Markus Andersson Trojer

Use of microcapsules as controlled release devices for coatings

Biofouling of surfaces is a considerable problem in many industrial sectors and for the public community in general. The problem is usually approached by the use of functional coatings and most of such antifouling coatings rely on the effect of biocides. However, a substantial drawback is the poor control over the release of the biocide as well as its degradation in the paint. Encapsulation of the biocides in microcapsules is a promising approach that may overcome some of the problems associated with the more traditional ways of incorporating the antifouling agent into the formulation. In this review, we summarize more than a decade of microcapsule research from our lab as well as from other groups working on this topic. Focus will be on two coacervation-based encapsulation techniques; the internal phase separation method and the double emulsion method, which together enable the encapsulation of a broad spectrum of biocides with different physicochemical properties. The release of the biocide from core-shell particles and from encapsulated biocides in coatings is treated in detail. The release behaviour is interpreted in terms of the physicochemical properties of the core-shell particle and the coating matrix. In addition, special attention is given to the experimental release methodology and the implementation of proper diffusion models to describe the release. At the end of the review examples of antifouling properties of some coatings against common biofoulers are presented.

Charged microcapsules for controlled release of hydrophobic actives. Part III: the effect of polyelectrolyte brush- and multilayers on sustained release.

Poly(methyl methacrylate) microspheres have been prepared by the internal phase separation method using either of the three conventional dispersants poly(vinyl alcohol) (PVA), poly(methacrylic acid) (PMAA), or the amphiphilic block copolymer poly(methyl methacrylate)-block-poly(sodium methacrylate). The block copolymer based microsphere, which has a polyelectrolyte brush on the surface, was surface modified with up to two poly(diallyldimethylammonium chloride)-poly(sodium methacrylate) bilayers. The microspheres were loaded with the hydrophobic dye 2-(4-(2-chloro-4-nitrophenylazo)-N-ethylphenylamino)ethanol (Disperse Red 13) and its release from aqueous dispersions of microspheres with the different surface compositions was measured by spectrophotometry. The burst fraction, burst rate and the diffusion constant were determined from a model combining burst and diffusive release. Out of the three dispersants, the block copolymer gave the slowest release of the dye, with respect to both burst release and diffusive release. A very pronounced further reduction of the diffusion constant was obtained by applying polyelectrolyte multilayers on top of the microspheres. However, the diffusion constant was very weakly dependent on further polyelectrolyte adsorption and one polyelectrolyte bilayer appeared to suffice.

Charged microcapsules for controlled release of hydrophobic actives Part II: Surface modification by LbL adsorption and lipid bilayer formation on properly anchored dispersant layers

Charge microcapsules with a dodecane core and a poly(methyl methacrylate) (PMMA) shell have been prepared via the internal phase separation method using ionic dispersants. The microcapsules have subsequently been surface modified with polyelectrolyte multilayers and lipid bilayers. Two types of ionic dispersant systems have been investigated: a small set of ionic amphiphilic block copolymers of poly(methyl methacrylate)-block-poly(sodium (meth)acrylate) type and an oil-soluble anionic surfactant, sodium 1,5-dioxo-1,5-bis(3,5,5-trimethylhexyloxy)-3-((3,5,5trimethylhexyloxy)carbonyl)pentane-2-sulfonate, in combination with a water-soluble polycation, poly(diallyldimethylammonium chloride). The Layer-by-Layer adsorption of the polyelectrolyte pair poly(diallydimethylammonium chloride) (350,000 g/mol) and poly(sodium methacrylate) (15,000 g/mol) was successfully made on both microcapsule systems with the formation of very thin multilayers as indicated with quartz crystal microbalance with dissipation monitoring (QCM-D) measurements on model surfaces. Formation of a lipid bilayer on the surface of the microcapsules from liposomes with a charge opposite that of the capsule surface was also proven to be successful as indicated by the ζ-potential of the microcapsules, the characteristic frequency shift as measured with QCM-D and fluorescence recovery after photobleaching (FRAP) on model systems. However, the proper anchorage of the dispersants in the underlying PMMA surface was key for the successful surface modification.

Imidazole and Triazole Coordination Chemistry for Antifouling Coatings

Fouling of marine organisms on the hulls of ships is a severe problem for the shipping industry. Many antifouling agents are based on five-membered nitrogen heterocyclic compounds, in particular imidazoles and triazoles. Moreover, imidazole and triazoles are strong ligands for Cu 2+ and Cu +, which are both potent antifouling agents. In this review, we summarize a decade of work within our groups concerning imidazole and triazole coordination chemistry for antifouling applications with a particular focus on the very potent antifouling agent medetomidine. The entry starts by providing a detailed theoretical description of the azole-metal coordination chemistry. Some attention will be given to ways to functionalize polymers with azole ligands. Then, the effect of metal coordination in azole-containing polymers with respect to material properties will be discussed. Our work concerning the controlled release of antifouling agents, in particular medetomidine, using azole coordination chemistry will be reviewed. Finally, an outlook will be given describing the potential for tailoring the azole ligand chemistry in polymers with respect to Cu 2+ adsorption and Cu 2+ Cu + reduction for antifouling coatings without added biocides.

The effect of pH on charge, swelling and desorption of the dispersant poly(methacrylic acid) from poly(methyl methacrylate) microcapsules

Poly(methyl methacrylate) microcapsules have been prepared using the solvent evaporation technique with poly(methacrylic acid) (PMAA) as dispersant. The charge, swelling and desorption of PMAA from the microcapsules after treating the suspension with base have been followed using microelectrophoresis, X-ray photoelectron spectroscopy and quartz crystal microbalance with dissipation monitoring on model PMMA surfaces. Basic treatment of the microcapsule suspension leads to temporary colloidal stability through the introduction of charges on the PMAA chain. However, the increase in charge causes a continuous desorption of PMAA from the microcapsule surface, eventually leading to aggregation. If instead poly(diallyldimethylammonium chloride) is added to the base treated microcapsule suspension, good colloidal stability is obtained.

The Importance of Proper Anchoring of an Amphiphilic Dispersant for Colloidal Stability

Highly stable poly(methyl methacrylate) (PMMA) based microcapsule suspensions without excess dispersant are obtained via the solvent evaporation route using poly(methyl methacrylate)-block-poly(sodium methacrylate) or poly(methyl methacrylate)-block-poly(sodium acrylate) diblock copolymers as dispersant. The stable suspension is characterized by a high ζ-potential that does not change with time or after washing steps. It is indirectly proven on model PMMA surfaces using quartz crystal microbalance with dissipation monitoring that the PMMA block of the copolymer is embedded in the underlying PMMA microcapsule. Such anchoring of the dispersant is key for the good colloidal stability.

Controlled release of a microencapsulated arduous semi-hydrophobic active from coatings: Superhydrophilic polyelectrolyte shells as globally rate-determining barriers.

Polymethylmethacrylate-based microcapsules containing the antimicrobial agent 2-n-octyl-4-isothiazolin-3-one (OIT) decorated by an anchored polyelectrolyte brush consisting of an amphiphilic diblock copolymer of polymethylmethacrylate-block-poly(sodium methacrylate) type have been formulated via a coacervation technique. The polyelectrolyte brush surface provided the microcapsule with a high and stable surface charge density. This enabled further surface modification of the colloidal particle with a thin and dense polyelectrolyte multilayer using the layer-by-layer technique. The addition of the highly charged and hydrophilic polyelectrolyte multilayer assembled on the microcapsule surface resulted in a considerable decrease of the release rate of the encapsulated OIT in aqueous suspension, corresponding to a 40 times reduction of the effective OIT diffusion coefficient in the polymethylmethacrylate matrix. Moreover, the release of encapsulated or freely dispersed OIT from coatings as a function of the matrix density was evaluated and analyzed within the framework of applied diffusion models. Encapsulation of OIT in polyelectrolyte multilayer composite microcapsules was found to significantly prolong the release and render the release rate more or less independent of the matrix density. In addition, the long-term antimicrobial properties of the coatings were evaluated in terms of their susceptibility for biofouling using the fungus and common biofouler Aspergillus niger as model organism. The results clearly demonstrated that the use of encapsulated OIT gave a significantly prolonged surface protection and allowed for the determination of the critical surface flux. The polyelectrolyte multilayer has therefore been recognized as the rate-determining barrier for OIT. The matrix density has a minor influence on the release rate of encapsulated OIT from these microcapsules and this concept may very well be expanded to cover a broad range of hydrophobic and semi-hydrophobic biocides.