WO2012083011A1 - Surface résistante aux salissures biologiques - Google Patents

Surface résistante aux salissures biologiques Download PDF

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Publication number
WO2012083011A1
WO2012083011A1 PCT/US2011/065134 US2011065134W WO2012083011A1 WO 2012083011 A1 WO2012083011 A1 WO 2012083011A1 US 2011065134 W US2011065134 W US 2011065134W WO 2012083011 A1 WO2012083011 A1 WO 2012083011A1
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Prior art keywords
biofouling
structures
biofouling resistant
polymer
resistant
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PCT/US2011/065134
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English (en)
Inventor
Vincent D. Mcginniss
Erik W. Edwards
Christine M. Mattingly
Dave Masterson
Ramanathan S. Lalgudi
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Battelle Memorial Institute
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Publication of WO2012083011A1 publication Critical patent/WO2012083011A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1681—Antifouling coatings characterised by surface structure, e.g. for roughness effect giving superhydrophobic coatings or Lotus effect
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B17/00—Methods preventing fouling
    • B08B17/02—Preventing deposition of fouling or of dust
    • B08B17/06—Preventing deposition of fouling or of dust by giving articles subject to fouling a special shape or arrangement
    • B08B17/065—Preventing deposition of fouling or of dust by giving articles subject to fouling a special shape or arrangement the surface having a microscopic surface pattern to achieve the same effect as a lotus flower

Definitions

  • biofouling which is the undesired accumulation of microorganisms, algae and/or marine animals on the surface of the structure.
  • the biofouling on a surface may be initiated by the original of a film containing organic matter and dissolved
  • macromolecules such as polysaccharides, proteins and protein fragments, followed by bacteria, microalgae, protozoan, algae and invertebrates.
  • Biofouling can cause substantial problems that may result in economical loss. For example, it can cause problems for marine structure systems, such as boat hulls and petroleum platform columns, and for marine aquaculture. With respect to boat hulls, biofouling can decrease the performance of the boat, such as by decreasing boat speed and adding weight, and it can create an undesirable appearance on the boat surface. After a surface has been subjected to biofouling, various costly and labor intensive mechanical and or chemical methods can be used to remove the biofouling.
  • microstructured surfaces have been developed to prevent or reduce biofouling.
  • U.S. Patent 7,650,848 (Univ. of Florida Research Foundation), issued January 26, 2010, discloses a polymer coating including a structured surface having features (scales) to resist bioadhesion.
  • the surface has a topography comprising a pattern defined by a plurality of spaced apart features attached to or projected into a base article.
  • the features each have at least one microscale dimension.
  • Similar microstructured surfaces are disclosed in U.S. Patent 7,143,709 (Univ. of Florida Research Foundation), issued December 5, 2006.
  • This invention relates to a biofouling resistant surface comprising a surface having microscale surface structures, nanoscale surface structures on the microscale surface structures, and biofouling resistant chemical functionality on the surface.
  • this invention relates to a biofouling resistant surface comprising: a structured surface having microscale surface structures that are resistant to biofouling; and a biofouling resistant chemical functionality on the surface.
  • this invention relates to a biofouling resistant surface comprising: a structured surface having surface structures resistant to biofouling; and an active polymeric system on the structured surface that functions as a battery when exposed to seawater.
  • the battery function changes over time, and the changing battery function causes a changing structure of the polymeric system that resists biofouling.
  • Fig. 1 is a schematic of one embodiment of the invention showing micro- scale, nano-scale and chemical-scale surface features.
  • Fig. 2 shows optical micrographs of silicon "master” patterns as part of a pattern multiplication process for producing a biofouling resistant surface.
  • Fig. 3 is a photograph of a tile array of PDMS replicants of the silicon master.
  • Fig. 4 is a photograph showing cured polyurethane on the PDMS tile array.
  • Fig. 5 shows optical micrographs of the replicated, positive nickel patterns.
  • Fig. 6 is a photograph of a patterned 5" by 5" nickel article generated as a result of the pattern multiplication process.
  • Fig. 7 is an overview of the pattern replication process used in transferring silicon patterns to nickel patterns.
  • Fig. 8 is an SEM image showing nanoscale topography created by self- assembled diblock copolymer domains on a nickel substrate.
  • Fig. 9 is a photograph showing a thin film of PS-b-PMMA floated from a glass slide onto a water surface.
  • Fig. 10 is an SEM image showing a nanoscale patterned surface generated on a flat nickel substrate.
  • Fig. 1 1 is an SEM image showing nanoscale surface structures on a microscale patterned nickel surface.
  • Fig. 12 shows the chemical structure of a crosslinkable tertiary amine salt used for generating crosslinked zwitterionic films.
  • Fig. 13 shows the chemical structure of the first zwitterionic molecule investigated in this work.
  • Fig. 14 shows the chemical structure of the second zwitterionic molecule investigated in this work.
  • Fig. 15 shows the chemical structure of the third zwitterionic molecule investigated in this work.
  • Fig. 16 is a bar graph showing protein adhesion to surfaces coated with crosslinked zwitterionic copolymer.
  • Fig. 17 is another bar graph showing protein adhesion to surfaces coated with crosslinked zwitterionic copolymer.
  • Fig. 18 is an SEM image showing a surface after removal from one month storage in Florida estuarial waters.
  • Fig. 19 is an SEM image showing another surface after removal from one month storage in Florida estuarial waters.
  • Fig. 20 is a diagram showing one embodiment of a process for producing a biofouling resistant surface.
  • Fig. 21 is an SEM image of a crosslinked, nanoporous L-b-L generated film.
  • Fig. 22 is a diagram showing hydrophobic particles embedded in a surface coating to disrupt the ability of proteins/biofilm to form on the surface.
  • Fig. 23 is a photograph contrasting biofouling resistant surfaces with control surfaces after one month of field exposure.
  • Fig. 24 is a diagram showing components of a system to reduce biofouling on surfaces, containing micron sized features, nanoscale features, cationic surface charges, and active components that acts as a battery in seawater.
  • Fig. 25 is an SEM image showing self-assembled nanoscale structures that reduce protein adhesion on substrates.
  • Fig. 26 is a diagram showing an active polymer system that serves as a battery when exposed to sea water.
  • Fig. 27 is a diagram showing an electroactive polymer/battery system.
  • the invention relates to a three-tiered hierarchical system for preventing biofouling which consists of (1) microscale surface structures, (2) nanoscale surface structures and (3) chemical level architectural control over the thin film surfaces. Techniques are described for replicating the microscale surface structures over large areas, generating nanoscale surface structures on top of the microscale surface structures and generating water insoluble surface chemistries which are effective at reducing biofouling.
  • Microscale and nanoscale surface structures can be combined with chemical scale functionalities to provide systems that exhibit advanced functions beyond those that would be found if any of the components (microscale structure, nanoscale structure, chemical scale functionality) was implemented individually.
  • This idea is shown schematically in Figure 1 , which presents the idea in terms of a coating or panel applied on the surface of a boat.
  • the biofouling resistant surface includes microscale surface structures which are hierarchically coupled to a nanoscale surface structure which also has an added chemical functionality designed to reduce biofouling.
  • This development relating to a biofouling resistant surface focuses on three components: (1) generating microscale surface structures over a large surface area in engineering substrates (e.g. metal panels, polymer plaques and similar materials); (2) generating nanoscale surface structures on the same engineered substrates using methods such as self-assembly of diblock polymers; and (3) using chemical functionalities to reduce biofouling.
  • engineering substrates e.g. metal panels, polymer plaques and similar materials
  • Microscale surface structures are generated in engineering materials including polydimethylsiloxane (PDMS), polyurethane (PU) and nickel as follows.
  • Initial “Master” surface structures are generated using lithographic procedures.
  • a "tile” consisting of a 1" by 1" patterned area is fabricated in silicon consisting of smaller 0.5" by 0.5" areas that are patterned with structures having characteristic dimensions of 1, 2, 10 and 20 micrometers.
  • Optical micrographs of the original silicon wafer patterns are shown in Figure 2.
  • the patterned silicon wafer is then cut using a scribe or other cutter.
  • the silicon "Master” is replicated into a negative image in PDMS by casting the patterned surface with Accutrans transparent replicating silicone #78516 from Ultronics Inc.
  • microscale surface structures may also be useful for the prevention of biofouling, including hexagonally close packed cylinders with characteristic dimensions on the order of 1-250 micrometers.
  • the above-described overall process represents an example of "pattern multiplication" in which a small, patterned area is reproduced multiple times to generate a larger patterned area.
  • the overall pattern multiplication process, and images of the patterned articles from each step of the process, are shown in Figure 7.
  • diblock copolymers are employed to produce hierarchically ordered nanoscale domains on the microscale surface structures.
  • a 1.0 wt% solution of polystyrene and polymethyl methacrylate is prepared in toluene. This solution is spun cast onto a silicon wafer at 1400 rpm. The resulting film is approximately 47 mm thick. The films are then annealed in a vacuum oven for about three days at 180°C to induce a nanophase separation of the polystyrene and the polymethyl methacrylate domains.
  • the PMMA is then removed by treating in a UV oven for a total dose of 1.2 mJ/cm2 and rinsing with glacial acetic acid to remove the degraded methyl methacrylate domains.
  • An image of the resulting nanoscale surface structure is shown in Figure 8.
  • a topographically patterned nickel surface prepared using the replication methods described above, is coated with a floated nickel film.
  • a floated PS-b_PMMA film is created from a 0.75% solution of PS-b-PMMA in toluene followed via spin casting at 1600 rpm. Films prepared under these conditions on a silicon wafer have a thickness of 40 nm. After annealing at high temperature the films have the appearance shown in Figure 11. In this manner nanoscale surface structures can be hierarchically placed on microscale surface structures by generating ultrathin (e.g. about 40 nanometer) freestanding films, placing them on the patterned surface and annealing.
  • ultrathin e.g. about 40 nanometer
  • chemical surface coatings are provided that have an inherently antifouling surface chemistry in addition to the microscale and nanoscale surface structures described above.
  • Any suitable chemical surface coatings can be used.
  • zwitterionic molecules can be effective at preventing protein and whole organism fouling.
  • zwitterionic molecules are highly hydrophilic and have a tendency to dissolve rapidly in water.
  • many methods for immobilizing zwitterionic molecules at surfaces require advanced surface polymerization techniques that may not be applicable for large area surfaces.
  • the present development provides new methods for generating non-water soluble films of zwitterionic chemicals.
  • zwitterionic monomeric compounds and copolymerizing those compounds with a crosslinkable monomer, for example, a monomer containing a tertiary amine, such as dimethyl amino ethyl methacrylate (DMAEMA, Sigma- Aldrich Catalog Number 234907, chemical structure shown in Figure 12).
  • a crosslinkable monomer for example, a monomer containing a tertiary amine, such as dimethyl amino ethyl methacrylate (DMAEMA, Sigma- Aldrich Catalog Number 234907, chemical structure shown in Figure 12).
  • DMAEMA dimethyl amino ethyl methacrylate
  • a method for generating water insoluble, zwitterionic polymers is described briefly below.
  • a mixture of the zwitterionic molecule and dimethyl amino ethyl methacrylate is prepared and polymerized using atom transfer radical polymerization (ATRP) or polymerization techniques.
  • a method for generating copolymers of the zwitterionic moieties and the dimethyl amino ethyl methacrylate is to employ azobis- (2-methylpropionitrile) as an initiator in aqueous solutions at high temperature.
  • the polymers are purified by precipitation in methanol and are dissolved in various aqueous solutions.
  • Thin films of the polymers are prepared by spin-casting from aqueous solution onto glass slides.
  • the films are then crosslinked by placing them in 1-2 wt% solutions of a, a '-Dichloro-p-xylene contained in a short chain alkane for 24-72 hours. In this manner a thin crosslinked film is generated at the water/n-alkane interface, rendering the bulk film insoluble in future aqueous solutions.- The solubility of films is tested by allowing the films to sit overnight in an aqueous solution.
  • the above-described method may be referred to as a "grafting-to" method for generating crosslinked films of zwitterionic compounds that have been
  • a crosslinkable polymer such as poly dimethyl amino-ethyl methacrylate (PDMAEMA)
  • PDMAEMA poly dimethyl amino-ethyl methacrylate
  • the efficacy of the crosslinked zwitterionic films may be checked by two methods. First, the films are tested by placing them in the presence of a modified, fluorescent mussel foot protein and determining how much of the mussel foot protein adheres to the surface after a set incubation time. Control surfaces of Poly dimethyl siloxane (PDMS) and Poly dimethylamino-ethyl methacrylate (PDMAEMA) are also tested in this protocol.
  • PDMS Poly dimethyl siloxane
  • PDMAEMA Poly dimethylamino-ethyl methacrylate
  • Films from the protein fouling test are also sent to the Florida Materials Research Facility for testing in marine environments. Samples are placed in estuarial water for one month, removed from estuarial water, and photographs are taken to document the degree of biofouling. Images of two films are shown in Figure 18 and Figure 19. After one month of fouling the films resist algae fouling as evidenced by the algae that is present on the back, uncoated side of the slide.
  • a biofouling resistant surface can be produced use lithography or a similar technique to generate a microscale pattern on the surface. Techniques are described to generate the pattern over a larger surface area. Nanoscale surface structures are provided on the microscale structures, for example by using self-assembling polymers to generate nanoscale domains. Finally, a biofouling resistant surface chemistry is provided on the surface.
  • the biofouling resistant surface includes a structured surface having surface structures resistant to biofouling, and a plurality of polyelectrolyte layers deposited on the structured surface, the polyelectrolyte layers functioning as a coating that resists biofouling.
  • the biofouling resistant surface may be characterized as a surface structured, polyelectrolyte multilayer, sacrificial coating to prevent biofouling.
  • the coatings may be based on sacrificial layers of layer-by-layer assembled polyelectrolyte multilayers that have been deposited on a structured surface. The following aspects may be included in the implementation of the surface.
  • the biofouling resistant surface includes a structured surface having surface structures resistant to biofouling.
  • the surface structures are microscale in size.
  • the surface may have characteristic length scales on the order of 1-5 microns.
  • the depths of the structures may be from 500 nm to 5 microns.
  • the structured surface can be produced by any suitable method. For example, it can be generated by a self assembling material such as a diblock copolymer or a homopolymer blend.
  • the structured surface could also be a type disclosed in the above-mentioned patents, which are incorporated by reference herein.
  • the structured surface is functionalized chemically such that the outermost surface is hydrophobic (water contact angle greater than 90 degrees). Any suitable chemical providing such a surface can be used.
  • polyelectrolyte multilayers are deposited on the surface.
  • Methods for layer-by-layer polyelectrolyte deposition are well known.
  • Figure 20 is an illustration of layer-by-layer
  • polyelectrolyte deposition Figure 21 is an SEM image of the resulting film.
  • polymers that function as polyelectrolytes are known.
  • the polyelectrolyte layers are alternating layers of positively and negatively charged polymers.
  • the polyelectrolyte layers include nanoscale surface structures.
  • all of the individual layers or any of the layers may be crosslink by any suitable method, for example by the use of UV light.
  • polystyrene sulfonate may be used as the anion in the layer-by-layer assembly and can be crosslinked with high intensity UV light. The degree of crosslinking affects the performance of the sacrificial coating.
  • the polyelectrolyte layers include a crosslinked positively charged polymer on the outermost surface.
  • the biofouling resistant surface described above will provide (a) some surface topography that can reduce biofouling, and (b) multiple layers of a slowly dissolving polyelectrolyte.
  • a slowly dissolving polyelectrolyte can be used, for example, a quaternary ammonium salt such as a polyvinylpyrridine quaternary salts, copolymers of polyfluorvinylpyrridine with poly 2-vinylpyrridine, copolymers of polyfluorvinylpyrridine with polystyrene, copolymers of polydimethylamino ethylmethacrylate with polymethylmethacrylate, quad salts of polyethylene imine, and others.
  • the polyelectrolyte layers are ultra-thin coatings of positively and negatively charged polymers, sequentially, and the structure includes a positively charged polymer as the outermost layer which is crosslinked using U V light or another method.
  • the result can be a positively charged nanoscale surface structure coating that is made insoluble in water through the crosslinking.
  • the present invention relates to a biofouling resistant surface comprising a structured surface having microscale surface structures that are resistant to biofouling, and a biofouling resistant chemical functionality on the surface.
  • the biofouling resistant chemical functionality on the surface can be provided in any suitable manner, using any suitable materials and methods.
  • the biofouling resistant chemical functionality comprises a surface coating.
  • the surface coating comprises hydrophobic particles embedded in a carrier layer.
  • the surface coating comprises charged microparticles or nanoparticles embedded in a polymer carrier layer. The charged particles may be hydrophobic particles or may provide biofouling resistance by other means.
  • the particles are located on the outermost surface of the coating.
  • Figure 22 shows an example of a surface coating that includes a carrier layer and hydrophobic particles embedded in the outermost surface of the carrier layer. The hydrophobic groups disrupt the ability of proteins/biofilm to form on the surface.
  • Figure 23 shows a surface after one month of field exposure. The upper right quarter of the surface was treated with a polymer coating having hydrophobic particles embedded in the surface. It is seen that this part of the surface is relatively free from biofouling. In contrast, the bottom half of the surface was untreated and it is covered with biofouling (mussels and other biofouling organisms).
  • the charged particles comprise cationic particles.
  • Any suitable cationic particles can be used.
  • the cationic particles comprise metal particles.
  • Other cationic materials include quaternary ammonium salts, dimethyl amino ethylmethacrylate, allylamine hydride, polyvinylpyrridine, and polyvinylpyrridine quad salts.
  • Any suitable hydrophobic materials can be used for producing particles.
  • silicon-based materials and fluorocarbon-based materials are generally hydrophobic.
  • Some particular examples are polysiloxanes, tetrafluoroethylenes, fluorinated ethylene polymers, polystyrenes, polymethyl methacrylates, acrylics, and methacrylics.
  • the size of the particles can range from a few hundred nanometers to tens of microns.
  • the cationic particles comprise particles of fluorinated polymer having cationic groups at both ends. Any suitable types of fluorinated polymer and cationic groups can be used. In one example, as shown below, such particles can be produced by reaction of 3-(triethoxysilyl)propyl- isocyanate with hydrocarbon polyether polyols having fluorinated side chains, and then reaction with (3-aminopropyl)-trimethoxysilane.
  • a copolymer of a vinylpyrridine quad salt with a fluorinated methacrylate could be used.
  • the polymer carrier layer of the surface coating can be any suitable polymer or a mixture of different polymers.
  • the polymer carrier layer comprises a polysiloxane such as polydimethyl siloxane and/or a cationic derivative of polydimethyl siloxane.
  • the cationic particles are attached to the structured surface via chemical or physical attachment.
  • the structured surface is a metal substrate.
  • the surface coating comprises one or more polymers that resist biofouling without the inclusion of charged particles.
  • such polymers could be used in combination with charged particles.
  • the surface coating comprises one or more polycationic polymers such as poly(dimethylaminomethyl methacrylate), poly(allylamine hydrochloride), poly(vinyl pyridine), poly (vinyl pyrollidone), polydimethylsiloxane, or mixtures thereof.
  • the polycationic polymers are mixed with polyethylene glycol (PEG) functionalized methacrylates such as disclosed in Edwards et al, Angew. Chemie, Int. Ed. (2008).
  • the surface coating comprises one or more polycationic polymers that are attached to the structured surface via chemical or physical attachment.
  • the polymers can be grafted to the surface by a surface initiated polymerization method such as atom transfer radical polymerization (ATRP).
  • ATRP atom transfer radical polymerization
  • the structured surface is a metal substrate.
  • the biofouling resistant surface also includes a structured surface having microscale surface structures that are resistant to biofouling.
  • Any suitable type of structured surface can be used, including any suitable surface structures and made from any suitable material(s).
  • the microscale surface structures comprise a plurality of raised structures having a length within a range of from about 1 micrometer to about 250 micrometers.
  • the microscale surface structures comprise scales.
  • the structured surface is of a type disclosed in the above-mentioned patents assigned to the
  • the structured surface further has biofouling resistant nanoscale surface structures on the microscale surface structures.
  • the nanoscale surface structures may have dimensions on the order of 10 nanometers to 1 micron.
  • Such nanoscale surface structures can be produced by any suitable method using any suitable materials.
  • the nanoscale surface structures are created using self-assembly block copolymers or incompatible homopolymer blends.
  • microscale surface structures can be generated in engineering materials using the above-described "pattern multiplication" process in which a small, patterned area is reproduced multiple times to generate a larger patterned area.
  • the nanoscale surface structures can be generated on the microscale surface structures by any suitable method.
  • they can be generated by the above- described method employing diblock copolymers to produce hierarchically ordered nanoscale domains on the microscale surface structures.
  • the invention in another embodiment, relates to a biofouling resistant surface that comprises a structured surface having surface structures resistant to biofouling, and an active polymeric system on the structured surface that functions as a battery when exposed to seawater.
  • the battery function changes over time, and the changing battery function causes a changing structure of the polymeric system that resists biofouling.
  • the surface structures of the structured surface are microscale sized structures.
  • the active polymeric system is in
  • the biofouling resistant surface is provided as a three-tiered hierarchical system that combines multiple components to reduce biofouling of the surface.
  • the three components are (1) a hierarchical microscale and nanoscale surface structure, (2) patterned in an active polymeric system that serves as a battery when exposed to seawater, (3) which contains cationic surface charges.
  • Microscale or micron-sized surface structures enhance the resistance of a surface to biofouling. Coupling the micron-sized surface structures with nanoscale surface structures has been found to reduce the degree to which proteins remain attached to a substrate, and thereby to reduce biofouling.
  • the nanoscale surface structures are self-assembling polymer structures. A representative scanning electron micrograph of self-assembling polymers is shown in Figure 25. These self-assembling materials have the advantages of self assembly such as an ability to self-organize, and no need to manipulate materials at the nanoscale. Thus, by coupling these self-assembling nanoscale surface structures to larger, microscale surface structures, a system is created with biofouling resistance that exceeds the biofouling resistance of surfaces that contain only one or the other of the surface structures.
  • the biofouling resistant surface includes cationic charges on the surface of the polymeric system that resist biofouling. Such cationic charges are shown in Figure 24.
  • the cationic surface charges are detrimental to animal cellular membranes.
  • cationic surface particles can be used to enhance the hydrophobicity of the surface. These two effects are useful for reducing biofouling of the surface.
  • cationic surface charges are incorporated in the hierarchical surface structures described above.
  • the battery function of the active polymeric system can be provided by any suitable structures and materials.
  • the battery function is provided by a plurality of battery cells each including a first polymer functioning as an anode and a second polymer functioning as a cathode. These active battery components are shown in Figure 24, and Figure 26 shows an example of such a battery cell.
  • the battery cells also include a third polymer that is an electrolyte and absorbs seawater.
  • electrically conductive polymer systems self-assemble into battery-like cells that become active when exposed to seawater.
  • These battery cells can be formed into a coating that becomes electrically active when placed in seawater, as shown in Figure 27.
  • the coating When the coating is activated the positive (+) anode would attract anionic carboxylic acid groups on a flexible polymer chain and the cathode (-) would attract protonated amine groups that could also be tethered to the coating surface.
  • the active battery cells in the coating degrade and lose their power the carboxylic anions and protonated cations would no longer be influenced by the cell charges and would move away from the surface of the coating which should change the environment around which fouling organisms are attracted.
  • the battery cells degrade new cells would be exposed from within the bulk of the coating and the process can then be repeated.
  • the invention in another embodiment, relates to a biofouling resistant surface that comprises a structured surface having surface structures resistant to biofouling, and an electroactive polymer on the structured surface.
  • a battery is in contact with the electroactive polymer. The functioning of the battery changes over time. The changing battery function causes a changing structure of the electroactive polymer that resists biofouling.
  • the structured surface functions as a cathode of the battery.
  • the anode of the battery consists of aluminum and carbon or similar materials in contact with the electroactive polymer.
  • the electroactive polymer can be patterned in certain embodiments.
  • the surface structures of the structured surface are microscale sized structures.
  • the surface structure design may include one or more of the following components: (1) an electrode (cathode) located on the surface of a material exposed to a biofouling environment; (2) the cathode may be patterned with characteristic length scales on the order of lOOnm - 10 microns; (3) an electroactive polymer layer which contacts the cathode; the polymer layer may be patterned, for example by using a self-assembled polymer or phase separating polymer blend as an etching mask; and (4) an anode consisting of primarily aluminum and carbon in contact with the electroactive polymer.
  • the system in the example as outlined in (1) - (4) acts as a battery when submerged in salt water.
  • the battery performance degrades over time, and the electroactive polymer structure changes as the battery performance degrades.
  • the change in polymer surface structure can result in an enhanced resistance to biofouling of the surface. This is a biomimetic approach to reducing biofouling that relies on structured, electroactive polymers, that are contained between the anode and the cathode of a battery. If the anode or the cathode of the battery degrades over time, it is possible to slowly change the structure of the electroactive polymer over time. This slow change in surface structure may provide a dynamic surface structure that reduces the susceptibility of a surface to biofouling.
  • the biofouling resistant surface includes surface structures and electroactive polymer on top of the surface structures. By combining movement of that polymer with the characteristics of the surface structures, the surface can provide resistance to biofouling through the combination of motion of the polymer and structure of the underlying polymer.
  • patterns can be created by using self-assembling materials to create the surface structures.
  • the hierarchical microscale and nanoscale surface structure of the biofouling resistant surface can be produced by any suitable method.
  • microscale surface structures can be generated in engineering materials using the above-described "pattern multiplication" process in which a small, patterned area is reproduced multiple times to generate a larger patterned area.
  • the nanoscale surface structures can be generated on the microscale surface structures by the above-described method employing diblock copolymers to produce hierarchically ordered nanoscale domains on the microscale surface structures.

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Abstract

L'invention concerne une surface résistante aux salissures biologiques qui comprend une surface comportant des structures de surface à l'échelle microscopique, des structures de surface à l'échelle nanoscopique sur les structures de surface à l'échelle microscopique et une fonction chimique résistante aux salissures biologiques sur la surface. Dans un autre mode de réalisation, une surface résistante aux salissures biologiques comprend une surface structurée comportant des structures de surface à l'échelle microscopique qui sont résistantes aux salissures biologiques, et une fonction chimique résistante aux salissures biologiques sur la surface. Dans un autre mode de réalisation, une surface résistante aux salissures biologiques comprend une surface structurée comportant des structures de surface résistantes aux salissures biologiques, et un système polymère actif sur la surface structurée qui fonctionne comme une batterie lorsqu'il est exposé à l'eau de mer. La fonction de la batterie change avec le temps, et le changement de fonction de la batterie provoque un changement de structure du système polymère qui résiste aux salissures biologiques.
PCT/US2011/065134 2010-12-15 2011-12-15 Surface résistante aux salissures biologiques WO2012083011A1 (fr)

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US20130183262A1 (en) * 2011-10-27 2013-07-18 Kenneth J. Wynne Antimicrobial polymeric compositions
US10661496B2 (en) 2015-03-09 2020-05-26 Conopco, Inc. Process for surface modification of materials
CN113604145A (zh) * 2021-08-18 2021-11-05 厦门昕钢防腐工程科技有限公司 一种生物蛋白/纳米阻锈剂/聚氨酯复合涂料及制备方法
CN115028888A (zh) * 2022-05-12 2022-09-09 中国石油大学(华东) 一种基于激光诱导仿生织构化的水下柔性防污皮肤装置
CN115895322A (zh) * 2022-09-21 2023-04-04 浙江悦茂科技发展有限公司 抗污涂层及抗污自洁排水管道系统
US11766822B2 (en) 2019-08-20 2023-09-26 3M Innovative Properties Company Microstructured surface with increased microorganism removal when cleaned, articles and methods
US11965120B2 (en) 2018-04-05 2024-04-23 3M Innovative Properties Company Gel adhesive comprising crosslinked blend of polydiorganosiloxane and acrylic polymer

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US20130183262A1 (en) * 2011-10-27 2013-07-18 Kenneth J. Wynne Antimicrobial polymeric compositions
US10117436B2 (en) 2011-10-27 2018-11-06 Virginia Commonwealth University Antimicrobial polymeric compositions
US10661496B2 (en) 2015-03-09 2020-05-26 Conopco, Inc. Process for surface modification of materials
US11965120B2 (en) 2018-04-05 2024-04-23 3M Innovative Properties Company Gel adhesive comprising crosslinked blend of polydiorganosiloxane and acrylic polymer
US11766822B2 (en) 2019-08-20 2023-09-26 3M Innovative Properties Company Microstructured surface with increased microorganism removal when cleaned, articles and methods
CN113604145A (zh) * 2021-08-18 2021-11-05 厦门昕钢防腐工程科技有限公司 一种生物蛋白/纳米阻锈剂/聚氨酯复合涂料及制备方法
CN115028888A (zh) * 2022-05-12 2022-09-09 中国石油大学(华东) 一种基于激光诱导仿生织构化的水下柔性防污皮肤装置
CN115028888B (zh) * 2022-05-12 2022-12-13 中国石油大学(华东) 一种基于激光诱导仿生织构化的水下柔性防污皮肤装置
CN115895322A (zh) * 2022-09-21 2023-04-04 浙江悦茂科技发展有限公司 抗污涂层及抗污自洁排水管道系统

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