02638762/02/$10.00+0.

00 # Institution of Chemical Engineers Trans IChemE, Vol 80, Part A, January 2002

MATHEMATICAL MODELLING OF A SELF-POLISHING ANTIFOULING PAINT EXPOSED TO SEAWATER: A PARAMETER STUDY

SREN KIIL1 , CLAUS E. WEINELL2 , MICHAEL S. PEDERSEN 2 and KIM DAM-JOHANSEN 1
1

Department of Chemical Engineering, Technical University of Denmark, Lyngby, Denmark. 2 Hempels Marine Paints A=S, Lyngby, Denmark.

fundamental mathematical model for a self-polishing antifouling paint was used to conduct a parameter study. The aims were to show how a mathematical model can reduce the amount of experimental work needed to estimate the behaviour of selfpolishing antifouling paints at different conditions, and to suggest ways of controlling biocide release rates. A case study with an antifouling paint based on the well-known tributyltin selfpolishing copolymer system showed that the rate of paint polishing was in uenced, to various degrees, by the following parameters: seawater pH and concentration of NaCl, pigment particle size, pigment volume concentration of the paint, the rate of pigment dissolution, and the pore size distribution of the leached layer. The modelling approach can be applied to any type of self-polishing antifouling paint provided that kinetic, solubility and diffusivity data are available for the pertinent rate-in uencing steps. Keywords: self-polishing antifouling paint; mathematical modelling; chemical product engineering; controlled release; pigment leaching; TBT-polymer hydrolysis.

INTRODUCTION The attachment and growth of animal and plant organisms on arti cial structures immersed in marine waters, termed fouling, are of major consequence to any boat or ship exposed to seawater for prolonged periods. The increased drag on the ship raises fuel and machine requirements for maintaining speed and the loss of earning for a ship immobilized in dry-dock can be signi cant. Various ways of avoiding the fouling of ships are under development1, but presently fouling is fought by the use of antifouling paints, which release biocides into the seawater at controlled rates2,3. Since the early 1970s, the most effective systems have been the tributyltin self-polishing copolymer (TBT-SPC) based paints, which are presently used on approximately 70% of the world eet of ocean-going ships4. However, concern about the environmental effects of TBT-based antifouling paints on oysters and marine snails has grown5. According to Ryle6, this has motivated the Marine Environment Protection Committee (MEPC) under the International Maritime Organization (IMO) to work towards a global legally-binding instrument to ensure prohibition on the application of organotin compounds, which act as biocides in anti-fouling systems on ships by 1 January 2003, and a complete prohibition of these biocides in antifouling paints on ships by 1 January 2008. Therefore, the future challenge is to develop a polymer system, which may act as a controlled release vehicle for suitable antifouling biocides, but having no side effects to non-target organisms and no accumulation potential in the environment. Alternatively, novel ways of avoiding the fouling must be introduced. 45

The present tin-free self-polishing copolymer systems, which all use some kind of acrylic backbone polymer similar to that used in the TBT-SPC systems, have been described by Gerigk et al.4. These paint systems are based on copper, zinc, or silyl acrylates. Other self-polishing paints, which use gum rosin as their base, are available6. Fibre composites are also described to reinforce mechanical properties of self-polishing paints6. Recently, a self-polishing paint employing a cross linked copolymer with a hydrolysable group built into the backbone was presented7. However, all these systems have to demonstrate their longterm performance under different fouling conditions and to prove that the increased release of any new biocides and their metabolites do not bear unknown environmental risks. Another paint type under development is the siliconebased foul release paint, which provides a very smooth and slippery surface6. No biocides are needed because the action of the vessel moving through the water simply washes fouling off. However, its use is presently restricted to fast moving vessels (around 30 knots) and the price is around ve times the cost of TBT-based paints. A further drawback is that the coatings are soft and therefore prone to damage. In the development of antifouling paints, the approach of the paint industry has mainly been that of experiments7,8. Only a few theoretical attempts have been reported and these were all done on the insoluble matrix type paints914, which are no longer among the preferred antifouling paints. In our earlier work15, we showed how to develop a fundamental mathematical model of a self-polishing antifouling paint. As a case study, simple paints based on the well-known TBT-SPC technology were chosen. One of the

46

KIIL et al.

reasons for this choice was that a detailed understanding of the unique mechanism of TBT-SPC systems may provide a basis for the development of alternative environmentally safe systems4. Furthermore, kinetic and solubility data, suf ciently detailed to develop a model, was only available in the literature for this particular polymer system. Finally, the principles used to model TBT-based paints are of a general nature and therefore applicable to other antifouling paints based on similar controlled release mechanisms. In this work, a parameter study is performed using the mathematical model. The in uence of both seawater conditions and paint composition are investigated. It is hoped that the simulations presented will serve to illustrate the strength of having a fundamental paint model and support the development of novel self-polishing antifouling paints by suggesting ways of controlling biocide release rates.

Figure 1. Schematic illustration (cross section view) of the behaviour of a self-polishing antifouling paint comprised of an active polymer, a retarder, and Cu2O particles. After Kiil et al.15.

GENERAL COMMENTS ON SIMULATIONS Paint rotary or ship tests of antifouling paints are very time consuming15,16 and it is therefore of interest to reduce the amount of experimental work. One way to do this is by using a mathematical model, employed to perform simulations at the relevant process conditions. As an illustration, the results to be presented in this work would probably take several years to generate by means of a traditional paint rotor. It should be kept in mind, however, that the consequence of estimating paint polishing rates and the extent of paint pigment leaching from simulations, at conditions not studied experimentally, is that rate-in uencing steps, not accounted for in the model, may be important at the new conditions. Therefore, it is always worth performing at least a few rotary experiments to verify simulations. With particular reference to the simulations of this work, it is important to realize, as discussed elsewhere15, that the present model should only be used for quantitative studies of certain well-de ned paints. These should have a one-phase binder system consisting of an active copolymer of tributyltin methacrylate (TBTM) and methyl methacrylate (MMA) and a retarder (i.e. an inert hydrophobic copolymer which reduces the solubility of the binder phase) of butyl methacrylate (BMA) and MMA, as well as a pigment phase of the commonly employed pigment Cu2O, which becomes biocidal upon dissolution. The effects of additives, extenders (or llers), and insoluble pigments are not included in the model. However, the polishing rates of the paint systems considered are comparable to those exhibited by typical commercial tin-based paint systems15 and so the model contains the most essential chemistry and mass transport phenomena needed to describe the basic paint behaviour.

MATHEMATICAL MODEL The mathematical model was presented and veri ed against experimental rotary data in our earlier work15 and here will only be given a concise description. The physical processes that arise when the TBT- and Cu2O-based antifouling paints are exposed to seawater are shown schematically in Figure 1. Moving seawater slowly erodes the active polymer through hydrolysis (self-polishing effect), thereby releasing the biocidal groups in the form of TBTCl(aq).

Ions, present in seawater, diffuse into the porous polymer matrix, ahead of the eroding polymer front, and dissolve the pigment particles at the dissolving pigment front, resulting in the formation of a leached (i.e. Cu2O depleted) layer. The dissolved copper forms a complex with Cl CuCl2 or 2 CuCl3 and diffuses out through the leached layer. In the bulk seawater, the copper complexes are oxidized to Cu2 . Throughout the leached layer, the hydrolysis of the active polymer takes place, thereby establishing a TBT-polymer conversion pro le15. Consequently, two moving fronts, the dissolving pigment front and the eroding polymer front, are established. After some time, the thickness of the leached layer becomes constant. In subsequent sections, this is referred to as the stable leached layer thickness. Figure 2 shows a scanning electron microscopy (SEM) photograph of an antifouling paint, where the two fronts can be clearly seen. In summary, the model includes the following rate-in uencing steps: Dissolution of pigment particles; hydrolysis and erosion of the active polymer binder; effective diffusion in the leached layer; and external mass transport of relevant species. The overall purpose of the model is to estimate the position of the moving polymer and pigment fronts at all values of time and any relevant parameter combination. Here, it should be emphasized that all the above ratephenomena are strongly coupled. For instance, the rate of movement of the dissolving pigment front is dependent on the position of the polymer front because the rate of 2 diffusion of reaction products CuCl2 and CuCl3 is determined, in part, by the diffusion path (the width of the leached layer). Similarly, the rate of movement of the polymer front is determined by the TBT-conversion pro le in the leached layer15, which again is a function of the time of seawater exposure of the binder phase. The magnitude of the latter is controlled by the relative rate of movement of the pigment and polymer fronts. Estimation of physical and chemical constants needed in the model, as well as the uncertainties of these, is described elsewhere15. However, the model is based on an adjustable parameter, Xmax, which deserves elaboration. The parameter has a physical meaning because it represents the conversion of TBT-groups at the surface of the paint lm at which the active polymer is released into seawater15. It may vary, to various degrees, according to any changes in seawater conditions, paint composition or ship speed. No method has yet been identi ed which allows the value of Xmax to be estimated in advance. Presently, however, it is possible to estimate the value of Xmax, for a paint that has been exposed
Trans IChemE, Vol 80, Part A, January 2002

SELF-POLISHING ANTIFOULING PAINT

47

Figure 2. SEM photograph (magni cation 2000 ) showing part of the cross section of a self-polishing antifouling paint (pigment volume concentration of 40 vol.%) that has been exposed to seawater for 47 days at 20 knots and 25 C. The leached layer and the Cu2O particles in the unreacted paint lm can be clearly seen.

to given conditions, using SEM combined with energydispersive X-ray (EDX) analysis. In all the simulations presented in this work, the value of Xmax was kept at a xed value of 0.75 (estimated from experimental data in our earlier work15. The reason for the constant value of Xmax is that all the parameters considered here are assumed to have a negligible in uence on Xmax. Hence, the simulated changes in seawater behaviour with variations in pertinent parameters are due solely to changes in diffusion or chemical reaction rates. Finally, it should be mentioned that no adjustable parameters, apart from Xmax, are contained in the model. RESULTS AND DISCUSSION In order to investigate the effects of relevant parameter changes on the behaviour of a self-polishing antifouling paint, simulations were performed with the mathematical model. The rate of polishing and the stable thickness of the leached layer were considered in the parameter study. The reason for this choice is that these two variables can be measured using rotary or full-scale ship tests15. Thus, practising engineers in the marine paint industry are used to reporting measurements in terms of polishing rate and leached layer thickness. However, release rates of active components are also estimated by the model and could have been used just as well in the analysis. A set of standard parameter values (Table 1) for the paint composition and seawater conditions was chosen as a Base Case and the study, presented below, involves perturbations from the Base Case with respect to seawater and paint formulation parameters. It should be mentioned that the quantitative effects of the various parameter changes might differ in paints with other contents of BMA=MMA copolymer than the selected Base Case paint. The effects of two very important parameters, seawater temperature and ship speed, were investigated in our earlier work15 by both simulations and rotary experiments and will therefore not be discussed here. Seawater Parameters In this section, the in uence of external parameters on the paint behaviour is investigated.
Trans IChemE, Vol 80, Part A, January 2002

Table 1. Parameters of the Base Case. The seawater composition was obtained from Grasshof17. 1.0 knots 0.514 m s 1 1.850 km hr 1.
Parameter Temperature of seawater ( C) pH of seawater () Seawater content of NaCl (g=litre) Seawater content of MgSO4, 7H2O (g=litre) Seawater content of NaHCO3 (g=litre) Speed (knots) Paint content of Cu2O (percentage by solids volume) Paint content of active binder (percentage by solids volume) Paint content of retarder (percentage cby solids volume) Impurity content of Cu2O (wt%) 25 8.2 32 14 0.2 20 40 54 6 4

In uence of seawater pH Typical values of pH for surface seawater lie between 8.0 and 8.218, but in polluted waters or near river mouths, in areas with low limestone contents of the underlying rock, the pH may vary more. In Figure 3, the effect of seawater pH on the rate of polishing and the stable thickness of the leached layer is shown. An assumption underlying those simulations, and which should be mentioned here, is that the solubility of the partially hydrolysed active polymer is independent of pH in the range studied. It can be seen on the gure that the rate of polishing goes up when the pH is lowered. Changing the pH from 8.2 to 8.0 increases the polishing rate by 18%. The reason for this behaviour is that the rate of dissolution of Cu2O is proportional to the concentration of H 19. Thus when the latter increases, the rate of movement of the pigment front is increased. This also leads to a faster rate of movement of the polymer front, because the movements of the two fronts are coupled. However, the rate of movement of the polymer front is not enhanced as much as the pigment front leading to an increased thickness of the leached layer. The hydrolysis rate of the active polymer binder is also dependent on seawater pH20, but, contrary to the rate of pigment dissolution, the hydrolysis rate decreases with lower values of pH. However, the weak pH-dependency of the hydrolysis rate does not in uence the results to any signi cant extent. The importance of the ndings in Figure 3 is that the lifetime of a self-polishing antifouling paint, to some extent, is dependent on the pH value of the local seawater.

48

KIIL et al.

where the salinity is low, the rate of polishing is expected to be very slow or to stop completely. The thickness of the leached layer is not very sensitive to the concentration of NaCl in the range studied. To explain this, it can be mentioned that the rate of Cu2O dissolution and hydrolysis is taken to be second and rst order in the concentration of Cl , respectively. However, according to the model, simulations show less in uence towards the rate of dissolution of Cu2O than towards the rate of hydrolysis resulting in a low sensitivity of the leached layer thickness towards a change in the concentration of Cl .
Paint Formulation Parameters In this section is illustrated how the mathematical model can be used as a product engineering tool with respect to paint formulation.
Figure 3. Effect of pH of seawater on the polishing rate and the stable thickness of the leached layer. A pH value of 8.2 corresponds to the Base Case. Other parameters are given in Table 1.

In uence of seawater concentration of NaCl The salinity of the world oceans is fairly uniform with an average of about 3.5 wt%18. However, there may be local variations in the salinity near, for instance, river mouths. The relative amounts of the various salt components in seawater are practically constant with NaCl being the most abundant species. The latter salt in uences both the rate of Cu2O dissolution and the rate of hydrolysis15 in that both reaction rates are increased by an increase in the concentration of NaCl. The effect of the concentration of NaCl on the polishing rate and the stable thickness of the leached layer is shown in Figure 4. It can be seen that quite large changes in the concentration of NaCl are needed to alter the polishing behaviour of the paint to any signi cant extent. Decreasing the concentration of NaCl from 0.55 M (that of the Base Case) to 0.4 M causes a reduction in the polishing rate of about 37%. However, in areas with brackish or fresh water,

In uence of Cu2O particle size Most (if not all) present self-polishing antifouling paints use the pigment Cu2O as one of the main biocides, because the Cu2 ion, which is particularly effective against animal fouling16, is released upon dissolution of the pigment. The Cu2O particles present in commercial paints are usually ground to a suitable particle size distribution (PSD) to avoid cracks in the paint upon drying, as well as to ensure certain properties of the paint21. An example of a typical PSD of ground Cu2O is shown in Figure 5. As discussed in our earlier work, the particle size should not in uence, directly, the rate of Cu2O dissolution in a paint because the pigment pro le is very steep near the dissolving pigment front, whereby dissolution of Cu2O particles, regardless of shape, approximates to dissolution from a slab into seawater. However, the rate of conversion of the active polymer binder in the leached layer is dependent on Cu2O particle size because the active surface area per unit volume of the leached layer is a function of the PSD of Cu2O in the

Figure 4. Effect of seawater concentration of NaCl on the polishing rate and the stable thickness of the leached layer. A concentration of about 0.55 M corresponds to the Base Case. Other parameters are given in Table 1.

Figure 5. PSD of Cu2O in an antifouling paint after exposure to a mechanical shaker. The measurement was done using a Malvern Analyser employing laser diffraction21. The particle diameter on the x-axis is the equivalent spherical volume diameter. Notice the logarithmic axis.

Trans IChemE, Vol 80, Part A, January 2002

SELF-POLISHING ANTIFOULING PAINT unreacted paint lm (i.e. the empty polymer matrix, comprising the leached layer, is a template of the Cu2O particles which have dissolved). Furthermore, as discussed in a subsequent section, the pore size distribution of the leached layer will be affected by both particle size and shape, perhaps leading to changes in the rate of effective diffusion of relevant species in the leached layer. This possible effect is not included in the mathematical model and must be kept in mind when considering the simulations. In the model, the Cu2O particles are assumed to be spherical with zero porosity and the mechanical strength of the leached layer is assumed independent of Cu2O particle size. This latter assumption has not been justi ed, due to lack of experimental data. In Figure 6 is shown how the polishing and leaching behaviour of the paint is in uenced by particle size (i.e. spherical particle diameter) of a monodisperse PSD. Relating a monodisperse distribution to what is common practice in the paint industry, it is important to realize that the neness of grind measured for a paint provides the maximum particle size, whereas for a monodisperse distribution the particle size is uniform. Thus, even though the neness of grind has been measured to, say, 50 mm, for a given paint, it may still contain many particles much smaller than 50 mm as may be evidenced by considering the data of Figure 5. Here, it should be mentioned that the use of a monodisperse distribution in Figure 6 is not a limitation of the model, but simply a way of presenting simulation results in a comprehensible form. All other simulations in this work are based on the complete PSD provided in Figure 5. It can be seen on Figure 6 that changing the particle size from 10 to 0.1 mm increases the rate of polishing from 6.9 to 22.1 mm=month. However, reducing the particle size from 20 to 10 mm only changes the polishing rate from 5.2 to 6.9 mm=month. Thus, Cu2O particle size does not appear to be a key parameter in the formulation of paints with certain controlled release rates of biocides, though very small particles appear to increase the polishing rate signi cantly. In relation to this conclusion, it should be mentioned that a

49

neness of grind of only a few microns is probably not a practical option. The stable thickness of the leached layer is quite sensitive to particle size (Figure 6). When lowering the particle size from 20 to 0.1 mm, the leached layer thickness decreases from about 46 mm to about 1 mm. The reason for the low thickness at very small particle sizes is that the active surface area available for hydrolysis per unit volume of the leached layer is inversely proportional to particle size. Thus, it leads to an increased rate of movement of the polymer front when the particle size is reduced, whereby the polymer front catches up with the pigment front at suf ciently small particle sizes. Another aspect that should be mentioned here is the effect of including inert particles (such as insoluble TiO2) in the paint. Due to the fact that these particles do not dissolve in seawater, they will block the active surface area in the leached layer until the moment at which they are released at the paint surface and this should reduce the rate of polishing. Additionally, the particles are expected to reduce the rate of effective diffusion in the leached layer, thereby decreasing the rate of leaching and polishing. However, a quantitative estimation of the effect of inert particles is not possible with the present model. In uence of pigment volume concentration The pigment volume concentration (PVC) of an antifouling paint is often allowed to vary within a certain range. If it exceeds the critical pigment volume concentration (CPVC)22, there is insuf cient binder to ll out the space among the pigment particles, thereby leading to a porous lm before the paint has even been exposed to seawater. On the other hand, the PVC must be high enough to ensure that some particles are in contact with other particles, thereby creating a pore network in the leached layer when the soluble pigment particles dissolve in seawater. If the PVC gets too low the polishing rate will be very slow. The lower limit for the PVC is typically about 10 vol.%, but preferably the PVC should be somewhere between 30 and 45 vol.%, depending on the CPVC of a given paint23. For the model paint of this work (Table 1), the CPVC can be estimated to 57 vol.% using density and oil absorption data for Cu2O22. It should be mentioned that the porosity of the unreacted paint lm (i.e., prior to seawater exposure) was assumed to be 0. This is a reasonable assumption because the PVC values considered in the simulations are far from the CPVC. Consequently, in the model the porosity of the leached layer, formed at later times, will originate solely from dissolving pigment particles. The estimated effect of PVC on the rate of polishing and the thickness of the leached layer is shown in Figure 7. When performing these simulations, Cu2O was replaced by binder material as the PVC was lowered. In the model, it was assumed that the mechanical strength of the leached layer is independent of the PVC in the range studied. Additionally, the simulations in Figure 7 were performed under the assumption of no pores of the leached layer being isolated (i.e. all pores are interconnected). This assumption probably becomes more questionable as the PVC is reduced to smaller values. Finally, it should be mentioned that the PVC range investigated, 3050 vol.%, corresponds to a reduced PVC (i.e. the ratio of PVC to CPVC) of 0.53 0.88. Thus, all paint formulations explored have PVCs

Figure 6. Effect of Cu2O particle size of a monodisperse PSD on the polishing rate and the stable thickness of the leached layer. In the Base Case simulation (not shown on this gure), the polydisperse PSD of Figure 5 was used. Other parameters are given in Table 1.

Trans IChemE, Vol 80, Part A, January 2002

50

KIIL et al.

Figure 7. Effect of the pigment volume concentration (PVC) of the paint on the polishing rate and the stable thickness of the leached layer. A PVC of 40 vol.% corresponds to the Base Case. The CPVC of the paint was estimated to about 57 vol.%22. Other parameters are given in Table 1.

below CPVC. This is important because many paint properties change drastically at or near the CPVC22 and these phenomena are not included in the present model. It can be seen in Figure 7 that the rate of polishing decreases by about 30% and the stable thickness of the leached layer increases about 67% when the PVC is lowered from 50 to 30 vol.%. This is due to several factors. First of all, the rate of movement of the pigment front is expected to increase when the PVC is lowered, since less Cu2O needs to dissolve. However, the rate of effective diffusion of all species in the leached layer decreases, because the porosity is lowered. Additionally, the rate of conversion of the active polymer binder is decreased because the active surface area of the leached layer is decreased when the porosity goes down. The combined action of these rate phenomena is re ected in the simulations shown in Figure 7. It is important to realize that reducing the PVC of Cu2O leads to a lower rate of release of Cu2 . According to the model, the rate of release of Cu2 is reduced from 114 to 74 mg=(cm2 day) when the PVC is reduced from 45 to 35 vol.%. The rate of release of TBTCl, on the other hand, is practically unaffected by this change in PVC. The reason for the latter is that the effect of a lower polishing rate is counterbalanced by an increased paint content of active binder material.
In uence of rate of pigment dissolution The rate of pigment dissolution is very important for the overall rate of polishing of the paint15. It may therefore be of interest to change the rate of dissolution of Cu2O (or other soluble pigments used in antifouling paints for that matter) in an attempt to control the biocide release rate. One way of changing the rate of dissolution of a given pigment type could perhaps be to produce heterogeneous particles with some pigment replaced by a more or less soluble component. This was done, for instance, by Carlton24, who changed the rate of dissolution of Cu2O particles from antifouling paints by an oxidation technique. In Figure 8 the way in which polishing rate and stable thickness of the leached layer would be in uenced by a

Figure 8. Effect of the rate of dissolution of Cu2O (expressed as a dimensionless rate constant for the dissolution reaction) on the polishing rate and the stable thickness of the leached layer. A value of unity for the ratio k=ko corresponds to the Base Case. Notice the logarithmic axis. Other parameters are given in Table 1.

possible change in the rate of dissolution of Cu2O is shown. Simulations were done by varying the rate constant, k, of the dissolution reaction. It can be seen that changing the rate of dissolution may be a key parameter to controlling the rate of polishing, though the practical aspects of introducing such a change is more challenging than varying for instance pigment particle size. Reducing the rate of dissolution would, according to simulations, lower the polishing rate as well as the thickness of the leached layer. At a suf ciently low rate of dissolution, the slow rate of movement of the pigment front allows the polymer front to catch up, thereby almost eliminating the leached layer. It can also be seen on the gure, that the rate of dissolution must be increased by several orders of magnitude to reach the maximum polishing rate and that the latter is only about 35% higher than that of the Base Case. The reason why the polishing rate reaches an asymptotic value when k is increased is that the rate of effective diffusion of CuCl2 2 and CuCl3 in the leached layer at this point becomes a dominant rate-step in the dissolution process. Additionally, the dissolution reaction is reversible, which means that an increase in the rate constant for the forward reaction also increases that of the reverse reaction15.
In uence of pore size distribution of the leached layer The pore size distribution of the leached layer is largely determined by the PSD and shape of the Cu2O particles present in the unreacted paint lm. It may therefore be of interest to know if the pore size distribution has an in uence on the rate of polishing. One way to investigate this is to consider the sensitivity of model simulations with respect to the tortuosity factor, t, which is given by the ratio of the constriction factor and the tortuosity25. The tortuosity is the actual distance a molecule travels between two points divided by the shortest distance between the two points, whereas the constriction factor for the pores accounts for Trans IChemE, Vol 80, Part A, January 2002

SELF-POLISHING ANTIFOULING PAINT

51

any variation in the cross-sectional area normal to diffusion. The tortuosity factor is a function of the porosity and the pore size distribution26 and the effect of t on the polishing rate and the stable thickness of the leached layer is shown in Figure 9. Increasing t from a value of 2.5 (that of the Base Case) to 6 decreases the rate of polishing by 25% and the thickness of the leached layer by 30%. These reductions are due to a hindered effective diffusion of all relevant ions and species in the leached layer because the effective diffusivity is inversely proportional to the tortuosity factor25. The importance of these ndings is that if it is possible to alter the value of t then it may be possible to control, to some extent, the rate of polishing. One way to alter t without changing the porosity (i.e. the content of Cu2O or other soluble pigments in the paint) is to change the diffusion path. This can perhaps be done using Cu2O particles with novel shapes, which, upon dissolution, would leave behind tortuous pores. It should be remembered, however, that changing the particle shape (or size for that matter) might also change the active surface area of the leached layer. Additionally, the neness of grind used for a paint pigment in a commercial paint (typically less than 40 mm) could be dif cult to combine with the establishment of well-de ned particle shapes. Other Applications of Mathematical Paint Models Planning of rotary experiments with the aid of simulations Mathematical paint models may suggest how best to perform rotary or ship paint tests, because they can estimate the impact of a given parameter change (as shown in earlier sections). If, for instance, the model estimates that a temperature change of, say, 10 C only produces a change in the polishing rate that is within the uncertainty of the experimental data then it is probably not worthwhile to conduct the experiment at the temperature considered. Hence, in this case a temperature change larger than 10 C may be needed to reveal any change in the paint behaviour with temperature. The importance of this conclusion can be

con rmed, quantitatively, by considering the data of Kiil et al.15. Quality control by the use of simulations Once a suf ciently detailed model has been developed for a given paint and, to some extent, veri ed against experimental data, it may be used to support a quality control function. Simulations can estimate the sensitivity of polishing and leaching rates, at given conditions, with respect to relevant paint components and thereby perhaps suggest critical limits for raw material properties such as impurity contents or oil absorption data of pigments. This type of information can be obtained directly from traditional rotary experiments, but a mathematical model can cover a much wider range of conditions than would be practical using a paint rotor. However, a combination of rotary tests and simulations is recommended. CONCLUSIONS It has been shown how a fundamental paint model can be used to investigate the effects of various parameter changes on the polishing and leaching behaviour of a self-polishing antifouling paint. Based on simulations, some suggestions were given on how to control the biocide release rates from a formulation and paint production point of view. A general conclusion from the parameter study is that the amount of experimental work needed to perform a parameter study of an antifouling paint can be reduced by supplementing laboratory studies with the development of fundamental paint models. Additionally, simulations may suggest how best to perform rotary investigations. Furthermore, models for existing paints may help to identify the properties that new ef cient and environmentally safe antifouling paints should possess. It is important to remember, however, that mathematical models must always, to some extent, be veri ed against experimental data as shown in Kiil et al.15. NOMENCLATURE
BMA CPVC k ko
MMA PVC PSD SPC TBT TBTM Xmax

butyl methacrylate critical pigment volume concentration rate constant for the Cu2O dissolution, mol=((mol=m3)3 m2 s) rate constant for the Cu2O dissolution at Base Case conditions, mol=((mol=m3)3 m2 s) methyl methacrylate pigment volume concentration particle size distribution self-polishing copolymer tributyltin tributyltin methacrylate value of surface conversion at which the active polymer is released into seawater

Greek symbols t tortuosity factor

REFERENCES
1. Swain, G. W., 1998, Biofouling control: A critical component of drag reduction, International Symposium on Seawater Drag Reduction, Newport, RI, USA, 2224 July, The Naval Undersea Warfare Center, Newport, 155161. 2. Warnez, M. and Hansen, O., 1982, Self-polishing polymers for antifouling paints, Federation of Scandinavian Paint and Varnish Technologists, 10th Congress, 1113th October, Copenhagen, 7.17.26.

Figure 9. Effect of the tortuosity factor, t, on the polishing rate and the stable thickness of the leached layer. A value of 2.5 for t corresponds to the Base Case. Other parameters are given in Table 1.

Trans IChemE, Vol 80, Part A, January 2002

52

KIIL et al.
17. Grasshoff, K., 1976, Methods of seawater analysis, (Verlag Chemie, Berlin). 18. Capurro, L. R. A., 1970, In: Grif th, D. E (Ed.) Oceanography for Practicing Engineers, (Barnes & Noble Inc., New York). 19. Ferry, J. D. and Carritt, D. E., 1946, Action of antifouling paints: solubility and rate of solution of cuprous oxide in sea water, Ind Eng Chem, 38(6): 612617. 20. Hong-xi, C., Mei-ying, Y., Huai-min, G. and Jing-hao, G., 1988, Studies on the hydrolysis of the organotin polymers. I. Hydrolytic rates of poly(tributyltin methacrylate) and poly(tributyltin methacrylate-comethyl methacrylate). Fujian Shifan Daxue Xuebao, 4(2): 618X (in Chinese). 21. Rawle, A., 1996, Particle sizing in the paint industry, European Coatings Journal, 4: 195198. 22. Patton, T. C., 1979, Paint Flow and Pigment Dispersion, 2nd Ed., (John Wiley & Sons, New York). 23. Gitlitz, M. H. and Leiner, H. H., 1986, Erodible Ship-Bottom Paints for Control of Marine Pouling, US Patent Number: 4,593,055. 24. Carlton, J.N., 1997, Composite Cuprous Oxide Powder, US Patent, PCT=US97=00423, WO 97=31054. 25. Fogler, H. S., 1986, Elements of Chemical Reaction Engineering, (Prentice-Hall, Englewood Cliffs), New Jersey. 26. Carniglia, S. C., 1986, Construction of the tortuosity factor from porosimetry, J Catal, 102: 401418.

3. Anderson, C. D., 1995, Tin vs. Tin-free Antifoulings, Conf Proc Protecting the Ship While Safeguarding the Environment. London, 56 April, Society of Wetland Scientists, Kansas, USA, 112. 4. Gerigk, U., Schneider, U. and Stewen, U., 1998, The present status of TBT copolymer antifouling paints versus TBT-free technology, Prepr Ext Abstr ACS Natl Meet, 38(1): 9194. 5. Champ, M. A. and Seligman, P. F., 1996, Organotin: Environmental Fate and Effects, (Chapman & Hall, London). 6. Ryle, M., Are TBT alternatives as good?, 1999, The Motor Ship, January issue, 3439. 7. Kuo, P. and Chuang, T., 1999, Surface-fragmenting, self-polishing, tinfree antifouling coatings, J Coat Tech, 71(893): 7783. 8. Bowmer, C. T. and Ferrari, G., 1989, A new approach to the development and testing of antifouling paints, J Oil & Colour Chemists Assoc, 72(10): 391396. 9. Marson, F., 1969, Antifouling paints. I. Theoretical approach to leaching of soluble pigments from insoluble paint vehicles, J Appl Chem, 19(4): 9399. 10. De la Court, F. H. and De Vries, H. J., 1973, Leaching mechanism of cuprous oxide from antifouling paints, J Oil Colour Chem Ass, 56(8): 388395. 11. Marson, F., 1974, Antifouling paints. II. More detailed examination of the effect of pigment volume concentration, J Appl Chem Biotechnol, 24(9): 515527. 12. Monaghan, C. P., Kulkarni, V. H. and Good, M. L., 1978, Further evaluation of a diffusion model for the characterization of the leaching properties of several conventional antifouling coatings, Report TR-7 Order No. AD-A056150, Gov. Rep. Announce. Index (U. S.), 78(21): 171175. 13. Kruglitskii, N. N., Avilov, V. O., Batyuk, V P. and Shkurovich, M. Y., . 1983, Mathematical modeling of the leaching of biologically active substances from anticorrosive antifouling coatings, Dopov Akad Nauk Ukr RSR, (1): 3033 (in Russian). 14. Caprari, J. J., Meda, J. F., Damia, M. P. and Slutzky, O., 1990, A mathematical model for leaching in insoluble matrix lms, Ind Eng Chem Res, 29: 21292133. 15. Kiil, S., Weinell, C. E., Pedersen, M. S. and Dam-Johansen, K., 2001, Analysis of self-polishing antifouling paints using rotary experiments and mathematical modelling, Ind Eng Chem Res, 40(18): 3906 3920. 16. Anderson, C. D., 1998, TBT and TBT-free antifouling paints ef ciency and track record, IBC UK Conferences Limited, IBC, London, U.K., 112.

ACKNOWLEDGEMENT
S. K. is grateful to Michel Warnez for the many interesting discussions and advice on paint chemistry. Financial support of S. K. by J. C. Hempels Foundation is gratefully acknowledged.

ADDRESS
Correspondence regarding this paper should be addressed to Assistant Professor S. Kiil, Department of Chemical Engineering, Technical University of Denmark, Building 229, DK-2800 Lyngby, Denmark. E-mail: sk@kt.dtu.dk The manuscript was received 26 March 2001 and accepted for publication after revision 16 July 2001.

Trans IChemE, Vol 80, Part A, January 2002