WO2024086390A2 - Surfaces polymères glissantes régulables - Google Patents

Surfaces polymères glissantes régulables Download PDF

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Publication number
WO2024086390A2
WO2024086390A2 PCT/US2023/069637 US2023069637W WO2024086390A2 WO 2024086390 A2 WO2024086390 A2 WO 2024086390A2 US 2023069637 W US2023069637 W US 2023069637W WO 2024086390 A2 WO2024086390 A2 WO 2024086390A2
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WIPO (PCT)
Prior art keywords
polymer
lubricating liquid
substrate
polymer layer
article according
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PCT/US2023/069637
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English (en)
Inventor
Stefan KOLLE
Amos Meeks
Jack Alvarenga
Joanna Aizenberg
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President And Fellows Of Harvard College
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Publication of WO2024086390A2 publication Critical patent/WO2024086390A2/fr

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    • 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

Definitions

  • the instant application relates to slippery polymer surfaces.
  • the instant application relates to controllable slippery polymer surfaces.
  • Polymer materials with oils dispersed within the bulk of the polymer can be used as repellant or fouling-release coatings.
  • One challenge in the production of slippery surfaces has been to prepare them over large surfaces in a quick and efficient process.
  • An additional challenge has been to identify surface coatings that can remain slippery for long periods of time, particularly when exposed to dynamic flow conditions.
  • a further desirable attribute is the ability to apply slippery coatings readily and securely to a range of underlying surfaces.
  • an article in one aspect, includes a polymer layer under an external force causing the polymer layer to be under a first compressive mechanical stress; and a lubricating liquid within the polymer layer, the lubricating liquid being at a concentration within the polymer layer such that the lubricating liquid forms a stable overlayer over the surface of the polymer layer when the polymer layer is under the external force and the lubricating liquid does not form the stable overlayer over the surface of the polymer layer when the polymer layer is not under compressive stress.
  • the polymer layer is formed by adding the lubricating liquid to one or more polymer precursors followed by curing the polymer precursors.
  • the article further includes a substrate under tension, the polymer layer is disposed on the substrate, and the external force on the polymer layer is applied by the tension of the substrate.
  • the polymer layer is formed by adding the lubricating liquid to one or more polymer precursors and applying the lubricating liquid and one or more polymers to the substrate, followed by curing the polymer precursors.
  • the substrate is under an external tension caused by an external tensile force during curing of the polymer layer, the external tension being greater than the tension.
  • releasing the external tensile force causes the substrate to change from the external tension to the tension.
  • the external tensile force is caused by stretching the substrate in at least one direction.
  • the external tensile force is caused by compressing the substrate in at least one direction.
  • the external tensile force is caused by stretching the substrate in two directions.
  • the external tensile force is caused by compressing the substrate in at least two directions.
  • the external tensile force is caused by radially expanding the substrate. [0017] In some embodiments, the external tensile force is caused by radially compressing the substrate.
  • the external tensile force is caused by a stimulus applied to the substrate.
  • the stimulus is selected from one or more of light, chemical, electromagnetic, thermal, shape memory, pressure, or mechanical stimulus.
  • the external force applied by the substrate is a radial force.
  • the external force applied by the substrate includes a component in the direction substantially parallel to a surface of the substrate on which the polymer layer is disposed.
  • the external force applied by the substrate includes a component in the direction substantially perpendicular to a surface of the substrate on which the polymer layer is disposed.
  • the substrate includes a stretchable material.
  • the substrate includes an elastomer.
  • the substrate includes one or more of silicone rubber, polyurethane, polyisoprene, polyethylene, polybutadiene, nitrile rubber, ethylene propylene rubber (EPM, EPDM), neoprene rubber, and fluoroelastomers.
  • silicone rubber polyurethane, polyisoprene, polyethylene, polybutadiene, nitrile rubber, ethylene propylene rubber (EPM, EPDM), neoprene rubber, and fluoroelastomers.
  • the external force includes a component in a direction parallel with the surface of the polymer layer on which the stable liquid overlayer is formed.
  • the external force includes a compressive external force and the first compressive mechanical stress includes a component in a direction parallel to the external force.
  • the external force is a stretching external force and the first compressive mechanical stress includes a component in a direction perpendicular to the external force.
  • the external force is a compressive mechanical force and the polymer is under a tensile mechanical stress including a component in a direction perpendicular to the external force.
  • the external force is caused by stretching the polymer layer.
  • the external force is caused by inflation.
  • the inflation is pneumatic inflation.
  • the external force is caused by flow induced pressure.
  • the first compressive mechanical stress is uniaxial.
  • the first compressive mechanical stress is biaxial.
  • the first compressive mechanical stress is radial.
  • the external force is caused by applying a stimulus to the polymer layer.
  • the stimulus is selected from one or more of light, chemical, electromagnetic, thermal, shape memory, pressure, or mechanical stimulus.
  • the polymer includes a shape memory alloy, and the first compressive mechanical stress is caused by a shape change of the shape memory alloy.
  • the lubricating liquid includes one or more of silicone oils, siloxanes, silicate esters, mineral oils, hydrocarbons, halogenated hydrocarbons liquid, polyalphaolefins, perfluorocarbons, polyfluoroalkyl ethers, polyolefins, esters with long alkyl chains, polyalkylene glycols, or polyphenyl ethers, perfluorinated liquids, and partially fluorinated liquids.
  • the lubricating liquid includes one or more of alkanes, olefins, saturated alkanes, and unsaturated olefins.
  • the lubricating liquid includes one or more of halogenated alkanes, halogenated olefins, and halogenated aromatic compounds.
  • the lubricating liquid includes one or more of fluorocarbons, perfluorocarbons, hydrofluorocarbons, hydrofluorocarbon-oligomers, compounds having partially fluorinated ponytails, partially fluorinated oils, partially fluorinated greases, fluorosilicones, tertiary perfluoroalkylamines (such as perfluorotri-n- pentylamine, FC-70, perfluorotri-n-butylamine FC-40, etc.
  • fluorocarbons such as perfluorotri-n- pentylamine, FC-70, perfluorotri-n-butylamine FC-40, etc.
  • perfluoroalkylsulfides and perfluoroalkylsulfoxides perfluoroalkylethers, perfluorocycloethers (like FC-77) and perfluoropolyethers (such as KRYTOX family of lubricants by DuPont), perfluoroalkylphosphines and perfluoroalkylphosphineoxides, perfluorohexyl-octane, perfluorohexyl-ethane, perfluorobutyl-butane, perflurophenanthren, perfluorooctane, perfluorophenathrene, and their analogues, homologues, oligomers, polymers.
  • the polymer layer includes one or more of silicone rubber, fluorosilicone, polydimethylsiloxane, vinyl methyl silicone, polyurethane, natural and synthetic polyisoprenes, polyethylene, polybutadiene, nitrile rubber, polyacrylic rubber, ethylene propylene rubber (EPM, EPDM), neoprene rubber, perfluoroelastomers, polyether block amides (PEBA), chlorosulfonated polyethylene, ethylene-vinyl acetate, polyether urethane, perfluorocarbon rubber, fluorinated hydrocarbon.
  • silicone rubber fluorosilicone
  • polydimethylsiloxane vinyl methyl silicone
  • polyurethane natural and synthetic polyisoprenes
  • polyethylene polybutadiene
  • nitrile rubber polyacrylic rubber
  • EPM ethylene propylene rubber
  • neoprene rubber perfluoroelastomers
  • PEBA polyether block amides
  • the polymer includes carbon black, titanium oxide, silica, alumina, nanoparticles, or a combination thereof.
  • the polymer layer includes a porous polymer layer.
  • an article in one aspect, includes a substrate under tension; a polymer layer on the substrate; and a lubricating liquid within the polymer layer, where the lubricating liquid is at a concentration within the polymer layer such that no stable overlayer is formed over a surface of the polymer layer, and the substrate is configured to cause a first compressive mechanical stress on the polymer layer when the tension is released, where the first compressive mechanical stress is sufficient to cause the lubricating liquid to form a stable overlayer on the polymer layer.
  • the substrate when the tension is released, the substrate is under a residual tension that is less than the tension.
  • the tension includes a component in a direction parallel with a surface of the substrate.
  • the first compressive mechanical stress includes a component in the direction parallel with a surface of the substrate.
  • the tension is caused by stretching the polymer layer.
  • the tension is caused by inflation.
  • the inflation is pneumatic inflation.
  • the tension is caused by flow induced pressure.
  • the first compressive mechanical stress is uniaxial.
  • the first compressive mechanical stress is biaxial.
  • the first compressive mechanical stress is radial.
  • the tension is caused by applying a stimulus to the substrate.
  • the stimulus is selected from one or more of light, chemical, electromagnetic, thermal, shape memory, pressure, or mechanical stimulus.
  • the substrate includes a shape memory alloy, and the first compressive mechanical stress is caused by a shape change of the shape memory alloy.
  • the polymer layer is formed by adding the lubricating liquid to one or more polymer precursors and applying the lubricating liquid and one or more polymers to the substrate, followed by curing the polymer precursors.
  • the substrate is under an external tension caused by an external tensile force during curing of the polymer layer, and the external tension is greater than the tension.
  • releasing the external tensile force causes the substrate to change from the external tension to the tension.
  • the external tension is the same as the tension.
  • the external tension is different than the tension.
  • the external tensile force is caused by stretching the substrate in at least one direction.
  • the external tensile force is caused by compressing the substrate in at least one direction.
  • the external tensile force is caused by stretching the substrate in two directions.
  • the external tensile force is caused by compressing the substrate in at least two directions.
  • the external tensile force is caused by radially expanding the substrate.
  • the external tensile force is caused by radially compressing the substrate.
  • the external tensile force is caused by a stimulus.
  • the stimulus is selected from one or more of light, chemical, electromagnetic, thermal, shape memory, pressure, or mechanical stimulus.
  • the lubricating liquid includes one or more of silicone oils, siloxanes, silicate esters, mineral oils, hydrocarbons, halogenated hydrocarbons liquid, polyalphaolefins, perfluorocarbons, polyfluoroalkyl ethers, polyolefins, esters with long alkyl chains, polyalkylene glycols, or polyphenyl ethers, perfluorinated liquids, and partially fluorinated liquids.
  • the lubricating liquid includes one or more of alkanes, olefins, saturated alkanes, and unsaturated olefins. [0076] In some embodiments, the lubricating liquid includes one or more of halogenated alkanes, halogenated olefins, and halogenated aromatic compounds.
  • the lubricating liquid includes one or more of fluorocarbons, perfluorocarbons, hydrofluorocarbons, hydrofluorocarbon-oligomers, compounds having partially fluorinated ponytails, partially fluorinated oils, partially fluorinated greases, fluorosilicones, tertiary perfluoroalkylamines (such as perfluorotri-n- pentylamine, FC-70, perfluorotri-n-butylamine FC-40, etc.
  • fluorocarbons such as perfluorotri-n- pentylamine, FC-70, perfluorotri-n-butylamine FC-40, etc.
  • perfluoroalkylsulfides and perfluoroalkylsulfoxides perfluoroalkylethers, perfluorocycloethers (like FC-77) and perfluoropolyethers (such as KRYTOX family of lubricants by DuPont), perfluoroalkylphosphines and perfluoroalkylphosphineoxides, perfluorohexyl-octane, perfluorohexyl-ethane, perfluorobutyl-butane, perflurophenanthren, perfluorooctane, perfluorophenathrene, and their analogues, homologues, oligomers, polymers.
  • the polymer layer includes one or more of silicone rubber, fluorosilicone, polydimethylsiloxane, vinyl methyl silicone, polyurethane, natural and synthetic polyisoprenes, polyethylene, polybutadiene, nitrile rubber, polyacrylic rubber, ethylene propylene rubber (EPM, EPDM), neoprene rubber, perfluoroelastomers, polyether block amides (PEBA), chlorosulfonated polyethylene, ethylene-vinyl acetate, polyether urethane, perfluorocarbon rubber, fluorinated hydrocarbon.
  • silicone rubber fluorosilicone
  • polydimethylsiloxane vinyl methyl silicone
  • polyurethane natural and synthetic polyisoprenes
  • polyethylene polybutadiene
  • nitrile rubber polyacrylic rubber
  • EPM ethylene propylene rubber
  • neoprene rubber perfluoroelastomers
  • PEBA polyether block amides
  • the polymer includes carbon black, titanium oxide, silica, alumina, nanoparticles, or a combination thereof.
  • the polymer layer includes a porous polymer layer.
  • the substrate includes a stretchable material.
  • the substrate includes an elastomer.
  • the substrate includes one or more of silicone rubber, polyurethane, polyisoprene, polyethylene, polybutadiene, nitrile rubber, ethylene propylene rubber (EPM, EPDM), neoprene rubber, and fluoroelastomers.
  • silicone rubber polyurethane, polyisoprene, polyethylene, polybutadiene, nitrile rubber, ethylene propylene rubber (EPM, EPDM), neoprene rubber, and fluoroelastomers.
  • a method of making an article includes: adding a lubricating liquid to one or more polymer precursors; and curing the one or more polymer precursors to form a polymer layer dispersed with the lubricating liquid, wherein the lubricating liquid is added to the polymer precursors at a concentration such that, after forming the polymer layer the lubricating liquid does not form a stable overlayer on a surface of the polymer layer; and applying an external force to the polymer layer such that the polymer layer is under a first compressive mechanical stress sufficient to cause the lubricating liquid to form the stable overlayer on the surface of the polymer layer.
  • the external force includes a component in a direction parallel with the surface of the polymer layer on which the stable overlayer is formed.
  • the external force includes a compressive external force and the first compressive mechanical stress includes a component in a direction parallel to the external force.
  • the external force is a stretching external force and the first compressive mechanical stress includes a component in a direction perpendicular to the external force.
  • the external force is a compressive mechanical force and the polymer is under a tensile mechanical stress including a component in a direction perpendicular to the external force.
  • the external force is caused by stretching the polymer layer.
  • the external force is caused by inflation.
  • the inflation is pneumatic inflation.
  • the external force is caused by flow induced pressure.
  • the first compressive mechanical stress is uniaxial.
  • the first compressive mechanical stress is biaxial.
  • the first compressive mechanical stress is radial.
  • the external force is caused by applying a stimulus to the polymer layer.
  • the stimulus is selected from one or more of light, chemical, electromagnetic, thermal, shape memory, pressure, or mechanical stimulus.
  • the polymer includes a shape memory alloy, and the first compressive mechanical stress is caused by a shape change of the shape memory alloy.
  • the lubricating liquid includes one or more of silicone oils, siloxanes, silicate esters, mineral oils, hydrocarbons, halogenated hydrocarbons liquid, polyalphaolefins, perfluorocarbons, polyfluoroalkyl ethers, polyolefins, esters with long alkyl chains, polyalkylene glycols, or polyphenyl ethers, perfluorinated liquids, and partially fluorinated liquids.
  • the lubricating liquid includes one or more of alkanes, olefins, saturated alkanes, and unsaturated olefins.
  • the lubricating liquid includes one or more of halogenated alkanes, halogenated olefins, and halogenated aromatic compounds.
  • the lubricating liquid includes one or more of fluorocarbons, perfluorocarbons, hydrofluorocarbons, hydrofluorocarbon-oligomers, compounds having partially fluorinated ponytails, partially fluorinated oils, partially fluorinated greases, fluorosilicones, tertiary perfluoroalkylamines (such as perfluorotri-n- pentylamine, FC-70, perfluorotri-n-butylamine FC-40, etc.
  • fluorocarbons such as perfluorotri-n- pentylamine, FC-70, perfluorotri-n-butylamine FC-40, etc.
  • perfluoroalkylsulfides and perfluoroalkylsulfoxides perfluoroalkylethers, perfluorocycloethers (like FC-77) and perfluoropolyethers (such as KRYTOX family of lubricants by DuPont), perfluoroalkylphosphines and perfluoroalkylphosphineoxides, perfluorohexyl-octane, perfluorohexyl-ethane, perfluorobutyl-butane, perflurophenanthren, perfluorooctane, perfluorophenathrene, and their analogues, homologues, oligomers, polymers.
  • the polymer layer includes one or more of silicone rubber, fluorosilicone, polydimethylsiloxane, vinyl methyl silicone, polyurethane, natural and synthetic polyisoprenes, polyethylene, polybutadiene, nitrile rubber, polyacrylic rubber, ethylene propylene rubber (EPM, EPDM), neoprene rubber, perfluoroelastomers, polyether block amides (PEBA), chlorosulfonated polyethylene, ethylene-vinyl acetate, polyether urethane, perfluorocarbon rubber, fluorinated hydrocarbon.
  • silicone rubber fluorosilicone
  • polydimethylsiloxane vinyl methyl silicone
  • polyurethane natural and synthetic polyisoprenes
  • polyethylene polybutadiene
  • nitrile rubber polyacrylic rubber
  • EPM ethylene propylene rubber
  • neoprene rubber perfluoroelastomers
  • PEBA polyether block amides
  • the polymer includes carbon black, titanium oxide, silica, alumina, nanoparticles, or a combination thereof.
  • the polymer layer includes a porous polymer layer.
  • a method of making an article includes providing a substrate under an external tension caused by an external force; and forming a polymer layer on the substrate under the external tension by: adding a lubricating liquid to one or more polymer precursors, and curing the one or more polymer precursors on the substrate under the external tension to form the polymer layer dispersed with the lubricating liquid on the substrate, wherein the lubricating liquid is added to the polymer precursors at a concentration such that, after forming the polymer layer: the lubricating liquid does not form a stable overlayer on a surface of the polymer layer while the substrate is under the external tension, and releasing the external force causes the polymer layer to be under a first compressive mechanical stress resulting from the residual tension of the substrate, and the first compressive mechanical stress is sufficient to cause the lubricating liquid to form a stable overlayer on a surface of the polymer layer.
  • the method further includes forming a stable overlayer of lubricating liquid on the surface of the polymer layer by releasing the external force on the substrate such that the polymer layer is caused to be under a first compressive mechanical stress resulting from a residual tension of the substrate, and the first compressive mechanical stress is sufficient to cause the lubricating liquid to form the stable overlayer on the surface of the polymer layer.
  • the residual tension that is less than the external tension is less than the external tension.
  • the method further includes applying a second external force to the substrate such that the stable overlayer is absorbed by the polymer layer.
  • the external tension includes a component in a direction parallel with a surface of the substrate.
  • the first compressive mechanical stress includes a component in the direction parallel with a surface of the substrate.
  • the first compressive mechanical stress is uniaxial.
  • the first compressive mechanical stress is biaxial.
  • the external tension is caused by stretching the substrate in at least one direction.
  • the external tension is caused by compressing the substrate in at least one direction.
  • the external tension is caused by stretching the substrate in two directions.
  • the external tension is caused by compressing the substrate in at least two directions.
  • the external tension is caused by radially expanding the substrate.
  • the external tension is caused by radially compressing the substrate.
  • the external tension is caused by a stimulus.
  • the stimulus is selected from one or more of light, chemical, electromagnetic, thermal, shape memory, pressure, or mechanical stimulus.
  • the lubricating liquid includes one or more of silicone oils, siloxanes, silicate esters, mineral oils, hydrocarbons, halogenated hydrocarbons liquid, polyalphaolefins, perfluorocarbons, polyfluoroalkyl ethers, polyolefins, esters with long alkyl chains, polyalkylene glycols, or polyphenyl ethers, perfluorinated liquids, and partially fluorinated liquids.
  • the lubricating liquid includes one or more of alkanes, olefins, saturated alkanes, and unsaturated olefins.
  • the lubricating liquid includes one or more of halogenated alkanes, halogenated olefins, and halogenated aromatic compounds.
  • the lubricating liquid includes one or more of fluorocarbons, perfluorocarbons, hydrofluorocarbons, hydrofluorocarbon-oligomers, compounds having partially fluorinated ponytails, partially fluorinated oils, partially fluorinated greases, fluorosilicones, tertiary perfluoroalkylamines (such as perfluorotri-n- pentylamine, FC-70, perfluorotri-n-butylamine FC-40, etc.
  • fluorocarbons such as perfluorotri-n- pentylamine, FC-70, perfluorotri-n-butylamine FC-40, etc.
  • perfluoroalkylsulfides and perfluoroalkylsulfoxides perfluoroalkylethers, perfluorocycloethers (like FC-77) and perfluoropolyethers (such as KRYTOX family of lubricants by DuPont), perfluoroalkylphosphines and perfluoroalkylphosphineoxides, perfluorohexyl-octane, perfluorohexyl-ethane, perfluorobutyl-butane, perflurophenanthren, perfluorooctane, perfluorophenathrene, and their analogues, homologues, oligomers, polymers.
  • the polymer layer includes one or more of silicone rubber, fluorosilicone, polydimethylsiloxane, vinyl methyl silicone, polyurethane, natural and synthetic polyisoprenes, polyethylene, polybutadiene, nitrile rubber, polyacrylic rubber, ethylene propylene rubber (EPM, EPDM), neoprene rubber, perfluoroelastomers, polyether block amides (PEBA), chlorosulfonated polyethylene, ethylene-vinyl acetate, polyether urethane, perfluorocarbon rubber, fluorinated hydrocarbon.
  • silicone rubber fluorosilicone
  • polydimethylsiloxane vinyl methyl silicone
  • polyurethane natural and synthetic polyisoprenes
  • polyethylene polybutadiene
  • nitrile rubber polyacrylic rubber
  • EPM ethylene propylene rubber
  • neoprene rubber perfluoroelastomers
  • PEBA polyether block amides
  • the polymer includes carbon black, titanium oxide, silica, alumina, nanoparticles, or a combination thereof.
  • the polymer layer includes a porous polymer layer.
  • a method includes: providing an article including a polymer layer and a lubricating liquid within the polymer layer at a concentration such that the lubricating liquid does not form a stable overlayer over a surface of the polymer layer when the polymer layer is not under compressive stress; and applying an external force to the polymer layer such that the polymer layer is under a first compressive mechanical stress sufficient to cause the lubricating liquid to form a stable overlayer on the surface of the polymer layer.
  • the article further includes a substrate under tension, and the polymer layer is disposed on the substrate and the external force on the polymer layer is applied by the tension of the substrate.
  • the external force is caused by stretching the substrate in at least one direction.
  • the external force is caused by compressing the substrate in at least one direction.
  • the external force is caused by stretching the substrate in two directions.
  • the external force is caused by compressing the substrate in at least two directions.
  • the external force is caused by radially expanding the substrate.
  • the external force is caused by radially compressing the substrate.
  • the external force is caused by a stimulus applied to the substrate.
  • the stimulus is selected from one or more of light, chemical, electromagnetic, thermal, shape memory, pressure, or mechanical stimulus.
  • the external force applied by the substrate is a radial force.
  • the external force applied by the substrate includes a component in the direction substantially parallel to a surface of the substrate on which the polymer layer is disposed.
  • the external force applied by the substrate includes a component in the direction substantially perpendicular to a surface of the substrate on which the polymer layer is disposed.
  • the substrate includes a stretchable material.
  • the substrate includes an elastomer.
  • the substrate includes one or more of silicone rubber, polyurethane, polyisoprene, polyethylene, polybutadiene, nitrile rubber, ethylene propylene rubber (EPM, EPDM), neoprene rubber, and fluoroelastomers.
  • the external force includes a component in a direction parallel with the surface of the polymer layer on which the stable liquid overlayer is formed.
  • the external force includes a compressive external force and the first compressive mechanical stress includes a component in a direction parallel to the external force.
  • the external force is a stretching external force and the first compressive mechanical stress includes a component in a direction perpendicular to the external force.
  • the external force is a compressive mechanical force and the polymer is under a tensile mechanical stress including a component in a direction perpendicular to the external force.
  • the external force is caused by stretching the polymer layer.
  • the external force is caused by inflation.
  • the inflation is pneumatic inflation.
  • the external force is caused by flow induced pressure.
  • the first compressive mechanical stress is uniaxial.
  • the first compressive mechanical stress is biaxial.
  • the first compressive mechanical stress is radial.
  • the external force is caused by applying a stimulus to the polymer layer.
  • the stimulus is selected from one or more of light, chemical, electromagnetic, thermal, shape memory, pressure, or mechanical stimulus.
  • the polymer includes a shape memory alloy, and the first compressive mechanical stress is caused by a shape change of the shape memory alloy.
  • the method further includes applying a second external force to the polymer such that the stable overlayer is absorbed by the polymer layer.
  • the second external force causes the polymer layer to be under a second compressive mechanical stress that is insufficient to cause the lubricating liquid to form a stable overlayer.
  • the second external force causes the polymer layer to be under tension. [0162] In some embodiments, the second external force causes the polymer layer to be under no stress.
  • the lubricating liquid includes one or more of silicone oils, siloxanes, silicate esters, mineral oils, hydrocarbons, halogenated hydrocarbons liquid, polyalphaolefins, perfluorocarbons, polyfluoroalkyl ethers, polyolefins, esters with long alkyl chains, polyalkylene glycols, or polyphenyl ethers, perfluorinated liquids, and partially fluorinated liquids.
  • the lubricating liquid includes one or more of alkanes, olefins, saturated alkanes, and unsaturated olefins.
  • the lubricating liquid includes one or more of halogenated alkanes, halogenated olefins, and halogenated aromatic compounds.
  • the lubricating liquid includes one or more of fluorocarbons, perfluorocarbons, hydrofluorocarbons, hydrofluorocarbon-oligomers, compounds having partially fluorinated ponytails, partially fluorinated oils, partially fluorinated greases, fluorosilicones, tertiary perfluoroalkylamines (such as perfluorotri-n- pentylamine, FC-70, perfluorotri-n-butylamine FC-40, etc.
  • fluorocarbons such as perfluorotri-n- pentylamine, FC-70, perfluorotri-n-butylamine FC-40, etc.
  • perfluoroalkylsulfides and perfluoroalkylsulfoxides perfluoroalkylethers, perfluorocycloethers (like FC-77) and perfluoropolyethers (such as KRYTOX family of lubricants by DuPont), perfluoroalkylphosphines and perfluoroalkylphosphineoxides, perfluorohexyl-octane, perfluorohexyl-ethane, perfluorobutyl-butane, perflurophenanthren, perfluorooctane, perfluorophenathrene, and their analogues, homologues, oligomers, polymers.
  • the polymer layer includes one or more of silicone rubber, fluorosilicone, polydimethylsiloxane, vinyl methyl silicone, polyurethane, natural and synthetic polyisoprenes, polyethylene, polybutadiene, nitrile rubber, polyacrylic rubber, ethylene propylene rubber (EPM, EPDM), neoprene rubber, perfluoroelastomers, polyether block amides (PEBA), chlorosulfonated polyethylene, ethylene-vinyl acetate, polyether urethane, perfluorocarbon rubber, fluorinated hydrocarbon.
  • silicone rubber fluorosilicone
  • polydimethylsiloxane vinyl methyl silicone
  • polyurethane natural and synthetic polyisoprenes
  • polyethylene polybutadiene
  • nitrile rubber polyacrylic rubber
  • EPM ethylene propylene rubber
  • neoprene rubber perfluoroelastomers
  • PEBA polyether block amides
  • the polymer includes carbon black, titanium oxide, silica, alumina, nanoparticles, or a combination thereof.
  • the polymer layer includes a porous polymer layer.
  • FIG. 1 A shows a schematic of the fabrication processes for a post-cure lubricating liquid infusion coating (i.e., i-polymer), according to certain embodiments.
  • FIG. IB shows a schematic of the fabrication processes for a pre-cure lubricating liquid addition (one-pot) coating (i.e., o-polymer), according to certain embodiments.
  • FIG. 2A shows a polymer layer incorporating lubricating liquid under no mechanical stress, according to certain embodiments.
  • FIG. 2B shows a polymer layer incorporating lubricating liquid under a compressive stress, according to certain embodiments.
  • FIG. 3 A shows a schematic of the structure of a polymer, according to certain embodiments.
  • FIG. 3B shows a schematic of the structure of a polymer formed by post-cure lubricating liquid infusion (i.e., i-polymer), according to certain embodiments.
  • FIG. 3C shows a schematic of the structure of a polymer formed by pre-cure addition of lubricating liquid (one-pot), according to certain embodiments.
  • FIG. 3D shows theoretical chemical potential of oil of i-PDMS and o-PDMS as a function of the swelling ratio, according to certain embodiments.
  • FIG. 3E shows the theoretical chemical potential of o-PDMS as a function of uniaxial or biaxial stretch relative to unswollen dimensions, according to certain embodiments.
  • FIGS. 4A-4D show a method of forming a lubricating liquid overlayer over a polymer layer using a substrate under tension, according to certain embodiments.
  • FIG. 5 A shows a graph of the shear modulus of i-PDMS (white bar) and o-PDMS (gray bar), according to certain embodiments.
  • FIG. 5B shows detection of a lubricating liquid overlayer on i-PDMS by atomic force microscopy (AFM), according to certain embodiments.
  • FIG. 5C shows detection of a lubricating liquid overlayer on o-PDMS by atomic force microscopy, according to certain embodiments.
  • FIG. 6A shows anti-adhesion performance of o-PDMS, i-PDMS, Intersleek 700 and a PDMS control coating against bacteria (Cellulophaga lytica), according to certain embodiments.
  • FIG. 6B shows anti-adhesion performance of o-PDMS, i-PDMS, Intersleek 700 and a PDMS control coating against microalgal diatoms (Navicula incerla). according to certain embodiments.
  • FIG. 6C shows anti-adhesion performance of o-PDMS, i-PDMS, Intersleek 700 and a PDMS control coating against mussels (Geukerisia demissa), according to certain embodiments.
  • FIG. 6D shows anti-adhesion performance of o-PDMS, i-PDMS, Intersleek 700 and a PDMS control coating against barnacles (Amphibalanus amphitrite), according to certain embodiments.
  • FIGS. 7A-7D show fouling coverage and composition on PDMS control (FIG.
  • FIG. 8 shows representative images of the treated panels showing the fouling trends observed on each coating (PDMS, IS700, o-PDMS and i-PDMS) over time, according to certain embodiments.
  • FIG. 9A shows mussel spat densities on PDMS, IS700, o-PDMS and i-PDMS treatments in week 8, according to certain embodiments.
  • FIG. 9B shows representative images on the mussel spat accumulation patterns on each treatment type (PDMS, IS700, o-PDMS and i-PDMS), according to certain embodiments.
  • FIGS. 10A-10D show fouling trends on PDMS (FIG. 10A), IS700 (FIG. 10B), o- PDMS (FIG. 10C), and i-PDMS (FIG. 10D) in Morro Bay over a 15-month immersion period from May 2015 to September 2016, according to certain embodiments.
  • FIGS. 11 A-l IB show encrusting bryozoan (FIG. 11 A) and barnacle (FIG. 1 IB) adhesion strength to PDMS, IS700, o-PDMS and i-PDMS in Morro Bay, according to certain embodiments.
  • FIG. 12 shows barnacle adhesion strength to PDMS, IS700, o-PDMS and i-PDMS at Port Canaveral after 4- and 7-months static immersion
  • FIGS. 13A-13D show fouling trends on PDMS (FIG. 13 A), IS700 (FIG. 13B), o- PDMS (FIG. 13C), and i-PDMS (FIG. 13D) in Singapore Harbor in a 24-month immersion period from June 2015 to May 2017, according to certain embodiments.
  • FIGS. 14A-14B show compression induction to induce lubricating overlayer formation in o-PDMS: o-PDMS samples in stress-free state (FIG. 14 A), and o-PDMS under 20% compressive strain (FIG. 14B), according to certain embodiments.
  • FIGS. 15A-15D show wetting behavior of compressed o-PDMS: initial water droplet (FIG. 15 A), droplet pulled along the o-PDMS once (FIG. 15B), and droplet pulled along surface a second time (FIG. 15C, FIG. 15D showing image using different lighting), according to certain embodiments.
  • FIGS. 16A-16C show wetting behavior of stress-free o-PDMS using water droplet interaction analysis: initial water droplet (FIG. 16A), droplet pulled along the o-PDMS once (FIG. 16B), and droplet pulled along surface a second time (FIG. 16C), according to certain embodiments.
  • FIGS. 17A-17D show wetting behavior of o-PDMS under 30% compressive strain over time: compressed o-PDMS after 5 days of continuous compression (FIG. 17A), control free-stress o-PDMS after 5 days (FIG. 17C), compressed o-PDMS after 10 days of continuous compression (FIG. 17B), and a control free-stress o-PDMS after 10 days (FIG. 17D), according to certain embodiments.
  • the materials disclosed herein form a lubricating liquid overlayer upon application of a stress.
  • formation of a stable overlayer provides non-fouling properties that can be maintained over time.
  • formation of a stable overlayer provides low-friction properties that can be maintained over time.
  • the formation of the lubricating liquid overlayer can be controlled or induced by application of stress to the polymer network.
  • slippery surfaces can be turned on or off by controlling formation of a lubricating liquid overlayer by application of stress.
  • an article including a polymer layer under an external force causing the polymer layer to be under a first compressive mechanical stress; and a lubricating liquid within the polymer layer, the lubricating liquid being at a concentration within the polymer layer such that the lubricating liquid forms a stable overlayer over the surface of the polymer layer when the polymer layer is under the external force and the lubricating liquid does not form the stable overlayer over the surface of the polymer layer when the polymer layer is not under compressive stress.
  • the materials disclosed herein can be formed by pre-cure addition of lubricating liquid to polymer precursors.
  • pre-cure addition lubricating liquid results in a stress-free polymer with lubricating liquid dispersed within the polymer matrix.
  • the lubricating liquid dispersed within the polymer does not form an overlayer in this stress-free state.
  • application of a stress or external force increases the chemical potential of the lubricating liquid dispersed within the polymer, causing formation of a lubricating liquid overlayer.
  • the lubricating liquid forms a stable layer over a surface of a polymer.
  • the chemical affinity of the polymer and lubricating liquid is such that the lubricating liquid stably wets and adheres to the polymer surface.
  • the lubricating liquid overlayer is stabilized over the polymer surface by van der Waals, capillary forces, or combination thereof.
  • the lubricating overlayer, or slippery surface, of the present disclosure is extremely smooth, which creates a defect-free surface that can reduce contact angle hysteresis and adhesion of external matter.
  • the lubricating overlayer exhibits anti-adhesive, drag reduction, and anti-fouling properties.
  • the slippery surfaces of the present disclosure can prevent adhesion of a wide range of materials. Exemplary materials that do not stick onto the surface include liquids, liquid mixtures, complex fluids, microorganisms, solids, and gases (or vapors).
  • liquids such as water, oil-based paints, hydrocarbons and their mixtures, organic solvents, complex fluids such as crude oil, liquids containing complex biological molecules (such as proteins, sugars, lipids, etc.) or biological cells and the like can be repelled.
  • lubricating liquids can be both pure liquids and complex fluids.
  • the polymers disclosed herein can be designed to be omniphobic, hydrophobic and/or oleophobic/hydrophilic.
  • biological materials such as biological molecules (e.g., proteins, polysaccharides, and the like), biological fluids (e.g., urine, blood, saliva, secretions, and the like), biological cells, tissues and entire organisms such as bacteria, protozoa, spores, algae, insects, small animals, viruses, fungi, and the like can be repelled by the lubricating layer.
  • biological molecules e.g., proteins, polysaccharides, and the like
  • biological fluids e.g., urine, blood, saliva, secretions, and the like
  • biological cells tissues and entire organisms
  • bacteria protozoa
  • spores e.g., algae, insects, small animals, viruses, fungi, and the like
  • solids like ice, frost, paper, sticky notes, glues or inorganic particle-containing paints, sand, dust particles, food items, common household contaminants, and the like can be repelled or easily cleaned from the lubricating layer.
  • the materials disclosed herein include a polymer (e.g., such as a rubber or elastomer) that includes a dispersed lubricating liquid having a chemical affinity for that polymer material.
  • the polymer is crosslinked.
  • the chemical affinity creates a solvent effect that causes the polymer to absorb an amount of the liquid.
  • the liquid absorbing effects noted herein are distinguished from capillary action of liquids in nano- and microporous media in that the interaction is on a molecular level.
  • the lubricating liquid interacts with the polymer due to intermolecular interactions such as solvation.
  • the enthalpy of mixing between the polymer and the lubricating liquid is sufficiently low so that they mix readily with each other when mixed together, and/or undergo energetically favorable chemical interactions between each other.
  • capillary effects are driven by the surface energy considerations at the interface of a solid and a liquid, resulting in wicking of the liquid into well-defined preexisting microscopic channels without swelling of the underlying solid.
  • dispersed lubricating liquid in the polymer can act as a reservoir for formation of a lubricating liquid overlayer at the surface of the polymer. Therefore, after formation of a lubricating liquid overlayer, such materials can maintain a lubricating liquid overlayer at the surface of the polymer.
  • the polymer is porous. In some embodiments, pores of the polymer can be used as reservoirs for the lubricating liquid.
  • the materials disclosed herein can provide self-replenishing, nonsticking, and controllable slippery behavior towards a broad range of fluids and solids, such as aqueous liquids, cells, bodily fluids, microorganisms and solid particles such as ice.
  • fluids and solids such as aqueous liquids, cells, bodily fluids, microorganisms and solid particles such as ice.
  • the coated articles can exhibit a slippery surface for extended time periods, without the need for replenishing the lubricating liquid.
  • FIGS. 1 A-1B shows two exemplary methods of forming a polymer that includes a lubricating liquid dispersed within the polymer.
  • Materials that include polymers and lubricating liquid dispersed within the polymer can be formed by infusing a cured polymer with lubricating liquid or by pre-cure addition of lubricating liquid to polymer precursors.
  • the method of forming a polymer with dispersed lubricating liquid results in materials with different properties, including different mechanical properties and differences in the ability to form and maintain a lubricating overlayer.
  • a lubricating liquid can be infused into the polymer post-cure to produce a polymer that is referred to herein as an “i-polymer.”
  • FIG. 1 A shows general steps of preparing an i-polymer.
  • the polymer is polydimethylsiloxane (PDMS) and the lubricating liquid is silicone oil.
  • PDMS polydimethylsiloxane
  • this method can be applied to any combination of polymer and lubricating liquid having a chemical affinity.
  • the i-polymer coating is prepared by curing the polymer, followed by infusing with a lubricating liquid in a simple post-cure infusion procedure.
  • an i-polymer coating is prepared employing following steps: curing the prepolymers or monomers of the polymer, and then immersing the cured polymer in a lubricating liquid bath and allowing the polymer and lubricating liquid to come to equilibrium.
  • this process can result in 45-50 wt% of silicone uptake within the cured PDMS polymer.
  • the i-polymer is porous.
  • the lubricating liquid infused within the i-polymer exerts a swelling force on the i-polymer network.
  • the lubricating liquid infused within the i-polymer expands or swells the i-polymer network, exerting a stress on the i-polymer network.
  • an i-polymer is prepared by infusing silicone oil into an elastomeric matrix.
  • a cross-linked i-polymer is capable of increasing its volume up to several folds by absorbing large amounts of infused lubricating liquid or oil.
  • a swollen polymer network is held together by molecular strands that are connected by chemical bonds (cross-links).
  • a cross-linked polymer is capable of increasing its volume several folds by absorbing large amounts of lubricating liquids.
  • the liquid absorbing effects noted herein are distinguished from capillary action of liquids in nano- and microporous media in that the interaction is on a molecular level.
  • a lubricating liquid is added before curing prepolymers or monomers of the polymer in a process referred to as “one-pot” approach to produce a polymer referred to as a “o-polymer.”
  • FIG. IB shows general steps of preparing an o-polymer.
  • the polymer is PDMS elastomer
  • the lubricating liquid is a silicone oil.
  • this method can be applied to any combination of polymer and lubricating liquid disclosed herein. As shown in FIG.
  • a polymer coating is prepared by employing the one-pot approach by adding a lubricating liquid to the uncured polymer (e.g., prepolymer or polymer precursors such as monomers) and then curing the mixture.
  • a lubricating liquid e.g., prepolymer or polymer precursors such as monomers
  • approximately 50 weight percentage (wt%) of a compatible silicone oil is added to the uncured PDMS to produce the o-PDMS.
  • one-pot approach includes adding a portion of miscible but unbound lubricating liquid to the precursor mixture containing prepolymers or monomers.
  • the lubricating liquid after curing, the lubricating liquid is chemically unbound to the polymer matrix.
  • the lubricating liquid within the o-polymer does not exert a stress on the o-polymer network.
  • the lubricating liquid within the o- polymer does not exert a swelling force on the o-polymer network.
  • the o-polymer is in a stress-free state after curing.
  • the lubricating liquid is dispersed within the o-polymer.
  • the one-pot approach can further improve longevity of slipperiness and anti-fouling function of the polymer surface.
  • the added unbound lubricating liquid molecules in the precursor mixture reside between the crosslinked polymer network providing additional lubricity and easy chain rotations. This results in faster swelling and increased swelling ratio than pure cross-linked polymer network without added lubricating liquid. This also allows for further intake of lubricating liquid molecules during swelling, potentially leading to increased longevity of slippery and non-fouling functions.
  • an i-polymer with an equilibrium concentration of lubricating liquid will form a lubricating liquid overlayer.
  • an o-polymer with the same concentration of lubricating liquid as an i-polymer at equilibrium will not form an overlayer of lubricating liquid, even though the i-polymer having the same concentration of lubricating liquid will form an overlayer of lubricating liquid.
  • FIGS. 2A-2B show an example of applying an external force to an o-polymer to form a lubricating liquid overlayer.
  • an o-polymer 200 includes a lubricating liquid 202 dispersed within a polymer matrix 201.
  • o-polymer 200 is free of any mechanical stress, as shown in FIG. 2A, no overlayer of lubricating liquid is formed.
  • the concentration of lubricating liquid 202 within the polymer matrix 201 is such that it does not allow formation of an overlayer of lubricating liquid when the o-polymer 200 is not under a compressive mechanical stress, even though the same concentration of lubricating liquid in an i-polymer would result in the formation of a lubricating liquid overlayer.
  • a lubricating liquid overlayer 203 can be formed when the o- polymer 200 is subject to a sufficient external force or experiences a sufficient mechanical stress.
  • o-polymer 200 is under an external force that causes the o-polymer 200 to have a compressive mechanical stress.
  • the concentration of lubricating liquid 202 within the polymer matrix 201 is such that lubricating liquid 202 forms a stable overlayer 203 over the surface of the o- polymer 200 when a sufficient external force is applied (FIG. 2B) and lubricating liquid 202 does not form stable overlayer 203 over the surface of the o-polymer 200 when the o-polymer 200 is not under a stress (e.g., when not under the external force) (FIG. 2A).
  • an external force or stress to an o-polymer, it is possible to achieve beneficial properties of an i-polymer (e.g., formation of a lubricating liquid overlayer) while also obtaining benefits of the one-pot process, including shorter processing times and use of a smaller amount of material.
  • infusing a polymer with lubricating liquid includes placing a polymer in a volume of lubricating liquid and waiting until the system reaches equilibrium.
  • a one-pot method can form a polymer with dispersed lubricating liquid in less time and using a smaller volume of lubricating liquid.
  • an o-polymer with dispersed lubricating liquid that does not form a lubricating liquid overlayer in a stress-free state can be used for on-demand formation of a lubricating liquid overlayer, for example, by applying a sufficient external force to the o-polymer.
  • an o-polymer in an inactivated state e.g., stress free or under a stress insufficient to form lubricating liquid overlayer
  • an inactivated o-polymer inactivated state (e.g., stress free or under a stress insufficient to form lubricating liquid overlayer)
  • an inactivated o-polymer provides easy handling, packaging, and transportation because of lack of a “slippery” overlayer of lubricating liquid.
  • such o-polymer is easier to cut and machine in comparison to corresponding i-polymer because of a lack of the slippery overlayer.
  • such o-polymer films can be easily die-cut/stamped into desired dimensions and the film can then be attached to final product using adhesive.
  • such o-polymer is easier to handle for installation because of a lack of slippery overlayer of lubricating liquid.
  • such o-polymer is easy to handle and work with because of a lack of slippery overlayer of lubricating liquid in comparison to the i-polymer having the same concentration of lubricating liquid but having the slippery overlayer.
  • one-pot formulation of medical-grade silicone polymer and lubricating liquid is coated onto a pre-stretched substrate (i.e. polyurethane, rubber, textiles).
  • a pre-stretched substrate i.e. polyurethane, rubber, textiles.
  • lubricating liquid migrates to the surface to form a stable repellant overlayer.
  • such o-polymer can be used for providing on-demand release of lubricating liquid overlayer by applying the external force when desired.
  • the lubricating liquid within on-demand o-polymer lasts longer because the overlayer is formed only when needed, in contrast to a corresponding i-polymer of the same lubricating liquid concentration, in which the lubricating liquid overlayer is always present and therefore may be exposed to damage and loss from external forces.
  • the lubricating liquid dispersed within the o-polymer exhibits improved shelflife because the lubricating liquid is stored within the o-polymer network.
  • the overlayer of the lubricating liquid forms on the surface only when needed, thereby limiting the exposure of the lubricating liquid to the elements of nature only when in use.
  • the o-polymer exhibits lower crosslinking density than the i-polymer.
  • the lower crosslinking density in the o-polymer than in the i-polymer is attributed to some crosslinking molecules in the o-polymer causing joining of two parts of the same monomer chain rather than two different monomer chains. In some embodiments, this results in the o-polymer exhibiting lower elastic properties than the i-polymer.
  • the framework disclosed herein can be used to design materials capable of forming a lubricating liquid overlayer over a polymer surface.
  • the framework disclosed herein can be used to tune the chemical potential of lubricating liquids dispersed within the polymer based on the properties of the polymer, the properties of the lubricating liquid, and forces applied to the polymer.
  • the framework disclosed herein can be used to design one-pot polymers (o-polymers) capable of forming a lubricating liquid overlayer.
  • the framework disclosed herein can be used to design one-pot polymers (o-polymers) capable of forming a lubricating liquid overlayer by applying an external force or causing a stress within the polymer.
  • a mechanistic model based on the Flory-Rehner theory of swelling a polymer (e.g., an elastomer network) in a small molecule solvent (e.g., a lubricating liquid), explains the effects of processing parameters on the divergent properties of o-polymer and i-polymer.
  • the model can be applied to two polymerization conditions, both with the same number of polymerizable monomers, m, and crosslinking molecules, but one with some concentration of lubricating liquid that acts as an inert diluent in the polymer.
  • Flory and Rehner formulate the free energy of the swelling polymer as including a stretch term and a mixing term:
  • FIGS. 3A-3C show a schematic of the polymer networks modeled in this nonlimiting example.
  • the black lines represent polymer chains of the polymer network 301 and dots indicate crosslinks 305.
  • FIG. 3A shows a polymer network 301 before addition of a lubricating liquid.
  • FIG. 3B shows a polymer network formed by infusion (i- polymer).
  • FIG. 3C shows a polymer network formed by a one-pot method (o-polymer). The arrows in FIG. 3C indicate formation of ineffective crosslinks.
  • the total number of crosslinking molecules can still be incorporated into the network through the creation of loops, in which a crosslinker unites two parts of the same chain rather than two different chains (arrows in FIG. 3C). These ineffective crosslinks do not contribute to the mechanical network structure, as they are essentially equivalent to a shorter single chain. Thus, compared to an i-polymer (FIG. 3B), an o-polymer will have a smaller number of effective crosslinks that contribute to the network structure.
  • an o-polymer is predicted to have a significantly lower elastic modulus than an i-polymer of the exact same final composition, in agreement with the observed values of shear modulus for the non-limiting example of i- PDMS infused with silicone oil (FIG. 5 A).
  • the N of o-polymer can be determined by noting that G ⁇ N.
  • NOPDMS NiPDMsGoPDMs/GiPDMS.
  • NOPDMS 0. 11 mol L -1 .
  • the mechanistic model described herein can be used to calculate the chemical potential of polymers (including i-polymers and o-polymers) under different conditions.
  • FIGS. 3D-3E show a non-limiting example of the calculated chemical potential of silicone oil in PDMS.
  • FIG. 3D shows the calculated chemical potential of the silicone oil in o-PDMS and i-PDMS as a function of the swelling ratio using this model and the measured values above.
  • the dashed black line indicates the equilibrium swelling ratio of i-PDMS and the equivalent composition of the as-prepared o-PDMS.
  • the o-PDMS has a large negative value for the chemical potential at this composition, indicating the much higher energy cost of removing oil from the PDMS matrix compared to swollen i-PDMS. From this, it can be calculated that i-PDMS would need to lose ⁇ 20% of its initial oil content in order to have a chemical potential equivalent to as-prepared o-PDMS.
  • the mechanistic model described herein can be used to identify conditions under which a lubricating liquid overlayer will form.
  • the mechanistic model described herein can be used to calculate the chemical potential of a lubricating liquid in a polymer.
  • a non-limiting example of a PDMS system is presented here for the purpose of explaining liquid overlayer formation.
  • LEL lubricating liquid overlayer
  • the formation of such a layer is in line with experimental and theoretical work showing the preferential segregation of oligomers at the surface of an elastic matrix.
  • the driving force for this separation is the preferable interaction of the smaller oligomers with the external environment, which may be energetically driven or driven by the entropic attraction of chain ends to the surface.
  • Dynamic contact angle hysteresis measurements can be used to estimate the change in interfacial energy due to dynamic surface lubrication of the water-PDMS interface.
  • Spontaneous lubrication reduces the interfacial energy by about 11.5 mJ m -2 , providing an estimation for the driving force of creating a LOL at the water-PDMS interface.
  • the chemical potential (p) of the lubricating liquid is the energy cost to remove lubricating liquid from the polymer and move it to an overlayer. When the chemical potential is negative, lubricating liquid will remain within the polymer. When the chemical potential is zero, there is no cost to move lubricating liquid from the bulk of the polymer to the overlayer, and lubricating liquid can be removed from the bulk of the polymer to form or maintain an overlayer.
  • the free energy cost of removing lubricating liquid from a polymer matrix and confining it to lubricating liquid region or layer at the interface will be approximately equal to the chemical potential of the lubricating liquid in the polymer, p. If this cost is comparable to the free energy gain from creating a lubricating liquid overlayer, then it may inhibit the overlayer’s formation. In a saturated i-polymer, u 0 J/mol, providing no barrier to LOL formation.
  • « ⁇ 0 (e.g., u -100 J/mol for o-PDMS), which means that there is an energy cost to remove a portion of the lubricating liquid from the polymer to form a lubricating liquid overlayer.
  • the energy cost to remove a 10 nm layer of silicone oil from the o- PDMS matrix is on the order of 1 mJ m -2 , and 10 mJ m -2 for a 100 nm layer.
  • the energy costs to remove lubricating liquid from the polymer are comparable to the estimated driving force for lubricating liquid overlayer formation, suggesting that lubricating liquid overlayer formation could be greatly inhibited in o-polymer compared to i- polymer.
  • the mechanistic model described herein can be used to determine the effect of applied stress on lubricating liquid overlayer formation.
  • the mechanistic model described herein can be used to calculate the chemical potential of a lubricating liquid in a polymer under stress.
  • the mechanistic model described herein can be used to calculate the stress at which a lubricating liquid overlayer would form.
  • FIG. 3E shows the calculated chemical potential of o- PDMS as a function of uniaxial or biaxial stretch relative to its unswollen dimension.
  • the as-prepared stretch of 1.19 corresponds to the zero-stress state with a negative chemical potential.
  • compressive stress quickly raises the chemical potential, removing the barrier to form a full lubricating liquid overlayer.
  • biaxial compression of a polymer coating can be achieved without difficulty.
  • a polymer can be adhered to a prestretched surface that is relaxed after curing, for example, as is done for dielectric elastomer actuators.
  • the mechanistic model describing one pot polymers (o- polymers) and infused polymers (i-polymers) based on the Flory-Rehner theory of swelling an elastomer network in a small molecule solvent provides an explanation for the different performance of these materials and a framework to design one pot polymers that perform similarly to infused polymers (e.g., by forming a lubricating liquid overlayer).
  • the model suggests that for the two polymerization conditions, both with the same number of polymerizable monomers m and crosslinking molecules v, o-polymers necessarily have a smaller value of N due to the lower density of effective crosslinks, which leads to longer chains and thus fewer chains per volume.
  • o-polymers with the same composition will have significantly lower elastic modulus than i-polymers, due to the linear relationship between shear modulus and crosslinking density.
  • the chemical potential p is thus essentially zero in i-polymer, leading to the facile formation of a lubricating liquid overlayer when under no external force, while in o-polymers, p is high enough to maintain the lubricating liquid in the bulk of the polymer and inhibit its travel to the interface or surface to form a lubricating layer (FIG. 3D).
  • the long-term performance of i-polymer therefore, can be determined by its ability to form and retain a lubricating liquid.
  • thermodynamic estimations provided above indicate that an i-polymer would need to lose a portion of its lubricating liquid loading (e.g., 20% of its lubricating liquid loading in the non-limiting example of PDMS loaded with silicon oil) to have a p value comparable to o-polymer. While fouling release events and shear stresses may remove some lubricating liquid from the surface, this lubricating liquid can be quickly replenished and total losses do not approach this threshold.
  • a portion of its lubricating liquid loading e.g. 20% of its lubricating liquid loading in the non-limiting example of PDMS loaded with silicon oil
  • the identification of a critical p value for the formation of a lubricating liquid overlayer can be used to assess the longevity of the i-polymer holistically and to guide the optimal design of coatings, including formation of a lubricating liquid overlayer on o-polymers.
  • the theoretical framework e.g., Flory-Rehner theory
  • the p of o-polymers can be reduced to zero through the application of a compressive stress during or after polymerization, providing a way to create controllable, on-demand coatings using the simpler o-polymer process. In some embodiments, this can allow for the application of o-polymers as slippery coatings with tunable wettability.
  • the theoretical framework described above provides guidance for the design and optimization of o-polymers that include a lubricating liquid within the polymer.
  • the chemical potential increases with the swelling ratio, which is a function of lubricating liquid concentration.
  • a lubricating liquid overlayer can form over a polymer surface.
  • an o-polymer of the same swelling ratio (or concentration) has a lower chemical potential and therefore would not form a lubricating liquid overlayer.
  • the chemical potential can be increased, enabling the formation of lubricating liquid overlayer, by increasing concentration.
  • the chemical potential can be increased, enabling the formation of lubricating liquid overlayer, by applying a compressive stress, without the need to increase concentration of lubricating liquid.
  • FIGS. 3D-3E therefore provide two non-limiting examples of parameters that can be selected to tune the chemical potential of a polymer that incorporates a lubricating liquid and thereby control the formation of a lubricating liquid overlayer. Numerous other parameters can be modified to tune the chemical potential and formation of a lubricating liquid overlayer, and combination of these parameters can be modified to design a polymer with desired properties using the theoretical framework described herein.
  • the chemical potential can be tuned by modifying temperature. In some embodiments, increasing temperature can increase the chemical potential. In some embodiments, chemical potential increases linearly with temperature. [0249] In some embodiments, the chemical potential can be tuned by the concentration of lubricating liquid. For example, the chemical potential increases as the concentration of lubricating liquid increases.
  • the chemical potential can be tuned by applying a force to the polymer or causing a stress within the polymer.
  • the chemical potential can be increased by causing a compressive stress.
  • the stress is applied by an external force.
  • the stress is biaxial.
  • the stress is uniaxial.
  • the chemical potential can be decreased by stretching or applying tension to the polymer.
  • the chemical potential can be tuned by modifying the density of crosslinks or effective crosslinks.
  • the chemical potential can be decreased by increasing the number of crosslinks. For example, in some embodiments, increasing the number of crosslinks increases the stiffness of the polymer and increases the energy cost for lubricating liquid to infiltrate the polymer, thereby reducing the cost to release the lubricating liquid to the overlayer.
  • the chemical potential can be tuned based on the choice of polymer and lubricating liquid. In some embodiments, the chemical potential can be tuned by the molecular weight or viscosity of the lubricating liquid. In some embodiments, the chemical potential can be tuned by the solubility parameters of the lubricating liquid. In some embodiments, the chemical affinity can be tuned by the enthalpy of mixing or Flory- Huggins interaction parameter of the lubricating liquid and polymer. In some embodiments, the chemical potential can be tuned by the chemical affinity of the polymer and lubricating liquid. In some embodiments, a high chemical affinity corresponds to a low enthalpy of mixing or low interaction parameter.
  • the chemical potential depends on the interfacial energies of the materials in the system, including the interfacial energy between the polymer and lubricating liquid, the interfacial energy between the polymer and medium at the polymer surface, and the interfacial energy between the lubricating liquid and the medium at the surface of the polymer.
  • a lubricating liquid can be selected to have a low interfacial energy between the lubricating liquid and polymer, relative to the interfacial energy between the polymer and the medium.
  • forming the lubricating liquid overlayer decreases interfacial energy at the surface, and the cost of removing lubricating liquid from bulk of the polymer to the lubricating overlayer can be counteracted by the decrease in interfacial energy at the surface.
  • the chemical potential can be tuned using fully-biodegradable oils or unique polymer-oil formulations for which the chemical potential is sufficiently low, such that the free energy cost of removing oil from the polymer to the free interface to form a lubricating liquid overlayer is low.
  • the polymer, lubricating liquid, and concentration of lubricating liquid can be selected to design a material with tunable properties.
  • the properties of such a material, including whether an overlayer is formed can be tuned or controlled by applying a stress.
  • the polymer, lubricating liquid, and concentration of lubricating liquid can be selected to form an o-polymer that forms a lubricating liquid overlayer when the polymer is under a stress (e.g., a compressive stress) but does not form a lubricating liquid overlayer when the polymer is not under a stress. In this way, a lubricating liquid overlayer can be switched on or off by introducing a force to the polymer.
  • the polymers disclosed herein include a lubricating liquid at a concentration such that the lubricating liquid does not form an overlayer over the polymer when the polymer is not under a compressive stress (e.g., in a stress-free state or under tension) and the lubricating liquid forms an overlayer when the polymer is under compressive stress.
  • the concentration of lubricating liquid to achieve such a polymer will be determined based on the choice of materials (e.g., on the chemical affinity of the polymer and lubricating liquid). In some embodiments, the concentration of lubricating liquid is about 10 wt% to 70 wt%.
  • the concentration of lubricating liquid depends on the polymer system (e.g., the combination of lubricating liquid and polymer). In some embodiments, the concentration of lubricating liquid is about 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt %, 40 wt %, 45 wt %, 50 wt %, 55 wt %, 60 wt %, 65 wt %, 70 wt % or the concentration is in any range bounded by any two values disclosed herein.
  • the polymer disclosed herein is disposed on a substrate under tension, and the compressive stress is caused by the substrate.
  • the substrate includes a stretchable material.
  • the substrate is an elastomer.
  • substrates include polyurethanes, rubber, textiles, and combinations thereof.
  • an o-polymer coating that does not form a lubricating liquid overlayer in a stress-free state but forms the lubricating liquid layer when under an external force, is beneficial because such o-polymer coating saves on overall processing time and cost of the coating compared to the i-polymer coating having the same concentration of the lubricating liquid.
  • o-polymers do not require long post-cure infusions to reach equilibrium concentration of the lubricating liquid (e.g., up to 48 hours for the i- PDMS). This saving in processing time for o-polymers also results in a lower overall processing cost for the o-polymers coating compared to the i-polymers having the same concentration of the lubricating liquid.
  • an o-polymer coating that does not form a lubricating liquid overlayer in a stress-free state but forms the lubricating liquid layer when under an external force, is beneficial because of improved dimensional stability of an o-polymer system compared to an i-polymer system.
  • improved dimensional stability can contribute to improved adhesion.
  • an o-polymer coating that does not form a lubricating liquid overlayer in a stress-free state but forms the lubricating liquid layer when under an external force, is beneficial because of improved adhesion properties.
  • chemical attachment of an i-polymer system to a substrate after infusion can be challenging.
  • an o-polymer can be attached to a substrate while in a state where a lubricating liquid does not form, and a force or stress can be applied to form a lubricating liquid overlayer after attachment.
  • an o-polymer coating having a first concentration of dispersed lubricating liquid that does not form a lubricating liquid overlayer in a stress-free state but forms the lubricating liquid layer when under an external force is beneficial over the o-polymer coating having a second, higher concentration of dispersed liquid that allows formation of lubricating liquid overlayer in a stress-free state.
  • the o- polymer coating with first concentration of the dispersed lubricating liquid uses less lubricating oil than the o-polymer coating with the second concentration of the dispersed lubricating liquid, thus improving handling and processing cost.
  • such a polymer is thinner and light.
  • an o-polymer would need to absorb a much larger amount of lubricating liquid than an i- polymer.
  • o-PDMS will have to attain a minimum swelling ratio of approximately 2.8, whereas i-PDMS has a chemical potential of zero at an equilibrium swelling ratio of approximately 1.8.
  • o-PDMS coating will be bulkier and more expensive to make than the corresponding i-PDMS coating with the overlayer because it contains more lubricating liquid.
  • a compression can be applied to the post-cured o-PDMS to form an overlayer.
  • an o-PDMS coating having a swelling ratio of about 1.8 i.e., equilibrium concentration of the corresponding i- PDMS
  • applying a biaxial compressive strain of about 0.1 on such o-PDMS coating yields a free energy of approximately OJ/mol (increase of about 200 J/mol), reduce the chemical potential of the lubricating liquid to zero, allowing for formation of oil overlayer.
  • the formation of the lubricating liquid overlayer can be controlled or induced by application of stress to the polymer network.
  • slippery surfaces can be turned on or off by controlling formation of a lubricating liquid overlayer by application of stress to the polymer.
  • a compressive stress within the polymer reduces the chemical potential of the lubricating liquid within the polymer. In some embodiments, the compressive stress is sufficient to remove a portion of the lubricating liquid from the bulk of the polymer to form a stable overlayer over the surface of the polymer.
  • a force is applied to the polymer layer such that the polymer layer is under stress.
  • the external force applied to the polymer includes a component applied in a direction parallel with the surface of the polymer on which the lubricating liquid overlayer is formed.
  • the external force is a compressive force and the compressive stress within the polymer includes a component parallel the external force.
  • the external force is a stretching force and the compressive stress includes a component in a direction perpendicular to the external force.
  • the external force is a compressive mechanical force and polymer is under a tensile mechanical stress that includes a component in a direction perpendicular to the external force.
  • the external force is biaxial. In some embodiments, the external force is uniaxial. In some embodiments the external force is radial.
  • the external force is caused by stretching the polymer layer.
  • the external force is caused by inflation, e.g., pneumatic inflation.
  • the external force is caused by flow induced pressure (e.g., for a polymer coated on an internal or external surface of a pipe).
  • such a pipe can be flexible and capable of expanding under internal pressure.
  • the external force is caused by pressurizing the polymer layer (e.g., by putting the polymer layer under a hydrostatic pressure).
  • the external force is applied by bending the polymer layer. For example, bending a polymer layer can introduce compressive stress in a first region of the polymer layer and tension in a second region of the polymer.
  • an external force can be applied locally to form a lubricating liquid overlayer over a portion of the polymer. In some embodiments, an external force can be applied locally using an indenter.
  • an external force can be applied by applying a stimulus to the polymer layer.
  • a compressive stress can be caused by applying a stimulus to the polymer layer.
  • the polymer layer includes a stimuli- responsive polymer.
  • stimuli-responsive polymers can change their shape and/or dimensions, thereby introducing a compressive stress, in response to one or more stimuli through external influences: for example, the effect of light, temperature, pressure, an electric or magnetic field, or a chemical stimulus.
  • the chemical stimulus is a cross-linking agent or a swelling agent.
  • the polymer layer includes an embedded shape memory alloy.
  • a shapememory alloy changes its shape in response to a stimuli: for example the effect of light, temperature, pressure, an electric or magnetic field, or a chemical stimulus.
  • a compressive stress can be caused by a shape change of a shape memory alloy embedded within or disposed on a polymer layer.
  • a polymer layer can be coated onto a medical device (e.g., a stent) that includes a shape memory alloy.
  • compression can be introduced to the polymers disclosed herein during curing of the polymer layer.
  • compression can be caused by curing the polymer on a pre-stressed or pre-stretched substrate, e.g., a substrate under tension.
  • an article including a substrate under tension; a polymer layer on the substrate; and a lubricating liquid within the polymer layer, the lubricating liquid being at a concentration within the polymer layer such that no stable overlayer is formed over a surface of the polymer layer, wherein the substrate is configured to cause a first compressive mechanical stress on the polymer layer when the tension is released, the first compressive mechanical stress being sufficient to cause the lubricating liquid to form a stable overlayer on the polymer layer.
  • FIGS. 4A-4D show an exemplary method of introducing compressive stress to a polymer 400 incorporating lubricating liquid 402 during curing.
  • a substrate 404 is stretched by applying an external tension by an external force.
  • a polymer 400 can be formed on the stretched substrate 404.
  • the polymer 400 includes a polymer matrix 401 and lubricating liquid 402 incorporated within the polymer matrix.
  • the polymer is formed by a one-pot method (e.g., by adding the lubricating liquid to polymer precursors before curing).
  • a lubricating liquid overlayer does not form over the polymer while the tension is maintained because the lubricating liquid is at a concentration such that the chemical potential of the lubricating liquid is less than zero when the tension is applied.
  • the external force applying the external tension can be released, causing the substrate to contract.
  • the substrate cannot contract to its original pre-stretch dimensions, resulting in a residual tension in the substate 404 and compression within the polymer matrix 401.
  • the residual tension is less than the external tension.
  • the compression in the polymer increases the chemical potential of the lubricating liquid. In the example shown in FIG. 4C, the compression in the polymer is sufficient to cause a portion of the lubricating liquid 402 to be removed from bulk of the polymer 400 and form an overlayer 403 over the surface of the polymer.
  • the substrate after curing, can be maintained at a tension that is less than the external tension.
  • the external force applied during curing can be released such that the external tension is reduced to a lesser tension.
  • this lesser tension is selected such that the chemical potential of the lubricating liquid is less than zero and a lubricating liquid overlayer does not form over the surface of the polymer.
  • the substrate contracts, resulting in a residual tension in the substrate and a compression in the polymer.
  • the compression in the polymer is sufficient to cause a portion of the lubricating liquid to be removed from the bulk of the polymer and form an overlayer over the surface of the polymer.
  • the compression in the polymer is not sufficient to cause a portion of the lubricating liquid to be removed from the bulk of the polymer and form an overlayer over the surface of the polymer.
  • an overlayer can be formed by applying an external force (e.g., additional compressive stress) to the polymer.
  • the substrate 404 can subsequently be removed.
  • the polymer when a pre-stretched substrate is removed, the polymer will return to its original dimensions (e.g., a relaxed or stress-free state).
  • the chemical potential when a pre-stretched substrate is removed, the chemical potential will decrease to that of a stress-free polymer.
  • the lubricating liquid overlayer will be reabsorbed by the bulk of the polymer.
  • the external tension is be caused by stretching the substrate in at least one direction. In some embodiments, the external tension is caused by stretching the substrate in two directions. In some embodiments, the substrate is stretched uniaxially. In some embodiments, the substrate is stretched biaxially. In some embodiments, the external tension is caused by compressing the substrate in at least one direction. In some embodiments, the external tensile force is caused by compressing the substrate in at least two directions.
  • a substrate can have a spherical or cylindrical shape.
  • a substrate can introduce radial forces.
  • a substrate can be stretched radially by inflating the substrate.
  • the amount of stretch in the substrate can be modified by modifying the inflation pressure.
  • a substrate can be inflated to a first pressure, introducing tension in the substrate, and a polymer including dispersed lubricating liquid can be formed on the surface on the substrate while the substrate is at a first pressure.
  • a compressive stress can be caused in the polymer by changing the inflation pressure (e.g., by decreasing the inflation pressure to a second pressure).
  • the compressive stress is sufficient that a lubricating liquid overlayer forms over the polymer.
  • an external tensile force is caused by radially expanding the substrate.
  • an external tensile force is caused by radially compressing the substrate.
  • an external force can be applied by applying a stimulus to the substrate.
  • a tension in the substrate can be caused by applying a stimulus to the substrate.
  • the substrate includes a stimuli-responsive material.
  • stimuli-responsive materials can change their shape and/or dimensions, thereby introducing a compressive stress, in response to one or more stimuli through external influences: for example, the effect of light, temperature, pressure, an electric or magnetic field, or a chemical stimulus.
  • the chemical stimulus is a cross-linking agent or a swelling agent.
  • the polymer layer includes a shape memory alloy.
  • a shape-memory alloy changes its shape in response to a stimuli: for example the effect of light, temperature, pressure, an electric or magnetic field, or a chemical stimulus.
  • a compressive stress can be caused by a shape change of a shape memory alloy embedded within or disposed on a polymer layer.
  • a polymer layer can be coated onto a medical device (e.g., a stent) that includes a shape memory alloy.
  • the materials disclosed herein include a polymer and a suitable lubricating liquid.
  • the appropriate polymers, lubricating liquids, and polymer and lubricating liquid combinations can be identified based on the theoretical framework described above.
  • the polymer preferentially includes a dispersed lubricating liquid on the surface rather than a fluid, complex fluids or undesirable solids to be repelled such that the lubricating liquid overlayer, once formed, cannot be displaced by the liquid or solid to be repelled.
  • the lubricating liquid acts as a better solvent toward the underlying polymer than the liquid to be repelled.
  • the polymer is a cross-linked polymer. In some embodiments, the polymer is a gel capable of being swollen with the lubricating liquid. In some embodiments, the polymer has an affinity for the lubricating liquid.
  • the polymer material can be chosen from a wide range of rubbers and elastomers, and other polymers. In some embodiments, the polymer is compressible. In some embodiments, the polymer swells significantly in the presence of certain solvent lubricating liquids.
  • the polymer can include rubber or elastomeric polymers, which rubbers or elastomeric polymers known to swell in the presence of an appropriate solvating liquid. In some embodiments, the polymer is a nonporous material.
  • the polymer is a covalently cross-linked polymer.
  • the polymer is a simple single polymer or complex mixture of polymers, such as polymer blends or co-polymers and the like.
  • the nature and degree of crosslinking can change the properties of the polymer. For example, cross-linking density can be used to control how much the polymer will swell (e.g., a lightly cross-linked polymer may swell more than a highly cross-linked polymer) or how much lubricating liquid can be dispersed within the polymer.
  • crosslinking density can be used to control the stiffness of the polymer matrix or the chemical potential of a lubricating liquid dispersed within the polymer.
  • the crosslinks can be physical and therefore reversible and/or readily disruptible by solvation so that the swelling ratio is large and/or the swelling rate is high.
  • the polymer is a copolymer or blend polymer or a composite material (e.g., a mixture of polymers containing nanoparticles or microscale filler materials).
  • the polymer is a copolymer of covalently and physically cross-linked blocks.
  • the polymer can be patterned into regions that would subsequently have different degrees of swelling upon addition of lubricating liquid.
  • the polymer includes silicone rubber, fluorosilicone, polydimethylsiloxane, vinyl methyl silicone, polyurethane, natural and synthetic, polyurethane, natural and synthetic polyisoprenes, polyethylene, polybutadiene, nitrile rubber, polyacrylic rubber, ethylene propylene rubber (EPM, EPDM), neoprene rubber, perfluoroelastomers, fluoroelastomers, polyether block amides (PEBA), chlorosulfonated polyethylene, ethylene-vinyl acetate, polyether urethane, perfluorocarbon rubber, fluorinated hydrocarbon or combination thereof.
  • silicone rubber fluorosilicone, polydimethylsiloxane, vinyl methyl silicone, polyurethane, natural and synthetic, polyurethane, natural and synthetic polyisoprenes, polyethylene, polybutadiene, nitrile rubber, polyacrylic rubber, ethylene propylene rubber (EPM, EPDM), neoprene
  • the polymer includes natural and synthetic elastomers.
  • Non-limiting examples of polymers include Ethylene Propylene Diene Monomer (EPDM, a terpolymer of ethylene, propylene and a diene component), natural and synthetic polyisoprenes such as cis-l,4-polyisoprene natural rubber (NR) and trans- 1,4-polyisoprene gutta-percha, isoprene rubber, chloroprene rubber (CR), such as polychloroprene, Neoprene, Baypren, Butyl rubber (copolymer of isobutylene and isoprene), Styrene-butadiene Rubber (copolymer of styrene and butadiene, SBR), Nitrile rubber (copolymer of butadiene and acrylonitrile, NBR), also called Buna N rubbers, Epichlorohydrin rubber (ECO), Polyacrylic rubber (ACM
  • the polymer is a fluoropolymer.
  • fluoropolymers include polytetrafluoroethylene (Teflon), polyvinylfluoride, polyvinylidene fluoride, fluorocarbon [chlorotrifluoroethylenevinylidene fluoride] (Viton, Fluorel), Fluoroelastomer [Tetrafluoroethylene-Propylene] (AFLAS), perfluorinated elastomer [perfluoroelastomer] (DAI-EL, Kalrez), tetrafluoroethylene (Chemraz), perfluoropolyether, and combinations thereof.
  • the polymer is a fluorosilicone having a PDMS backbone and some degree of fluoro-aliphatic side chains.
  • fluorinated groups in a fluorosilicone include trifluoropropyl, non-afluorohexylmethyl, and fluorinated ethers.
  • fluorosilicones have variable amounts of fluorosubstitution and lengths of fluorinated side groups.
  • the polymer includes fluoroalkyl side chains.
  • Non-limiting examples of such polymers include polyfumerate, polymethacrylate, and polyacrylate with fluoroalkyl side chains. In some embodiments such fluoroalkyl side chains have 3, 5, 7, 8, 9, 10, 11, 16, or 18 carbons.
  • the polymer includes a polyester, polyethylene terephthalate (PET), polyethylene (PE, HDPE, LDPE), polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polypropylene (PP), polystyrene (PS, HIPS), polyamides (PA, Nylons), acrylonitrile butadiene styrene (ABS), poly ethylene/ Acrylonitrile Butadiene Styrene (PE/ ABS), polycarbonate (PC), polycarbonate/acrylonitrile butadiene styrene (PC/ABS), polyurethanes (PU), melamine formaldehyde (MF), phenolics (PF) or (phenol formaldehydes, polyetheretherketone (PEEK), polyetherimide (PEI), polylactic acid (PLA), polyalkyl methacrylate (like PMMA), urea-formaldehyde (UF), and combinations thereof.
  • PET polyethylene terephthalate
  • the prepolymer or base resin is selected such that it is compatible with the lubricating liquid.
  • the prepolymer is selected to provide preferential wetting by the lubricating liquid in the cured state, and/or is selected because it is able to wet and stably adhere the lubricating liquid in the cured state.
  • the prepolymer is nonreactive but miscible with the lubricating liquid.
  • the exemplary prepolymer is stable and non-reactive with the lubricating liquid, miscible with the lubricating liquid in the prepolymer state, and miscible with the polymer such that is becomes dispersed within the polymer upon curing.
  • the exemplary prepolymer is stable and non-reactive with the lubricating liquid, miscible with the lubricating liquid in the prepolymer state, but immiscible and able to self-segregate from the lubricating liquid as it cures.
  • the curing agent also desirably is chemically non-reactive or substantially non-reactive with the lubricating liquid.
  • the polymer precursors can include precursors of perfluorinated and/or polyfluorinated polymers.
  • fluorinated alternating aryl/alkyl vinylene ether (FAVE) polymers can be prepared from addition polymerization of aryl trifluorovinyl ethers (TFVEs) with 1,4-butanediol or 4-hydroxybenzyl alcohol.
  • polymer precursors for an o-polymer includes a monomer, a base resin, or a prepolymer.
  • the base resin or prepolymer for o- polymer can include polymerizable monomers, terminal-group functionalized oligomers or polymers, side-group functionalized oligomers or polymers, telechelic oligomers or polymers.
  • the exemplary telechelic polymers or end-functionalized polymers are macromolecules with two reactive end groups and are used as cross-linkers, chain extenders, and important building blocks for various macromolecular structures, including block and graft copolymers, star, hyperbranched or dendritic polymers.
  • telechelic polymers or oligomers can enter into further polymerization or other reactions through its reactive end-groups.
  • An exemplary telechelic polymer is a di-end- functional polymer where both ends possess the same functionality. In some embodiments, where the chain-ends of the polymer are not of the same functionality they are termed endfunctional polymers.
  • Exemplary telechelic polymers include polyether diols, polyester diols, polycarbonate diols, and polyalcadiene diols.
  • Exemplary end-functionalized polymers also include polyacrylates, polymethacrylates, polyvinyls, and polystyrenes.
  • the ratio of lubricating liquid to resin is as high as high as 2:1.
  • the polymer precursor can be a perfluoroalkyl or polyfluoroalkyl monomer, such as perfluoroalkyl methacrylates.
  • an initiator may be included to initiate polymerization.
  • photoinitiators, thermal initiators, a moisture-sensitive catalyst or other catalyst can be included.
  • polymerization is affected by exposure of the compositions to a suitable trigger, such as light, including ultraviolet energy, thermal energy or moisture.
  • the prepolymer precursor includes fluorinated monomers or oligomers having some degree of unsaturation, such as (perfluorooctyl)ethyl methacrylate, or end functionalized with other reactive moi eties that can be used in the curing process.
  • the monomers can be allyl based and include allyl heptafluorobutyrate, allyl heptafluoroisopropyl ether, allyl lH,lH-pentadecafluorooctyl ether, allylpentafluorobenzene, allyl perfluoroheptanoate, allyl perfluorononanoate, allyl perfluorooctanoate, allyl tetrafluoroethyl ether, and allyl trifluoroacetate.
  • the monomers can be itacone- or maleate-based and include hexafluoroisopropyl itaconate, bis(hexafluoroisopropyl) itaconate; bis(hexafluoroisopropyl) maleate, bis(perfluorooctyl)itaconate, bis(perfluorooctyl)maleate, bis(trifluoroethyl) itaconate, bis(2,2,2-trifluoroethyl) maleate, mono-perfluorooctyl maleate, and mono-perfluorooctyl itaconate.
  • the monomer can be acrylate- and methacrylate (methacrylamide)-base and include 2-(N-butylperfluorooctanesulfamido)ethyl acrylate, lH,lH,7H-dodecafluoroheptyl acrylate, trihydroperfluoroheptyl acrylate, 1H,1H,7H- dodecafluoroheptyl methacrylate, trihydroperfluoroheptyl methacrylate, 1H,1H,11H- eicosafluoroundecyl acrylate, trihydroperfluoroundecyl acrylate, 1H,1H,11H- eicosafluoroundecyl methacrylate, trihydroperfluoroundecyl methacrylate, 2-(N- ethylperfluorooctanesulfamido)ethyl acrylate, 2-(N- e
  • suitable monomers include pentafluorostyrene, perfluorocyclopentene, 4-vinylbenzyl hexafluoroisopropyl ether, 4- vinylbenzyl perfluorooctanoate, vinyl heptafluorobutyrate, vinyl perfluoroheptanoate, vinyl perfluorononanoate, vinyl perfluorooctanoate, vinyl trifluoroacetate, tridecafluoro- 1, 1,2,2- tetrahydrooctyl- 1,1 -methyl dimethoxy silane, tridecafluoro- 1,1,2, 2-tetrahydrooctyl-l- dimethyl methoxy silane, and cinnamate.
  • silicone monomers can be used, such as PDMS precursor (i.e. Sylgard® 184), l,4-bis[dimethyl[2-(5-norbornen-2-yl)ethyl]silyl]benzene, 1,3- di cyclohexyl- 1,1, 3, 3-tetrakis(dimethylsilyloxy)disiloxane, 1, 3-di cyclohexyl- 1,1, 3, 3- tetrakis(dimethylvinylsilyloxy)disiloxane, 1, 3-di cyclohexyl- 1,1, 3, 3-tetrakis[(norbornen-2- yl)ethyldimethylsilyloxy]disiloxane, 1,3-divinyltetramethyldisiloxane, 1, 1, 3, 3,5,5- hexamethyl-l,5-bis[2-(5-norbomen-2-yl)ethy
  • polymer precursors include crosslinkers.
  • crosslinking density can be used to modify property of the resulting polymer, including stiffness, chemical potential of a lubricating liquid within the polymer, and ability of a lubricating liquid to be dispersed within a polymer.
  • the lubricating liquid is selected such that the material to be repelled (or does not adhere) is not soluble or miscible in the lubricating liquid layer, which contributes to the low adhesion exhibited by the material to be repelled.
  • the enthalpy of mixing between the two should be sufficiently high (e.g., water/oil; insect/oil; ice/oil, etc.) that they phase separate from each other when mixed together, and/or do not undergo substantial chemical reactions between each other.
  • the lubricating liquid and the material to repel are substantially chemically inert with each other so that they physically remain distinct phases/materials without substantial mixing between the two.
  • a lubricating liquid can be selected to have a viscosity that provides appropriate lubricity and longevity properties.
  • the viscosity of the lubricating liquid affects the lubricating liquid secretion rate.
  • the lubricating liquid has a low viscosity.
  • a low viscosity lubricating liquid provides increased mobility and movement to the surface to rapidly form the slippery surface and to induce fast sliding of contaminants off the surface and re-lubrication of the surface layer.
  • the lubricating liquid is selected based on the availability or desired surface properties (hydrophilicity, oleophobicity, etc.).
  • exemplary lubricating liquids include hydrophilic, hydrophobic and oleophobic liquids, such as fluorinated lubricants (liquids or oils), silicones, silicone oils, siloxanes, mineral oil, plant oil, hydrocarbons, halogenated hydrocarbons, water (or aqueous solutions including physiologically compatible solutions), ionic liquids, polyolefins, including polyalpha-olefins (PAO), esters, synthetic esters, esters with long alkyl chains, polyalkylene glycols (PAG), polyphenyl ethers, phosphate esters, alkylated naphthalenes (AN), aromatics and silicate esters and combinations thereof.
  • Non-limiting examples of silicones include silicon tetraethoxide, tetraethyl orthosi
  • the lubricating liquid is a perfluorinated liquid or partially fluorinated liquid.
  • partial fluorination leads to a stepwise reduction in specific gravity, while hydrogenation leads to augmented polarization and increased lipophilic or silicone-solvent properties.
  • the lubricating liquid includes multiple classes of partially fluorinated inert liquids, including oligomers and mixtures. The physical and chemical properties make partially fluorinated inert liquids suitable for this application, as well. A number of types and classes of such liquids are listed throughout this application and in the examples.
  • Non-limiting examples of perfluorinated liquids or partially fluorinated liquids include fluorocarbons, perfluorocarbons, hydrofluorocarbons, hydrofluorocarbon-oligomers, compounds having partially fluorinated ponytails, partially fluorinated oils, partially fluorinated greases, fluorosilicones, tertiary perfluoroalkylamines (such as perfluorotri-n-pentylamine, FC-70, perfluorotri-n-butylamine FC-40, etc.
  • perfluoroalkylsulfides and perfluoroalkylsulfoxides perfluoroalkylethers, perfluorocycloethers (like FC-77) and perfluoropolyethers (such as KRYTOX family of lubricants by DuPont), perfluoroalkylphosphines and perfluoroalkylphosphineoxides, perfluorohexyl-octane, perfluorohexyl-ethane, perfluorobutyl -butane, perflurophenanthren, perfluorooctane, perfluorophenathrene, and their analogues, homologues, oligomers, polymers, mixtures, and combinations thereof.
  • perfluoroalkyls are linear or branched.
  • the lubricating liquid includes a hydrofluorocarbon oligomer.
  • hydrofluorocarbon oligomers include two to four hydrofluorocarbon molecules and have viscosity between 90 and 1750 mPas.
  • hydrofluorocarbon oligomers include a star-shaped molecular structure with polar, hydrogenated molecules at the center.
  • long-chain perfluorinated carboxylic acids e.g., perfluorooctadecanoic acid and other homologues
  • fluorinated phosphonic and sulfonic acids fluorinated silanes, and combinations thereof are used as the lubricating liquid.
  • perfluoroalkyl group in these compounds are linear or branched, and some or all linear and branched groups are only partially fluorinated.
  • the lubricating liquid includes fluorinated oils and liquids.
  • fluorinated oils and liquids include glutarate, camphorate, tricarballylate, phosphate, phosphonate, ether phospho-nitrilate, and cyanurate derivatives of partly fluorinated alcohols.
  • Non-limiting examples of partly fluorinated alcohols include Bis(y’-amyl) 3 -methylglutarate, Bis(y'-heptyl) 3 -methylglutarate, Bis(y'-heptyl) 2- methylglutarate, Bis(y'-heptyl) d-camphorate, Bis(y'-heptyl) 2,2'-dimethyl-methylglutarate, Bis(y' -heptyl) 3, 3 -dimethyl-m ethylglutarate, Tris(y'-amyl) tricarballylate, 1, 2,4,5- Tetrakis( ⁇
  • the lubricating liquid is a hydrocarbon.
  • hydrocarbons include alkanes, olefins, and their liquid higher homologues, such as oligomers and polymers.
  • the lubricating liquid is a saturated alkane, an unsaturated olefin, or one of their liquid oligomers or polymers.
  • the lubricating liquid is a halogenated hydrocarbon, including halogenated alkanes, halogenated olefins and aromatic compounds.
  • the lubricating liquid is mineral oil, which includes light mixtures of higher alkanes from a mineral source.
  • the lubricating liquid is plant oil or other ester with a long alkyl chain.
  • the lubricating liquid is an organosilicone compound (e.g. silicone elastomer or silicone oil).
  • the lubricating liquid is matched chemically with the polymer that it is dispersed within.
  • the lubricating liquid and polymer have a chemical affinity for one another.
  • the enthalpy of mixing between the polymer and the lubricating liquid is sufficiently low so that they mix readily with each other when mixed together.
  • the Flory -Huggins interaction parameter between the polymer molecules and the lubricating liquid is sufficiently low so that they mix readily with each other when mixed together.
  • the lubricating liquid has a high solubility or miscibility with the polymer. In some embodiments, a high solubility or miscibility increases lubricating liquid concentration that can be dispersed in the polymer. In some embodiments, a high solubility or miscibility improves excretion dynamics of the lubricating liquids. In some embodiments, a high solubility or miscibility minimizes phase separation of the lubricating liquid. In some embodiments, the lubricating liquid is capable of swelling the polymer as well. In some embodiments, the lubricating liquid is selected so that it remains within the bulk of the polymer, rather than self-secreting or sweating out of the polymer without added stress.
  • the lubricating liquid and polymer have a chemical affinity for one another.
  • the lubricating liquid can be a hydrophobic liquid such as silicone oil, hydrocarbons, and/or the like.
  • a silicone elastomer e.g., which is covalently cross-linked
  • a dispersed silicone oil e.g., such as methyl, hydroxyl, or hydride- terminated PDMS.
  • Hydride-terminated PDMS has been demonstrated to show good swelling and dispersion with a range of lubricating liquids.
  • Hydroxyl-terminated silicone oil in PDMS is also another type of swellable polymer providing oleophobic/hydrophilic surface.
  • a fluorinated polymer is combined with a perfluorinated or fluorinated liquid to form a fluorogel.
  • a butyl rubber is combined with mineral oil.
  • a silicone is combined with a silicone oil.
  • lubricating liquids can contain analogues, homologues, oligomers, polymers, and mixtures of the lubricating liquids listed in Table 1.
  • Table 1 Exemplary combinations of polymers and lubricating liquids.
  • the polymer layer containing the lubricating liquid incorporates amphiphilic properties, hybrid material approaches, or active substances.
  • the lubricating liquid within the polymer layer not only improves the FR coating performance, but is also biodegradable.
  • the materials described herein include a substrate, for example a substrate on which the polymer layer is disposed.
  • the substrate material includes a stretchable material.
  • the substrate includes an extensible material.
  • the substrate includes an elastomer.
  • the substrate is transparent.
  • the lubricating liquid has a low solubility in the substrate.
  • a substrate can be selected such that the lubricating liquid has a low solubility in the substrate and the substrate therefore does not uptake the lubricating liquid.
  • the substrate does not react with the lubricating liquid.
  • the substrate has good adhesion with the polymer.
  • adhesion between the polymer and substrate can be modified using adhesion promoters.
  • Non-limiting examples of substrates include silicone rubber, polyurethane, polyisoprene, polyethylene, polybutadiene, nitrile rubber, ethylene propylene rubber (EPM, EPDM), neoprene rubber, fluoroelastomers, or a combination thereof.
  • pre-stressed substrate is a material with a sufficiently high elongation at yield.
  • the pre-stressed substrate is a polymer that can be elongated by 50%- 1000%.
  • the pre-stressed substrate includes textiles/fabrics, woven mesh materials, shape memory alloy, metals, and combination thereof.
  • a method of making an article including: adding a lubricating liquid to one or more polymer precursors; and curing the one or more polymer precursors to form a polymer layer dispersed with the lubricating liquid, the lubricating liquid is added to the polymer precursors at a concentration such that, after forming the polymer layer the lubricating liquid does not form a stable overlayer on a surface of the polymer layer; and applying an external force to the polymer layer such that the polymer layer is under a first compressive mechanical stress sufficient to cause the lubricating liquid to form the stable overlayer on the surface of the polymer layer.
  • the polymers disclosed herein are formed by a one-pot method, e.g., by pre-cure addition of a lubricating to polymer precursors.
  • the polymer is formed by adding a lubricating liquid to one or more polymer precursors before curing, followed by curing to form a polymer layer with the lubricating liquid dispersed within the polymer.
  • a lubricating liquid can be added to polymer precursors such that the lubricating liquid can be dispersed within the polymer while curing.
  • a lubricating liquid can also be a solvent for the prepolymer composition.
  • pre-cure addition of a lubricating liquid results in a stress-free polymer with lubricating liquid dispersed within the polymer matrix.
  • the lubricating liquid dispersed within the polymer does not form an overlayer in this stress-free state.
  • an external force or stress can be applied to the polymer during or after curing to form a lubricating liquid overlayer.
  • low molecular polymer precursors can be ‘cured’ or solidified by reaction of end-functionalized polymers with curing agents, which increases the molecular weight of the macromolecule.
  • curing agents include other oligomers or polymers with two or more reactive groups, or with bifunctional crosslinking agents.
  • Exemplary telechelic polymers include polyether diols, polyester diols, polycarbonate diols, and polyalcadiene diols.
  • Exemplary end-functionalized polymers also include polyacrylates, polymethacrylates, polyvinyls, and polystyrenes.
  • a force is applied to the polymer layer such that the polymer layer is under a compressive stress.
  • the compressive stress reduces the chemical potential of the lubricating liquid within the polymer.
  • the compressive stress is sufficient to reduce the chemical potential and to remove a portion of the lubricating liquid from the bulk of the polymer to form a stable overlayer over the surface of the polymer.
  • a compressive stress can be introduced to a polymer layer in any of the methods described herein, for example, as described in the section titled “Controlling formation of a lubricating liquid overlayer by application of stress.”
  • compression can be introduced to the polymers disclosed herein during curing of the polymer layer.
  • compression can be caused by curing the polymer on a pre-stressed or pre-stretched substrate, e.g., a substrate under tension.
  • a tension can be introduced to a substrate in any of the methods described herein, for example, as described in the section titled “Controlling formation of a lubricating liquid overlayer by application of stress.”
  • a method of making an article including: providing a substrate under an external tension caused by an external force; and forming a polymer layer on the substrate under the external tension by: adding a lubricating liquid to one or more polymer precursors, and curing the one or more polymer precursors on the substrate under the external tension to form the polymer layer dispersed with the lubricating liquid on the substrate; wherein the lubricating liquid is added to the polymer precursors at a concentration such that, after forming the polymer layer: the lubricating liquid does not form a stable overlayer on a surface of the polymer layer while the substrate is under the external tension, and releasing the external force causes the polymer layer to be under a first compressive mechanical stress resulting from the residual tension of the substrate, the first compressive mechanical stress being sufficient to cause the lubricating liquid to form a stable overlayer on a surface of the polymer layer.
  • the polymer is porous.
  • the pore size of the o-polymer can be controlled by adding a portion of miscible but non-binding (i.e., no covalent bonding can be formed) lubricating liquid to the precursor mixture of the o- polymer.
  • the pores of the o-polymer are nano- or micro-sized.
  • the o-polymer has reduced population of pores compared to pure polymer of same stoichiometry because the added lubricating liquid reduces the viscosity of the precursor mixture.
  • addition of lubricating liquid in o- polymer promotes coalescence and Ostwald ripening of water droplets before the polymer has completely cured.
  • a polymer is made using a one-pot method in a micro emulsion templating process that includes the lubricating liquid (e.g., silicone oil) in the method.
  • a porous o-polymer is formed using a micro emulsion templating process in which the lubricating liquid is added during the process.
  • the disclosed o-polymer is a PDMS matrix with dispersed silicone oil within the bulk of the matrix. In some embodiments, the highest amount of silicone oil incorporated into the o-PDMS system is 200 PHR.
  • a fluorogel-based o-polymer is formed by one-pot method in which lubricating liquid is added to precursors of the fluorogel.
  • the precursor for fluorogel includes perfluorooctylethyl acrylate (PFOA), PFOEA-50, PFOEA- 50, and PFHEA-95.
  • the lubricating liquid for fluorogel includes FC- 70 and Krytox 100.
  • a thermoplastic polymer can be mixed with a lubricating liquid and a plasticizer and formed into the desired end shape by injection molding.
  • exemplary polymers for use in such applications include low molecular weight polyolefins.
  • LLDPE, LDPE, HDPE, or PP pellets can be compounded with a lubricating liquid such as mineral oil or soybean oil or paraffin and can be molded.
  • low molecular weight counterpart of each type of polyolefin resins can also serve as a lubricating liquid component when compounding and molding.
  • a composition of a mixture of prepolymers or monomers and lubricating liquid can be formed by various mixing methods.
  • the composition of the mixture can be pre-conditioned (e.g., aging, soft-baking) to control the viscosity and consistency of the mixture for a selected application method (casting, molding, spraying, etc.).
  • the mixture can be applied onto a substrate and solidified (photo-curing, thermal-curing, moisture-curing, chemical curing, etc.) to form a shape or a coating layer.
  • the mixture can be molded to a free-standing 2D (sheets, films) or 3D (tubes, pipes, bottles, containers, optics, and other shapes) objects.
  • the flowable composition can be applied in a continuous process, for example, by providing a continuous plastic sheet as the substrate, which can be fed out from a supply mandrel and directed into an application zone, where the flowable composition is applied by spraying screen printing dip coating, blade drawing and the like.
  • the coated plastic sheet optionally can be directed into a second zone where curing is initiated, for example, by exposure to UV or thermal energy.
  • a composition of a mixture of prepolymers or monomers and lubricating liquid can be applied in a continuous process.
  • the polymer precursor with curing agent and lubricating liquid can be combined and the mixture can be applied to a substrate as it continually passes underneath an applicator.
  • the applicator can spray or paint, squeegee or extrude the composition onto the moving substrate.
  • the substrate can then move into a second zone for curing, e.g., by passing through a heated zone or under irradiation.
  • a composition of a mixture of prepolymer or monomers and lubricating liquid is well-suited for applications on large surfaces, particularly where the underlying surface is irregular and not homogeneous.
  • the composition can be applied to adhesive-backed films so that the resultant o-polymer coting can be applied as an adhesive strip to other surfaces.
  • the adhesive o-polymer product can be applied to medical devices and consumer goods where slippery properties are desired.
  • a film including the polymers disclosed herein can be diecut or stamped into desired dimensions. In some embodiments, a film including the polymers disclosed herein can be applied to a surface using methods including roll-to-roll coating, spray casting, and blade-casting.
  • a method including providing an article comprising a polymer layer and a lubricating liquid within the polymer layer at a concentration such that the lubricating liquid does not form a stable overlayer over a surface of the polymer layer when the polymer layer is not under compressive stress; and applying an external force to the polymer layer such that the polymer layer is under a first compressive mechanical stress sufficient to cause the lubricating liquid to form a stable overlayer on the surface of the polymer layer.
  • the polymers disclosed herein can be designed such that formation of a lubricating liquid overlayer can be controlled by modifying the chemical potential (e.g., by application or release of stress).
  • the surface lubricity or slipperiness can be turned on by increasing the chemical potential such that lubricating liquid is removed from the bulk of the polymer to form a lubricating liquid overlayer, and under other conditions, the surface lubricity can be turned off by decreasing the chemical potential such that lubricating liquid is absorbed into the polymer to remove the lubricating liquid overlayer.
  • a polymer incorporating a lubricating liquid can be maintained without an overlayer e.g., in a deactivated state) until installation or use.
  • maintaining a polymer in a deactivated state can make handling easier, for example, because the polymer is not slippery during installation.
  • maintaining a polymer in a deactivated state can improve shelf life, for example, because the lubricating liquid can be stored in the bulk, reducing evaporation of the lubricating liquid.
  • the overlayer can be deactivated when not needed and activated by applying an external force to increase the longevity of the coating.
  • maintaining a polymer in a deactivated state can improve cleanliness by reducing dust accumulation.
  • surface lubricity can be activated by turning the lubricating liquid layer on or off “on demand” or via “time-release” or delayed release via the application or release of stress.
  • a lubricating liquid overlayer can be turned on by applying an external force to the polymer.
  • An external force can be introduced to a polymer layer in any of the methods described herein, for example, as described in the section titled “Controlling formation of a lubricating liquid overlayer by application of stress.”
  • the external force includes a component applied in a direction parallel with the surface of the polymer on which the lubricating liquid overlayer is formed.
  • the external force that turns on the overlayer is a compressive force that increases the chemical potential of the lubricating liquid by causing a compressive stress within the polymer or increasing the compressive stress within the polymer.
  • the external force is a compressive force and the compressive stress within the polymer includes a component parallel to the external force. In some embodiments, the external force is a stretching force and the compressive stress includes a component in a direction perpendicular to the external force. In some embodiments, the force is biaxial. In some embodiments, the force is uniaxial. In some embodiments, the external force is a compressive mechanical force and polymer is under a tensile mechanical stress that includes a component in a direction perpendicular to the external force.
  • a lubricating liquid overlayer can be turned off by applying an external force to the polymer.
  • An external force can be introduced to a polymer layer in any of the methods described herein, for example, as described in the section titled “Controlling formation of a lubricating liquid overlayer by application of stress.”
  • the external force that turns off the overlayer includes a component applied in a direction parallel with the surface of the polymer on which the lubricating liquid overlayer is formed.
  • the external force that turns off the overlayer is a tensile force that reduces chemical potential of the lubricating liquid by decreasing the compressive stress in the polymer or by introducing tension to the polymer.
  • the external force is a tensile force and the stress within the polymer includes a component parallel the external force. In some embodiments, the external force is a compressive force and the stress includes a component in a direction perpendicular to the external force. In some embodiments, the force is biaxial. In some embodiments, the force is uniaxial.
  • the external force can be applied by mechanical stretching, pneumatic inflation (e.g., by altering inflation pressure) or flow-induced pressure (e.g., for a polymer coated on an interior or exterior surface of a pipe).
  • a pipe can be flexible and capable of expanding under internal pressure.
  • a polymer can be disposed on a substrate, and an external force can be applied by stretching or compressing the substrate.
  • the external force is caused by pressurizing the polymer layer (e.g., by putting the polymer layer under a hydrostatic pressure).
  • the external force is applied by bending the polymer layer. For example, bending a polymer layer can introduce compressive stress in a first region of the polymer layer and tension in a second region of the polymer.
  • an external force can be applied locally to form a lubricating liquid overlayer over a portion of the polymer. In some embodiments, an external force can be applied locally using an indenter.
  • an external force can be applied by applying a stimulus to the polymer layer or substrate.
  • a compressive stress can be caused by applying a stimulus to the polymer layer or substrate.
  • the polymer layer includes a stimuli-responsive polymer or substrate.
  • stimuli- responsive materials can change their shape and/or dimensions, thereby introducing a compressive stress, in response to one or more stimuli through external influences: for example, the effect of light, temperature, pressure, an electric or magnetic field, or a chemical stimulus.
  • the chemical stimulus is a cross-linking agent or a swelling agent.
  • the polymer layer or substrate includes a shape memory alloy.
  • a shape-memory alloy changes its shape in response to a stimuli: for example the effect of light, temperature, pressure, an electric or magnetic field, or a chemical stimulus.
  • a compressive stress can be caused by a shape change of a shape memory alloy embedded within or disposed on a polymer layer.
  • a polymer layer can be coated onto a medical device (e.g., a stent) that includes a shape memory alloy.
  • a silicone polymer containing an oil serves as a fouling-release coating for marine applications.
  • the silicone polymer containing the oil is used for prevention and removal of marine biofouling on submerged surfaces.
  • the silicone polymer containing the oil is used as a foulingrelease (FR) coating, which minimizes the adhesion of marine fouling organisms.
  • the silicone polymer containing the oil incorporates amphiphilic properties, hybrid material approaches, or active substances.
  • the silicone polymer containing the oil not only improves the FR coating performance, but is also biodegradable.
  • a polymer layer containing a lubricating liquid serves as a fouling-release coating for marine applications.
  • the polymer layer containing the lubricating liquid is used for prevention and removal of marine biofouling on submerged surfaces.
  • the polymer layer containing the lubricating liquid is used as a fouling-release (FR) coating, which minimizes the adhesion of marine fouling organisms.
  • the exemplary applications of disclosed o-polymer include an anti-ice coating for the lower section of roofs, an anti-fouling coating on cooling towers, marine structures, an anti-graffiti coating on walls, signs, and other outdoor structures, an anti-sticking surface finish, particularly to large surface areas, as anti-fouling tubes and pipes (e.g. medical catheters, biomass/biofuel producing reservoirs, such as algae-growing trays and tubes), aquarium windows coated with o-polymer for anti-fouling, as self-cleaning optics and as self-cleaning and easy-cleaning coating on optics, windows, solar panels.
  • an anti-ice coating for the lower section of roofs an anti-fouling coating on cooling towers, marine structures, an anti-graffiti coating on walls, signs, and other outdoor structures
  • an anti-sticking surface finish particularly to large surface areas
  • anti-fouling tubes and pipes e.g. medical catheters, biomass/biofuel producing reservoirs, such as algae-growing trays and tubes
  • exemplary applications of the disclosed o-polymer include medical devices, including medical implants, stents, and silicone implants.
  • exemplary applications include deployable structure, e.g., tents or inflatables.
  • elastomer mixture was applied to the surface of 1.5 cm steel discs (NDSU bacterial biofilm assays), 4” x 8” steel plates (NDSU mussel/barnacle assays and Port Canaveral, Morro Bay and Singapore Harbor field studies), and 1/8” thick, 6 14/16 ”x 6 14/16 ” glass plates (Scituate Harbor field study). They were then surface activated using a 2 min, 250W, oxygen plasma (Femto PCCE plasma cleaner, Diener electronic GmbH, Ebhausen, Germany). Excess silicone prepolymer was removed by spinning slides at 1000 rpm for 60 s via spin coating (Spincoat G3P-15, SCS, Indianapolis, USA) to achieve an approximate -100pm thickness.
  • elastomer mixture was applied to the surface of 1.5 cm diameter steel discs (NDSU bacterial biofilm assays), 4” x 8” steel plates (NDSU mussel/barnacle assays and Port Canaveral, Morro Bay and Singapore Harbor field studies), and 1/8” thick, 6 14/16 ”x 6 14/16 ” glass plates (Scituate Harbor field study).
  • the surface was then activated using a 2 min, 250W, oxygen plasma.
  • Excess silicone prepolymer was removed by spinning at 300 rpm for 60 s via spin coating. After spin-coating, the samples were cured in an oven at 70°C for 4 h.
  • Coatings Akzo Nobel
  • Intersleek 757 topcoat was mixed in 15:4: 1 (A:B:C) ratios and mixed by hand using a glass stir rod. This mixture was applied via spin coating at 750 rpm for 60 seconds to achieve a coating thickness of ⁇ 150pm on the discs, steel plates, and glass plates. The surfaces were then activated using a 2 min oxygen plasma exposure at 250W. Coatings were left to cure for at least 2 days at room temperature before testing.
  • AFM detection of lubricating liquid layer i-PDMS, o-PDMS and PDMS control surfaces were investigated using atomic force microscope (AFM) (JPK instruments, CellHesion200) using cantilevers (BudgetSensors) with spring constant of 5.45 N/m. The setpoint was 19.74 nN, the pulling length was 20 pm and the extent speed was 1 pm/s.
  • i-PDMS and o-PDMS coatings each contain ⁇ 50 wt% free silicone oil within the PDMS matrix. Observed differences in material properties arise from the fabrication process of the coatings, where the oil is added either before curing (o-PDMS) or infused into the polymerized material after curing the PDMS matrix (i-PDMS).
  • the i-PDMS, o-PDMS, and oil-free PDMS control coatings were adhered to a steel or glass substrates.
  • the coating thickness was initially set at ⁇ 100 pm for PDMS control and o-PDMS coatings. Due to the swelling process involved in the production of the i-PDMS from the PDMS control coating, the i-PDMS coating thickness increased to ⁇ 150 pm.
  • the Intersleek 700 treatment also produced a coating with the thickness of - 150 pm according to manufacturer instructions.
  • FIG. 5 A shows the shear modulus of i-PDMS (white bar) and o-PDMS (gray bar).
  • i-PDMS was measured to be 2.4 times stiffer than o-PDMS (through nano-indentation) due to the swelling of the i-PDMS coating.
  • FIGS. 5B-5C show lubricating liquid overlayer detection using atomic force microscopy (AFM) for o-PDMS (FIG. 5C) and i-PDMS (FIG. 5B).
  • the light grey curve represents the “extend” curve (the AFM tip approaching and then contacting the sample).
  • the dark is the inverse “retract” curve, showing the adhesive force experienced by the AFM tip.
  • This adhesive force is much higher for i-PDMS ( ⁇ 26 nN) compared to o-PDMS ( ⁇ 5 nN) due to the presence of the lubricating liquid layer on i-PDMS.
  • Bacteria Biofilm Retraction (Cellulophaga lytica)'. The characterization of bacteria biofilm retraction on coatings prepared in 24-well plates has been described in detail previously. Briefly, overnight cultures of the marine bacterium Cellulophaga lytica in marine broth were harvested via centrifugation (10,000xg for 10 minutes) and rinsed three times with sterile artificial seawater (ASW). The bacteria were then re-suspended in ASW supplemented with 0.5 g/L of peptone and 0.1 g/L of yeast extract to achieve a final cell density between 107-108 cells/mL.
  • ASW sterile artificial seawater
  • Microalgae Cell Attachment (Navicula incerta)'. The characterization of microalgae cell attachment to coatings prepared in 24-well plates has been described in detail previously. Briefly, five-day-old cultures of the microalgae (diatom) Navicula incerta were rinsed three times with ASW and re-suspended in Guillard’s F/2 medium to achieve a final cell density of 105 cells. ml -1 . One ml of the microalgae suspension was added to each well of the coated plates and incubated statically at 18°C for 2 h in an illuminated growth chamber (photon flux density 46 pm m -2 s -1 ).
  • microalgae suspension was subsequently discarded, the coatings were extracted with 1.0 ml of dimethyl sulfoxide for 15 min, and the resulting eluates were transferred to 96-well plates and measured for fluorescence of chlorophyll (Ex: 360 nm; Em: 670 nm) using a Tecan Safire 2 multi-well plate spectrophotometer.
  • Marine Mussel Attachment and Adhesion (Geukensia demissa): The assessment of marine mussel attachment and adhesion was carried out using a customized protocol derived from previously published methods. Freshly collected adults of the ribbed mussel Geukensia demissa (3-5 cm in size) were obtained from the Duke University Marine Laboratory in Beaufort, North Carolina, USA, and housed in an ASW aquarium tank system with continuous monitoring and maintenance of pH (8.0-8.2) and salinity (35 ppt).
  • the mussels were removed from the ASW aquarium tank system and the total number of mussels exhibiting attachment of byssus threads was recorded for each surface.
  • the rod of each attached mussel was then secured to an individual 5N load cell of a custom-built, tensile force gauge outfitted with six load cells to enable simultaneous measurements of all attached mussels.
  • the total force required to detach the byssus threads for each mussel was recorded (1 mm/s pull rate) and the average pull-off force value (Newtons) for all attached mussels was calculated for each coating surface.
  • FIGS. 6A-6D show comparative performance of o-PDMS, i-PDMS, Intersleek 700 and a PDMS control coating (PDMS with no coating) in marine fouling assays.
  • the i-PDMS coating had the best performance in the C. lytica biofilm retraction assay and had the smallest remaining biofilm coverage (7.41% ⁇ 5.74%), followed by Intersleek 700 (34.74% ⁇ 22.83%). PDMS control and o-PDMS showed no retraction at all in this assay.
  • i-PDMS was also the best performing coating in the A. amphitrite barnacle adhesion assay, with barnacle adhesion strength to the i-PDMS (0.018 MPA ⁇ 0.003 MPA) being significantly lower than that of PDMS control, o-PDMS and Intersleek 700.
  • i-PDMS showed a significantly stronger fouling-release performance than o-PDMS during all assays, with the exception of the N incerta microalgal assay, where neither of the two coatings performed differently from the PDMS control.
  • the results summary and the statistical analysis for the laboratory studies can be found in Tables 2-6.
  • FIGS. 7A-7D show fouling coverage and composition on PDMS control (FIG. 7A), Intersleek 700 (IS700) (FIG. 7B), o-PDMS (FIG. 7C), and i-PDMS (FIG. 7D) over a 6-month emersion period at Scituate Harbor, MA.
  • FIGS. 7A-7D show fouling coverage and composition on PDMS control (FIG. 7A), Intersleek 700 (IS700) (FIG. 7B), o-PDMS (FIG. 7C), and i-PDMS (FIG. 7D) over a 6-month emersion period at Scituate Harbor, MA.
  • FIGS. 7A-7D show fouling coverage and composition on PDMS control (FIG. 7A), Intersleek 700 (IS700) (FIG. 7B), o-PDMS (FIG. 7C), and i-PDMS (FIG. 7D) over a 6-month emersion period at Scitu
  • FIGS. 7A-7D show % coverage by slime, solitary tunicates, red algae, green algae, colonial tunicates, hydroids, brown algae, mussels, encrusting bryozoans, and composite fouling (combination of hard and soft fouling organisms growing on top of another). Combination fouling is considered to be the heaviest, most problematic fouling category.
  • FIG. 8 shows representative images of the treated panels (17.5 cm * 17.5 cm) showing the fouling trends observed on each coating (PDMS control, Intersleek 700 (IS700), o-PDMS, and i-PDMS) after 4 weeks, 8 weeks, 12 weeks, 16 weeks, 20 weeks, and 24 weeks.
  • the number of samples for each coating type (N) 5.
  • FIGS. 7A-7D and FIG. 8 the first fouling community to establish was a thin biofilm (or ‘slime’) on all surfaces until week 4. From week 6 onwards these biofilms started to recede, and mussel spat (Mytilus edulis) started to settle on all coatings. [0366] As shown in FIGS. 9A-9B, the settlement of the mussels was quantified at week 8, when the mussel spat was large enough to be counted (approximately 0.5 mm in length).
  • i-PDMS showed the most promising performance at the Scituate Harbor field site, effectively preventing the build-up of the dominant mussel community and delaying the onset of fouling for a period of 4 months. While o-PDMS did not prevent the build-up of the mussel community, it showed sufficient fouling-release properties by the end of the study. In contrast, the PDMS control only showed limited fouling release properties and retained half of its hard-fouling coverage.
  • Field site (Morro Bay, CA, USA): The Cal Poly test site is located near the mouth of Morro Bay (35°22'10" N, 120°51'48” W) and is subjected to a temperate marine environment. It is a floating dock that raises and lowers with the tidal cycle so the panels remain at a constant depth of approximately one meter. The temperature and salinity fluctuate seasonally from 11.2-22.3°C and 13-35%o. Morro Bay’s fouling community is diverse and changes seasonally. barnacle recruitment usually occurs from summer to early fall and late winter to spring. The heaviest fouling occurs between spring and fall.
  • the fouling community consists of sponges, tunicates, tubeworms, hydroids, anemones, tube-dwelling amphipods, arborescent and encrusting bryozoans and several species of barnacles, the most abundant of which is Balanus crenatus. The most dominant species is an invasive encrusting bryozoan Watersipora subtorquata.
  • Hard-fouling field adhesion studies (Morro Bay and Port Canaveral): Hard- fouling adhesion studies of barnacles were conducted according to ASTM D5618-94 by selecting life barnacles, applying shear force to the base of the organism and measuring the removal force. Adhesion failure must be between the organism and the surface for a reading to be valid. The removed organisms are retained and returned to the laboratory where their base plate is measured with a scanner or from measurements of the basal plate diameter in the field. The shear strength of adhesion (MPa) is calculated by dividing the force of removal (Newtons) by the area of the organism base (square millimeters). At the Morro Bay field site this methodology has been adapted for the use on encrusting bryozoans.
  • FIGS. 10A-10D show fouling trends on PDMS (FIG. 10A), IS700 (FIG. 10B), o- PDMS (FIG. 10C), and i-PDMS (FIG. 10D) in Morro Bay over a 15-month immersion period from May 2015 to September 2016.
  • FIGS. 10A-10D show % coverage by soft fouling, hard fouling, and biofilm.
  • the black line in each dataset corresponds with a pressure washing treatment in March 2016 removing all adhered fouling. Any growth from April 2016 onwards represents a newly established fouling community after pressure-washing the panels.
  • Number of samples (N) 5.
  • barnacle adhesion strength on i-PDMS compared with the other coatings could not be conducted, as there was no barnacle settlement on i-PDMS during the study period.
  • barnacle adhesion was significantly lower on Intersleek 700 than on o-PDMS and significantly lower on o-PDMS than on the PDMS control.
  • Tables 9-11 The results summary and the statistical analysis for the encrusting bryozoan and barnacle adhesion can be found in Tables 9-11.
  • Table 9 Summary table of the encrusting bryozoan and barnacle adhesion studies in Morro Bay, showing means and standard deviations of all tested coatings.
  • Field site (Port Canaveral, FL, USA): The FIT field site is located inside Port Canaveral (28°24'27" N, 80°37'38" W) along the central east coast of Florida. The port was created in 1953 and is a hub for cruise and cargo ships, US Navy, Coastguard, fishing vessels and recreational boats. The site is located in a subtropical environment and the water temperature fluctuates between 20-32 deg C, with an average salinity of 35 ⁇ 1.2 ppt. It is an area of high fouling activity with seasonal variation in fouling organisms. The biofouling community in warmer months is dominated by calcareous tubeworms, barnacles, colonial tunicates, and encrusting bryozoans. In cooler months, biofilms and arborescent bryozoans dominate.
  • Hard-fouling field adhesion studies (Morro Bay and Port Canaveral): Hard- fouling adhesion studies of barnacles were conducted at Port Canaveral according to ASTM D5618-94 by selecting life barnacles, applying shear force to the base of the organism and measuring the removal force. Adhesion failure must be between the organism and the surface for a reading to be valid. The removed organisms are retained and returned to the laboratory where their base plate is measured with a scanner or from measurements of the basal plate diameter in the field. The shear strength of adhesion (MPa) is calculated by dividing the force of removal (Newtons) by the area of the organism base (square millimeters).
  • Field site (Singapore Harbor, Singapore): The TMSI test site is located at the Republic of Singapore Yacht Club (RSYC) on the south-west coast of Singapore (1° 17’40” N, 103°45’37” E). Surface water temperatures are relatively high for most part of the year, ranging between 27 to 31 °C. Salinities in the near-coastal areas are typically estuarine, and fluctuate between 20-30 ppt. The most common hard macrofouling organisms observed at the site on panels during the period were tubeworms. Several species of serpulid tubeworms may be found at the test site, especially on unprotected surfaces, including Spirobranchus krausii, Hydroides spp. and Ficopomatus sp.
  • Spirorbid worms were typically abundant throughout the year. Three species of barnacles, Amphibalanus reticulatus, A. cirratus and A. amphitrite occur. The most common mollusc occurring on the panels were Dendrostrea cf. foliaceum and Anomia sp. Soft-fouling on the panels was dominated by encrusting sponges and colonial tunicates. Bryozoans such as Bugula sp. occurs sporadically but the actual fouling cover recorded is always low as the area of contact with the panel surfaces is small and they are usually attached to secondary substrata. Slime coverage was aggressive on all substrates especially during the NE monsoon months.
  • FIGS. 13A-13D show % coverage by soft fouling, hard fouling, and biofilm.
  • the i-PDMS and Intersleek 700 treatments effectively prevented the development of hard fouling communities on coating surface.
  • the fouling communities on both coatings are largely dominated by microalgal biofilms, confirming the results of the laboratory microalgae assay that showed significant diatom adhesion to all coatings (FIG. 6B).
  • Soft fouling was largely absent in the first year of the study ( ⁇ 10% coverage) but became more prominent in the second year with a maximum soft-fouling coverage of - 20% on i-PDMS and - 45% on IS700.
  • the Singapore field results support the general performance trend seen in the Scituate field study and in laboratory assays, with i-PDMS showing the best fouling prevention performance, followed by IS700, o-PDMS, and the PDMS control exhibiting the least fouling prevention performance.
  • Statistical analysis The statistical analysis and bar charts of the adhesion and count data was conducted with GraphPad Prism 8.0.2. Comparative analysis between the treatments was conducted as unpaired t-tests.
  • o-PDMS has a smaller value of N due to the lower density of effective crosslinks, which leads to longer chains and thus fewer chains per volume.
  • o-PDMS with the same number of polymerizable monomers m and crosslinking molecules v will have significantly lower elastic modulus than i-PDMS, due to the linear relationship between shear modulus and crosslinking density.
  • This prediction matches well with our observed shear moduli of 555 kPa and 1342 kPa for o-PDMS and i-PDM,S respectively (Fig. 5 A).
  • the lower elastic modulus of o-PDMS may explain some of its enhanced antifouling performance and reduced adhesion strength of fouling organisms compared to neat, oil-free PDMS (Figs. 6A-6D, 7A-7D, 8), as it has been shown that the shear stress needed T to de-adhere a foulant from a soft elastic surface scales as r ⁇ is the work of adhesion.
  • the improved performance of i-PDMS which is 2.4 times stiffer than o-PDMS (FIG. 5 A), cannot be explained completely with this logic.
  • a thin stable lubricating liquid overlayer (LOL) on its surface. While both experimental (FIG. 5C) and theoretical analyses show that a LOL does not form on o-PDMS at the same silicone oil concentration when not under a stress. This LOL could help to mitigate fouling in multiple ways.
  • the lubricating liquid overlayer could mask the surface, preventing fouling organisms from recognizing it as a suitable solid substrate.
  • the lubricating liquid overlayer also increases surface slipperiness, minimizing the force / weight required to release attached fouling organisms.
  • the LOL is likely responsible for the strong biofilm retraction forces seen in the C. lytica bacterial assay (FIG.
  • FRCs fouling release coatings
  • This theory provides guidance for the future design and optimization of fouling release coatings (FRCs), such as the ability of o-PDMS to form a LOL under biaxial stress, or the optimization of FRC’s composition using fully- biodegradable oils or unique polymer-oil formulations for which the chemical potential is sufficiently low, indicating the low energy cost of removing oil from the matrix and its travel to the free interface to form LOL.
  • FRCs fouling release coatings
  • FIGS. 14A-14B show an experimental set up for application of compression to o- PDMS.
  • Compressed o-PDMS was examined for lubricating liquid overlayer formation, o- PDMS samples were formed by using one-pot method using 10: 1 Sylgrardl84 with 50 wt% loading with lOcSt methyl-terminated silicone oil system.
  • the as-prepared samples were 10 mm x 10 mm x 8.48 mm size.
  • the samples were compressed by 20% of their shortest dimension to induce the formation of lubricating oil overlayer as predicted by the mechanistic model.
  • FIG. 14A shows four samples of stress-free o-PDMS in relaxed state to be used as controls.
  • FIGS. 15A-15D show wetting behavior of compressed o-PDMS (scale bar 1mm) from FIG. 14B. Traces of lubricating liquid were found under the o-PDMS samples, after 3 days of compression (at 20%). The presence of a lubricating oil overlayer was investigated by observing for imprints of a 10 pl droplet on the sample surface. First, as shown in FIG. 15 A, a water droplet was positioned on the surface of the compressed o-PDMS. Next, as shown in FIG. 15B, when the droplet was pulled along the surface once and displaced from the original position. As shown in FIG.
  • FIG. 15C shows the droplet was pulled along the surface for a second time.
  • FIG. 15D shows the same image as FIG. 15C with different lighting and with droplet imprints on the lubricating liquid marked by a dotted line.
  • the imprints shown in FIG. 15C are an artifact of the wetting ridge formed by the lubricating liquid lubricating liquid lubricating liquid lubricating liquid lubricating liquid at the air-droplet interface.
  • the imprints indicate formation of a lubricating liquid overlayer on the compressed o-PDMS surface.
  • FIGS. 16A-16C show wetting behavior of control o-PDMS that was not under compression (scale bar Im) from FIG. 14 A.
  • FIG. 16A shows the initial position of a droplet.
  • FIGS. 16B and 16C show the droplet pulled along the surface once and a second time, respectively.
  • the water droplet in contrast to the compressed o-PDMS, on the control o-PDMS surface, the water droplet resisted movement from its original position.
  • FIGS. 15A-15D and 16A-16C indicate reduced friction/pinning of the water droplets on compressed o-PDMS compared to the control. Additionally, the water droplets left faint imprints on compressed o-PDMS but not on the control o-PDMS, indicating the presence of a thin lubricating liquid layer on compressed o- PDMS but not on control o-PDMS. This indicates facile and smooth droplet mobility due to formation of a lubricating liquid overlayer on compressed o-PDMS but not on control o- PDMS.
  • FIGS. 17A-17D show the effect of compression on lubricating liquid formation after compression 5 and 10 days of compression.
  • Optical imaging of the surface of compressed o-PDMS and control o-PDMS was performed to investigate the presence of lubricating oil overlayer.
  • the compressed o-PDMS sample was maintained at a mechanical compressive strain of 30% and observed after 5 days and 10 days.
  • o-PDMS appears to be mechanically stable under 30% compression (no tearing or breaking observed).
  • FIG. 17A after 5 days under continuous compression, discrete oil “puddles” measuring approximately 100 pm in diameter were observed on the surface of the compressed o-PDMS.
  • FIG. 17A shows that after 5 days under continuous compression, discrete oil “puddles” measuring approximately 100 pm in diameter were observed on the surface of the compressed o-PDMS.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un article comprenant une couche polymère soumise à une force extérieure mettant la couche polymère sous une première contrainte mécanique de compression; ainsi qu'un liquide lubrifiant contenu dans la couche polymère, le liquide lubrifiant se trouvant en une concentration dans la couche polymère de manière que le liquide lubrifiant forme une surcouche stable sur la surface de la couche polymère lorsque la couche polymère est soumise à la force extérieure et le liquide lubrifiant ne forme pas de surcouche stable sur la surface de la couche polymère lorsque la couche polymère n'est pas soumise à une force de compression.
PCT/US2023/069637 2022-07-05 2023-07-05 Surfaces polymères glissantes régulables WO2024086390A2 (fr)

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US63/358,518 2022-07-05

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