WO2010033288A2 - Durable polymer-aerogel based superhydrophobic coatings: a composite material - Google Patents
Durable polymer-aerogel based superhydrophobic coatings: a composite material Download PDFInfo
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- WO2010033288A2 WO2010033288A2 PCT/US2009/049205 US2009049205W WO2010033288A2 WO 2010033288 A2 WO2010033288 A2 WO 2010033288A2 US 2009049205 W US2009049205 W US 2009049205W WO 2010033288 A2 WO2010033288 A2 WO 2010033288A2
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- C—CHEMISTRY; METALLURGY
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
- C09D133/12—Homopolymers or copolymers of methyl methacrylate
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/006—Anti-reflective coatings
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1637—Macromolecular compounds
- C09D5/165—Macromolecular compounds containing hydrolysable groups
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1681—Antifouling coatings characterised by surface structure, e.g. for roughness effect giving superhydrophobic coatings or Lotus effect
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0043—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
- D06N3/0063—Inorganic compounding ingredients, e.g. metals, carbon fibres, Na2CO3, metal layers; Post-treatment with inorganic compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- 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
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- 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
- D10B2401/13—Physical properties anti-allergenic or anti-bacterial
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249971—Preformed hollow element-containing
- Y10T428/249972—Resin or rubber element
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249987—With nonvoid component of specified composition
- Y10T428/24999—Inorganic
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249987—With nonvoid component of specified composition
- Y10T428/249991—Synthetic resin or natural rubbers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
Definitions
- the subject matter of this invention relates to protective coatings and, more particularly, to polymer-aerogel composites.
- Aerogels are unique solids with up to 99% porosity. Such large porosities confer a number of useful properties to aerogels, including high surface area, low refractive index, low dielectric constant, low thermal-loss coefficient, and low sound velocity.
- the potential of aerogels has not generally been realized because conventional supercritical aerogel processing is energy intensive and conventional areogels lack durability.
- most superhydrophobic coatings contain fluorine which can be environmentally unfriendly and may not be cost effective to manufacture.
- the method can include providing a superhydrophobic coating solution, the superhydrophobic coating solution including a surface derivatized polysilicate aerogel dispersed in a first solvent, the polysilicate aerogel including a three dimensional network of silica particles having surface functional groups derivatized with a silylating agent, The method can also include adding a polymer solution to the superhydrophobic coating solution to form a polymer- aerogel blend solution, wherein the polymer solution can include one or more polymers dispersed in a second solvent and dissolving the polymer in the polymer-aerogel blend solution at a first temperature.
- the method can further forming a polymer-aerogel composite coating by applying the polymer-aerogel blend solution to a substrate surface while keeping the polymer-aerogel blend solution at the first temperature, such that the polymer wets the aerogel in the polymer-aerogel composite coating.
- an article including a surface, wherein the surface comprises at least one region and a polymer-aerogel composite coating disposed over the at least one region, wherein the polymer-aerogel composite coating can include a polymer and an ultra high water content catalyzed polysilicate aerogel , the polysilicate aerogel including a three dimensional network of silica particles having surface functional groups derivatized with a silylating agent and a plurality of pores, wherein the polymer-aerogel composite coating has a water contact angle of at least about 140° and a contact angle hysteresis of less than about 1°.
- FIG. 1 shows a method for preparing a polymer-aerogel composite coating in accordance with the present teachings.
- FIG. 2 schematically illustrates a cross section of a portion of an exemplary article in accordance with the present teachings.
- the numerical values as stated for the parameter can take on negative values.
- the example value of range stated as "less that 10" can assume negative values, e.g. - 1 , -2, -3, - 10, -20, -30, etc.
- hydrophobic and hydroophobicity refer to the wettability of a surface (e.g., a coating surface) that has a water contact angle of approximately 85° or more.
- a hydrophobic surface is described as having a low contact angle hysteresis if the difference between advancing and receding contact angles is less than 1°.
- FIG. 1 shows an exemplary method 100 for preparing a polymer-aerogel composite coating, for example, an exemplary polymer-aerogel composite coating 210 is shown in FIG. 2.
- the method 100 can include a step 101 of providing a superhydrophobic coating solution.
- the superhydrophobic coating solution can include a surface derivatized polysilicate aerogel dispersed in a first solvent, the polysilicate aerogel including a three dimensional network of silica particles having surface functional groups derivatized with a silylating agent.
- the step 101 of providing a superhydrophobic coating solution can include providing an ultra high water content acid catalyzed polysilicate aerogel formed using a third solvent, at least one alkoxy silane precursor, water, and an acid, wherein the polysilicate aerogel can include a three dimensional network of silica particles having surface functional groups and a plurality of pores.
- a fluid can be disposed in the plurality of pores.
- Exemplary fluid can include, but is not limited to, first solvent, one or more reaction products of the acid catalyzed hydrolysis of the alkoxy silane, and un-reacted materials such as, for example, alkoxy silane precursor.
- the alkoxy silane precursor can be organically modified silane monomers having a general formula of, for example, (R') x Si(OR) 4-x , wherein x is 1 or 2 and R and R 1 can be the same or different and can include an organic group, such as, for example, an alkyl, an alkenyl, an alkynyl, an aryl group, or combinations thereof.
- the alkoxy silane precursor can include one or more silane compounds including, but not limited to, methyltrimethoxy silane, vinyltrimethoxy silane, dimethyldiethoxy silane, methacryloxypropyltrimethoxy silane, mercaptopropyltrimethoxy silane, chloropropyltrimethoxy silane, bromopropyltrimethoxy silane, iodopropyltrimethoxy silane, and chloromethyltrimethoxy silane, tetraethoxysilane, tetramethoxysilane, and 1 ,2- bls(triethoxysilyl) ethane.
- silane compounds including, but not limited to, methyltrimethoxy silane, vinyltrimethoxy silane, dimethyldiethoxy silane, methacryloxypropyltrimethoxy silane, mercaptopropyltrimethoxy silane, chloropropyltrimethoxy silane, bromopropyl
- the third solvent can be any suitable liquid such as, for example, methanol, ethanol, and any organic solvent at least partially miscible with water.
- the acid can be any suitable acid such as, for example, 1.0 N hydrochloric acid and any source of hydrogen ions.
- the ultra high water content acid catalyzed polysilicate aerogel can be formed using a third solvent, at least one alkoxy silane precursor, water, and an acid, such that a molar ratio of water to alkoxy silane precursor can be in the range of about 10 to about 80, which leads to the distinction of 'ultra high water' content. In some embodiments the molar ratio of water to alkoxy silane precursor can be greater than about 80.
- the polysilicate aerogel can be formed by first adding the third solvent to the alkoxy silane precursor, followed by the addition of water and the acid to form a reaction mixture.
- the reaction mixture can then be agitated and placed at a temperature in the range of about 15°C to about 80 0 C for a period of approximately 1 day to approximately 90 days, and in some cases by placing the reaction mixture at a temperature in the range of about 4O 0 C to about 60 0 C for a period of approximately 3 days to approximately 10 days.
- the polysilicate aerogel can be rather firm and can have appearance from transparent to opaque depending upon the third solvent used.
- the polysilicate aerogel should not be loose at this stage; tapping the bottom of the reaction vessel should result in a reverberation throughout the polysilicate aerogel. Excess water and higher levels of acid catalyst can render the hydrolysis portion of the synthesis the dominating process and limiting the condensation.
- the step 101 of providing a superhydrophobic coating solution can also include replacing the fluid disposed in the plurality of pores of the polysiiicate aerogel with a fourth solvent.
- the polysilicate aerogel can be broken up to form a broken gel before adding a second solvent to the broken gel.
- any suitable solvent immiscible with the third solvent can be used as the fourth solvent, such as, for example, hexane.
- the broken gel in the fourth solvent can be kept at a temperature in the range of about 40 0 C to about 60 0 C for at least about 30 minutes to allow solvent exchange. And finally excess of the fourth solvent and the fluid can be removed from the broken gel. These steps can be repeated at least once, preferably thrice to allow replacement of most of the fluid disposed in the plurality of pores of the polysilicate aerogel.
- Fresh fourth solvent can be added to the polysilicate aerogel before storing in a cold storage at a temperature of less than about 10 0 C.
- the step 101 of providing a superhydrophobic coating solution can further include derivatizing the surface functional groups of the polysilicate aerogel using one or more silylating agents to form a surface derivatized polysilicate aerogel.
- the derivatization of the surface functional groups of the polysilicate aerogel can include gradually adding a silyiating agent adding to the polysilicate aerogel due to s ⁇ ylation reaction being exothermic in nature.
- silane can be used as the silylating agent, such as, for example, trimethylchlorosiiane, trichloromethylsilane, trichlorooctylsilane, hexamethyldisilazane, and any reactive silane including at least one hydrophobic ligand.
- Siiylation reaction may result in bubbling of the solvent and once the bubbling stops, the polysilicate aerogel can be stored in the silyiating agent at a temperature in the range of about 40 0 C to about 60 0 C for about 6 hours to about 10 hours to form a surface derivatized polysilicate aerogel and an excess of the silylating agent can be removed, While not intending to be bound by any specific theory, it is believed that the second solvent helps in the transport of the silylating agent for reaction with the surface functional groups, such as, for example, surface hydroxyl moieties of the polysiiicate aerogel .
- the step 101 of providing a superhydrophobic coating solution can also include forming a coating solution of the surface derivatized polysilicate aerogel in the first solvent
- the coating solution of the surface derivatized polysilicate aerogelgel in the first solvent can be formed by first washing the surface derivatized polysilicate aerogel with an excess of fourth solvent and washing the surface derivatized polysilicate aerogelgel with the first solvent at least twice before adding the first solvent to the surface derivatized polysilicate aerogel to form a coating solution.
- the surface derivatized polysilicate aerogel can be sonicated to break up aggregates and redispersed the surface derivatized polysilicate aerogel in the first solvent.
- any suitable first solvent can be used, such as, for example, ethanol.
- the first solvent can be the same as the third solvent. In other the first solvent can be different from the third solvent.
- the surface derivatized polys ⁇ icate aerogel in the superhydrophobic coating solution can have a concentration in the range of about 0.1 wt.% to about 30 wt.% and in other cases from about 0.5 wt.% to about 10 wt.%.
- the first solvent can be the same as the third solvent.
- the method 100 for preparing a polymer-aerogel composite coating can also include a step 102 of adding a polymer solution to the superhydrophobic coating solution to form a polymer-aerogel blend solution, wherein the polymer solution can include one or more polymers dispersed in a second sumble.
- Any suitable polymer can be used in the formation of the polymer-aerogel blend solution that can bond with the aerogel matrix and provide structural reinforcement.
- Exemplary polymer can be any suitable copolymer, homopolymer, or polymer blend of one or more polymers, including, but not limited to, poly(methyl methacrylate), polystyrene, poly(butyl methacrylate), ⁇ oly(te/i-butyl methacrylate), ⁇ ly(methyl acrylate), poly(butyl acrylate), poly(te/f-butyl acrylate), polyfperfluorooctyl methacrylate), and any suitable vinyl polymer.
- Any suitable second solvent can be used to dissolve the polymer, such as, for example, toluene, acetone, xylene, and ethyl acetate.
- the second solvent can be a system of solvents rather than a single solvent.
- the polymer in the polymer solution can have any suitable concentration depending upon various factors, including, but not limited to, polymer type, molecular weight of the polymer, molecular weight distribution of the polymer, etc. In some cases, the polymer in the polymer solution can have a concentration in the range of about 1 wt% to greater than about 50 wt.% and in other cases from about 5 wt.% to about 50 wt.%.
- the superhydrophobic coating can be present in a major amount and the polymer solution can be present in a minor amount, wherein the major amount refers to volume fraction of more than about 0.5 by and minor amount refers to volume fraction of less than about 0.5.
- the polymer solution can be added to the superhydrophobic coating solution at a volume fraction of about 0.05 to about 0.25 and in other cases about 0.1 to about 0.15.
- the polymer solution can be added to the superhydrophobic coating solution in any desired amount.
- the method 100 for preparing a polymer-aerogel composite coating can also include a step 103 of dissolving the polymer in the polymer-aerogel blend solution at a first temperature and a step 104 of forming a polymer-aerogel composite coating by applying the polymer-aerogel blend solution to a substrate surface while keeping the polymer-aerogel blend solution at the first temperature or at a temperature greater than the first temperature, such that the polymer wets the aerogel in the polymer-aerogel composite coating.
- the step of dissolving the polymer in the polymer-aerogel blend solution at a first temperature can include heating the polymer- aerogel blend solution along with stirring at a first temperature until the polymer dissolves.
- the first temperature can be at least about 100 0 C, in other cases at least about 50 0 C, and in some other cases can be at least about room temperature.
- the polymer-aerogel blend solution can be applied to the substrate surface using any suitable technique, such as, for example, dip coating, brush coating, roller coating, spray coating, spin coating, casting, and flow coating. Any suitable material can be used for the substrate surface, such as, for example, metal, silicon wafers, glass, ceramics, plastics, and fabrics.
- the step 104 of forming a polymer-aerogel composite coating can further include heating the substrate to a second temperature greater than the first temperature.
- the second temperature can be in the range of about 50 0 C to about 300 0 C and in some cases about 100 0 C to about 250 0 C.
- heating the substrate at the second temperature may not be necessary if the polymer component is well dispersed and wets in the aerogel matrix.
- heating to the second temperature depends on a variety of factors, including, but not limited to, second solvent, polymer, polymer content, etc.
- FIG. 2 schematically illustrates a cross section of a portion of an exemplary article 200, in accordance with various embodiments of the present teachings.
- the exemplary article 200 can include a surface 220, the surface 220 including at least one region 230 and a polymer-aerogel composite coating 210 disposed over the at least one region 230, wherein the polymer-aerogel composite coating 210 can have a water contact angle of at least about 140° and a contact angle hysteresis of less than about 1°.
- the polymer-aerogel composite coating 220 can include one or more polymers and an ultra high water content acid catalyzed polysilicate gel, wherein the polysilicate aerogel can include a three dimensional network of silica particles having surface functional groups derivatized with a silylating agent and a plurality of pores.
- Any suitable polymer that can bond with the aerogel matrix and provide structural reinforcement can be used in the polymer-aerogel composite coating 210.
- Exemplary polymer can be any suitable copolymer, homopolymer, or polymer blend of one or more polymers, including, but not limited to, poly ⁇ methyl methacrylate), polystyrene, poly(butyl methacrylate), poly(fert- butyl methacrylate), poly(methyl acrylate), poly(butyl acrylate), poly(terf-butyl acrylate), poly ⁇ perfluorooctyl methacrylate), or any suitable vinyl polymer.
- Exemplary silylating agent can include, but are not limited to, trimethylchlorosilane, trichloromethylsilane, trichlorooctylsilane, hexamethyldisilazane, or any reactive silane including at least one hydrophobic ligand.
- the polymer-aerogel composite coating 210 can include one or more polymers in any suitable amount. In some cases, the polymer can be present in the polymer-aerogel composite coating in an amount from about 5 % by volume to about 50 % by volume. However, the polymer can be present in the poiymer-aerogel composite coating in any suitable amount that can still preserve the functional surface roughness of the aerogel component of the polymer-aerogel composite.
- the polymer-aerogel composite coating 210 can have a thickness from about 0.2 ⁇ m to about 3 ⁇ m.
- the exemplary polymer-aerogel composite coating 210 as disclosed herein can have a low refractive index in the range of about 1.0 to about 1.2 at about 600 nm and can be optically transparent. [0028] In certain embodiments, the polymer-aerogel composite coating 210 can resist corrosion for about 1800 hours or longer.
- the exemplary article 200 can include, but is not limited to an antenna, a window, an automobile, an aircraft, a building, a textile, a boat, a partially and/or fully submerged structure in water and the polymer-aerogel composite coating 210 can be used for a wide variety of applications, including, but not limited to, self-cleaning surface, anti-reflective coating, anti-icing coating, a defogging coating, an anti-microbial coating, a stain resistant coating, and a drag reduction coating in water environment
- the disclosed polymer-aerogel composite coating 210 can be applied on the wings of aircraft for the prevention of ice buildup.
- the polymer-aerogel composite coating 210 as disclosed herein offer all the benefits of other superhydrophobic materials, but provides far more durability, including abrasion resistance than conventional aerogels. Furthermore, the polymer-aerogel composite coatings 210 of the present disclosure are less costly and are safe for biological applications. Also, by not utilizing fluoro-alkyl silanes and similar fluorinated reagents in the manufacture of the polymer-aerogel composite coating 210, of the present disclosure, the polymer-aerogel composite coating 210 and the methods 100 of making them are environmentally friendly.
- Example 1 Preparation of polymeric component polvf methyl methacrylate) for the polymer-aerogel composite
- the polymer, poly(methyl methacrylate) was prepared in about 25 ml scintillation vial without a cap. Methyl methacrylate was polymerized thermally using azobisisobutyronitrile (AIBN) as an initiator and dodecanethiol as a chain transfer agent to skew the resulting molecular weight distribution.
- AIBN azobisisobutyronitrile
- the weight fractions of the reagents used to prepare the polymer are given in Table 1. [0034] Table 1 Material Name weight fraction
- TMCS trimethylchlorosilane
- Example 3 Preparation of polymer-aerogel composite coating
- Example 2 In an about 25 ml scintillation vial, added the superhydrophobic coating solution of Example 2 at a volume fraction of about 0.8696. Added the polymer/toluene solution of Example 1 at a volume fraction of about 0.1304 to the superhydrophobic coating solution of Example 2 to form a polymer-aerogel blend solution. Heated the polymer-aerogel blend solution to about 50 °C and agitated until the polymer was dissolved.
- the substrate was heated at a temperature in the range of about 180 0 C to about 200 0 C for at least about 2 minutes to form a polymer-aerogel composite film having a thickness of about 144 nm.
- the as is polymer-aerogel composite film showed a water contact angle of about 159.40° and 159.30°.
- the polymer-aerogel composite film showed a water contact angle of about 143.00° and 142.50°.
- the destructive wearing testing was done by vigorously rubbing the polymer-aerogel composite film with a finger covered by a rubber giove.
- the polymer-aerogel composite film showed abrasion resistance.
- a 1 B 1 and C means any of the following: either A, B, or C alone; or combinations of two, such as A and B 1 B and C 1 and A and C; or combinations of three A, B and C.
Abstract
Description
Claims
Priority Applications (8)
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AU2009293609A AU2009293609A1 (en) | 2008-06-30 | 2009-06-30 | Durable polymer-aerogel based superhydrophobic coatings: a composite material |
CN2009801252844A CN102099428A (en) | 2008-06-30 | 2009-06-30 | Durable polymer-aerogel based superhydrophobic coatings: a composite material |
CA 2727778 CA2727778A1 (en) | 2008-06-30 | 2009-06-30 | Durable polymer-aerogel based superhydrophobic coatings: a composite material |
JP2011516802A JP2011526958A (en) | 2008-06-30 | 2009-06-30 | Durable, polymer-airgel based superhydrophobic coating: composite material |
US13/121,150 US8663742B2 (en) | 2008-06-30 | 2009-06-30 | Durable polymer-aerogel based superhydrophobic coatings, a composite material |
EP20090814933 EP2294147A2 (en) | 2008-06-30 | 2009-06-30 | Durable polymer-aerogel based superhydrophobic coatings: a composite material |
US14/157,918 US9249333B2 (en) | 2008-06-30 | 2014-01-17 | Durable polymer-aerogel based superhydrophobic coatings: a composite material |
US14/981,400 US10837139B2 (en) | 2008-06-30 | 2015-12-28 | Durable polymer-aerogel based superhydrophobic coatings: a composite material |
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US7714308P | 2008-06-30 | 2008-06-30 | |
US61/077,143 | 2008-06-30 |
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US14/157,918 Division US9249333B2 (en) | 2008-06-30 | 2014-01-17 | Durable polymer-aerogel based superhydrophobic coatings: a composite material |
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EP (1) | EP2294147A2 (en) |
JP (1) | JP2011526958A (en) |
KR (1) | KR20110042267A (en) |
CN (1) | CN102099428A (en) |
AU (1) | AU2009293609A1 (en) |
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Also Published As
Publication number | Publication date |
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US9249333B2 (en) | 2016-02-02 |
US20160130449A1 (en) | 2016-05-12 |
JP2011526958A (en) | 2011-10-20 |
US20110206925A1 (en) | 2011-08-25 |
US20140134907A1 (en) | 2014-05-15 |
CN102099428A (en) | 2011-06-15 |
CA2727778A1 (en) | 2010-03-25 |
US8663742B2 (en) | 2014-03-04 |
KR20110042267A (en) | 2011-04-26 |
EP2294147A2 (en) | 2011-03-16 |
US10837139B2 (en) | 2020-11-17 |
AU2009293609A1 (en) | 2010-03-25 |
WO2010033288A3 (en) | 2010-07-01 |
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