WO2023228162A1 - Procédés et matériaux pour réduire la corrosion ou l'encrassement - Google Patents

Procédés et matériaux pour réduire la corrosion ou l'encrassement Download PDF

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Publication number
WO2023228162A1
WO2023228162A1 PCT/IB2023/055473 IB2023055473W WO2023228162A1 WO 2023228162 A1 WO2023228162 A1 WO 2023228162A1 IB 2023055473 W IB2023055473 W IB 2023055473W WO 2023228162 A1 WO2023228162 A1 WO 2023228162A1
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WIPO (PCT)
Prior art keywords
gas
samples
overlay
plasma
layer
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PCT/IB2023/055473
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English (en)
Inventor
Jas Pal Badyal
Joe RAWLINSON
Patrick Cahill
Grant Hopkins
Original Assignee
Jas Pal Badyal
Rawlinson Joe
Patrick Cahill
Grant Hopkins
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Priority claimed from AU2022901438A external-priority patent/AU2022901438A0/en
Application filed by Jas Pal Badyal, Rawlinson Joe, Patrick Cahill, Grant Hopkins filed Critical Jas Pal Badyal
Publication of WO2023228162A1 publication Critical patent/WO2023228162A1/fr

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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/08—Organic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/14—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by electrical means
    • B05D3/141—Plasma treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/022—Non-woven fabric
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/54—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
    • D04H1/56—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving in association with fibre formation, e.g. immediately following extrusion of staple fibres
    • D04H1/565—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving in association with fibre formation, e.g. immediately following extrusion of staple fibres by melt-blowing
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
    • D04H3/16—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between thermoplastic filaments produced in association with filament formation, e.g. immediately following extrusion
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/02—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements ultrasonic or sonic; Corona discharge
    • D06M10/025—Corona discharge or low temperature plasma
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/08—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with halogenated hydrocarbons
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/62—Plasma-deposition of organic layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2201/00—Polymeric substrate or laminate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2201/00—Polymeric substrate or laminate
    • B05D2201/02—Polymeric substrate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2507/00—Polyolefins
    • B05D2507/01—Polyethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2507/00—Polyolefins
    • B05D2507/02—Polypropylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
    • B05D5/083—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface involving the use of fluoropolymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/24—Organic non-macromolecular coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0253—Polyolefin fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B63—SHIPS OR OTHER WATERBORNE VESSELS; RELATED EQUIPMENT
    • B63B—SHIPS OR OTHER WATERBORNE VESSELS; EQUIPMENT FOR SHIPPING 
    • B63B59/00—Hull protection specially adapted for vessels; Cleaning devices specially adapted for vessels
    • B63B59/04—Preventing hull fouling
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/02—Moisture-responsive characteristics
    • D10B2401/021—Moisture-responsive characteristics hydrophobic
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/10—Physical properties porous
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2505/00—Industrial
    • D10B2505/20—Industrial for civil engineering, e.g. geotextiles

Definitions

  • the invention relates to a method of separating the surface of an object from contained or surrounding liquid by a layer of a gas and materials for use in this method.
  • the invention relates in particular to a method of reducing the fouling, especially the biofouling, of the surfaces of objects immersed in freshwater or seawater.
  • Biofouling is the accumulation of microorganisms, plants, and other creatures (primarily invertebrates, such as barnacles) on submerged surfaces.
  • invertebrates such as barnacles
  • biofouling occurs on manmade structures like ship hulls, aquaculture equipment, or pontoons and jetties it causes major problems because it degrades the surfaces and increases drag and weight.
  • the increased drag from biofouling significantlyincreases carbon emissions from the international shipping fleet, representing a notable contributor to climate change.
  • the increased weight can cause structural damage to aquaculture equipment.
  • Biofouling also represents a biosecurity threat because it allowsinvasive species to establish and spread within the environment.
  • Biofouling management strategies include preventing the settlement of organisms, inhibiting the growth of settled organisms, and manually removing organisms that have grown on surfaces.
  • Foul-release coatings are also available that reduce attachment strength of fouling, meaning that it sloughs off via shear stress. Foul-release coatings can be effective and have minimal environmental concerns, but are applicable to only some scenarios (i.e., fast-moving ships in near continual service). Non-coating technologies are mostly mechanical and are particularly preferred in aquaculture where the avoidance of negative environmental impacts and associated risks to food safety are paramount. The need for improved antifouling technologies is urgent and globally important.
  • the microscopic architecture of the lotus leaf means that water cannot penetrate nanofolds on the surface. Pockets of air trapped within the microscopic architecture of the lotus leaf mean water droplets become suspended in the Cassie-Baxter state and readily roll off the surface. The topography network of barbs and barbules of the feathers of birds also provides for a high degree of water repellency via the same mechanism.
  • the superhydrophobicity of hierarchical structures observed in nature has been the inspiration for the development of fabrication methods for producing artificial superhydrophobic surfaces. Known fabrication methods include particle deposition, sol-gel techniques, plasma treatments, vapour deposition and casting techniques.
  • the publication of Schimmel (2015) discloses the use of large area biomimetic microstructures as gas-retaining layers.
  • the layers are composed of protruding elements spaced apart so that no liquid droplets can become disposed between the elements when the layers are submerged.
  • the gas retaining layer is formed from or coated with a hydrophobic material.
  • An embossed plastic resin or an embossed lacquer is disclosed as the preferred gas-retaining layer.
  • the gas-retaining layers can be used on watercraft to reduce corrosion and fouling.
  • the gas-retaining layers may be fed with a gas directly or via a gas permeable ply.Although the desired characteristics and possible uses of the gas-retaining layers are disclosed, a detailed description of their fabrication is not.
  • the publication of Schimmel (2021) discloses structured, gas holding surfaces for improving the friction-reducing properties of gas layers held under a liquid and for the simultaneous suppression of turbulence.
  • the gas holding surfaces seek to overcome the limitations of air microbubble technology with regard to the avoidance of corrosion or fouling.
  • the gas holding structures disclosed are characterised in that they include projecting longitudinal structures parallel to the flow direction of the liquid.
  • An ideal antifouling technology would provide a broad-spectrum effect against many fouling species, exhibit superior efficacy even in static conditions, cost effectiveness, and ease of integration in existing infrastructure. It is an object of the present invention to provide a technology that provides at least some of these desiderata. It is an object of the present invention to provide a method of reducing corrosion or fouling of submerged surfaces. It is an object of the present invention to provide overlays for use in a method of reducing corrosion or fouling of submerged surfaces. It is an object of the present invention to provide structures that are less susceptible to corrosion or fouling when submerged. These objects are to be read in the alternative with the object at least to provide a useful choice.
  • a method of reducing the corrosion or fouling of a surface of an object immersed in or containing a liquid is provided.
  • the fouling is biofouling
  • the liquid is an aqueous solution. More preferably, the fouling is biofouling, and the liquid is freshwater or seawater.
  • the method comprises applying to the surface of the object an overlay comprising a thickness of a gas permeable gasphilic liquid repellent material.
  • the overlay is used to entrap a layer of gas at the surface of the object when it is immersed in the liquid.
  • the surface of the object is thereby separated from the liquid in which it is immersed.
  • Gas may be delivered to replenish or supplement the layer of gas.
  • the gas may be delivered to replenish or supplement the layer of gas continuously or periodically.
  • the method comprises fabricating the object from a gas permeable gasphilic liquid repellent material.
  • the object entraps a volume of gas at the surface and within the body of the object when it is immersed in the liquid.
  • Gas may be delivered to replenish or supplement the volume of gas.
  • the gas may be delivered to replenish or supplement the volume of gas continuously or periodically.
  • the liquid repellent material when the liquid is an aqueous solution the liquid repellent material is a hydrophobic material, preferably a superhydrophobic material.
  • the liquid repellent material may be both hydrophobic and oleophobic.
  • the gas may be a biocidal gas.
  • biocidal gases include chlorine, hydrogen peroxide, ozone.
  • the biocidal gas may be delivered periodically at a concentration effective to remove any residual biofouling.
  • the surface is preferably a solid surface. More preferably, the surface is a solid outer surface. Most preferably, the surface is a solid outer surface, and the object is selected from the group consisting of: hulls, pontoons and pylons.
  • the method is used in situations where it is desirable to at least reduce direct contact between the liquid and the surface of the solid. The reduction may be a reduction in either or both of the area over which the liquid is in direct contact with the surface of the solid or the period of time for which the liquid is in direct contact with the surface of the solid.
  • the situations where this embodiment of the method is advantageously used include reducing the biofouling of the surfaces of the hulls of vessels and the surfaces of the continuously or periodically submerged portions of freshwater or marine installations.
  • Such installations include pontoons and pylons used in the construction of marinas.
  • the first embodiment of the method of the first aspect comprises contacting the surface with an overlay comprising a thickness of a gas permeable gasphilic liquid repellent material and then delivering air to the second (outer) face of the overlay.
  • the delivering air to the second (outer) face of the overlay may be continuously or periodically.
  • the delivering air to the second (outer) face of the overlay may be either directly to the second (outer) face or via the thickness of the overlay.
  • an overlay may occur before the surface is submerged.
  • the surface may become submerged due to the object being immersed in the liquid, e.g., when a vessel is launched from a dry dock or a pylon is installed.
  • the surface may become submerged due to the liquid engulfing the object, e.g., at high tide.
  • the object is preferably an item of clothing or equipment used in liquid environments. Examples of such objects are used in aquaculture, diving and swimming. More preferably, the object is a net. Most preferably, the object is a fish pen net.
  • an overlay for use in the method of the first aspect comprises a thickness of a gas permeable gasphilic liquid repellent material.
  • the overlay has a first (inner) face and a second (outer) face.
  • the overlay may be a laminate.
  • the overlay is a laminate the thickness of a gas permeable gasphilic liquid repellent material provides the second (outer) face of the overlay.
  • the overlay is a flexible overlay.
  • the material is a porous substrate.
  • the substrate may be selected from the group consisting of: aerogels, cements, ceramics, confined fibres, confined particles, confined platelets, felts, foams, metals, non-woven fibres, sinters, woven fibres, and knitted fibres (including warp knitted fibres).
  • the pore diameter of the porous substrate is less than 50 pm.
  • the fibre diameter is less than 50 pm.
  • the substrate is preferably a polymer.
  • the polymer may be of natural, semisynthetic or synthetic origin.
  • the polymer may be selected from the group consisting of: cellulose, elastomers, lignin, polyamide, polycarbonates, polyester, polyethylene, polypropylene, polysiloxanes, viscose and blends thereof.
  • the polymer is selected from the group consisting of: cellulose, lignin, polyamide, polyester, polyethylene, polypropylene, viscose and blends thereof. More preferably, the polymer is polypropylene.
  • the material is selected from the group consisting of: melt blown non-woven polyolefin material (such as polyethylene or polypropylene), microfiber cloth (composed of 20% (w/w) polyamide and 80% (w/w) polyester), and perforated cloth (composed of 30% (w/w) polyester and 70% (w/w) viscose).
  • melt blown non-woven polyolefin material such as polyethylene or polypropylene
  • microfiber cloth composed of 20% (w/w) polyamide and 80% (w/w) polyester
  • perforated cloth composed of 30% (w/w) polyester and 70% (w/w) viscose
  • the material may be superhydrophobic low contact angle hysteresis zinc oxide coated textile.
  • the surfaces of the interstices delimiting the pores of the porous substrate are made liquid repellent. More preferably, the surfaces of the interstices delimiting the pores of the porous substrate are made hydrophobic. Most preferably, the surfaces of the interstices delimiting the pores of the porous substrate are made superhydrophobic.
  • the liquid repellent material may be both hydrophobic and oleophobic.
  • the surfaces of the interstices delimiting the pores of the porous substrate are made gasphilic.
  • Substrates may be made liquid repellent by one of a number of known methods according to their composition.
  • Known methods of increasing the hydrophobicity of substrates include plasma enhanced and hot filament chemical vapour deposition, electrochemical deposition, fluorination, plasma micro roughening (including oxygen plasma micro roughening), sol-gel processing, nano particle deposition, electrospinning, inductive coupling plasma method, chemical etching, wet chemical reaction and hydrothermal reaction.
  • the material is a porous substrate, methods that increase the hydrophobicity of the surfaces of the interstices delimiting the pores of the substrate are preferred. Increasing the hydrophobicity of the surfaces of the interstices delimiting the pores of the substrate by exposure to a plasma is preferred.
  • CF 4 carbon tetrafluoride
  • the surfaces of the interstices delimiting the pores of the porous substrate are fluorinated.
  • a sample of the thickness of gas permeable gasphilic water repellent material is characterised in that it is capable of maintaining an entrapped layer of air for a period of time of at least 4 days when the sample is held parallel to the surface of a column of water with the upper face of the sample 95 mm below the surface of the column of water (hydrostatic pressure of 0.93 kPa). During the period of time for which the entrapped layer of gas is maintained air permeates the entire thickness of the gas permeable gasphilic liquid repellent material.
  • the overlay is used in a method of entrapping a layer of gas at a surface of a solid otherwise in contact with a liquid.
  • the gas permeable gasphilic overlay is used in circumstances where it is desirable to at least reduce direct contact between the liquid and the surface of the solid.
  • the reduction may be a reduction in either or both of the area over which the liquid is otherwise in direct contact with the surface of the solid or the period of time for which the liquid is otherwise in direct contact with the surface of the solid.
  • the circumstances where the overlay is advantageously used include application to the hulls of ships and other vessels and application to the surfaces of the continuously or periodically submerged portions of freshwater or marine installations. Such installations include pontoons and pylons used in the construction of marinas. Use of the gas permeable gasphilic overlay reduces biofouling of the surface of the structure to which it is applied.
  • the gas will typically be air and the liquid will typically be water.
  • the surface of the gas permeable gasphilic water repellent material will have a liquid contact angle hysteresis value of 30° or less, and a liquid sliding angle of 10° or less.
  • a fouling resistant object fabricated from a gas permeable gasphilic liquid repellent material is provided.
  • the object is an item of clothing or equipment used in liquid environments. Examples of such objects are used in aquaculture, diving and swimming. More preferably, the object is a net. Most preferably, the object is a fish pen net.
  • the fouling resistant object is a net for use in fish pens and the fouling is biofouling.
  • a marine installation or vessel comprising an overlay of the second aspect applied to at least a portion of the surface of the marine installation or vessel is provided.
  • a method of preparing an overlay of the second aspect comprises exposing a thickness of a porous substrate to a plasma for a period of time and at a power sufficient to provide the gas permeable gasphilic liquid repellent material of the overlay.
  • the plasma is a carbon tetrafluoride (CF 4 ) plasma.
  • the porous substrate is a flexible porous substrate.
  • fouling in particular biofouling
  • biofouling is just one form of contamination of an object or surface. It is anticipated that all forms of contamination arising from the contact of a liquid with a surface may be advantageously controlled through use of these aspects and embodiments.
  • concentration or ratio specified is the initial concentration or ratio. Where values are expressed to one or more decimal places standard rounding applies. For example, 1.7 encompasses the range 1.650 recurring to 1.749 recurring.
  • Figure 1 Diagrammatic representation of a volume of gas entrapped at the surface of a solid by the use of an overlay.
  • Figure 2(a) Apparatus for hydrostatic breakthrough test.
  • Figure 2(b) Solid-liquid interface entrapped gas layer bubble chamber.
  • FIG. 3 Scanning electron microscopy (SEM) images of non-woven polypropylene: (a-c) 20 g m -2 untreated; (d-f) 20 g m -2 CF 4 plasma treated (30W, 0.2 mbar, 2 min); and (g-i) 35 g m -2 untreated.
  • SEM scanning electron microscopy
  • Figure 4 CF 4 plasma treatment of non-woven polypropylene: (a) static water contact angle values as a function of electrical discharge power; (b) hydrostatic breakthrough pressure as a function of electrical discharge power; and (c) hydrostatic breakthrough pressure at various electrical discharge powers (0-50W, 0.2 mbar, 2 min) plotted against respective static water contact angle values.
  • Figure 6 Photographs of gas bubble formation on the submerged sample upper surface in the glass bubble chamber: (a) untreated non-woven polypropylene (small bubbles spreading around the surface); (b) CF 4 plasma treated non-woven polypropylene (30W, 0.2 mbar, 2 min) (large bubble gas spreading around the surface); (c) untreated mallard feather (large bubble); and (d) comparison of nitrogen gas bubble diameters formed in the trapped gas layer at the solidliquid interface.
  • Figure 8 Photographs of CF 4 plasma treated and untreated samples of microfibre cloth after 0, 1, 4, 7, 10 and 15 days of immersion in the trapped gas layer apparatus. Images of the untreated sample are shown after 0 and 1 days to show there is no change in appearance.
  • Figure 9 Photographs of CF 4 plasma treated and untreated samples of perforated all-purpose cloth after 0, 1, 2 and 3 days of immersion in the trapped gas layer apparatus. Images of the untreated sample are shown after 0 and 1 days to show there is no change in appearance.
  • Figure 10 Comparison of the longevities of the gas layer entrapped at the surface of CF 4 plasma treated samples of melt blown non-woven polypropylene (20 g m -2 and 35 g m -2 ), microfibre cloth, and perforated all-purpose cloth.
  • FIG. 11 Photographs of treated and untreated samples of non-woven polypropylene material after 0, 4, 8, 14, 21, 27 and 28 days of immersion in the trapped gas layer apparatus.
  • a modified solar air pump was used to introduce 1.9 ⁇ 0.8 mL (mean ⁇ standard deviation of 3 pumps) of air bubbles to the lower surface of the material once every 2 h.
  • FIG. 12 Photographs of untreated (a) and CF 4 plasma treated (b) samples of perforated all-purpose cloth in the trapped gas layer apparatus at point of maximum surface bubble diameter (nitrogen gas delivered from below at a rate of 30 mL/min).
  • FIG. 13 Photographs of untreated (a) and CF 4 plasma treated (b) samples of microfibre cloth in the trapped gas layer apparatus at point of maximum surface bubble diameter (nitrogen gas delivered from below at a rate of 30 mL/min).
  • FIG. 15 Biofouling experiment using treated and untreated melt blown nonwoven polypropylene (20 g m -2 ) showing samples after 0 and 7 days of immersion. Air bubbles were continuously released under samples A to D but not samples E to H.
  • the invention resides at least in part in the entrapment of a volume of gas within and at the surface of the porous substrate of which the overlay is comprised or the object is fabricated.
  • the porous substrate is permeable to gas, e.g., air, while substantially excluding the passage of liquid, e.g., water.
  • the passage of liquid is substantially excluded by both the dimensions of the interstices (pores) of the substrate and the surfaces (walls) delimiting the interstices having been made liquid repellent.
  • the surfaces delimiting the interstices can be made liquid repellent, while retaining the dimensions of the interstices, by a number of known methods.
  • the surfaces (walls) can be made liquid repellent by exposing the porous substrate to a carbon tetrafluoride (CF 4 ) plasma.
  • CF 4 carbon tetrafluoride
  • CF 4 plasma treatment can be used to increase the hydrophobicity of polymers. Surface fluorination rather than surface etching or deposition of plasma polymer results.As disclosed in the publication of Godfrey et al (2001) the CF 4 plasma is capable of permeating a porous substrate. During treatment of the samples of porous substrate described here, the CF 4 plasma readily permeates the thickness of the porous substrate. The surfaces delimiting the interstices of the porous substrate are thereby made liquid repellent.
  • the longevity of the layer of gas entrapped at the surface of the overlay is attributed to the layer being a first portion of the total volume of the gas entrapped at the surface of the submerged solid, the second portion of the total volume of the gas entrapped at the surface of the submerged solid occupying the interstices of the porous substrate.
  • the terms "entrapment” and the phrase “entrapped at” are used to describe the circumstance where the volume of the gas forming the layer is continuous with the volume of the gas occupying the interstices of the porous substrate. The circumstance is to be distinguished from the circumstance where the total volume of the gas forming layer is held at the surface (cf. Schimmel (2015) and Schimmel (2021)) and an overlay comprising a porous substrate of the type described here is not used.
  • FIG. 1 The circumstance where a layer of gas is entrapped at the surface, i.e., the volume of the gas forming the layer is continuous with the volume of the gas occupying the interstices of the porous substrate, is represented diagrammatically for an overlay in Figure 1.
  • a layer of gas (1) is shown separating the surface (2) of the overlay (3) from the liquid (4) in which the solid (5) is immersed.
  • the thickness (6) of the overlay (3) is a porous substrate that is permeated by the gas (1) while excluding the liquid (4).
  • the boundary (7) of the liquid is identified by a broken line. It will be understood that this boundary (7) is dynamic, and the layer of gas (1) may traverse the surface (2).
  • the layer of gas (1) may be replenished or supplemented by the delivery of additional volumes of gas to the surface (2) either directly to the (outer) face (A), or via the thickness (6) of the overlay (3) (B).
  • Means for delivering additional volumes of gas to the surface are known. The publications of Bullard et al (2010), Scardino and Lewis (2009) and Hopkins et al (2021) disclose examples of such means.
  • Other contemplated means for delivering additional volumes of gas to the surface might make use of a chemical reaction, a photochemical reaction, plasmachemical reaction, electrochemical reaction, or electrolysis, at or in the vicinity of the surface.
  • Samples (35 mm x 70 mm approx.) were cut from a thickness of a porous substrate to be treated. Samples were cut from the following materials:
  • a fine melt blown non-woven polypropylene material (20 gm 2 , Product No. M020A1WMS, Don & Low Limited) having a fibre diameter of 3.4 ⁇ 1.9 pm;
  • a fine melt blown non-woven polypropylene material (35 g m -2 , Product No. M035A1WOO, Don & Low Limited) having a fibre diameter of 4.1 ⁇ 2.3 pm;
  • a microfibre cloth composed of 20/80 %(w/w) polyamide/polyester
  • the samples were cleaned by immersion in a 50:50 (v/v) solvent mixture of cyclohexane (+99.5 %, Fischer Scientific UK Limited) and propan-2-ol (+99.5 %, Fischer Scientific UK Limited) for 3 h. The samples were then dried in air at ambient temperature for at least 2 h.
  • Plasma chemical surface functionalisation utilised carbon tetrafluoride feed gas (CF 4 ,+99.7 % purity, Air Products and Chemicals Inc) and was conducted in a cylindrical glass reactor (5 cm internal diameter, 470 cm 3 volume, base pressure lower than 9 x 10 -3 mbar, and a leak rate better than 6 x 10 -10 mol s -1 ) enclosed in a Faraday cage (Hynes et al (1996): Ehrlich and Basford (1992)).
  • the reactor was connected to a 30 L min -1 two-stage rotary pump (model E2M2, Edwards Limited) via a liquid nitrogen cold trap.
  • An inductorcapacitor impedance matching network was used to minimise the standing-wave ratio for power transmission from a 13.56 MHz radio frequency (RF) generator (model ACG-3, ENI Technology Inc) to a copper coil (10 turns, spanning 8 cm) wound externally around the glass chamber.
  • RF radio frequency
  • the reactor was scrubbed with detergent, rinsed with propan-2-ol, and oven-dried at 200 °C.
  • a continuous wave air plasma was then ignited at 50 W power and 0.2 mbar pressure for at least 30 min in order to remove any remaining contaminants, followed by ignition of a continuous wave CF 4 gas plasma at 30 W power and 0.2 mbar pressure for 10 min to condition the glass reactor walls. Samples were placed against the interior chamber wall avoiding any overlap.
  • the system was evacuated to base pressure and purged with CF 4 gas at a pressure of 0.2 mbar for 15 min.
  • the CF 4 electrical discharge was then reignited at various RF powers and allowed to run for 2 min.
  • the RF power generator was switched off, and CF 4 gas allowed to purge the chamber for a further 5 min.
  • the system was evacuated to base pressure and vented to atmosphere.
  • samples were exposed to CF 4 plasma on one face, whilst both sides were sequentially CF 4 plasma treated for solid- liquid interface trapped gas layer longevity, bubble, and biofouling experiments.
  • Samples were mounted onto carbon disks supported on aluminium stubs (part no. Sill, TAAB Laboratories Equipment Limited) and then coated with a thin gold layer (5-10 nm, Polaron E500 SEM Coating Unit, Quorum Technologies Limited).
  • Surface topography images were acquired using a scanning electron microscope (model Vega 3LMU, Tescan Orsay Holdings a.s.) operating in the secondary electron detection mode, in conjunction with an 8 kV accelerating voltage and a working distance of 8-11 mm.
  • Static water contact angles were measured using 7 ⁇ L high purity water droplets (BS 3978 grade 1) and a video contact angle goniometer (VGA 2500 XE, AST Products Limited). Smaller size droplets could not be dispensed from the water syringe needle tip due to the highly liquid repellent nature of the surface of treated samples. Droplet images were analysed using ImageJ software in conjunction with the Dropsnake plugin (Stadler et al (2006)). Static water contact angle values were calculated from measurements taken at three random points on each of three separate samples, and the propagated standard deviation used for the error value.
  • the brass connector fitting containing the sample was attached to a 1 m long graduated glass cylinder (1-inch outer diameter and 23 mm internal diameter).A burette was used to pour water into the top of the graduated tube at a flowrate of 30 mL/min.
  • Entrapped gas was indicated by the formation of a layer of gas at the surface of samples submerged in water.
  • OFMO030001500002069A, Klingersil C4400, Klinger Limited were used to secure each 35 mm x 35 mm square of sample onto a glass support ring such that the sample completely covered the outer gasket and support ring holes.
  • Four strips of adhesive tape (part no. SLT1629146, Henkel Limited) were used to press the two outer gasket seals tightly against the sample and the glass support ring.
  • the cylindrical glass bubble chamber was filled with water to 10 cm above the internal glass support lip, and then the pre-assembled gasket-sample-glass support ring-gasket assembly was lowered into the glass bubble chamber to rest on the internal glass support lip to create an entrapped gas layer at a hydrostatic pressure of 0.93 kPa (9.5 cm of water above the test sample upper face).
  • the upper solid-liquid interface of the entrapped gas layer was visible to the naked eye and gave the sample surface a shimmering silvery appearance due to the total internal reflection of light at the liquid-gas interface characteristic of the superhydrophobic state (Rathgen and Mugele (2010)).
  • nitrogen gas bubbles were introduced at a flowrate of 30 cm 3 min -1 through a 4 mm glass tube inlet into the bottom of the glass bubble chamber regulated with an adjustable fine control needle valve (model MN, CT Platon Limited) and monitored using a gas flowrate meter (model Flostat NG, CT Platon Limited). Diameters of at least 15 gas bubbles visible in the upper surface trapped gas layer of each submerged test sample were measured from videos filmed using a 12-megapixel camera (model A1688, Apple Inc.). Bubble surface diameter values were calculated from the average diameter of three separate samples, and the propagated standard deviation used for the error value.
  • the gas tube inlet of the glass bubble chamber was sealed off using plastic wrapping film (product no. PM-999, Amcor pic) prior to filling the system with water.
  • the glass bubble chamber was then filled with water up to 10 cm above the glass support lip (9.5 cm above the upper face of the sample) and the pre-assembled gasket-sample-glass support ring-gasket assembly was lowered into the glass bubble chamber to rest on the internal glass support lip.
  • Test samples placed into cylindrical glass bubble chambers were photographed on a daily basis until the appearance of a shiny silver upper face (gas layer) disappeared.
  • the upper water level was topped up regularly to avoid evaporation effects by pouring water down the chamber side walls to maintain a steady and even hydrostatic pressure across the upper face of the sample.
  • a light source (model no. G1330, Gritin Company) was placed 10 cm behind each glass chamber to improve visibility of the gas layer.
  • samples were left undisturbed.
  • Static entrapped gas layer longevity values were calculated as the average from at least nine separate samples, and the standard deviation used for the error value.
  • the entrapped gas layer was considered to have collapsed either when the upper face of the sample lost its shiny silvery appearance or when the sample bulged upwards due to the blockage of gas transport through the sample as a consequence of the air layer located on the lower face of the sample having at least partially collapsed (liquid ingress) (Park et al (2019); Huo et al (2019)).
  • Entrapped air layer longevity values were calculated as the average from at least three separate samples, and the standard deviation used for the error value.
  • a large plastic tank (115 L) filled with water from a duck pond was used for biofouling experiments.
  • Four samples of material were mounted in the lid of a closable LDPE plastic box (model no. HPL822B, Locknlock Company) and the box immersed in the tank.
  • the temperature of the water in the tank was in the range 9 to 13 °C during the experiments.
  • the surfaces of the non-woven polypropylene materials consist of continuous random fibrous structures. Fibre diameters are in the micron range and the features of the surface are at a scale comparable to the features of superhydrophobic surfaces occurring in nature (Rijke (1968); Elowson (1984)). Importantly, the fibres appear to remain largely unchanged following 30 W CF 4 plasma exposure. This is attributable to the mild conditions employed (Hopkins et al (1996)). No noticeable structural differences were evident between treated and untreated samples of non-woven polypropylene.Additionally, there were no noticeable structural differences between the 20 g m -2 and 35 g m -2 textiles.
  • the fibrillar topography and hydrophobicity of the surface of non-woven polypropylene material provides untreated samples with high static water contact angle values (148.3 ⁇ 4.6° and 149.6 ⁇ 3.1° for the 20 g m -2 and 35 g m -2 textiles respectively).
  • Untreated samples of the microfibre cloth and the perforated all-purpose cloth exhibited a water contact angle of 0°. Water droplets are absorbed into the thickness of these porous substrates as is characteristic of hydrophilic materials.
  • samples of the perforated all-purpose cloth to CF 4 plasma treatment resulted in a more dramatic increase in hydrophobicity, with a static water contact angle value of 146.1 ⁇ 6.5° being observed for treated samples of this cloth.
  • samples of the microfibre cloth displayed a static water contact angle value of 140.5 ⁇ 13.3°.
  • the displayed contact angle value is likely not a true reflection of the water repellency of these samples.
  • a 30 W electrical discharge power was considered to be optimal for increasing the hydrophobicity (as determined by the static water contact angle) of samples of material and cloth.
  • Microfibre cloth (20/80 %(w/w) polyamide/polyester)
  • This improvement in the longevities of the entrapped gas layers is attributed to a combination of the greater depth of the porous hierarchical structure of the cloth and the hydrophobicity of the surfaces throughout the body of the cloth arising from the CF 4 plasma treatment. This combination results in increased volumes of gas being entrapped at the surface for longer periods of time.
  • the higher weight non-woven polypropylene (35 g m -2 grade) has significantly shorter trapped gas layer lifetimes for both untreated (1.3 ⁇ 0.5 days) and CF 4 plasma treated samples (2.7 ⁇ 0.5 days) compared to their 20 g m -2 grade counterparts (2.5 ⁇ 0.9 days and 4.8 ⁇ 1.1 days respectively).
  • these textiles have similar fibre diameters, static water contact angles, and trapped gas layer surface bubble diameters, it is likely that the material bulk properties also contribute towards trapped gas layer longevity.
  • the longevities of entrapped gas layers with periodic replenishment of the gas layer were also evaluated. Greater surface reflectivity is an indicator of a thicker air layer (Xiang et al (2020)).
  • the entrapped gas layer was considered to have collapsed or dissipated when either: (i) the upper face of a sample lost its shiny silvery appearance, or (ii) the sample bulged upwards due to the transport of gas through the thickness of the sample being blocked. This latter observation was attributed to the gas layer located at the lower face of a sample having at least partially collapsed and the ingress of liquid.
  • the CF 4 plasma treated sample maintained an entrapped gas layer for a period of time of at least 28 days.
  • the period of time for which an entrapped gas layer may be maintained is substantially increased by periodic replenishment of the gas through the depth of the sample.
  • Microfibre cloth (20/80 %(w/w) polyamide/polyester)
  • netting for a fish pen is treated according to the method described here prior to use in the construction of the fish pen.
  • netting e.g., raschel netting
  • Raschel netting has an open construction, with a heavy, textured strand held in place by a much finer strand. They are fabricated by weaving strands of polymers such as polyamides and polyesters.
  • Strands of such polymers comprise an interconnecting network of micro-dimensioned pores, the porosity being a function of how the stands are formed.
  • the woven strands of the raschel netting therefore provide a porous substrate having an irregular, hierarchical surface structure.
  • the prefabricated netting is subjected to plasma chemical surface functionalisation in a reactor using carbon tetrafluoride as the feed gas to increase the hydrophobicity of the porous substrate.
  • the conditions are adjusted to minimise any reduction in the mechanical properties of the netting.
  • the fish pen is constructed using the treated netting. On immersion an entrapped layer of air is retained at the submerged surface of the netting.
  • the entrapped layer may be replenished by periodically releasing air from diffusers located below the netting of the fish pen.
  • the retention and replenishment of the entrapped layer of air may also be facilitated by the incorporation of diffusers into the weave of the netting.
  • the entrapped layer of air will also be replenished when portions of the netting are removed from the water, e.g., during periodic inspections, the replenished entrapped layer of air diffusing across the surface of the functionalised netting.
  • a means of reducing the biofouling of the netting of fish pens that does not disrupt the routine construction, operation and maintenance of fish pens is therefore provided.
  • an overlay is adhered to the outer surface of a pontoon used in the construction of a marina.
  • the overlay is adhered to the portions of the surface that are continuously or intermittently immersed in water.
  • the overlay is a flexible, asymmetric laminate comprising a melt blown non-woven sheet of polypropylene with a resilient porous backing. Prior to lamination the sheet of polypropylene has been subjected to plasma chemical surface functionalisation in a reactor using carbon tetrafluoride as the feed gas to provide a gas permeable gasphilic liquid repellent material as characterised here.
  • the porous backing of the laminate is adhered to the outer surface of the pontoon using a suitable marine adhesive such as polyurethane, e.g., AV510, Bostik Australia Pty Limited, Essendon Fields, Victoria, Australia).
  • a suitable marine adhesive such as polyurethane, e.g., AV510, Bostik Australia Pty Limited, Essendon Fields, Victoria, Australia.

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Abstract

L'invention concerne des procédés permettant de réduire la corrosion ou l'encrassement de surfaces immergées, en particulier les surfaces d'équipements, d'installations et de navires utilisés dans des environnements marins. Les procédés consistent à piéger un volume de gaz, tel que de l'air, au niveau de la surface immergée. Les procédés utilisent des matériaux repoussant les liquides, permettant aux gaz de former une fine couche autour d'eux et perméables aux gaz. L'invention concerne également des procédés de préparation de ces matériaux. Dans un mode de réalisation de ces procédés, des substrats poreux sont exposés à un plasma de tétrafluorure de carbone (CF4).
PCT/IB2023/055473 2022-05-27 2023-05-29 Procédés et matériaux pour réduire la corrosion ou l'encrassement WO2023228162A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003080258A2 (fr) * 2002-03-23 2003-10-02 University Of Durham Procede et appareil permettant la formation de surfaces hydrophobes
KR101465595B1 (ko) * 2013-07-11 2014-11-27 한국생산기술연구원 흡습-발수성 부직포 적층체
US20200216424A1 (en) * 2012-03-03 2020-07-09 Baden-Württemberg Stiftung Ggmbh Gas-containing surface cover, arrangement, and use
US20200362176A1 (en) * 2018-01-31 2020-11-19 Precision Fabrics Group, Inc. Porous polymer coatings

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003080258A2 (fr) * 2002-03-23 2003-10-02 University Of Durham Procede et appareil permettant la formation de surfaces hydrophobes
US20200216424A1 (en) * 2012-03-03 2020-07-09 Baden-Württemberg Stiftung Ggmbh Gas-containing surface cover, arrangement, and use
KR101465595B1 (ko) * 2013-07-11 2014-11-27 한국생산기술연구원 흡습-발수성 부직포 적층체
US20200362176A1 (en) * 2018-01-31 2020-11-19 Precision Fabrics Group, Inc. Porous polymer coatings

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