WO2015094917A1 - Film multicouche glaciophobe - Google Patents

Film multicouche glaciophobe Download PDF

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Publication number
WO2015094917A1
WO2015094917A1 PCT/US2014/069798 US2014069798W WO2015094917A1 WO 2015094917 A1 WO2015094917 A1 WO 2015094917A1 US 2014069798 W US2014069798 W US 2014069798W WO 2015094917 A1 WO2015094917 A1 WO 2015094917A1
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WO
WIPO (PCT)
Prior art keywords
multilayer film
film layer
film
layer
ice
Prior art date
Application number
PCT/US2014/069798
Other languages
English (en)
Inventor
Mark Andrew Harmer
Ken-Hsuan Liao
Robert Clayton Wheland
Original Assignee
E. I. Du Pont De Nemours And Company
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Publication date
Application filed by E. I. Du Pont De Nemours And Company filed Critical E. I. Du Pont De Nemours And Company
Publication of WO2015094917A1 publication Critical patent/WO2015094917A1/fr

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Classifications

    • 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
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36—After-treatment
    • C08J9/365—Coating
    • 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
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance
    • C09D5/1675—Polyorganosiloxane-containing compositions
    • 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
    • C09D5/1693—Antifouling paints; Underwater paints as part of a multilayer system
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2427/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes

Definitions

  • the present disclosure is directed toward a multilayer film and a substrate coated with the multilayer film that can be used for preventing icing in low temperature conditions.
  • the multilayer film includes a first layer and a second layer that is a relatively thin flexible layer able to flex with the first layer without forming permanent defects.
  • ice on substrates also called icing
  • the formation of ice can negatively affect many different types of structures including airplane wings, airplane bodies, wind turbine blades, wind turbines, power transmission lines, power transmission towers, oil rigs, marine structures, marine vessels, bridges, vehicles, buildings, radio antennas, cell phone towers, and solar panels.
  • the Federal Aviation Administration has set strict guidelines for dealing with ice accumulating of airplanes during the time the vehicle is on the ground and in-flight. Many wind turbines are designed to reduce power or shut of completely if too much ice accumulates on the spinning blades of the turbine.
  • a multilayer film comprising or consisting essentially of:
  • a first film layer comprising a polymer layer having a thickness greater than 0.9mm and a Shore A hardness of less than about 100, and a flex modulus in the range of from 1 kPa to 100 GPa;
  • the multilayer film has an ice adhesion of less than 1 .76 kg/cm 2 when a shear stress is applied to ice on a layer of the multilayer film according to the following test;
  • a layer of the multilayer film is applied to a horizontally situated aluminum plate
  • a shear stress is applied to the ice in a direction that is parallel to the applied layer of multilayer film.
  • the phrase "without separating from the first film layer”, means that the second film layer remains in contact with the first film layer after the multilayer film has been flexed two or more times without any area of the second film losing contact with the first film layer.
  • the phrase "without forming cracks” means that the multilayer film can be flexed two or more times without the formation of visible defects in the second film layer.
  • the multilayer film can be flexed five or more times without separating from the first layer and without forming visible defects in the second film layer.
  • the multilayer film can be flexed more than ten times without separating from the first layer and without forming visible defects in the second film layer.
  • the multilayer film of the disclosure is applied to the substrate.
  • a force sufficient to deform both the first and second film layers is then applied to the second film layer in a direction perpendicular to that of the film surface.
  • the force should be sufficient to cause a local deformation of the first and second film layers, but not deform the substrate.
  • Visible defects means changes in appearance to the second film layer that are visible to the naked eye or under magnification as high as 10 times.
  • the present disclosure relates to a multilayer film comprising or consisting essentially of A) a first layer comprising a polymer layer having a thickness of greater than 0.9 millimeters (mm), a Shore A hardness of less than 100 and a flex modulus, as determined by ASTM D790 or ISO 178, in the range of from 1 kPa to 100 GPa; and B) a second film layer applied to at least a portion of the first film layer, wherein the second film layer comprises or consists essentially of a polymer having a thickness less than 100 micrometers, a water contact angle higher than 60 degrees, and is sufficiently thin enough to be able to flex with the first film layer a) without separating from the first layer and b) without forming cracks.
  • the multilayer film when applied to a substrate, provides an ice adhesion value of less than 1 .76 kg/cm 2 (25 pounds/square inch (psi)) when a shear stress is applied to ice adhered to the multilayer film.
  • the value of the ice adhesion means the force applied to the ice that will separate the ice from the multilayer film.
  • the ice adhesion can be measured according to the following test;
  • the ice adhesion is less than 1 .41 kg/cm 2 (20 psi) or less than 1 .33 kg/cm 2 (19 psi) or less than 1 .26 kg/cm 2 (18 psi) or less than 1 .20 kg/cm 2 (17 psi) or less than 1 .12 kg/cm 2 (16 psi) or less than 1 .05 kg/cm 2 (15 psi), or less than 0.98 kg/cm 2 (14 psi) or less than 0.91 kg/cm 2 (13 psi) or less than 0.84 kg/cm 2 (12 psi) or less than 0.77 kg/cm 2 (1 1 psi) or less than 0.70 kg/cm 2 (10 psi) or less than 0.63 kg/cm 2 (9 psi) or less than 0.56 kg/cm 2 (8 psi) or less less than 0.77 kg/cm 2 (1 1 psi) or less than 0.70 kg/
  • the present disclosure also relates to a substrate wherein the multilayer film is applied to at least a portion of the substrate.
  • the substrate can include, for example, airplane wings, airplane bodies, wind turbine blades, wind turbines, power transmission lines, power transmission towers, oil rigs, marine structures, marine vessels, bridges, vehicles, buildings, radio antennas, cell phone towers, solar panel, glass, automobile coatings, and food containers.
  • the multilayer film can be applied to at least a portion of the substrate, for example, the leading edge of an airplane wing or the leading edge of a wind turbine blade.
  • the first film layer comprises a polymer having a thickness of greater than 0.9 mm and a Shore A hardness of less than about 100 and a flex modulus, as determined by ASTM D790 or ISO 178, in the range of from 1 kPa to 100 GPa.
  • the first film layer has a minimum thickness of 1 .0 mm, and in other embodiments, the minimum film thickness is 1 .5 mm.
  • the maximum thickness of the first film layer should not negatively impact the strength and durability of the multilayer film. It has been found that the force required to remove ice from the multilayer film can be dependent on the thickness of the first layer. If the first layer is too thin, then the second film layer is not able to be deformed and the force required to remove the ice increases. With an increasing thickness, the force required to remove the ice decreases until the thickness reaches a certain level at which point, increasing the thickness of the first film layer does not result in any further reduction in the force required to remove the accumulated ice.
  • the maximum film thickness of the first layer is about 10.0 mm. In other embodiments, the maximum film thickness of the first film layer is 5.0 mm, and in still further embodiments, is 3.5 mm.
  • the hardness of the first film layer is also important. In general, the softer the first film layer, the less force required to remove a layer of accumulated ice. In some
  • the Shore A hardness is less than 90. In other embodiments, the Shore A hardness of the first film layer is less than 85. In still further embodiments, the Shore A hardness is less than 80, or less than 75, or less than 70, or less than 65, or less than 60, or less than 55, or less than 50. It has generally been found that, with all other parameters being equal, the lower the Shore A hardness of the first film layer, the lower the force required to remove any accumulated ice from the multilayer film.
  • the flex modulus of the first film layer can be in the range of from 1 KPa to 10 GPa, and, in still further embodiments, the flex modulus can be in the range of from 1 kPa to 1 .4 GPa. In all cases, the flex modulus is determined by ASTM D790.
  • Suitable polymers for the first film layer can include either thermoplastic or thermoset elastomers, such as, for example, polyesters, polyurethanes, rubbers, such as, polybutadiene, styrene butadiene rubbers, polyisoprene, nitriles, ethylene propylene diene polymers, chlorosulfonated polyethylenes, ethylene-vinyl acetates, HYTREL thermoplastic polyester elastomers, polysiloxane elastomers, NEOPRENE ®
  • the first layer can comprise polysiloxane foam, polyurethane foam, a styrene foam or polyvinyl chloride foam.
  • the first film layer is a polysiloxane foam having a Shore A hardness of less than 10.
  • polysiloxane foam is available from MCS Industrial, as part number 31942014.
  • a second polysiloxane foam that is useful is available from MCS Industrial, as part number 31943863.
  • the second film layer is also a polymer layer and can be applied to at least a portion of the first film layer.
  • the second film layer has a thickness of less than 100 micrometers and a water contact angle of greater than 60 degrees.
  • the second film layer is applied to at least a portion of the first film layer in a sufficiently thin layer so that the second film layer is able to flex with the first film layer a) without separating from the first film layer and b) without forming visible defects in the second coating layer.
  • the thickness of the second film layer depends upon the flexibility of the polymer of the second film layer. The more flexible the polymer of the second film layer, the thicker that the second film layer can be made, up to the limit of about 100 micrometers. If the polymer of the second film layer is relatively less flexible, then the second film layer must be made thinner in order to be able to flex with the first film layer.
  • the second film layer is a continuous layer without any voids in the surface.
  • the polymer of the second film layer is a thermoplastic polymer or, in other embodiments, the polymer of the first film layer is a thermoset polymer.
  • the polymer of the second film layer is a fluoropolymer; a polysiloxane; a linear fluorosiloxane block copolymer; a graft fluorosiloxane copolymer; polyolefin, polystyrene, polyurethane, polyimide, polyvinyl chloride, polyvinyl fluoride or fluoropolymer elastomers, both available from E.I. du Pont de Nemours and Company, Wilmington, Delaware.
  • Suitable examples of films of the various polymers are known in the art and may be used provided that the polymer is able to form a durable film that has a contact angle of greater than 60 degrees. Certain polymers will be discussed in more detail below.
  • the polymer of the second film layer is a linear
  • fluorosiloxane block copolymer comprising or consisting essentially of one or more blocks of polysiloxane and one or more fluorine-containing blocks.
  • the fluorine- containing blocks can be produced by polymerizing a monomer mixture, wherein the monomer mixture comprises or consists essentially of one or more fluoroolefin monomers and one or more other comonomers.
  • the monomer mixture comprises or consists essentially of one or more fluoroolefin monomers and one or more comonomers of vinyl ester, alkyl vinyl ether and/or vinyl fluoroester.
  • Suitable fluoroolefin monomers include, for example, tetrafluoroethylene, hexafluoropropylene, vinylidene fluoride, perfluoroalkenes having in the range of from 4 to 12 carbon atoms, monochlorotrifluroethylene, trifluoroethylene, perfluoroalkyl vinyl ethers, vinyl
  • Suitable other monomers can include, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl caproate, vinyl laurate, alkyl vinyl ethers having an alkyl in the range of from 1 to 18 carbon atoms, such as, for example, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, lauryl vinyl ether or a cyclic alkyl group, such as, for example, cyclopentyl vinyl ether, cyclohexyl vinyl ether, adamantyl vinyl ether or bornyl vinyl ether.
  • Perfluoroalkyl vinyl ethers can include, for example, perfluoromethyl vinyl ether, perfluoroethyl vinyl ether and perfluoropropyl vinyl ether.
  • Vinyl fluoroesters can include, for example vinyl trifluoroacetate, vinyl
  • the one or more blocks of polysiloxane can be produced by initiating the polymerization of the monomer mixture with VPS-0501 and/or VPS-1001
  • the macroinitiators available from Wako Pure Chemical Industries, Ltd. Osaka, Japan.
  • the macroinitiators comprise a block of polysiloxane and upon initiation, provide a free radical source for the polymerization of the monomer mixture.
  • the polymer produced is a linear fluorosiloxane copolymer having both polysiloxane blocks and fluorine- containing blocks.
  • the polymer of the second film layer is a linear fluorosiloxane block copolymer wherein the fluoro-containing block polymerized from a monomer mixture comprising tetrafluoroethylene and vinyl acetate and using a polysiloxane macroinitiator.
  • Other methods for producing linear fluorosiloxane block copolymers are known and can be used.
  • the polymer of the second film layer is a graft
  • fluorosiloxane copolymer comprising or consisting essentially of a backbone
  • the graft arms of the fluorosiloxane graft copolymers can be introduced by the polymerization of a vinyl polysiloxane monomer, for example, vinyl
  • polydimethylsiloxane with any of the monomers mentioned above.
  • Other methods of producing graft poylsiloxane arms are known in the art and can be used.
  • fluorosiloxane copolymers whether they are linear block copolymers or graft copolymers can contain polysiloxane blocks having a number average molecular weight in the range of from 2,000 to 70,000 daltons. In other embodiments, the polysiloxane blocks can have a number average molecular weight in the range of from 3,000 to 65,000.
  • the polymer of the second film layer is a thermoplastic polymer free from or essentially free from monomers having the crosslinkable functional groups of hydroxyl, carboxyl, epoxy and/or isocyanate.
  • the phrase "essentially free from” means that the monomer mixture comprises less than 5 percent by weight of monomers having one of crosslinkable functional groups, based on the total weight of the monomer mixture. In other embodiments, the monomer mixture comprises less than 2 percent by weight of monomers having crosslinkable functional groups, and in still further embodiments, the monomer mixture comprises less than 1 percent by weight of monomers having a crosslinkable functional group. If these crosslinkable groups are present, the films are free from any corresponding crosslinking groups that are reactive with the crosslinkable groups.
  • the polymer of the second film layer can be a
  • fluoropolymer Suitable fluoropolymers are known in the art and may be used provided that the polymers are capable of forming thin film and have a water contact angle of greater than 60 degrees. Fluoropolymers are known in the art and can be produced by the polymerization of various fluorine-containing monomers, for example, tetrafluoroethylene, hexafluoropropylene, vinyl idene fluoride, perfluoroalkenes having in the range of from 4 to 12 carbon atoms, monochlorotrifluroethylene, trifluoroethylene, perfluoroalkyl vinyl ethers, vinyl fluoroesters or a combination thereof.
  • fluorine-containing monomers for example, tetrafluoroethylene, hexafluoropropylene, vinyl idene fluoride, perfluoroalkenes having in the range of from 4 to 12 carbon atoms, monochlorotrifluroethylene, trifluoroethylene, perfluor
  • the polymer of the second film layer can be a
  • polysiloxane Suitable polysiloxanes can be a polysiloxane elastomer. In some embodiments, the polysiloxane is a homopolymer or a copolymer of polydialkylsiloxane. In other embodiments, the polysiloxane is a homopolymer or a copolymer of
  • polysiloxane may include fluoro containing repeat units.
  • the polysiloxane can be a thermoplastic or a thermoset polymer.
  • the multilayer film can optionally have an adhesive layer between the first film layer and the second film layer, provided that the adhesive layer does not impact any of the parameters that are required by the second film layer, that is, the ability to flex with the first film layer without separating from the first film layer and without forming cracks. It is not intended to have any other layer between the first and second film layers except for the optional adhesive layer. Any additional layer between the first and second layer that would impact the ability of the second film layer to flex with the first film layer without separating from the first film layer and without forming cracks would not be desirable to include in the multilayer film.
  • the multilayer film can also optionally have an adhesive layer on at least a portion of the first film layer that is opposite the second film layer.
  • This optional adhesive layer can help to provide adhesion of the multilayer film to the substrate.
  • Any of the known adhesive agents can be used as the optional adhesive layers.
  • the optional adhesive layer between the substrate and the first film layer can be the same adhesive agent as is used in the layer interposed between the first film layer and the second film layer.
  • the optional adhesive agents can be different.
  • Suitable adhesive agents can include waterborne, solventborne, hot- melt or pressure sensitive adhesives, for example, epoxy adhesives, urethane adhesives, methacrylate adhesives, cyanoacrylate adhesives, polyvinyl acetate adhesives or a combination thereof.
  • Each adhesive should be tested for compatibility with the layers that it comes in contact with.
  • the adhesive agent should not compromise the multilayer film strength or durability.
  • any of the known double sided tapes can be used to adhere the multilayer film to the substrate.
  • the multilayer film can be produced in a number of ways. In some
  • the multilayer film can be produced prior to application to the substrate.
  • the first film layer can optionally be coated on one or both sides by one or more adhesive agents.
  • the second layer can then be applied onto at least a portion of the first film layer.
  • a release sheet can be applied to the adhesive layer opposite the second film layer.
  • the optional release sheet can be any of the conventional release sheet or films including those prepared by coating or impregnating a paper sheet or film with a releasant such as silicone, wax or fluorine resin; and films of synthetic resin having themselves releasability, such as polyethylene or polypropylene.
  • a release sheet allows the multilayer film to be produced at one location for use at a later time and place.
  • the multilayer film comprising the optional release sheet can be cut to the desired size, the release sheet can be removed and the multilayer film adhered to the substrate that is free from ice.
  • each layer, including the optional adhesive layer(s), of the multilayer substrate can be applied individually to the substrate.
  • an optional layer of adhesive agent can be applied to the substrate followed by the application of the first film layer to at least a portion of the applied adhesive layer.
  • a layer of adhesive agent can then be applied to at least a portion of the first film layer.
  • the second film layer can then be applied to at least a portion of the first film layer with or without the optional adhesive layer.
  • the first and/or the second film layers can be extruded or coextruded.
  • the second film layer can be deposited onto the first film layer from solution. Methods of solution deposition are known and can be used, for example, the second film layer can be spray-applied, rolled, dipped, brushed, flow-coated, curtain -coated, spin-coated, knife-coated or coated using a draw down bar.
  • the disclosure is also related to an article comprising the multilayer film.
  • the article can be any substrate that can be prone to ice accumulation, for example, airplane wings, airplane bodies, wind turbine blades, wind turbines, power transmission lines, power transmission towers, oil rigs, marine structures, marine vessels, bridges, vehicles, buildings, radio antennas, cell phone towers, solar panel, glass, automobile coatings, and food containers.
  • the multilayer film is not required to cover the entire substrate; it can cover at least a portion of the substrate.
  • the multilayer film can be applied to the substrate without any surface preparation of the substrate.
  • the surface of the substrate can be prepared by cleaning or otherwise creating a surface that provides an acceptable level of adhesion to the multilayer film.
  • the disclosure also relates to a method of preventing the accumulation of ice on the surface of a substrate comprising the steps of;
  • the method further can comprise the steps of:
  • the force can be applied to the ice, to the substrate, to the multilayer film or to a combination thereof. As long as the applied force provides energy greater than or equal to the ice adhesion value, the accumulated ice will release from the multilayer film and can be easily removed.
  • the force can be applied in any number of ways. For example, in the case of a wind turbine blade, the rotational energy applied during normal operation can be enough to remove any accumulated ice.
  • a rubber hammer or mallet striking the substrate surface in an area adjacent or relatively close to the multilayer film can provide the energy necessary to release the ice from the multilayer film.
  • VPS-0501 and VPS-1001 polydimethylsiloxane initiators and V-601 initiator are available from Wako Chemicals USA, Richmond, Virginia.
  • VAZO ® 88 initiator is available from E.I. du Pont de Nemours and Company, Wilmington, Delaware.
  • MCR-V21 , MCR-V31 and MCR-V41 monovinyl terminated polydimethylsiloxanes are available from Gelest, Inc. Morrisville, Pennsylvania.
  • 444DCB double-sided tape are available from 3MTM, St. Paul, Minnesota.
  • Silicone Foam is available from MCS Industrial, Melville New York as part
  • a Mark-10 Force Gauge M3-20, available from the Mark-10 Company, Copiague, New York was attached to a Harvard 33 syringe pump, available from Harvard Apparatus, Holliston, Massachusetts.
  • the loading shaft of the force meter was placed a short distance away from the cuvette and the syringe pump was turned on to run at a flow rate of 20 ml/min.
  • the maximum force was recorded from the time that the loading shaft contacted the cuvette until the ice separated from the multilayer film. This procedure to measure the force was repeated up to 9 times per multilayer film.
  • the data presented represents the average force of all the repetitions.
  • the polymer had an inherent viscosity in acetone at 25°C of 0.444 dL/gram.
  • a 13 C NMR run in acetone-d6 found the tetrafluoroethylene, vinyl acetate, and [OSi(CH 3 ) 2 ] units to be present in a molar ratio of 45/49/6 where it should be noted that the [OSi(CH 3 ) 2 units were incorporated as part of in-chain polydimethylsiloxane blocks having an average molecular weight of -5,000.
  • the reaction mixture, a viscous fluid with lumps of gel was transferred to a Teflon®-lined tray after which the reaction mixture was purged with nitrogen for ⁇ 3 days and then dried for 21 hours in an 80°C vacuum oven provided with a slow nitrogen bleed.
  • the contents of the autoclave were agitated as the reactants were heated reaching a maximum pressure of 435 psig at 91 °C and finishing 10 hours later at 96°C and 289 psig.
  • the reaction mixture a damp mass, was transferred to a Teflon® lined tray after which the reaction mixture was heated for 42 hours in a 78°C vacuum oven with a nitrogen bleed. This gave 60 g of stiff, white polymer.
  • reaction mixture a bubbly mass
  • Teflon®-lined tray where it was allowed to partially air dry after which it was heated for 48 hours in ⁇ 105°C vacuum oven with a nitrogen bleed. This gave 44 g of stiff, white polymer.
  • a -60 ml sample of vinyl acetate was run through 10 ml of Aldrich grade 12, 28- 200 mesh chromatographic silica gel in a column.
  • a 46 ml sample of vinyl acetate off the silica column was added to a flask containing 3 g of VPS-0501 initiator dissolved in 100 ml of ethyl acetate.
  • the contents of the flask were refluxed for 1 .75 hours.
  • the flask was cooled, another 100 ml of ethyl acetate was added, and refluxing under nitrogen resumed for another 2.67 hours. This afforded a viscous reaction mixture that weighed 167 g.
  • reaction mixture (about 80 g) was evaporated to gum on a rotary evaporator, the gum transferred to a Teflon®-lined tray, purged overnight in the tray with nitrogen, and then dried in a 75°C vacuum oven overnight with a nitrogen bleed. This gave 15 g of plastic.
  • a -60 ml sample of vinyl acetate was run through 10 ml of Aldrich grade 12, 28- 200 mesh chromatographic silica gel in a column.
  • a 46 ml sample of vinyl acetate off the silica column was added to a flask containing 5 ml of Gelest MCR -V21 monovinyl terminated polydimethylsilxoane and 0.1 of V-601 initiator dissolved in 100 ml of ethyl acetate.
  • the contents of the flask were refluxed for 4 hours at which point the magnetic stir bar became stuck to the bottom of the flask with precipitated polymer.
  • TFE-HFP copolymer fluoropolymer
  • This fluoropolymer is a TFE/HFP copolymer produced according to the methods given in US Patent 5,637,663.
  • Polymer 12 is soluble in perfluorinated solvents such as, FLUORINERT ® FC-75 or FLUORINERT ® FC-40 and the solutions are coatable on substrates yielding thin films.
  • Comparative Polymer 13 is CALIBRETM PC 201 -15 polycarbonate and is available from StyronTMLLC, Berwin, Pennsylvania.
  • Each of polymers 1 -13 were dissolved in an appropriate solvent to a final concentration of about 10% by weight. Several drops of the polymer solution were applied and uniformly distributed along the testing area of the first film layer with a draw down bar over the course of several passes. The solvent was evaporated in a vacuum oven at an appropriate temperature (ranging from 90°C to 150°C) until the solvent had been removed, about 1 to 2 hours. Each of the polymers 1 -13 were applied to the HYTREL ® 3078 elastomer film to provide a second film thickness in the range of from 10 to 50 micrometers. The polycarbonate layer was 10 micrometers.
  • polydimethylsiloxane blocks without the fluoro containing monomers (multilayer films 10 and 1 1 ) and second film layers that are composed of fluorine-containing monomers without polysiloxane blocks (multilayer film 12).
  • multilayer film #14 was prepared according to the preparation method for films 1 -13 using polymer #8 as the second film layer in a thickness of 10 to 20
  • multilayer film #15 was prepared according to the preparation method used for films 1 - 13 using polymer #8 as the second film layer at a thickness of 10-20 micrometers over a first film layer of NEOPRENE® WRT elastomer, available from E.I. du Pont de Nemours and Company, Wilmington, Delaware, and having a Shore A hardness of 55 and a thickness of 1 .82 mm. The results are shown in Table 2. TABLE 2
  • Polymer 8 was dissolved in chlorobenzotrifluoride at concentrations of 2.3 percent by weight and 7.0 percent by weight. The solutions were spin-coated onto a first film layer of NEOPRENE ® WRT elastomer to give multilayer films #16 and #17, respectively. A sample of polymer 8 was bar-coated onto NEOPRENE ® WRT elastomer to give multilayer film #18. Comparative mulitlayer film # 19 was produced by heat pressing at 70°C a sample of polymer 8 to form a film having a thickness of 900 ⁇ . The filnm was then solvent bonded to the NEOPRENE ® WRT elastomer.

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Abstract

La présente invention concerne un substrat sur lequel est collé un film multicouche présentant un très faible degré d'adhérence à la glace. Le film multicouche comprend une première couche qui est un polymère ayant une épaisseur supérieure à 0,9 mm et inférieure à 10 mm, une dureté Shore A inférieure à environ 100 et un module de flexion dans la plage de 1 kPa à 100 GPa. La deuxième couche de film du film multicouche est un polymère qui a une épaisseur inférieure à 100 micromètres, un angle de contact avec l'eau supérieur à 60 degrés et peut fléchir avec la première couche de film sans s'en séparer ou sans former de fissures. La glace adhérant à la deuxième couche de film peut être retirée par l'application d'un minimum de force sur la glace, sur le substrat ou sur le film multicouche.
PCT/US2014/069798 2013-12-17 2014-12-11 Film multicouche glaciophobe WO2015094917A1 (fr)

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CN108374769A (zh) * 2017-02-01 2018-08-07 歌美飒创新技术公司 相变材料在风力发电机中延迟结冰或引起除冰的应用
CN109190815A (zh) * 2018-08-22 2019-01-11 四川大学 输电线路在线防冰融冰超短期精准预测方法
US10273253B1 (en) 2017-10-10 2019-04-30 Ppg Industries Ohio, Inc. Method for producing an ionic liquid
US11312869B2 (en) 2019-07-18 2022-04-26 Integran Technologies Inc. Articles comprising durable water repellent, icephobic and/or biocidal coatings
US11319450B2 (en) 2019-07-18 2022-05-03 Integran Technologies Inc. Articles comprising durable icephobic coatings
US11713137B2 (en) 2019-10-25 2023-08-01 Goodrich Corporation Extruded elastomeric surface or erosion plys

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US5637663A (en) 1995-02-06 1997-06-10 E. I. Du Pont De Nemours And Company Amorphous tetrafluoroethylene-hexafluoropropylene copolymers
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US5637663A (en) 1995-02-06 1997-06-10 E. I. Du Pont De Nemours And Company Amorphous tetrafluoroethylene-hexafluoropropylene copolymers
WO2004106057A1 (fr) * 2003-05-27 2004-12-09 Exxonmobil Chemical Patents Inc. Couches de support et substrats pour articles façonnes a partir de stratifies d'ionomere
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Publication number Priority date Publication date Assignee Title
CN108374769A (zh) * 2017-02-01 2018-08-07 歌美飒创新技术公司 相变材料在风力发电机中延迟结冰或引起除冰的应用
EP3358180A1 (fr) * 2017-02-01 2018-08-08 Siemens Gamesa Renewable Engery Innovation & Technology, S.L. Utilisation de matériels de changement de phase pour retarder le glaçage ou causer le dégivrage dans des éoliennes
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US10851122B2 (en) 2017-10-10 2020-12-01 Ppg Industries Ohio, Inc. Method for producing an ionic liquid
CN109190815A (zh) * 2018-08-22 2019-01-11 四川大学 输电线路在线防冰融冰超短期精准预测方法
CN109190815B (zh) * 2018-08-22 2021-11-23 四川大学 输电线路在线防冰融冰超短期精准预测方法
US11312869B2 (en) 2019-07-18 2022-04-26 Integran Technologies Inc. Articles comprising durable water repellent, icephobic and/or biocidal coatings
US11319450B2 (en) 2019-07-18 2022-05-03 Integran Technologies Inc. Articles comprising durable icephobic coatings
US11661518B2 (en) 2019-07-18 2023-05-30 Integran Technologies Inc. Anisotropic icephobic coating
US11667798B2 (en) 2019-07-18 2023-06-06 Integran Technologies Inc. Anisotropic icephobic and biocidal coatings
US11713137B2 (en) 2019-10-25 2023-08-01 Goodrich Corporation Extruded elastomeric surface or erosion plys

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