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  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
  • B01J35/39—Photocatalytic properties
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  • B01D—SEPARATION
  • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
  • B01D53/34—Chemical or biological purification of waste gases
  • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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  • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
  • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
  • B01J21/063—Titanium; Oxides or hydroxides thereof
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  • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
  • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
  • B01J21/08—Silica
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  • B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
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  • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
  • B01J27/053—Sulfates
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  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • B01J27/06—Halogens; Compounds thereof
  • B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, germanium, tin or lead
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  • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • B01J27/24—Nitrogen compounds
  • B01J27/25—Nitrates
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  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/19—Catalysts containing parts with different compositions
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/0215—Coating
  • B01J37/0219—Coating the coating containing organic compounds
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
  • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
  • C23C18/125—Process of deposition of the inorganic material
  • C23C18/1262—Process of deposition of the inorganic material involving particles, e.g. carbon nanotubes [CNT], flakes
  • C23C18/1266—Particles formed in situ
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  • B01D—SEPARATION
  • B01D2255/00—Catalysts
  • B01D2255/20—Metals or compounds thereof
  • B01D2255/207—Transition metals
  • B01D2255/20707—Titanium
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01D2255/00—Catalysts
  • B01D2255/20—Metals or compounds thereof
  • B01D2255/207—Transition metals
  • B01D2255/20792—Zinc
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2255/00—Catalysts
  • B01D2255/30—Silica
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2255/00—Catalysts
  • B01D2255/80—Type of catalytic reaction
  • B01D2255/802—Photocatalytic
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  • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
  • B01J2231/005—General concepts, e.g. reviews, relating to methods of using catalyst systems, the concept being defined by a common method or theory, e.g. microwave heating or multiple stereoselectivity
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
  • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
  • B01J23/42—Platinum
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  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/001—General concepts, e.g. reviews, relating to catalyst systems and methods of making them, the concept being defined by a common material or method/theory
  • B01J2531/002—Materials
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  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/001—General concepts, e.g. reviews, relating to catalyst systems and methods of making them, the concept being defined by a common material or method/theory
  • B01J2531/008—Methods or theories
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  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
  • B01J35/45—Nanoparticles
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/0201—Impregnation
  • B01J37/0211—Impregnation using a colloidal suspension
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/0215—Coating

Definitions

• the present disclosure relates broadly to articles with photocatalytic properties, compositions that form photocatalytic coatings, and methods for making the same.
• Photocatalytic oxidation (PCO) of organic materials such as fingerprints, organic environmental pollutants, and microbes can be carried out by exposing crystalline titanium dioxide coating to ultraviolet light. This process creates hydroxyl radicals and super-oxide ions, which are highly reactive species that are capable of oxidizing organic material (e.g., into carbon dioxide and water).
• Titanium dioxide (titania, T1O2) exists in three crystalline modifications: rutile, anatase, and brookite.
• the photoactivity of T1O2 is well-understood.
• anatase shows the highest photocatalytic activity.
• the present disclosure provides a method of making a coatable composition, the method comprising:
• a first composition comprising silica nanoparticles dispersed in an aqueous liquid vehicle, wherein the silica nanoparticles have an average particle size of less than or equal to 100 nanometers, wherein the first composition has a pH greater than 6;
• Coatable compositions according to the present disclosure are useful, for example, for making photocatalytic articles.
• the present disclosure provides a method of making a photocatalytic article, the method comprising steps:
• the present disclosure provides a photocatalytic article made according to the foregoing method of the present disclosure.
• the present disclosure provides a photocatalytic composition
• a photocatalytic composition comprising an amorphous silica matrix containing titanium cations, wherein the amorphous silica matrix comprises interconnected silica nanoparticles having a particle size distribution with an average particle size of less than or equal to 100 nanometers, wherein a majority of the titanium cations are individually disposed in the amorphous silica matrix, and wherein the titanium metal cations comprise from 0.2 to 40 mole percent of the total combined moles of silicon and titanium cations.
• the present disclosure provides a photocatalytic article comprising a layer of an amorphous photocatalytic composition disposed on a surface of a substrate, wherein the amorphous photocatalytic composition comprises a silica matrix containing titanium cations, wherein the silica matrix comprises interconnected silica nanoparticles having a particle size distribution with an average particle size of less than or equal to 100 nanometers, wherein a majority of the titanium cations are individually disposed in the silica matrix, and wherein the titanium cations comprise from 0.2 to 40 mole percent of the total combined moles of silicon and titanium cations.
• photocatalytic compositions, and articles including them, according to the present disclosure have self-cleaning properties when exposed to light.
• Silica matrixes referred to herein may be amorphous or partially amorphous.
• dispersion of silica nanoparticles refers to a dispersion wherein individual silica nanoparticles are dispersed, and does not refer to a dispersion of fumed silica, which has sintered primary silica particles aggregated into chains;
• essentially free of means containing less than one by percent by weight of, typically less than 0.1 percent by weight of, and more typically less than 0.01 percent by weight of;
• essentially free of non-volatile organic compounds means containing less than one percent by weight of organic compounds having a boiling point above 150° Celsius at 1 atmosphere (100 kPa) of pressure;
• the term "individually disposed in the amorphous silica matrix" in reference to metal cations means that the metal cations are bound through oxygen to silicon, and are not present as a discrete metal phase;
• nanoparticle refers to a particle having a particle size of from 1 to 200 nanometers
• organic compound refers to any compound containing at least one carbon-carbon and/or carbon- hydrogen bond
• photocatalytic means capable of catalytically oxidizing organic material in the presence of ultraviolet light
• metal cation refers to a metal ion having a charge of at least 2+
• silica used in reference to silica nanoparticles and silica sols, refers to a compound represented by the formula SiC ⁇ 'nE ⁇ O, wherein n is a number greater than or equal to zero.
• FIG. 1 is a schematic side view of an exemplary photocatalytic article 100 according to the present disclosure.
• the initial composition comprises silica nanoparticles dispersed in an aqueous liquid medium, wherein the silica nanoparticles have a particle size distribution with an average particle size of less than or equal to 100 nanometers, and wherein the initial composition has a pH greater than 6.
• the silica nanoparticles have an average particle size of less than or equal to 100 nanometers
• the silica nanoparticles have an average particle size of less than or equal to 75 nm, less than or equal to 45 nm, less than or equal to 40 nm, less than or equal to 35 nm, less than or equal to 30 nm, less than or equal to 25 nm, less than or equal to 20 nm, less than or equal to 15 nm, or even less than 10 nm.
• the silica nanoparticles have an average particle size of at least 4 nm, although this is not a requirement.
• the average primary particle size may be determined, for example, using transmission electron microscopy.
• the term "particle size" refers to the longest dimension of a particle, which is the diameter for a spherical particle.
• silica particles with a particle size greater than 200 nm may also be included, but typically in a minor amount.
• the silica nanoparticles desirably have narrow particle size distributions; for example, a polydispersity of 2.0 or less, or even 1.5 or less.
• the silica nanoparticles have a surface area greater than 150 square meters per gram (m ⁇ /g), greater than 200 rn ⁇ /g, or even greater than
• the amount of the silica nanoparticles having an average particle size (e.g., diameter) of 40 nm or less is at least 0.1 percent by weight, and preferably at least 0.2 percent by weight, based on the total weight of the initial composition and/or coatable composition.
• the concentration of the silica nanoparticles having a particle size (e.g., diameter) of 40 nm or less is no greater than 20 percent by weight, or even no greater than 15 percent by weight, based on the total weight of the initial composition.
• the silica nanoparticles may have a polymodal particle size distribution.
• a polymodal particle size distribution may have a first mode with a particles size in the range of from 5 to 2000 nanometers, preferably 20 to 150 nanometers, and a second mode having a second particle size in the range of from 1 to 45 nanometers, preferably 2 to 25 nanometers.
• Nanoparticles (e.g., silica nanoparticles) included in the initial composition can be spherical or non-spherical with any desired aspect ratio.
• Aspect ratio refers to the ratio of the average longest dimension of the nanoparticles to their average shortest dimension.
• the aspect ratio of non-spherical nanoparticles is often at least 2: 1, at least 3: 1, at least 5: 1, or at least 10: 1.
• Non-spherical nanoparticles may, for example, have the shape of rods, ellipsoids, and/or needles.
• the shape of the nanoparticles can be regular or irregular.
• the porosity of coatings can typically be varied by changing the amount of regular and irregular-shaped nanoparticles in the coatable composition and/or by changing the amount of spherical and non-spherical nanoparticles in the coatable composition.
• the total weight of the silica nanoparticles in the initial composition is at least 0.1 percent by weight, typically at least 1 percent by weight, and more typically at least 2 percent by weight. In some embodiments, the total weight of the silica nanoparticles in the composition is no greater than 40 percent by weight, preferably no greater than 10 percent by weight, and more typically no greater than 7 percent by weight.
• Silica sols which are stable dispersions of silica nanoparticles in aqueous liquid media, are well- known in the art and available commercially.
• Non-aqueous silica sols also called silica organosols
• silica sol dispersions wherein the liquid phase is an organic solvent, or an aqueous mixture containing an organic solvent.
• the silica sol is chosen so that its liquid phase is compatible with the dispersion, and is typically an aqueous solvent, optionally including an organic solvent.
• the initial composition does not include, or is essentially, free of fumed silica, although this is not a requirement.
• Silica nanoparticle dispersions e.g., silica sols
• water or water-alcohol solutions are available commercially, for example, under such trade names as LUDOX (marketed by E. I. du Pont de Nemours and Co., Wilmington, Delaware), NYACOL (marketed by Nyacol Co., Ashland, Massachusetts), and NALCO (manufactured by Ondea Nalco Chemical Co., Oak Brook, Illinois).
• LUDOX marketed by E. I. du Pont de Nemours and Co., Wilmington, Delaware
• NYACOL marketed by Nyacol Co., Ashland, Massachusetts
• NALCO manufactured by Ondea Nalco Chemical Co., Oak Brook, Illinois.
• One useful silica sol is
• Acicular silica nanoparticles may also be used provided that the average silica nanoparticle size constraints described hereinabove are achieved.
• Useful acicular silica nanoparticles may be obtained as an aqueous suspension under the trade name SNOWTEX-UP by Nissan Chemical Industries (Tokyo, Japan).
• the mixture consists of 20-21 % (w/w) of acicular silica, less than 0.35% (w/w) of Na20, and water.
• the particles are about 9 to 15 nanometers in diameter and have lengths of 40 to 200 nanometers.
• the suspension has a viscosity of ⁇ 100 mPa at 25°C, a pH of about 9 to 10.5, and a specific gravity of about 1.13 at 20°C.
• acicular silica nanoparticles may be obtained as an aqueous suspension under the trade name SNOWTEX-PS-S and SNOWTEX-PS-M by Nissan Chemical Industries, having a morphology of a string of pearls.
• the mixture consists of 20-21 % (w/w) of silica, less than 0.2% (w/w) of Na20, and water.
• the SNOWTEX-PS-M particles are about 18 to 25 nanometers in diameter and have lengths of 80 to 150 nanometers.
• the particle size is 80 to 150 nm by dynamic light scattering methods.
• the suspension has a viscosity of ⁇ 100 mPas at 25°C, a pH of about 9 to 10.5, and a specific gravity of about 1.13 at 20°C.
• the SNOWTEX-PS-S has a particle diameter of 10-15 nm and a length of 80-120 nm.
• Low- and non-aqueous silica sols may also be used and are silica sol dispersions wherein the liquid phase is an organic solvent, or an aqueous organic solvent.
• the silica nanoparticle sol is chosen so that its liquid phase is compatible with the intended coating composition, and is typically aqueous or a low-aqueous organic solvent.
• Silica sols having a pH of at least 8 can also be prepared according to the methods described in U.S. Patent No. 5,964,693 (Brekau et al.).
• the initial composition can further include other nanoparticles, including, for example, nanoparticles comprising aluminum oxide, titanium oxide, tin oxide, antimony oxide, antimony- doped tin oxide, indium oxide, tin-doped indium oxide, or zinc oxide.
• nanoparticles comprising aluminum oxide, titanium oxide, tin oxide, antimony oxide, antimony- doped tin oxide, indium oxide, tin-doped indium oxide, or zinc oxide.
• the initial composition has a pH greater than 6, more typically greater than 7, more typically greater than 8, and even more typically greater than 9.
• the initial composition is essentially free of non- volatile organic compounds. In some embodiments, the initial composition is essentially free of organic surfactants.
• the aqueous liquid medium of the initial composition may comprise (in addition to water) at least one volatile organic solvent.
• suitable volatile organic solvents include those volatile organic solvents that are miscible with water such as, e.g., methanol, ethanol, isopropanol, and combinations thereof.
• methanol, ethanol, isopropanol, and combinations thereof volatile organic solvents that are miscible with water
• reduction or elimination of volatile organic compounds will be desirable, and advantageously the present disclosure may be practiced using initial compositions and/or coatable compositions that are essentially free of volatile organic solvent.
• the initial composition is acidified by addition of inorganic acid until it has a pH of less than or equal to 4, typically less than 3, or even less than 2 thereby providing the coatable composition.
• Useful inorganic acids include, for example, hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, perchloric acid, chloric acid, and combinations thereof.
• the inorganic acid is selected such that it has a pK a of less than or equal to two, less than one, or even less than zero, although this is not a requirement.
• the present inventors believe that some agglomeration of the silica nanoparticles occurs as the pH falls, resulting in a dispersion comprising agglomerated nanoparticles.
• Combination of the various ingredients in the above compositions may be carried out using any suitable mixing technique. Examples include stirring, shaking, and otherwise agitating the composition during or after addition of all components of the composition.
• Useful titanium compounds include, for example, TiOSOz ⁇ FFjO, TiOSOzj-FF ⁇ SOzj-xFFjO, TiO ⁇ 3 ⁇ 4, and TiCl 4 .
• Optional metal compound(s) may comprise a metal (or metal cation), other than titanium, in any of groups 2 through 15 (e.g., group 2, group 3, group 4, group 5, group 6, group 7, group 8, group 9, group 10, group 1 1 , group 12, group 13, group 14, group 15, and combinations thereof) of the Periodic Table of the Elements.
• groups 2 through 15 e.g., group 2, group 3, group 4, group 5, group 6, group 7, group 8, group 9, group 10, group 1 1 , group 12, group 13, group 14, group 15, and combinations thereof
• metal compound(s) may have a charge of n+, wherein n represents an integer > 2 (e.g., 2, 3, 4, 5, or 6), for example.
• the metal compounds should have sufficient solubility in water to achieve the desired level of metal incorporation in the resultant soil- resistant composition.
• the metal compound(s) may comprise metal salt(s).
• useful metal compounds include copper compounds (e.g., ⁇ (3 ⁇ 4 or Cu(N03)2), platinum compounds (e.g., ITjPtClg), aluminum compounds (e.g., ⁇ 1( ⁇ 3)3 ⁇ 9 ⁇ 2 ⁇ ), zirconium compounds (e.g., ZrCL ⁇ or
• ⁇ (3 ⁇ 4 ⁇ 8 ⁇ 20) zinc compounds (e.g. Zn(N03)2-6H20), iron compounds (e.g., FeC ⁇ FFjO or FeC ⁇ ), tin compounds (e.g., SnCl2 and SnCLj-SFF ⁇ O), and combinations thereof.
• zinc compounds e.g. Zn(N03)2-6H20
• iron compounds e.g., FeC ⁇ FFjO or FeC ⁇
• tin compounds e.g., SnCl2 and SnCLj-SFF ⁇ O
• Coatable compositions according to the present disclosure may further comprise one or more optional additives such as, for example, colorant(s), surfactant(s), thickener(s), thixotrope(s), or leveling aid(s).
• optional additives such as, for example, colorant(s), surfactant(s), thickener(s), thixotrope(s), or leveling aid(s).
• the coatable composition may comprise an added surfactant, however, the inventors have unexpected discovered that coatable compositions according to the present disclosure wet out at least some hydrophobic surfaces without added surfactant.
• the solids in the coatable composition may comprise from 30 to 99 percent by weight of silica, desirably from 60 to 97.5 percent by weight of silica, more desirably from 80 to 95 percent by weight of silica, although other amounts may also be used.
• the coatable composition may comprise from 0.2 to 40 mole percent by of metal ions contained in the metal compound(s) based on the total combined moles of silicon and metal ions
• metal ions including titanium compounds and optional non-titanium metal cations, preferably from 0.5 to 25 mole percent by of metal ions, more preferably from 1.0 to 20.0 percent by weight of metal ions, although other amounts may also be used.
• the coating composition is typically stable over long periods of time, over a range of temperatures, although this is not a requirement.
• the coating composition may be coated onto a substrate and at least partially dried, typically substantially completely dried.
• the coatable composition can be contacted with a surface of a substrate and at least partially dried to form a photocatalytic coated article.
• coatable compositions according to the present disclosure can be contacted with a surface of a substrate and at least partially dried to provide a defect- free layer with unexpected photocatalytic properties, even though anatase titania does not appear to be present.
• Suitable methods of drying the coatable composition include, for example, evaporation in air at about room temperature, ovens, heated air blowers, infrared heaters, and hot cans. Drying is typically carried out until the coatable composition is substantially completely dry, although this is not a requirement.
• the photocatalytic layer may be aged for a period of time such as for example, at least 1 hour (hr), at least 4 hrs, at least 8 hrs, at least 24 hrs, at least 72 hrs, at least 1 week, or even at least 2 weeks, during which time the soil-resistance of the photocatalytic layer may improve.
• photocatalytic article 100 comprises photocatalytic layer 1 10 disposed on surface 120 of substrate 130.
• suitable methods of contact the coatable composition with the surface of the substrate include roll coating, spray coating, gravure coating, dip coating, and curtain coating.
• the photocatalytic layer has a thickness in the range of from 0.02 to 100 microns, preferably 0.05 to 10.0 microns, although this is not a requirement.
• photocatalytic layers according to the present disclosure are at least substantially transparent; however, this is not a requirement.
• suitable substrates include virtually any dimensionally-stable material. Examples include glass substrates (e.g., mirrors, windows, windshields, tables, lenses, and prisms), metal substrates, ceramic substrates, organic polymer substrates (e.g., molded polymer articles, automotive paints and clearcoats, polymer films, retroreflective sheeting, indoor signage, and outdoor signage), and fabric (e.g., upholstery fabric).
• the substrate comprises at least one of glass or an organic polymer.
• the organic polymer comprises at least one of a polyester (e.g., polyethylene terephthalate or polybutylene terephthalate), polycarbonate, allyldiglycol carbonate, acrylics (e.g., polymethyl methacrylate (PMMA)), polystyrene, polysulfone, polyether sulfone, homo-epoxy polymers, epoxy addition polymers with polydiamines and/or polydithiols, polyamides (e.g., nylon 6 and nylon 6,6), polyimides, polyolefms (e.g., polyethylene and polypropylene), olefinic copolymers (e.g., polyethylene copolymers), and cellulose esters (e.g., cellulose acetate and cellulose butyrate), and combinations thereof.
• a polyester e.g., polyethylene terephthalate or polybutylene terephthalate
• polycarbonate e.g., polycarbonate, allyldig
• the present disclosure provides a method of making a coatable composition, the method comprising:
• a first composition comprising silica nanoparticles dispersed in an aqueous liquid vehicle, wherein the silica nanoparticles have an average particle size of less than or equal to 100 nanometers, wherein the first composition has a pH greater than 6;
• the present disclosure provides a method according to the first embodiment, wherein the silica nanoparticles have an average particle size of less than or equal to 50 nanometers.
• the present disclosure provides a method according to the first or second embodiment, wherein the at least one metal compound further comprises a zinc compound.
• the present disclosure provides a method according to any one of the first to third embodiments, wherein the at least one metal compound further comprises a tin compound.
• the present disclosure provides a method according to any one of the first to fourth embodiments, wherein the coatable composition is essentially free of organic non-volatile compounds.
• the present disclosure provides a method according to any one of the first to fifth embodiments, wherein the first composition further comprises polymer particles dispersed in the aqueous liquid vehicle.
• the present disclosure provides a coatable composition made according to the method of any one of the first to sixth embodiments,
• the present disclosure provides a method of making a photocatalytic article, the method comprising steps:
• the present disclosure provides a method according to the eighth embodiment, wherein the silica nanoparticles have an average particle size of less than or equal to 50 nanometers.
• the present disclosure provides a method according to the eighth or ninth embodiment, wherein the at least one metal compound further comprises a zinc compound.
• the present disclosure provides a method according to any one of the eighth to tenth embodiments, wherein the at least one metal compound further comprises a tin compound.
• the present disclosure provides a method according to any one of the eighth to eleventh embodiments, wherein the first composition further comprises polymer particles dispersed in the aqueous liquid vehicle.
• the present disclosure provides a method according to any one of the eighth to twelfth embodiments, wherein the substrate comprises glass or organic polymer.
• the present disclosure provides a method according to any one of the eighth to thirteenth embodiments, wherein the organic polymer comprises at least one of polyethylene terephthalate or polymethyl methacrylate.
• the present disclosure provides a method according to any one of the eighth to fourteenth embodiments, wherein the photocatalytic layer is optically clear.
• the present disclosure provides a method according to any one of the eighth to fifteenth embodiments, wherein the photocatalytic layer has a thickness in a range of from 0.02 to 100 microns.
• the present disclosure provides a method according to any one of the eighth to sixteenth embodiments, wherein the inorganic acid has a pK a of less than or equal to zero.
• step b) comprises acidifying the first composition to a pH of less than or equal to 2.
• the present disclosure provides a method according to any one of the eighth to eighteenth embodiments, wherein the coatable composition is essentially free of organic nonvolatile compounds.
• the present disclosure provides a photocatalytic article made according to the method of any one of the eighth to nineteenth embodiments.
• the present disclosure provides a photocatalytic article according to the twentieth embodiment, wherein the photocatalytic article comprises retroreflective sheeting.
• the present disclosure provides a photocatalytic composition
• a photocatalytic composition comprising an amorphous silica matrix containing titanium cations, wherein the amorphous silica matrix comprises interconnected silica nanoparticles having a particle size distribution with an average particle size of less than or equal to 100 nanometers, wherein a majority of the titanium cations are individually disposed in the amorphous silica matrix, and wherein the titanium metal cations comprise from 0.2 to 40 mole percent of the total combined moles of silicon and titanium cations.
• the present disclosure provides a photocatalytic composition according to the twenty-second embodiment, wherein the amorphous silica matrix contain further contains metal cations selected from the group consisting of copper compounds, platinum compounds, zinc compounds, iron compounds, tin compounds, and combinations thereof.
• the present disclosure provides a photocatalytic composition according to the twenty-second or twenty-third embodiment, wherein the silica nanoparticles have an average particle size of less than or equal to 50 nanometers.
• the present disclosure provides a photocatalytic composition according to any one of the twenty-second to twenty-fourth embodiments, wherein the silica nanoparticles have an average particle size of less than or equal to 25 nanometers.
• the present disclosure provides a photocatalytic composition according to any one of the twenty-second to twenty-fifth embodiments, wherein the photocatalytic composition is essentially free of organic non-volatile compounds.
• the present disclosure provides a photocatalytic article comprising a layer of an amorphous photocatalytic composition disposed on a surface of a substrate, wherein the amorphous photocatalytic composition comprises a silica matrix containing titanium cations, wherein the silica matrix comprises interconnected silica nanoparticles having a particle size distribution with an average particle size of less than or equal to 100 nanometers, wherein a majority of the titanium cations are individually disposed in the silica matrix, and wherein the titanium cations comprise from 0.2 to 40 mole percent of the total combined moles of silicon and titanium cations.
• the present disclosure provides a photocatalytic article according to the twenty-seventh embodiment, wherein the amorphous silica matrix further contains metal cations selected from the group consisting of copper compounds, platinum compounds, zinc compounds, iron compounds, tin compounds, and combinations thereof.
• the present disclosure provides a photocatalytic article according to the twenty-seventh or twenty-eighth embodiment, wherein the silica nanoparticles have an average particle size of less than or equal to 50 nanometers.
• the present disclosure provides a photocatalytic article according to any one of the twenty- seventh to twenty-ninth embodiments, wherein the silica nanoparticles have an average particle size of less than or equal to 25 nanometers.
• the present disclosure provides a photocatalytic article according to any one of the twenty- seventh to thirtieth embodiments, wherein the substrate comprises glass or an organic polymer.
• the present disclosure provides a photocatalytic article according to any one of the twenty- seventh to thirty-first embodiments, wherein the organic polymer comprises at least one of polymethyl methacrylate or polyethylene terephthalate.
• the present disclosure provides a photocatalytic article according to any one of the twenty-seventh to thirty-second embodiments, wherein the photocatalytic layer is optically clear.
• the present disclosure provides a photocatalytic article according to any one of the twenty-seventh to thirty -third embodiments, wherein the photocatalytic layer has a thickness in a range of from 0.02 to 100 microns.
• the present disclosure provides a photocatalytic article according to any one of the twenty- seventh to thirty-fourth embodiments, wherein the coatable composition is essentially free of organic non-volatile compounds.
• the present disclosure provides a photocatalytic article according to any one of the twenty- seventh to thirty- fifth embodiments, wherein the substrate comprises retroreflective sheeting.
• NALCO 1 1 15 (4 nm), NALCO 1050 (20 nm), and NALCO DVSZN004 (45 nm) colloidal silicas were obtained from Nalco Chemical Company, Naperville, Illinois under the respective trade designations NALCO 1 1 15, NALCO 1050, and NALCO DVSZN004 colloidal silica.
• PET film 50 micrometers thick was obtained from E.I. du Pont de
• TiOS04-2H20 was obtained from NOAH Technologies Corporation, San Antonio, Texas.
• Zn(N03)2'6H20 was obtained from Mallinckrodt Baker, Inc., Phillipsburg, New Jersey.
• Cu(N03)2-3H20 was obtained from Morton Thiokol Inc., Danvers, Massachusetts.
• SnCl4-5H20 was obtained from Sigma-Aldrich Co., Saint Louis, Missouri.
• Methylene blue was obtained from Mallinckrodt Inc., Paris, Kentucky.
• the dry coating thickness was about 100 nm to 300 nm.
• the coated samples were heated at 120°C for 10 minutes, and then heated at a temperature of from 300°C to 700°C for 2 minutes, as indicated.
• For PET substrate the coated samples were heated at 120°C for 10 minutes.
• Methylene blue was dissolved in deionized water and diluted to 1 mg/ml. Methylene blue solution was coated onto silica and titanium-modified silica coated surfaces on glass substrates using a dip coater at a drawing speed of 242.6 mm/min.
• Methylene blue was dissolved in deionized water and diluted to a concentration of 1 milligram/milliliter (mg/mL).
• the methylene blue solution was coated onto silica and titanium-modified silica coated surfaces on PET substrates using a #6 wire-wound coating rod.
• UVLAMP CHAMBERS USED FOR PHOTOCATALYTIC TESTING UV CHAMBER A The UV lamp chamber with a spectral output maximum at 365 nm was a
• UV CHAMBER B The UV lamp chamber with a spectral output maximum 254 nm was a planar bank of 6 germicidal lamps (Philips TUV G15T8 germicidal bulb, low-pressure mercury, 15 W,
• Coated glass slides or PET films were in the indicated UV lamp chamber for photocatalytic performance tests (above).
• the irradiation time was from 15 minutes to 5 hours, as indicated.
• Transmission and haze measurements were made using a HAZE-GUARD PLUS purchased from BYK-Gardner USA (Columbia, MD, USA). The transmission and absorbance at wavelengths from 300 nm to 900 nm were performed using a UV-Vis spectrometer from PerkinElmer Inc., Waltham,
• Acidified mixed silica nanoparticle dispersion Colloidal silica(s) NALCO 1 1 15, NALCO 1050, and NALCO DVSZN004 were diluted to with deionized water, and mixed in desired ratios.
• desired amounts of metal compounds were added to the silica solutions.
• Titanium-modified silica coating solutions were prepared by adding an aqueous solution of
• TiOS04-2H20 to the acidified silica nanoparticle solution suspensions.
• Comparative Example A (2.0 g) was mixed with 0.8571 g of a 10 weight percent TiOSOz ⁇ L ⁇ O solution in deionized water.
• the resulting acidified dispersion which contained 29.7 weight percent of TiOS04-2H20, was coated using a #6 wire -wound coating rod on flashlamp-treated PET film. The coated samples were heated at 120°C for 10 minutes.
• Comparative Example A (2.0 g) was mixed with 4.6667 g of a 10 weight percent TiOS04-2H20 solution in deionized water. The resulting acidified dispersion, which contained 69.3 weight percent of TiOS04-2H20, was coated using a #6 wire -wound coating rod on flashlamp-treated PET film. The coated samples were heated at 120°C for 10 minutes. Comparative Example A and Examples 1 -2 were coated with a solution of methylene blue (MB) in deionized water (1 mg/mL) using a #6 wire -wound coating rod, and dried at the room temperature. The dye coated samples were put into UV Chamber A and irradiated at 365 nm. The samples were taken out of the chamber for the measurement of percent transmission and haze every hour. The results are reported in Table 1. Results show that titanium-doped silica coatings have higher degradation rate of MB than the silica coating itself.
• the acidified-dispersion was coated using a #6 wire- wound coating rod on flashlamp-treated PET film. The coated samples were heated at 120°C for 10 minutes.
• Comparative Example B (2.0 g) was mixed with 0.8571 g of a 10 weight percent TiOSOz ⁇ L ⁇ O solution in deionized water.
• the resulting acidified dispersion which contained 29.7 weight percent of TiOS04-2H20, was coated using a #6 wire -wound coating rod on flashlamp-treated PET film. The coated samples were heated at 120°C for 10 minutes.
• Comparative Example B and Example 3 were coated with a solution of Methylene Blue (MB) in deionized water (1 mg/mL) deionized water solution using a #6 wire-wound coating rod, and dried at the room temperature.
• a sample of Comparative Example B that was not coated with methylene blue was also used.
• the dye coated samples were put into UV Chamber A and irradiated at 365 nm. The samples were taken out of the chamber for the measurement of percent transmission and haze every hour. The results are reported in Table 2. Results show that titanium-doped silica coatings have higher degradation rate of MB than the silica coating itself.
• Comparative Example B and Example 3 were coated with a solution of methylene blue (MB) in deionized water (1 mg/mL) using a #6 wire-wound coating rod, and dried at the room temperature.
• a sample of Comparative Example B that was not coated with methylene blue was also used.
• the dye coated samples were put into UV Chamber B and irradiated at 254 nm. The samples were taken out of the chamber for the measurement of percent transmission and haze every 15 minutes. The results are reported in Table 3. Results show that titanium-doped silica coatings have higher degradation rate of MB than the silica coating itself.
• Comparative Example B (180 grams) was mixed with 45.0 grams of TiOS04-2H20 solution (10 weight percent) to obtain 10 weight percent solution dispersion containing 19.8 weight percent of TiOS04-2H20. Fifty grams of the above mixture was diluted by deionized water to 100 grams, resulting in a 5 weight percent solids dispersion. The resulting acidified dispersion solution contained 19.8 weight percent of total solids TiOS04'2H 2 0
• Comparative Example B and Example 4 Three samples each of Comparative Example B and Example 4 were dip coated at a drawing speed of 242.6 mm/min on a SOLITE glass substrate. The coated samples were heated at 120°C for 10 minutes. Samples of Comparative Example B and Example 4 were further heated at 600°C for 2 minutes. Different samples of Comparative Example B and Example 4 were heated at 700°C for 2 minutes after their initial heating at 120°C for 10 minutes. The resulting six samples were coated by methylene blue (MB) with a concentration of 1 mg/mL deionized water solution using a dip coater at the same speed and dried at the room temperature.
• MB methylene blue
• the MB-coated samples were put in UV Chamber A. The samples were taken out from chamber for transmission measurement every hour. Results are reported in Table 4. The results indicate that the titanium-doped silica coatings have larger transmission changes than the silica coating itself after low and high temperature treatment.
• Comparative Example B (100 g) was mixed with 40.920 grams of (10 weight percent in deionized water). The resulting 10 weight percent solids acidified dispersion solution contained 28.8 weight percent of total solids TiOS0 4 -2H 2 0.
• Example 5 (45 g) was mixed with 45 grams of deionized water The resulting 5 weight percent solids acidified dispersion solution contained 28.8 weight percent of total solids TiOSOz ⁇ O.
• the titanium doped silica coating samples of EXAMPLES 5-6 were created by coating the dispersion solutions EXAMPLE 5 and EXAMPLE 6 using a #6 wire -wound coating rod on the PET substrates. All the coated samples were heated at 120 °C for 10 minutes. Samples of EXAMPLE 5 and EXAMPLE 6 were further coated with a methylene blue solution in deionized water (1 mg/mL) using a #6 wire -wound coating rod and dried at the room temperature. MB-coated samples of EXAMPLE 5 and EXAMPLE 6 were put into UV Chambers A or B for photocatalytic activity testing. Samples were taken out from the chambers for transmission measurement every 15 minutes for the samples in UV Chamber B, and every one hour for the samples in UV Chamber A. Results are reported in Tables 5 and 6.
• Comparative Example B (100 g) was mixed with 45.478 grams of Zn(N03)2'6H20 (10 weight percent in deionized water). The resulting 10 weight percent solids acidified dispersion solution contained 30.6 weight percent of total solids Zn(N03)2'6H20.
• Comparative Example C (45 g) was mixed with 45 grams of deionized water The resulting 5 weight percent solids acidified dispersion solution contained 30.6 weight percent of total solids of ⁇ ( ⁇ 0 3 ) 2 ⁇ 6 ⁇ 2 0.
• Comparative Example C and Example 7 were coated using a #6 wire-wound coating rod onto PET substrates. All the coated samples were heated at 120°C for 10 minutes. Two coated samples of Comparative Example C and two coated samples of Example 6 were further coated by a methylene blue solution in deionized water (1 mg/mL) using a #6 wire -wound coating rod, and dried at the room temperature. The MB-coated samples were put in the UV Chamber A or UV Chamber B for photocatalytic activity testing. The MB-coated samples were taken out from the chambers for transmission measurement every 15 minutes for the samples in UV Chamber B, and every one hour for the samples in UV Chamber A. Results are reported in Tables 5 and 6.
• Comparative Example B 100 grams was mixed with 40.920 grams of T1OSO4 TiOS04-2H20 (10 weight percent solids in deionized water) and 22.739 grams of Zn(N03)2'6H20 (10 weight percent solids in deionized water). The resulting 10 weight percent coating solution contained TiOS04-2H20 (24.7 weight percent) and Zn(N03)2-6H20 (13.6 weight percent).
• Example 8 (45.0 g) was diluted with 45.0 grams of deionized water.
• the resultant 5 weight percent solids coating solution contained 24.7 weight percent of total solids TiOS04-2H20 and 13.6 weight percent of total solids Zn(N03)2-6H20.
• Comparative Example B (100 g ) was mixed with 40.920 grams of TiOS04-2H20 (10 weight percent solids in deionized water) and 45.478 grams of Zn(N03)2'6H20 (10 weight percent solids in deionized water).
• the resulting 10 weight percent solids coating solution contained TiOS04-2H20 (21.7 weight percent of total solids) and Zn(N03)2-6H20 (23.9 weight percent of total solids).
• Example 10 (45.0 g) was diluted with 45.0 grams of deionized water. The resulting 5 weight percent solids coating solution contained TiOS04-2H20 (21.7 weight percent of total solids) and
• Examples 8-1 1 were coated using a #6 wire -wound coating rod onto PET film substrates. All the coated samples were heated at 120°C for 10 minutes. Two coated samples of each of Examples 8-1 1 were further coated with a methylene blue (MB) solution in deionized water (1 mg/mL) using a #6 wire -wound coating rod, and dried at the room temperature.
• MB methylene blue
• MB-coated samples were separately put into UV Chambers A and B for photocatalytic activity testing.
• the coated samples were taken out from the chambers for transmission measurement every 15 minutes for the samples in UV Chamber B and every one hour for the samples in UV Chamber A.
• the transmission changes of the coating samples after irradiation are reported in Tables 5 (using UV Chamber B) and 6 (using UV Chamber A). The results indicate that the bimetal zinc and titanium doped silica coatings have better photocatalytic performance than only titanium doped silica coatings.
• MB-coated samples were separately put into UV Chambers A and B for photocatalytic activity testing.
• the coated samples were taken out from the chambers for transmission measurement every 15 minutes for the samples in UV Chamber B and every one hour for the samples in UV Chamber A.
• the transmission changes of the coating samples after irradiation are reported in Tables 7 (using UV Chamber B) and 8 (using UV Chamber A).
• the results indicate that the bimetal zinc and titanium doped silica coatings have better photocatalytic performance than only titanium doped silica coatings.
• the results indicate that the bimetal zinc and titanium doped silica coatings on glass substrates have better photocatalytic performance than only titanium doped silica coatings.
• Coated samples of Comparative Example C, and Examples 5, 8, and 10 on soda- lime glass slides were made using a dip coater at a drawing speed of 242.6 mm/min on the soda-lime glass substrates. All the coated samples were heated at 120°C for 10 minutes, then at 700°C for 2 minutes. The coated samples were further dip coated with a methylene blue (MB) solution in deionized water (1 mg/mL), and dried at the room temperature.
• MB methylene blue
• the MB-coated samples were separately put into UV Chambers A and B for photocatalytic activity testing.
• the coated samples were taken out from the chambers for transmission measurement every 15 minutes for the samples in UV Chamber B and every one hour for the samples in UV Chamber A.
• the transmission changes of the coating samples after irradiation are reported in Tables 9 (using UV Chamber B) and 10 (using UV Chamber A).
• the results indicate that the bimetal zinc and titanium doped silica coatings have better photocatalytic performance than only titanium doped silica coatings.
• the results indicate that the zinc/titanium-doped silica coatings on glass substrates have better photocatalytic performance than only titanium-doped silica coatings after high temperature treatment at 700°C.
• Comparative Example B (100 g) was mixed with 40.920 grams of TiOS04-2H 2 0 (10 weight percent solids in deionized water) and 14.767 grams of SnCLi-5H 2 0 (10 weight percent solids in deionized water).
• the resulting 10 weight percent coating solution contained TiOS04-2H 2 0 (26.0 weight percent of total solids) and SnCLi-5H 2 0 (9.3 weight percent of total solids).
• Comparative Example B (100 g) was mixed with 40.920 grams of TiOS04-2H 2 0 (10 weight percent solids in deionized water) and 29.534 grams of SnCLi-5H 2 0 (10 weight percent solids in deionized water).
• the resulting 10 weight percent coating solution contained TiOS04-2H 2 0 (23.8 weight percent of total solids) and SnCLi-5H 2 0 (17.0 weight percent of total solids).
• Examples 5, 12, and 13 were coated onto PET film using a #6 wire-wound coating rod and onto soda-lime glass slides using a dip coater at a drawing speed of 242.6 mm/min. All of the coated samples were heated at 120°C for 10 minutes.
• the coated samples were further coated with a methylene blue (MB) solution in deionized water (1 mg/mL) using a #6 wire-wound coating rod or dip coated, and dried at the room temperature.
• MB methylene blue
• the MB-coated samples were separately put into UV Chambers A and B for photocatalytic activity testing.
• the coated samples were taken out from the chambers for transmission measurement every 15 minutes for the samples in UV Chamber B and every one hour for the samples in UV Chamber A.
• the transmission changes of the coating samples after irradiation are reported in Tables 1 1 (using UV Chamber B) and 12 (using UV Chamber A). Results are reported in Tables 1 1- 12. The results indicate that the tin/titanium-doped silica coatings have better photocatalytic performance than only titanium doped silica coatings.
• Reflection geometry data were collected in the form of a survey scan by use of a
• PANalytical Empyrean diffractometer copper K,,, radiation, and PIXcel detector registry of the scattered radiation.
• the diffractometer was fitted with variable incident beam slits and diffracted beam slits.
• the survey scan was conducted in a coupled continuous mode from 5 to 80 degrees (2 ⁇ ) using a 0.04 degree step size and 1200 second dwell time.
• X-ray generator settings of 40 kV and 40 mA were employed.
• the metal-doped colloidal silica dispersions were prepared by diluting NALCO 1 1 15 silica sol to 10 weight percent solids with deionized water, acidifying the diluted silica sol with concentrated HNO3 to a pH of about 2-3 and then adding a desired amount of aqueous metal compound solutions (10 weight percent SnCl 4 -5H 2 0, TiOS0 4 -2H 2 0, or ⁇ ( ⁇ 3) 2 ⁇ 6 ⁇ 2 0).
• Examples 14-16 are summarized below in the Table 13.
• the coated samples were then dried at room temperature, and then further cured at 120 °C for 10 min.
• the final coated samples were optically clear and transparent.
• the powders for analysis were collected by scraping the coating off from glass substrates.
• the samples thus prepared were analyzed according to the TEST METHOD FOR X-RAY SCATTERING ANALYSIS described above and the results are reported below in Table 13.
• the silica dispersions were prepared by diluting NALCO 1 1 15 silica sol to 10 weight percent solids with deionized water, and acidifying the diluted silica sol with concentrated HNO3 to a pH of about 2-3.
• the coated samples were then dried at room temperature, and then further cured at 120 °C for 10 min.
• the final coated samples were optically clear and transparent.
• the powders were collected by scraping the coating off from glass substrates, and then mixed with a desired amount of solid TiOS04-2H20 powder to have the same ratio of silica/metal compound as in Example 16.

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