed. Instead, the following mechanism
is hypothesized. Initially, the particles are separated from each others because they are
encapsulated in thin membranes of binder (the polymer phase). The particles at the
surface layer of the film are first dissolved, forming a saturated solution that diffuses
Figure 4.20 Simplified sketch (not to scale) for the possible leaching mechanisms of NaB from Sylgard® 184 coating: (a) Perfect packing of the particles; (b) Completeruptures of the thin membranes; (c) The existence of initial porosity of the matrix, whichis mainly composed of constricted narrowed channels. The first column represents thecoatings initially before immersion, the second column after some time t1 > 0, and thethird column after some time t2 > t1.
outward through the diffusion layer in contact with the coating surface. When such a
particle dissolves in water and being removed, a cavity separated by thin membranes
from other cavities and from the un-dissolved particles is resulted. Water diffuses into
the cavity and through the thin membrane to dissolve some of the un-dissolved particles.
Consequently, the resulting osmotic pressure ruptures the membrane and the cavities
become interconnected. This mechanism (the second mechanism) was first postulated by
Marson (1969). The third mechanism is that the matrix has an initial porosity generated
by the preparation condition (Figure 4.20c). Therefore, it could be possible for water to
diffuse through this initial spacing even though the particles are not initially connected,and then the porosity is increasing with time as more particles are dissolved. For the
third mechanism, it is possible that the initial porosity is very small, because it might be
composed mainly of constricted channels of very narrow spacing which spread out
throughout the matrix and connect the particles between each others. Water diffuses
through these channels from the dissolved particles region to the un-dissolved particles
region to dissolve the un-dissolved NaB particles, and then carries the dissolved NaB
molecules back out toward the surface layer of the coating. These constricted channels
exist initially could also be progressively increased during time of immersion. It is
possible that the width of these channels is very narrow (<< 1 µm), which is much
smaller than the diameter of particles, and it is also possible that the length of these
channels is very tortuous (i.e. θ >> 1); therefore the diffusion process slows downconsiderably during the slow leaching stage. In addition, Sylgard® 184 does absorb water
to approximately 0.1 wt% water/polymer (Banerjee et. al., 1997). The water absorbed by
the polymer phase may create molecular level pores which may be responsible for
wall interface (Adamson, 1990). If the wall is purely hydrophobic (i.e. purely PDMS), φ
is equal to or greater than 900, which implies that the pressure drop is zero or negative
and hence water flow will not be possible. If there is some NaB exist on the wall, which
is our speculation, φ will be less than 900 and hence the pressure drop will be positive and
consequently water flow will be possible through the capillary.
The above proposed mechanism is based on the assumption that NaB is totally
insoluble in the polymer phase. To check for the validity of this assumption, the
solubility of NaB in PDMS was estimated by the following equation, which wassuggested by Zaikov et al . (1988) for the estimation of electrolytes solubilities in
hydrophobic polymers:
— ln ФS = 1 + (VS / RT) (δS — δP)2 (4.24)
where ФS is the volume fraction of the solute (i.e. NaB in our case), VS is the molar
volume of the solute, and δS and δP are the solubility parameters of the solute and
polymer, respectively. By evaluation in equation (4.24), the solubility of NaB in PDMS
is 8 x 10-7 vol. %, which is close enough to zero to justify the above assumption.
In summary, in all the above possible mechanisms, the key point is that NaB is
insoluble in the polymer phase; therefore NaB diffusion is taking place through pores
(empty space) within the matrix, not through the continuum of the polymer phase. For
this case, as the porosity of the matrix increases it will be easier for water to diffuse into
the matrix and carry with it the dissolved compound, and hence the cumulative release of
4.5.2 Limitation of the simplified mass transfer model
The simplified model applied in section 4.5.1 has the advantage that it has explicit
analytical solution for the cumulative leaching as function of time:
Q = 2 CO (DA t/ π)1/2 (4.17)
However, it has several limitations. Before listing the limitations, the simplified model is
first applied to fit our experimental data, followed by the extraction of the model parameters, then more elaborations is made on the physical meaning of these extracted
parameters, as follow.
The experimental cumulative leaching data of the NaB/Sylgard® 184 samples
prepared at different set of conditions were fitted to equation (4.17) by plotting the Q data
against t1/2 at the early leaching time period (0 – 4 days), and the results are shown in
Figure 4.21 and Table 4.6. For the fitting analysis, only the sets of preparation conditions
that resulted in the aggregate size smaller than 15 µm were considered here, because
these were the optimized preparation conditions that resulted in samples of fine and
uniform dispersion. As shown in Figure 4.21 and Table 4.6, in most cases, a good linear
fit was observed, which could suggest that diffusion is the rate limiting step for
NaB/Sylgard® 184 system. From the slope of the linear fit, the apparent diffusion
coefficient (DA) for NaB/Sylgard® system for each set of preparation conditions was
calculated, and the results are summarized in Table 4.6. For all the samples, the apparent
Figure 4.21 Fitting of the cumulative leaching data for NaB/Sylgard®
184 coatings tothe simplified mass transfer model (equation 4.17). (a) Samples were prepared atdifferent NaB matrix loading, keeping the water/acetone ratio and the solvent/polymer ratio fixed at 50/50 and 20/80, respectively. (b) Samples were prepared at differentwater/acetone (W/A) ratios, keeping the NaB matrix loading and the solvent/polymer ratio fixed at 1 wt% NaB/matrix and 20/80 ratio, respectively. Points are experimentaldata and solid lines are linear fitting of the model.
Table 4.6 Data analysis for the results shown in Figure 4.21. The apparent diffusioncoefficient (DA) for NaB/Sylgard® system was obtained by fitting the experimentalleaching data to equation 4.17. The solvent/polymer ratio was 20/80, which was fixed for all samples. (Abbreviation: W: water, A: acetone).
diffusion coefficient was estimated to be in the order of 10 -11 cm2/s. The diffusion
coefficient value is in the same order of magnitude for all these samples because these
samples were shown previously in section 4.2 to have similar fine and uniform size
distribution, with no observed aggregate with size greater than 15 µm. However, this
value for the diffusion coefficient is extremely small, close to the typical values known in
solid-solid diffusion. However, it should be noticed that we define DA as the apparent
diffusion coefficient of NaB in the water-filled pores, not as the molecular diffusion of
NaB in the continuum of the polymer phase, because we believe that NaB has limited
solubility in the polymer phase. Therefore, the value of DA estimated here could bereasonable only if the porosity of the matrix is extremely small, where in this case the
physical meaning is that there is a large geometrical obstruction for NaB to diffuse
through the matrix.
Next, by applying the relation associated with the simplified model (DA = D ε / θ),
with considering DA to be ~ 10-11 cm2/s and D to be ~ 10-5 cm2/s (D is the molecular
diffusion of NaB in water, which is estimated here by an independent theory (equation
4.22) as described in section 4.5.1), this implies that the value of (ε/θ) is in the range of
10-6. This suggests that the system has very small porosity (ε) and very high tortuosity
(θ). However, we should here retain the physical meaning of the tortuosity. The
tortuosity is the ratio of the actual diffusion length to the ideal diffusion length.
Therefore, in most nonideal cases, the tortuosity most likely cannot be more than 10, and
in many examples in the drug-release literature it was assumed a value of 3 to 5.
Although many examples in the drug-release literature have reported a tortuosity value
above 1000, these values appear unrealistic and have no physical meanings. Thus, in the
most nonideal case, let’s assume a value of 10 for the tortuosity of our system. This
would predict an extremely low value of the porosity in the order of 10-5. This predicted
value for the porosity is an indication for the limitations of the simplified model, because
if the porosity is almost zero, NaB will not leach out due to the fact that NaB has limited
solubility in the polymer phase and has to find some porous space to get through.
One clear limitation for the simplified model is the incomplete description of the
porosity, and considering it as a time independent. From its physical meaning, the porosity is the empty volume inside the coating over the total volume. The empty
volume is any volume available inside the coating other than the continuum of the
polymer phase itself and the un-dissolved solid NaB particles phase. Therefore, it can be
qualitatively described as:
ε = ε0 + εn + εw
where ε0 is the initial porosity of the coating, εn is the empty spaces generated
progressively with time when the compound is released out, and εw is the porosity due to
water absorption by the polymer (as to be described in the next paragraphs). ε0 is
constant whereas εn and εw are time-dependent. However, the simplified model lumped
all these types together as a single constant value for the porosity, which is a clear
application of these parameters partially accounts for the heterogeneity of the system, two
problems arise here. First, the porosity is, in real situations, a function of time as more
active compound is released from the system, but the simplified model treats the porosity
as constant. Second, the tortuosity becomes at the end of the analysis almost as an
empirical parameter because it cannot be measured independently, and in many examples
in the drug-release literature it is either assumed a certain value or determined by fitting
the release data to the model. Although many examples in the drug-release literature
have reported a tortuosity value above 1000, these values appear unrealistic and have no
physical meanings. The second limitation is the over-simplification of treating the problem as a fixed-boundary problem. However, the problem is a moving boundary
problem because as more pores and channels are generated with time the boundary
condition inside the coating is moving inward and its location is not known in prior. The
third limitation is that it does not explicitly include the resistance to mass transfer in the
boundary layer surrounding the coating. The fourth limitation of the model is that it does
not explicitly account for the role of the diffusivity of water through the coating. In other
words, the diffusion coefficient of water in silicone membrane is absent in the simplified
model. The fifth limitation of the model is that it does not account for the dissolution
step resistance to mass transfer. These limitations can be avoided by re-deriving the mass
balance equations for each phase in the coating (the polymer phase, the solid NaB
particles phase, and the water-filled pores phase) separately, as shown in Appendix B.
To evaluate the coatings antibacterial behaviors, bacterial attachment studies
using fresh water containing indigenous enriched microbial consortium isolated from
Lake Erie water were performed. Pure silicone coatings and 1 wt% NaB containing
silicone coatings were submerged in the above water at periodic intervals up to one
month. Some representative biofilm morphologies are shown in Figure 4.22 for pure
Sylgard® 184 coatings and 1 wt% NaB-blended Sylgard® 184 coatings, for samples
prepared at the base-case conditions. As shown in Figure 4.22, the bacteria can be easilyidentified and differentiated, and it can be concluded that a clear reduction of bacterial
attachment was achieved for 1 wt% NaB/Sylgard® 184 coatings compared to Sylgard®
184 alone. The bacterial attachment images for NaB/Sylgard® 184 systems were further
quantified by counting the pixels to approximate the area coverage, and hence the %
reduction (% reduction = (1-A/B) 100, where A and B refer to the area coverage for NaB-
containing coatings and NaB-free coatings, respectively). As shown in Figure 4.23, for a
particular period of immersion, an average of 45 – 55% reduction in bacterial coverage
was achieved for 1 wt% NaB/Sylgard® 184 coatings as compared to Sylgard®184 alone.
For NaB-containing RTV11, the morphology was hard to be observed and the
bacteria were difficult to be identified from the pictures directly. To differentiate the
bacteria from other objects, the RTV11 coating surfaces were physically cleaned by
scotch tape, and pictures were taken before and after cleaning. For control RTV11
coatings, the surface became very clean after applying scotch tapes, indicating that the
Figures 4.22 Optical microscope images of the bacterial attachment study for NaB-Sylgard® 184 coating. (a, c) 1 wt% sodium benzoate-blended Sylgard® 184. (b, d) controlSylgard® 184. The coatings were immersed in water containing Lake Erie bacteria for 2weeks (a, b) and 4 weeks (c, d). Image size is (285 µm x 215 µm).
Figure 4.23: Antibacterial performance of 1 wt% NaB-incorporated Sylgard® 184coatings, compared to control Sylgard® 184 samples. The % reduction was defined as[(1-A/B) 100), where A and B refer to the area coverage of NaB-containing coatings and NaB-free coatings, respectively.
Figure 4.24 Optical microscopic (reflection bright field) images of bacterial attachmenton controlled RTV11 coatings after the coatings were immersed in water containing Lake
Erie bacteria for 28 days. (a) Half of the coatings surfaces were physically cleaned byscotch tape, and overall pictures [image size: (2850 x 2150) µm] were taken showing thecleaned area (right side of picture a) and the un-cleaned area (left side of picture a).Pictures (b) and (c) are the magnifications [image size: (285 x 215) µm] of the two area
removed objects were likely bacterial biofilm (Figure 4.24). For NaB-RTV11 coatings,
however, the morphology did not change much after applying the scotch tape, suggesting
that the irregularities seen were parts of the coatings surface and were not bacterial
biofilm. The irregularities seen in/on NaB-RTV11 coatings were mostly holes likely
generated by NaB leaching, and the reason that they were much larger than the holes seen
in/on NaB-Sylgard® 184 coatings was the much faster leaching of NaB from RTV11 than
from Sylgard® 184.
By comparing control samples of NaB-free RTV11 and NaB free-Sylgard
®
184, itwas observed that RTV11 had a higher tendency for biofilm formation than that of
Sylgard® 184, attributing to the fact that RTV11 has a slightly higher surface energy, bulk
modulus, and surface roughness than those of Sylgard® 184. Another reason for this
observation is that RTV11 experienced an increase in surface roughness upon immersion
in water due to slow surface erosion. Our scanning probe microscopy verified the
increase in the surface roughness value (R q, with a scan size of 80 µm x 80 µm) from 6.9
nm for as prepared RTV11 films to 11.8 nm for 14 day water-aged RTV11 films. For
Sylgard® 184, on the other hand, a previous study (Barrios et al ., 2005) verified that
Sylgard® 184 was fairly stable in water with no observed increase in surface roughness.
To summarize, a clear reduction in bacterial attachment on the NaB-treatedSylgard® 184 coatings was observed, which suggested that NaB could be effective in
inhibiting bacterial attachment when entrapped into Sylgard® 184 coating. Also, the
attachment study demonstrated that the antibacterial performance of NaB/Sylgard® 184
Table 5.1 Static water contact angles of BA-entrapped Sylgard® 184 coatings
compared to that of the controlled BA-free Sylgard
®
184 coatings. The (solvent: polymer) ratio was (20: 80) by mass.
Coatings Static contact angle
Control Sylgard® 184 106.1 ± 0.6
1 wt% BA/ Sylgard® 184 104.9 ± 1.8
Table 5.2 Static water contact angles of BA-entrapped RTV11 coatings compared tothat of the controlled BA-free RTV11 coatings. The (solvent: polymer) ratio was (20:80) by mass.
Coatings Static contact angle
Control RTV11 101.2 ± 0.5
1 wt% BA/ RTV11 98.7 ± 1.0
TABLE 5.3 Elastic modulus of BA-entrapped Sylgard® 184 films. The (solvent: polymer) ratio was (20: 80) by mass.
Capsaicin was incorporated into RTV11 coatings, up to a concentration of 1 wt%
in the matrix, using toluene as the common solvent. It was observed physically that the
capsaicin-blended RTV11 coatings were cured similarly as the capsaicin-free RTV11
coatings. Further examining the surface wettability, surface roughness, and elastic
modulus of the coatings confirmed this observation, as discussed below. The wettability
of the coatings was evaluated in terms of measuring the water contact angles. The
contact angles for RTV11 films containing various concentrations of capsaicin (0.1 – 1wt %) were measured, and the results are shown in Figure 5.1. RTV11 surfaces without
capsaicin had advancing, static, and receding contact angles of 103°, 100°, and 95°,
respectively. As shown in Figure 5.1, the advancing and static contact angles were
almost unaffected by the addition of capsaicin. The receding contact angles decreased
slightly as capsaicin concentration increased, a value of 87° for 1 wt% capsaicin was
observed. The indifference in the advancing and static contact angles between both
controlled RTV11 and capsaicin-incorporated RTV11 samples suggested that most
capsaicin molecules were entrapped inside the bulk of the polymer matrix rather than
aggregated to the surface. Otherwise, the advancing and the static contact angle are
expected to drop significantly due to the fact that capsaicin has a higher surface energy (~
45 mJ/m2) than PDMS (~ 20-24 mJ/m2). The surface energy of capsaicin reported here
was our predicted value, predicted by the group-contribution method following the
The elastic modulus of control RTV11 coatings and 1 wt % capsaicin/RTV11
coatings were measured, and the results are shown in Table 5.4. The elastic modulus for
RTV11 film was measured to be 1.56 MPa, which is consistent with the literature value
reported (Kohl & Bolstes, 2001). As shown in Table 5.4, the indifference in the elastic
modulus for the capsaicin free-RTV11 and capsaicin-blended RTV11 could indicate that
the low content of capsaicin (up to 1 wt %) was insignificant in affecting the curing
behaviors and bulk properties of RTV11, as the elastic modulus is expected to drop
significantly for the uncured coating. Based on this finding and comparing it with the
curing behaviors of the other compounds/matrices combinations that were tried in thecurrent study, and combined also with previous findings for other combinations tried in
our research group [zosteric acid in Sylgard® 184 and RTV11 matrices (Barrios, 2005),
and capsaicin in Sylgard® 184 matrix (Jaggari, 2003)], it is apparent to us now that
RTV11 matrix is much more resistant to poisoning than Sylgard® 184 matrix, because all
the above combinations were cured except capsaicin/ Sylgard® 184. This information is
useful to the coating formulation industry.
Table 5.4 Elastic modulus of capsaicin-entrapped RTV11 films. The (solvent: polymer) ratio was (20: 80) by mass.
For benzoic acid-incorporated Sylgard® 184 coatings, the preparation conditions
were systematically varied to examine their effects on the distribution and morphological
structures of benzoic acid inside the coating matrix. The coatings were prepared using
four different organic solvents (toluene, acetone, acetonitrile, and di-ethyl ether), whereas
keeping the other preparation conditions unchanged (1 wt% benzoic acid in the coating,and 20: 80 solvent: polymer mass ratio). As shown in Figure 5.2, large crystals were
observed inside the polymer matrix for all types of solvents used. Toluene was found to
result in the largest crystals (~ 600 ─ 1000 µm), and di-ethyl ether produced the smallest
ones (50 ─ 100 µm), whereas acetone and acetonitrile resulted in crystals somewhere in
between (~ 200 ─ 500 µm). The estimated size here refers to the average length (the
largest dimension) of the crystal. The number densities of the benzoic acid crystals were
(1 – 2) /mm2 and (7 – 8) /mm2 using toluene and acetone, respectively. For the case of
using toluene as the solvent, it is possible that occasionally, some large crystals could
span the entire thickness of the coating. From Figure 5.2, it is also clear that ether
resulted in a much uniform distribution of smallest crystals (the number density was (90 –
Figure 5.2 Optical microscope (bright field) images of resulting BA distribution in the bulk of Sylgard® 184 matrix when different solvent were used to mix BA with Sylgard® 184. (a) toluene, (b) acetone, (c) acetonitrile, and (d) ether. The concentration of BA inthe matrix was fixed at 1 wt%, and the (solvent: polymer) ratio was fixed at (20: 80) bymass. The image size is 2850 µm x 2400 µm for (a), and 1140 µm x 960 µm for (b)-(d).
Table 5.5 Physical parameters of relevance importance to the miscibility of BA/PDMS. V and δ are the molar volume and the solubility parameter of the material,respectively. δ12 is the difference in solubility parameters between the material andPDMS. χ 12 is the interaction parameter between the material and PDMS*.
MaterialV
(cm3/mol)
δ
(MPa)½
∆δ12
(MPa)½ χ 12
Boiling
point
(oC)
Toluene 106.8 18.2 a 3.3 0.469 110.6
Acetone 74.0 20.3 a 5.4 0.871 56
Acetonitrile 52.6 24.6 a 9.7 1.998 81.5
Ether 105 15.1 a 0.2 0.002 34.6
BA 92.5 22.9 b 8.0 2.389 -
a, b Values obtained from (Rodriguez, 1989) and (Bustamante et al ., 2000), respectively* For PDMS, the literature value of its solubility parameter (14.9 MPa½, from: Rodriguez, 1989) was used
and the results are presented in Table 5.5. First, the χ 12 values for benzoic acid/PDMS
mixture is 2.389, indicating that BA is likely not miscible with PDMS, as observed
experimentally. For the four solvents used in benzoic acid/PDMS systems, it is clear that
ether is most miscible with PDMS (χ 12 = 0.002), thus the domains of (ether + benzoic
acid) would likely be the smallest as ether being completely evaporated and resulting in
the smallest benzoic acid crystals as compared to other solvents. Experimentally, the
miscibility of PDMS in the four solvents used was tested in the current study by
dissolving PDMS in the four solvents used. It was observed that both ether and toluene
were very good solvents for PDMS; up to a concentration of 20 wt% PDMS/ether and 20
wt% PDMS/toluene were prepared, and excellent dissolution was observed. This
Figure 5.3 Optical microscope (transmission bright field) image of resulting capsaicindistribution in the bulk of Sylgard® 184 base material. Toluene was used as the commonsolvent. The concentration of capsaicin in the matrix was 1 wt%, and the (solvent: polymer) ratio was (20: 80) by mass. The image size is (570 x 480) µm.
capsaicin, δ2, which is not available in the literature. Alternatively, we predicted the
solubility parameter of capsaicin by the group contribution method, according to the
relation:
δ = (∑ Fi) / (M/ρ) (5.2)
where Fi is the molar attraction constant of group i in capsaicin structure, and M and ρ are
respectively the molecular weight (305.4 g/mol) and density (1.15 g/cm3) of capsaicin.
Two sets of Fis were used (Hoy’s and van Krevelen’s, both found in van Krevelen
(1972)), and the solubility parameter of capsaicin was 22.44 MPa1/2 and 25.77 MPa1/2 by
applying Hoy’s and van Krevelen’s data, respectively. Using the average of the two
estimated solubility parameters of capsaicin into equation (6.1), the χ 12 value for
capsaicin/PDMS system was estimated to be 9.092, indicating that capsaicin is
immiscible with PDMS. In Table 5.6, the properties of the solvent used (toluene) are also
summarized with the properties of capsaicin for comparison. Therefore, even when
capsaicin was mixed with silicone using a common miscible solvent (toluene, χ 12 =
0.469), it phased separated from silicone upon removal of the solvent, and resulted in the
formation of large capsaicin aggregates/crystals, as observed experimentally.
Table 5.6 Physical parameters of relevance importance to the miscibility of capsaicin/PDMS. V and
δare the molar volume and the solubility parameter of the
material, respectively. δ12 is the difference in solubility parameters between the materialand PDMS. χ 12 is the interaction parameter between the material and PDMS*.
MaterialV
(cm3/mol)
δ
(MPa)½
∆δ12
(MPa)½ χ 12
Toluene 106.8 18.2 a 3.3 0.469
Capsaicin 265.6 24.1 b 9.2 9.092
a, Values obtained from (Rodriguez, 1989). b` Value predicted in the current study by the group-contribution method (see text).* For PDMS, the literature value of its solubility parameter (14.9 MPa½, from: Rodriguez, 1989) was used.
Figure 5.4 Cumulative leaching of BA from its incorporated silicone coating: Sylgard® 184 (open symbols) or RTV11 (filled symbols). The common solvent used for BA/silicones were acetone (squares) and Toluene (circle). The initial concentration of BA
in all coatings was kept constant at 1 wt%., and the solvent/polymer ratios were keptconstant at 20/80 by weight for all combinations.
The crystal formation behavior of benzoic acid, as illustrated using various
solvents, could likely be the primary reason for its considerably high leaching. It is
possible in some occasions that some large crystals could span the entire thickness of the
coating, and therefore there will be little mass transfer resistance for BA to leach out.
The crystal formation and consequently high leaching of BA could be the main reason for
the relatively short period of antifouling effectiveness reported in the literature (Railkin,
1995), even though in that study a vinyl-rosin coating was used. Therefore, bacterial
attachment studies were not performed and not recommended in the current study for
BA/silicone coatings, because of three reasons. First, the bulk concentration of the bacterial solution at the initial days of immersion will be most likely much above the
EC50 of BA, which is about 7 ppm towards various types of bacteria (Haque et al ., 2005),
and consequently the coating will effectively inhibit bacterial attachment but by a toxic
mechanism. Second, after one month of immersion, most of the compound will leach out
from the coating and hence the coating will not be effective for reducing the bacterial
attachment for a longer time. Third, a considerable increase in surface roughness will be
expected for BA/silicone coatings during immersion in water because of the high
leaching rate of the compound, a factor that will accelerate bacterial attachment after
longer time.
5.3.2 Leaching of capsaicin
The capsaicin entrapped RTV11 coating (using toluene as the common solvent)
was subjected to leaching studies in static cells, and the results are shown in Figure 5.5.
Figure 5.5 Capsaicin cumulative mass per area (Q, in µg/cm2) released from 1 wt %capsaicin-incorporated RTV11 sheet (total mass and surface area of the sheet wererespectively 6.55 g and 114 cm2), plotted against time of immersion in DI water. Toluenewas used as the common solvent to mix capsaicin with RTV11, and the (solvent: polymer) ratio was (20: 80) by mass.
As shown in Figure 5.5, capsaicin leached out rapidly from RTV11 within the first 7
days, and then slowed down as time proceeded. The cumulative mass leached out after
the first and fourth weeks were about 161 and 198 µg/cm2, respectively. Approximately
35 % of capsaicin original mass had leached after one month of immersion. The leaching
rate (slope from the curve) for capsaicin from RTV11 coating were 75 µg/cm2/day and
1.6 µg/cm2/day during the slow and fast leaching periods, respectively. By extrapolation,
it would take approximately 8 months for capsaicin to leach out completely.
Capsaicin was also blended with RTV11 using ethanol as the solvent, and the
corresponding leaching data are shown in Figure 5.6. For this particular system, two
cases were considered: capsaicin was homogenized with RTV11 base polymer before (or
after) mixing with DBT catalyst. The objective here was to investigate the effect of
mixing order during the preparation conditions on the leaching behavior. To accurately
compare the mass flux, the surface area and thickness of the coatings were consistent for
both cases. As shown in Figure 5.6, at any particular time, the cumulative leaching was
higher if capsaicin was mixed afar adding the catalyst to the polymer base. This
experiment did show the importance of mixing the antifoulant/solvent mixture to the polymer base before adding the curing agent in order to get a more homogeneous coating
and consequently a more controllable leaching, although for the case of capsaicin its
leaching was just slowed down slightly. To summarize, the above experiments did also
show that the capsaicin leaching from RTV11 was relatively high, regardless of using
toluene or ethanol as the solvent, or regardless of the mixing order.
The relatively high leaching of capsaicin from RTV11 could be the results of the
following reasons. First, capsaicin is immiscible in silicones as discussed above (χ 12 =
9.09). Second, partial degradation and erosion of the RTV11 matrix in water, which has
been confirmed experimentally (Bullock et. al., 1999), could contribute and facilitate the
leaching. Third, RTV11 has a high content of inorganic fillers (32 wt% CaCO3), which
could lead to presence of “voids” in-between the filler particles and at the filler/polymer
interface and allow water molecules to seep into the silicone matrix through these empty
spaces and carry the dissolved capsaicin molecules with them as they leave the coatings.
5.4 Bacterial attachment evaluations for capsaicin-RTV11 coatings
5.4.1 Effect of immersion in water on coating’s properties
Before evaluating the antibacterial performance of the capsaicin - incorporated
RTV11 coating, it is worthwhile to examine the effects of the water type and the
immersion time on the coating properties. This is important in order to confirm that the
difference in bacterial attachment – if exist – is due solely to capsaicin leaching and not
due to a change in the coating properties. This factor was investigated by immersingcontrol samples of RTV11 coatings in different types of water and evaluating the surface
and bulk properties of the coatings, as discussed below.
Control capsaicin-free RTV11 coatings were immersed in two types of water
(sterilized DI water and enriched LE water) for up to 14 days to study the effect of water
type and immersion time on the wettability of RTV11. For coatings in sterilized DI
water, both static and dynamic water contact angles were taken; while for coatings in
enriched LE water, only static contact angles were taken. The results are presented in
Figure 5.7. The static contact angles almost remained constant at a value around 100° for
the 14 day immersion period, irrespective to the type of water used. The advancing
contact angles also remained almost constant at a value around 103°. In general, the
static contact angles resemble the advancing contact angles with slightly lower values
(Adamson, 1990). The receding contact angles, however, showed a gradual decrease,
down to a value of 80° at the end of 14 day period. Consequently, the contact angles
hysteresis (difference between the advancing and receding angles) increased from 8°
initially to 23° after 14 days of immersion. The increase in contact angles hysteresis is
possibly due to slow surface erosion, which would result in a slight increase in surface
roughness. Surface erosion could be the result of a continuous small mass loss of fillers
such as CaCO3 from RTV11, and the micro-pit formation on RTV11 surfaces upon
immersion in water (Bullock et. al., 1999). Our scanning probe microscopy also verified
the increase in the surface roughness value (R q, with a scan size of 80 µm x 80 µm) from
6.9 nm for as prepared RTV11 films (Figure 5.8(a)) to 11.8 nm for 14 day water-aged
RTV11 films (Figure 5.8(b)).
In addition, the wettability and surface roughness for water-aged 1 wt%
capsicin/RTV11 coatings were also evaluated. For 1 wt% capsaicin-blended RTV11
coatings immersed in DI water for 14 days, the advancing contact angles increased to a
value of 109°, whereas the receding contact angle decreased to a value of 79°. As a
result, the contact angles hysteresis increased from 16° initially to 30° after 14 days of
immersion, indicating an increase in surface roughness. The increase in surface
roughness for 1 wt % capsaicin-incorporated RTV11 coatings was confirmed by scanning
probe microscopy, where it was observed that the surface roughness increased
considerably from ~ 12 nm for as prepared capsaicin-treated RTV11 films (Figure 5.8(c))
to ~ 88 nm after 14 days of immersion (Figure 5.8(d)). The increase in surface roughnesshere is mainly due to the high leaching of capsaicin, where it is possible that capsaicin
could leave behind irregular surface geometries (mostly holes) when it leached out,
which would cause the surface roughness to increase significantly. By refereeing to the
Figure 5.7 Effect of water immersion time on the wettability of RTV11 films in termsof the static contact angles taken for RTV11 immersed in Lake Erie (Δ) and deionized
water (▲). The advancing (□) and receding () contact angles taken for RTV11immersed in deionized water are also presented. Error for each data point (average over 12 measurements) is presented by the vertical line.
leaching data, about 30 % of capsaicin original mass had leached after 14 days of
immersion. This amount is high enough for the surface roughness to increase
considerably.
A 42 day immersion period was used to study the effects of water immersion time
as well as bacteria and dissolved capsaicin on the bulk modulus of RTV11. As-prepared
RTV11 coatings were immersed in three different waters (sterilized DI water, enriched
LE water with bacteria, and sterilized LE-20 ppm water). As shown in figure 5.9, the
bulk modulus slightly decreased from 1.56 MPa to 1.37 MPa after the 42 days of immersion in all three waters, with no observed effect from the water type. This
indicates that bacterial attachment or dissolved capsaicin has minimum contribution to
the variation of the elastic modulus of RTV11. Two factors may contribute to the slight
decrease in bulk modulus. First is a slow leaching of CaCO3 filler from the bulk of the
RTV11 coating. Second reason could be a continuous loss of small amounts of RTV11
constituents other than CaCO3 (Bullock et. al., 1999). Previously, Wynne et. al. (2000)
performed a quantative mass loss experiment for RTV11 coatings immersed in DI water,
where they proved that the mass loss of RTV11 was about 0.8 wt% after 30 days of
immersion. This is in accordance with the general conclusion made by Brady (2000) that
hydrosilylation-cured PDMS – such as Sylgard® 184 - are stable in water whereas
polycondensation – cured PDMS – such as RTV11 - are not stable in water.
In summary, it can be summarized from this subsection that the type of water will
not have effect on the properties of the coatings and consequently will not have effect on
Figure 5.9 Effect of water type and immersion time on the elastic modulus of RTV11films immersed in different types of water samples (sterilized Lake Erie water: Δ,
enriched Lake Erie water:
○,and sterilized Lake Erie water with 20 ppm capsaicin:
□).
Error for each data point (average over 6 measurements) is presented by the vertical line.
the antibacterial performance of the coatings. However, immersion in water will cause
the surface roughness for capsaicin-blended coatings to increase considerably. This
considerable increase in surface roughness could enhance bacterial attachment, unless the
amount of capsaicin leached out is high enough to inhibit bacterial attachment, as to be
In order to evaluate the coatings antibacterial behaviors, bacterial attachment
studies using fresh waters containing indigenous enriched microbial consortium isolated
from Lake Erie water were performed. Some representative bacterial attachment images
are presented in Figure 5.10. As shown in the figure, much less bacteria were attached to
capsaicin-blended RTV11 coating as compared to RTV11 coating alone. By defining the
% reduction in bacterial coverage to be (1-A/B) 100, where A and B refer to the area
coverage for capsaicin-blended RTV11 coating and control RTV11 coating, respectively,the % reduction was estimated to be (58 ± 11) %. However, based on the leaching data
shown previously, the concentration of capsaicin in solution for the immersion period
shown in Figure 5.10 was approximately 4-6 ppm. This concentration was very close to
the EC50 of capsaicin [~ 5 to 20 ppm towards various bacteria (Xu et al. 2005)].
Therefore, we are not sure if the reduction of bacterial attachment on the capsaicin-
treated surface shown here is because of the bacteria simply died off or because of the
non-toxic mode of action of capsaicin.
In summary, the clear reduction in bacterial population on the capsaicin-treated
RTV11 coating suggests that capsaicin can effectively inhibit the attachment of bacteria
we tested. However, the antibacterial effectiveness of the capsaicin-treated RTV11
coating is likely short lived due to the relatively high leaching of capsaicin coupled with
the dramatic increases in surface roughness of the coatings when immersed in water.
the modulus do not expect to differ two much from the corresponding value of that of
control silicone coatings.
6.2 Miscibility of tannic acid in silicones
To roughly examine TA/silicones miscibility; optical microscopic images were
taken for the bulk of Sylgard® 184 contained the incorporated compound after drying off
the solvent. The solvent used here was acetone, and the solvent/polymer ratio was 20/80
by mass. As shown in Figure 6.2, small aggregates (~ 1 — 3 µm) were distributeduniformly throughout Sylgard® 184 matrix. The resulted aggregate size here was
considerably small, much smaller than the crystal size of benzoic acid and capsaicin, and
comparable to the minimum aggregate size obtained for sodium benzoate in Sylgard®
184. This could be attributed to the following reason. Acetone is a good solvent for
tannic acid. Also, acetone is quickly dried off, and has some miscibility with silicones.
However, as shown in figure 6.2, phase separation was observed clearly for the tannic
acid/ Sylgard® 184 system. This implies that, despite the excellent and fine distribution
of the compound inside the matrix, tannic acid is not soluble in the polymer phase. Also,
Figure 6.2 demonstrates the effect of the compound matrix loading on the aggregate size.
While increasing TA matrix loading from 1 wt% TA/polymer to 4 wt% TA/polymer had
resulted in increasing the number of aggregates, the aggregate size did not change
considerably. This result had some similarity with the effect of NaB matrix loading on
the aggregate size (Figure 4.6 in Chapter 4), and therefore they supported each others.
Figure 6.2 Optical microscope (transmission bright field) image of resulting TA
distribution in the bulk of Sylgard® 184 matrix: (a) 1 wt% TA/Polymer; (b) 4 wt%TA/Polymer. Acetone was used as the common solvent, and the solvent/polymer ratiowas 20/80 by mass. The image size is (570 x 480) µm.
The miscibility of tannic acid with silicones can be predicted by calculating the
interaction parameter, χ 12, which can be calculated according to the same previous
equation discussed before in chapter 4:
χ 12 = (V1/RT) (δ1 – δ2)2 (6.1)
However, equation 6.1 can not be used directly without knowing the solubility parameter
of tannic acid, δ2, which is not available in the literature. Alternatively, the solubility
parameter of tannic acid was predicted here by the group contribution method, according
where Ecoh, i and Vi are respectively the molar cohesion energy and molar volume of
group i in the structure of tannic acid. The values used here for Ecoh, i and Vi were
obtained from Fedors’ table (found in van Krevelen (1990)). Consequently, the predicted
value for the solubility parameter of tannic acid was 36.60 MPa1/2. By evaluating the
predicted solubility parameter of tannic acid into equation 7.1, the χ 12 value for tannic
acid/PDMS system was estimated to be 14.06, indicating that tannic acid was not soluble
in the polymer phase, as observed experimentally. In Table 6.1, the properties of thesolvent used (acetone) are also summarized with the properties of tannic acid and PDMS
for comparison.
Table 6.1 Physical parameters of relevance importance to the miscibility of tannicacid/PDMS system. δ is the solubility parameter of the material. δ12 is the difference insolubility parameters between the material and PDMS. χ 12 is the interaction parameter between the material and PDMS.
Material∆
(MPa)½
∆δ12
(MPa)½ χ 12
Tannic acid 36.6 a 21.7 14.06
Acetone 20.3 b 5.4 0.871
PDMS 14.9 b - -
a` Value predicted in the current study by the group-contribution method (see text). b, Values obtained from (Rodriguez, 1989).
Figure 6.3 Cumulative leaching of TA from its incorporated silicone coating:Sylgard® 184 () or RTV11 (▲). The common solvent used was acetone for both
combinations. The initial concentration of TA in both coatings was kept constant at 1wt%., and the solvent/polymer ratio was kept constant at 20/80 by weight for bothcombinations. Error for each data point (average over 2 batches) is presented by thevertical line.
two reasons could be attributed here to explain this observation. First, tannic acid had
shown the formation of fine distribution of very small aggregates (~ 1 — 3 µm) inside the
silicone matrix, and we have enough evidence now that the leaching will decrease if the
aggregate size decreases. Second, tannic acid has the largest molecular weight amongst
all the compounds investigated in the current study (the molecular weight of tannic acid
is 1700 g/mol, which is about 12 times higher than the molecular weight of sodium
benzoate), and it is well-known that in general the heavier molecule diffuses slower than
the lighter molecule.
The above results clearly showed the effect of the matrix type on the leaching of
tannic acid, where the leaching of tannic acid from RTV11 was higher than the leaching
from Sylgard® 184. This experimental result supports the previous finding for sodium
benzoate/silicones regarding the effect of the matrix type (section 4.4.4), where it wasobserved that the leaching of sodium benzoate from RTV11 coating was higher than the
leaching from Sylgard® 184. Therefore, the reasons for the observed matrix type on the
leaching of tannic acid are similar to what we discussed before in section 4.4.4 and need
not to be repeated.
In summary, it can be evident from the leaching data presented here that leaching of
TA from silicone coatings into water is very slow. This could be an advantage for TA-
incorporated coatings. For example, in the case if TA/silicone coatings are to be
immersed in bacterial water solution for evaluating the antibacterial performance, the
bulk water concentration of TA will be certainly much below the EC50 of TA [~ 118 ppm
(Xu et al., 2005)], and hence bacteria will not die, and hence if a reduction in bacterial
attachment observed most likely it will be by a non-toxic mode of action. However,
bacterial attachment was not performed here for TA/silicone coatings; because this is
advantage of controlling the release. On the other hand, the solvent-assisted blending
technique was not suitable for the cases of capsaicin and benzoic acid, owing to the
observation that these two compounds had shown the tendency of forming large crystals
inside the coatings, regardless the different solvents used to control the crystal size. The
formation of large crystals was the main reason for the fast leaching of benzoic acid and
capsaicin observed from the coating carriers, thus truncated their usage as antifoulants to
be incorporated into a coating by the solvent-assisted blending technique.
Based on the main findings obtained for the secondary objective, the toxicity of the compounds, and the costs of the compounds, sodium benzoate-incorporated Sylgard®
184 coating was selected in the current study as the model system. Such a model system
was used to determine, based on detailed experimental observations and theoretical
analysis, the miscibility-leaching relationship. Experimentally, sodium benzoate was
found to exhibit slow and controllable leaching by tuning the preparation conditions (the
solvent composition, solvent/polymer ratio, and compound/polymer ratio). A fine and
uniform aggregate size distribution (~ 3 µm) was obtained at a 20/80 solvent/polymer
mass ratio and at a solvent composition of 50/50 water/acetone mass ratio, which had
resulted in the lowest value for the steady leaching rate of about 0.1 µg/cm2/day.
Empirical correlations between the effects of the aggregate size and the matrix loading of
sodium benzoate and its leaching rate were obtained. It was concluded that increasing
the aggregate size had a sharp effect on increasing the leaching rate, whereas increasing
the matrix loading (up to 5 wt. %) had a mild effect on the leaching rate. Moreover, as a
supplementary corollary to the study, 1 wt% sodium benzoate/Sylgard® 184 coatings with
fine and uniform aggregate distribution exhibited enhanced antibacterial behaviors as
compared to Sylgard® 184 coatings alone. This suggested that sodium benzoate could be
an environmental friendly alternative to the currently used toxic biocides in antifouling
applications, and highlighted the benefit of applying the solvent assisted blending
technique as the incorporation method.
Theoretical thermodynamic analysis was performed for predicting the miscibility
of sodium benzoate with Sylgard® 184 matrix using acetone/water blends as the solvent.
The quaternary Flory-Huggins model was extended to include the electrostaticcontribution and the concentration-dependent interaction parameters. Comparison was
made between the theoretical miscibility trends and the experimental morphology trends.
The extended Flory-Huggins model was found to be more accurate than the original
Flory-Huggins model, and both did predict that the system was not miscible, as observed
experimentally. Both the original Flory-Huggins model and the extended Flory-Huggins
model also captured qualitatively most of the important effects of the preparation
conditions on the aggregate size of NaB in Sylgard® 184 matrix, and the limitations of
both models to accurately predict all the effects of all the preparation conditions were
likely attributed to the total ignorance of the dynamic drying. Nevertheless, the rough
prediction based on the thermodynamic models did qualitatively describe most of the
features of our system, and still useful as as a preliminary guide for selecting the
Theoretical mass transfer analysis was performed for the leaching of sodium
benzoate from Sylgard® 184 matrix, in an attempt to elucidate on the leaching
mechanism. Based on the analysis, and combing it with the results from the miscibility
and thermodynamic study, the following mechanism was proposed: “Sodium benzoate is
insoluble in the polymer phase; therefore, the diffusion of the compound is taking place
through pores (empty space) filled with water within the matrix, not through the
continuum of the polymer phase”. For our experimental conditions, where the highest
matrix loading was only 5 wt%, the small particles (~3 µm in size) uniformly distributed
in the matrix may not necessarily be connected to each other. Instead, constrictedchannels of very narrow spacing could spread out throughout the matrix and connect the
particles between each others to allow for water to diffuse through these channels and
dissolve the particles. In this case, the porosity would be very small and the diffusion
path would be very tortuous. This would slow down the leaching process extremely after
a longer period, unless the capillary rise is capable of enhancing the flow of water
through these constricted channels, which is our speculation.
7.2 Recommendations for future work
The current study concluded that sodium benzoate is the most attractive
antifoulant among the four antifoulants investigated in the current study. The followings
(recommendations 1-8) are recommended as a continuation of the current study to
which appears to be crucial. Further theoretical work is needed to combine the
dynamic effect with the thermodynamic model.
(6) Mass transfer analysis for the leaching study is also recommended if
recommendations 3 and 4 are to be applied. The existing drug release models
described in chapter 2 are expected to be adequate for this purpose, and the
selection of a model depends on the concentration of sodium benzoate in the
matrix and on the compound/polymer solubility (as described in details in section
2.4.1 and section 2.4.2).
(7) It is also recommended to incorporate sodium benzoate into real marine coatings,which belong to the class “self-polishing polymers”. In this case, the leaching
mechanism will be totally different from silicone coatings, because here both
matrix erosion and compound diffusion contribute to the release of the compound.
Mass transfer analysis for the leaching study is also recommended in parallel.
The drug release models described in section 2.4.1 and section 2.4.2 are not
adequate for this purpose. Instead, the model developed by Kill et al . (2002) for
the analysis of self-polishing antifouling coatings will be useful.
(8) The current study assessed the antifouling performance of sodium
benzoate/silicone coatings by conducting bacterial attachment studies. It is
recommended to asses the antifouling performance of the coatings by using the
common fouling organisms, such as algae, tubeworms and diatoms.
For benzoic acid and capsaicin, the current study proved that the leaching rates of
the compounds were high, due to large crystal formation of the compounds inside the
matrix. In order to utilize any of them as an effective antifoulants, alternative
incorporation methods other than the method described in the current study are required
in order to control the release of the compounds. Sundberg et. al . (1997) described two
methods to achieve constant slow release rate for a long period of service life. They
applied these two methods for controlling the release of Sea-nine 211 (a commercial
antifoulant). The first method, the “reservoir membrane” method, was a two-layer
coating: the base layer composed of a highly concentrated Sea-nine 211 homogenouesd
with a plasticizer, and a top layer composed of RTV silicone. The second method was by
microencapsulating the active compound before dispersing it in the polymer coating. Byapplying these methods, they were able to slow down and control the release rate of Sea-
nine 211 considerably. Recently, Xing et. al . (2004) reported an efficient experimental
procedure for producing capsaicin microcapsules. It will be useful to investigate the
possibility of applying these two methods in order to control the release of benzoic acid
and capsaicin.
Finally, a previous work in our research group (Barrios et al ., 2005) proved that
zosteric acid - another nontoxic antifouling compound – incorporated into silicone
coatings was effective in inhibiting bacterial attachment. Zosteric acid has shown some
similarity with sodium benzoate regarding the miscibility and leaching behavior from
silicone coatings, and continues to be attractive nontoxic antifouling compound.
Therefore, the recommendations listed for sodium benzoate (recommendations 1-8) are
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MATLAB FILE FOR SOLVING THE GENERAL MASS TRANSFER MODEL(EQUATION 4.19)
% program written by Abdulhadi AL-Juhni (2006) % file name: pores.m % this file is to calculate the concentration profiles of the compound
% inside % the coating, considering the boundary condition of non-zero surface % concentration %************************************************************
The m.file: pores.m
% M=20; no. of nodes % ISOTHERMAL % with external film resistance % no dissulotion % this case is when the AF compound has zero solubility in the
% matrix,and % Co << Cs(sol. of A in water) % therfore the mass transfer mechanism is by channelling/pore formation
function yd=pores(t,y); %data******************************* bm = 5; % bm = kl/D; dimensionless no % %************************************************************
% call the m file: matrixab20.m (to get the coefficients of A and B
matrix) matrixab20;
%matrix size [m,n]=size(y); yd=zeros(m,n);
%assign dummy variables; [h] denote the conc. of the AF compound at