WO2005044446A1 - Revetement photocatalytique nanocomposite - Google Patents

Revetement photocatalytique nanocomposite Download PDF

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Publication number
WO2005044446A1
WO2005044446A1 PCT/US2003/032110 US0332110W WO2005044446A1 WO 2005044446 A1 WO2005044446 A1 WO 2005044446A1 US 0332110 W US0332110 W US 0332110W WO 2005044446 A1 WO2005044446 A1 WO 2005044446A1
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WO
WIPO (PCT)
Prior art keywords
coating
powder
nano
photocatalytic
fumed silica
Prior art date
Application number
PCT/US2003/032110
Other languages
English (en)
Inventor
Man Loong Leong
Original Assignee
York International Corporation
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.)
Filing date
Publication date
Application filed by York International Corporation filed Critical York International Corporation
Priority to US10/557,011 priority Critical patent/US20070000407A1/en
Priority to CNA2003801105142A priority patent/CN1838993A/zh
Priority to PCT/US2003/032110 priority patent/WO2005044446A1/fr
Priority to AU2003282559A priority patent/AU2003282559A1/en
Priority to MYPI20041125A priority patent/MY178950A/en
Priority to TW093108740A priority patent/TWI304085B/zh
Publication of WO2005044446A1 publication Critical patent/WO2005044446A1/fr

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L9/00—Disinfection, sterilisation or deodorisation of air
    • A61L9/16—Disinfection, sterilisation or deodorisation of air using physical phenomena
    • A61L9/18—Radiation
    • A61L9/20—Ultra-violet radiation
    • A61L9/205—Ultra-violet radiation using a photocatalyst or photosensitiser
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
    • B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
    • B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
    • B01J27/1817—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with copper, silver or gold
    • B01J35/23—
    • B01J35/39—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • 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
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24F—AIR-CONDITIONING; AIR-HUMIDIFICATION; VENTILATION; USE OF AIR CURRENTS FOR SCREENING
    • F24F8/00—Treatment, e.g. purification, of air supplied to human living or working spaces otherwise than by heating, cooling, humidifying or drying
    • F24F8/10—Treatment, e.g. purification, of air supplied to human living or working spaces otherwise than by heating, cooling, humidifying or drying by separation, e.g. by filtering
    • F24F8/15—Treatment, e.g. purification, of air supplied to human living or working spaces otherwise than by heating, cooling, humidifying or drying by separation, e.g. by filtering by chemical means
    • F24F8/167—Treatment, e.g. purification, of air supplied to human living or working spaces otherwise than by heating, cooling, humidifying or drying by separation, e.g. by filtering by chemical means using catalytic reactions
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24F—AIR-CONDITIONING; AIR-HUMIDIFICATION; VENTILATION; USE OF AIR CURRENTS FOR SCREENING
    • F24F8/00—Treatment, e.g. purification, of air supplied to human living or working spaces otherwise than by heating, cooling, humidifying or drying
    • F24F8/20—Treatment, e.g. purification, of air supplied to human living or working spaces otherwise than by heating, cooling, humidifying or drying by sterilisation
    • F24F8/24—Treatment, e.g. purification, of air supplied to human living or working spaces otherwise than by heating, cooling, humidifying or drying by sterilisation using sterilising media
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
    • B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
    • B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
    • B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J35/30—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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

Definitions

  • This invention relates generally to coatings and methods of coating.
  • the invention relates to a novel nano composite photocatalytic coating used in heating, ventilation, air conditioning and refrigeration (HVACR) equipment, and to methods of applying the coating to such equipment.
  • HVACR heating, ventilation, air conditioning and refrigeration
  • the coating is stable in ultraviolet, high-oxidation and high-temperature environments, such as in forced air- circulating systems containing ultraviolet light as a purification mechanism.
  • the photocatalytic ingredients in the coating act as a catalyst when exposed to ultraviolet light to promote both photocatalytic oxidation of organic chemicals as well as the elimination of bacteria, viruses, dust mites, molds, spores, fungi and other pollutants by photocatalysis and biological enzymes.
  • Titanium dioxide is well known to act as catalyst in photocatalytic oxidation. When exposed to ultraviolet (UVA, UVB and UVC) light in a moist air environment, titanium dioxide photoreacts to generate free radicals. These free radicals react with nearby water molecules (H 2 O) to form hydroxyl radicals (OH-). The hydroxyl radicals react with pollutants such as volatile organic compounds (VOC) to degrade the organic structure of the pollutants, thereby forming harmless carbon dioxide (CO 2 ) and water vapor.
  • VOC volatile organic compounds
  • the free radicals and hydroxyl radicals also act to disrupt organic molecules in organic pollutants and pathogens such as bacteria, viruses, dust mites, molds, spores and fungi.
  • photocatalytic coatings contain organic polymers that degrade when exposed to photocatalytic oxidation activity, h particular, the degradation of organic polymer film forming substances, as well as organic and inorganic pigments, in known coatings results in premature aging, pulverizing, cracking, shedding and delaminating of the coating.
  • the highly oxidative nature of photocatalytic coatings also adversely affects their application on organic polymer substrates, since the substrate will be degraded by the photocatalytic properties of the coating.
  • titania (TiO 2 ) sol gel is widely used as a titanium dioxide- containing coating having photocatalytic oxidation properties.
  • the sol gel process uses inorganic and metal organic precursors at low temperature to synthesize a coating product which is either totally inorganic, or a combination of inorganic and organic materials.
  • the sol gel process is a multi-step process that involves appropriate organometallic compounds and alcohol-based mixtures and goes through hydrolysis and condensation reactions.
  • One titania sol gel process utilizes titanium isopropoxide:ethanol:water:nitric acid in a mole ratio of 1 :20:4:0.08.
  • Solution A is formed by dissolving titanium isopropoxide in ethanol
  • Solution B is formed by adding water and nitric acid into ethanol. Then, Solution B is added to Solution A by mixing evenly.
  • a transparent gel in homogenous gelation can be seen in a few minutes to several hours, depending on the temperature of the mixing. After application of the sol gel, curing by heat (such as an oven or heating tunnel) is required to produce a photocatalytic coating on the substrate.
  • a photocatalytic coating that can be easily prepared and applied and which has a working time sufficiently long so that it can be used in a production environment for application to surfaces having complex geometries.
  • the coating should be self-curing to avoid the need for expensive curing ovens or other type of curing equipment.
  • the coating should retain photocatalytic oxidation and antibacterial properties without degrading, particularly when used in HVAC systems such as a forced air-circulating system.
  • a prjmer coating that can be applied onto an organic substrate or other substrates to protect the substrate against undesirable oxidation by a subsequently applied photocatalytic coating of the present invention.
  • the present invention is directed to a nano-composite substantially inorganic photocatalytic coating, comprising a substantially inorganic binder up to about 50%, a fumed silica, a nano-sized photocatalytic powder, an inorganic anti-bacterial powder having the general fonnula of YX(PO 4 ) 3 plus an antimicrobial metal, where Y is an element selected from Group IA and IIA of the Periodic table and X is an element selected from Group IIIA, IV A, VA and VIA of the periodic table and the balance is an evaporable carrier liquid.
  • the amount of fumed silica, nano-sized photocatalytic powder and inorganic anti-bacterial powder is provided in an amount sufficient to provide thixotropic properties to the coating composition.
  • the thixotropic properties are very important in allowing the coating to be applied in an industrial setting. Even though the coating dries quickly, its curing time can be 12 hours or longer.
  • the thixotropic nature of the coating allows it to be applied to a surface by a variety of processes without running, slumping or sagging while it dries, and allows the coating to be worked as necessary while curing.
  • the terai thixotropic refers to a property of a material composition that enables it to flow when subjected to a mechanical force such as a shear stress or when agitated and return to a gel-like form when the mechanical force is removed.
  • a mechanical force such as a shear stress or when agitated and return to a gel-like form when the mechanical force is removed.
  • This definition is consistent with the definition of thixotropy as set forth in Hawley's Condensed Chemical Dictionary (Thirteenth Edition) and the Encyclopedia Britannica. This property allows the coating to be applied in a production or industrial setting to surfaces having complex geometries, including but not limited to tubes, while assuring complete coverage without exposing the tube as a result of slumping, running or dripping of the coating.
  • the coating of the present invention acts as a catalyst in the presence of ultraviolet (UV) light.
  • UV ultraviolet
  • the ultraviolet spectrum is broken into several bands.
  • UVA encompasses wavelengths in the range of 320-400 nanometers (nm).
  • UVB encompasses wavelengths in the range of 290-320 nanometers.
  • UVC encompasses wavelengths in the range of 200-290 nanometers.
  • the catalytic effect of the coating is dependent upon the band of ultraviolet light that is present, as different bands produce different effects.
  • the coating is a catalyst in photocatalytic oxidation and, in the presence of water molecules, ionizes the water to form hydroxyl (OH " ) radicals that oxidize organic molecules.
  • the hydroxyl radicals also disrupt the activities of airborne pathogens such as viruses, bacteria, dust mites, mold spores and fungi.
  • UVC also is used to destroy bacteria and viruses.
  • the present invention envisions using the coating on HVACR equipment in the presence of both UVA and UVC to take advantage of the photocatalytic oxidation of the coating and the ability of UVC to further destroy bacteria and viruses.
  • the coating has a composition, in weight percent, of an effective amount of substantially inorganic binder up to about 50%; about 0.5-5% fumed silica; about 1% to about 10% nano-sized photocatalytic powder; about 1% to about 10% inorganic anti-bacterial powder that includes an inorganic anti-bacterial powder of YX(PO 4 ) 3 and at least about 3% of an antimicrobial metal, where Y is an element selected from Group IA and IIA of the Periodic table and X is an element selected from Group ⁇ iA, IVA and VA of the periodic table and the balance an evaporable carrier liquid.
  • This composition of the coating by weight, after removal of the evaporable carrier liquid includes up to about 65% binder, about 7-14% fumed silica, about 13-28%o nanosized antibacterial powder and the balance, typically about 13-28%, photocatalytic powder. While the amount of fumed silica, nano-sized photocatalytic powder and inorganic anti-bacterial powder is provided in an amount sufficient to provide thixotropic properties to the coating composition, a composition that provides an amount of photocatalyst powder that is no more than 15% of the binder, an amount of antibacterial powder that is no more than 15% of the binder, an amount of hydrophilic fumed silica that is no more than 5% of the binder and the balance xylene is also a broad composition that is effective. Thus the composition is no more than about 11% antibacterial powder, no more than about 11% photocatalyst powder, no more than about 3.7%) fumed silica and the balance binder.
  • the method for applying the nano-composite substantially inorganic photocatalytic coating of the present invention includes the steps of providing quantities of the above-listed ingredients in the amounts required. After the ingredients are provided, the nano-sized photocatalytic powder is added to the carrier liquid and mixed to substantially uniformly distribute the powder in the carrier liquid. The inorganic antibacterial powder is also added to the carrier liquid and mixed to substantially uniformly distribute the inorganic powder in the carrier liquid. After the carrier liquid and the antibacterial powder are added to and mixed with the liquid, the fumed silica is then added to the mixture and mixing to substantially uniformly distribute the fumed silica in the mixture.
  • the inorganic binder is added to the evaporable carrier and mixed to substantially uniformly distribute the binder in the carrier.
  • the fumed silica, nano-sized photocatalytic powder and inorganic antibacterial powder, also provided in a nano-size, in the evaporable carrier provide thixotropic properties to the coating mixture.
  • the quantity of evaporable carrier liquid is then adjusted to provide the mixture with a viscosity suitable for application of the thixotropic mixture to a surface. The viscosity can be adjusted for different applications. Although the coating is gel-like after application, when subjected to mechanical forces, it will flow, and the viscosity will vary depending upon the amount of evaporable carrier liquid present.
  • fluidity/viscosity of a composition applied to the article will depend upon the method by which it is applied, as the coating will utilize a different fluidity/viscosity depending upon whether the coating is applied by dipping, spraying, brushing, etc.
  • the present invention In addition to the obvious advantages of the coating and its ability to act as a catalyst when exposed to UV radiation for photocatalytic oxidation of organic compounds, the present invention also enzymatically attacks micro-organisms such as bacteria and viruses.
  • the composition of the present invention provides a number of other advantages not found in prior art compositions.
  • An advantage of the present invention is that it includes no polymeric film that can decompose. As a result, the film has better resistance to aging, as it will not readily deteriorate by pulverizing, cracking, shredding or delaminating.
  • Another advantage of the present invention is that it quickly dries in air, and self-cures in air as a result of the evaporation of the solvent and without the need for a catalyst. As a result, no expensive heat curing furnaces or light curing equipment is required. Also, there is no need to monitor and protect the atmosphere for emissions from the curing composition, other than the emissions resulting from the evaporation of the solvent.
  • Another advantage of the present invention is the thixotropic nature of the composition. This allows the coating to better adhere to a substrate, even when the substrate has a complex geometry.
  • the thixotropic nature of the composition combined with the self-curing in air provides the coating mixture with a longer working time, thus making the coating suitable for production processes, such as application to HVACR equipment.
  • Yet another advantage of the present invention is that it is applied as a very thin coating, so that it adds very little weight to the structure to which it is applied. On curing, it forms a dense oxide protective scale. And although the coating is applied in very thin layers, the oxide scale provides the cured coating with low oxygen diffusivity.
  • the present invention provides a fast drying, durable, adherent and flexible nano composite coating that exhibits photocatalytic properties and superior anti-microbial properties, and which retains desirable coating properties in hostile environments such as heat, photocatalytic oxidation, and ultraviolet light environments.
  • the coating is easy to apply by any of a wide variety of coating apparatus and techniques, and is self-curing with no need to apply heat, microwaves, plasma, or infrared rays for curing.
  • the present invention further provides a primer coating that is suitable for use particularly on an organic substrate, although it may be used on any other substrate, to protect against undesirable oxidation by a subsequently applied photocatalytic coating.
  • the advantages the present coatings compared to known coatings include easy and fast production using commercially available mixing apparatus, application by a wide variety of coating teclmiques, and self-curing at room temperature.
  • the coatings of the present invention are more suitable and economical for mass-production applications such as in manufacturing and assembly factories for air handling equipment.
  • the present invention provides fast drying composite photocatalytic coatings, that are resistant to ultraviolet, oxidation and high temperature environments.
  • the photocatalytic coatings when exposed to UV acts as a catalyst for photocatalytic oxidation resulting in deodorizing, cleaning, and sterilizing of fluids such as air, gas, and liquids, as well as for disrupting the life cycle of micro organisms.
  • fluids such as air, gas, and liquids
  • the present invention further contemplates the use of a primer under the coating, particularly for use on organic surfaces to which the coating may not adequately bond.
  • This invention can be used in HVACR systems for air conditioners, dehumidifiers, refrigerators, heaters, coolers, air purifiers, deodorizers, ventilation fans and germicidal equipment.
  • HVACR applications and other applications in building and construction industries include use on the surface of concrete, caulk, gypsum, tiles, roofing, ceramic tiles, cultured stones, paints, ceilings, timbers, plastics, blinders, signage, furniture and grills.
  • the coated substrates and products when exposed to sunlight or ultraviolet light will deodorize, clean, repel micro-organisms, and sterilize organic compounds and stains.
  • the photocatalytic coating composition contains at least one photocatalytic ingredient, an inorganic binder, an inorganic anti-bacterial powder, and at least one organic solvent. Additional ingredients, such as thickening and anti-sagging agents, also are included to impart special properties to the coating enabling it to be used in an industrial manufacturing setting.
  • At least one photocatalytic ingredient is a nanostructured composite photo catalyst powder containing a transition metal or its oxide as the active photocatalytic agent.
  • titanium dioxide, TiO 2 is provided as the photocatalytic powder, preferably in a nanosize, about 75 nm or smaller.
  • the preferred anti-bacterial ingredient is a nano-structured powder of sodium (Na) a species of zirconium and a phosphate or phosphate salt that additionally includes at least about 3% (by weight) of silver.
  • One anti-bacterial ingredient is NaZr 2 (PO ) that includes at least about 3%> silver.
  • a preferred anti-bacterial powder is CYK-302 available from Chengyin Technology Co. Ltd.
  • the inorganic binder is preferably polyalkylphenylsiloxane, and the organic solvent is preferably xylene.
  • Densified hydrophilic fumed silica is provided as the anti-settling, thickening and anti- sagging agent.
  • all ingredients are provided as nano-sized particles.
  • Nanostructured composite photocatalyst powder - (hereinafter referred to as "NCPP") is an ultra fine white powder, with an average particle diameter of 30 to 50 nano meters.
  • NCPP contains an active ingredient containing a photocatalytic agent such as anatase titanium dioxide or another transition metal or its oxide, the active ingredient having a content of valid composition of equal or more than 80 percent.
  • a photocatalytic agent such as anatase titanium dioxide or another transition metal or its oxide
  • Other suitable transition metals include zirconium, molybdenum, niobium, hafnium, tantalum and oxides of these metals.
  • NCPP has a hydrophilic surface property that exhibits high surface activity when dry, and good dispersion properties in solution. The nanostructure composite character of the NCPP yields a high level of photocatalytic activity and a long lifespan.
  • NCPP is commercially available from Chengyin Technology Co., Ltd. under the trade names "CYC-1" and "CYC-2" and have the following properties:
  • P olyalkylphenylsiloxane - An inorganic substance in which the main chain contains no carbon atoms that is added as a binder. Behavior similar to that of an organic polymer can be developed, i.e., covalent bonding and cross-linking. It can be used as an intermediate for organic resin modification to improve oxidation resistance, thermal resistance, weather resistance, water resistance, gloss and electric properties. It is compatible with various organic resins such as alkyd, acrylic, epoxy, phenolic, polyester, polystyrene and silicone. It can be used for cold blending and modification.
  • polyalkylphenylsiloxane The appearance of polyalkylphenylsiloxane is yellowish transparent with the specific gravity of 1.07 at 25°C; viscosity of 20 cP at 25°C; 60% solid content; one hour curing time at 150°C; functional group of -OH (4-5%>); and can be diluted in solvent.
  • An exemplary polyphenylalkylsiloxane is commercially available from GE Toshiba Silicones Co., Ltd. under the trade name "TSR160.”
  • IABP Inorganic anti bacteria powder - Inorganic anti bacteria powder
  • the IABP contains an active ingredient having a photocatalytic agent of the formula YX(PO ) 3 , and a noble metal where Y is at least one metal selected from Group LA and IIA of the Periodic Table.
  • Y may include Na, K, Ca and Mg.
  • X is an element selected from Group IIIA, IVA and VA of the periodic table, and may include titanium, zirconium, yttrium, hafnium, tantalum, tungsten, molybdenum and oxides thereof.
  • the noble metal may include silver, gold, platinum, palladium, rhodium, combinations thereof and oxides thereof.
  • One preferred antimicrobial agent includes NaZr (PO ) 3> and at least about 3% by weight silver or its oxides.
  • the antimicrobial metal content is preferably more than about 3% of the total IABP by weight.
  • the active ingredient, silver may account for as much as 99%> of the IABP on a weight basis.
  • a preferred IABP is commercially available from Chengyin Technology Co., Ltd.
  • CYK-302 having a composition, in weight percent, of about 4.3% Na 2 0, about 43.9% P 2 O 5 , about 0.02% NiO, about 3.8% Ag, about 1% HfO 2 and the balance ZrO 2 and incidental impurities and has the following properties:
  • CYK-302 has an anti-bacteria rate of more than 99%, tested on Escherichia Coli, and is effective in a broad-spectrum manner as a result of its photocatalytic activity. Due to its small diameter and even scattering, the powder can be added without adversely affecting the properties of other powders and mixtures. CYK-302 can thus be applied in a wide variety of applications to impart antibacterial, anti-mildew, and anti-odor properties.
  • solvent An evaporable carrier liquid
  • solvent is added to provide for proper mixing of the components and for proper application of the coating to the surfaces of the components.
  • the solvent content can be adjusted to modify drying time and to provide an acceptable fluidity for application.
  • the coating of the present invention can be applied by brushing, spraying, dipping and rolling.
  • the fluidity/viscosity of the composition can be adjusted depending upon the methods of application. To achieve the proper fluidity, the amount of solvent is increased.
  • the solvent content is similarly adjusted to provide adequate fluidity/viscosity for other application methods. It will be understood by those skilled in the art that as the solvent content increases the drying time for the coating also increases.
  • Suitable solvents particularly useful with polyalkylphenylsiloxane include toluene, alcohol, methyl ethyl ketone, and propylene glycol monomethyl ether acetate. Of the several available alcohols, isopropyl alcohol is prefened. Any other solvent that is compatible with polyalkylphenylsiloxane and the other ingredients may be used, with environmentally friendly solvents preferred.
  • One preferred solvent is xylene (dimethylbenzene, C 6 H (CH 3 ) 2 ) - winch is made of three isomers, ortho-, meta-, and paraxylene.
  • Densified hydrophilic fumed silica - A colloidal form of silica made by combustion of silicon tetrachloride in hydrogen-oxygen furnaces.
  • the appearance of fumed silica is as fine white powder, preferably with an average primary particle size of about 12 nm and tap density of approximately 120 g/1.
  • the loss on drying based on 2 hours at 105°C is about 1.5% and the ignition loss based on 2 hours at 1000 °C dried material for 2 hours at 105°C is about 1%.
  • Its pH in 4% dispersion is about 3.7 to 4.7. It has more than 99.8%> of SiO 2 content based on ignited material.
  • Densified hydrophilic fumed silica is used as a thixotropy control of liquid system, binders and polymers; as anti-settling agent, thickening and anti-sagging agent; reinforcement of HCR-silicone rubber; improvement of free flow and anti-caking characteristics of powders; reduced dust development; and improved incorporation and handling due to a homogeneous and gentle densification.
  • An exemplary densified hydrophilic fumed silica is commercially available from Degussa AG under the trade name "Aerosil 200 VV 120.” The fumed silica imparts the important thixotropic properties to the coating of the present invention, allowing it to be applied by any of a number of processes successfully in industrial applications.
  • thixotropic properties allow the coating to be applied to a surface by any one of a number of processes such as spraying, dipping, brushing etc.
  • the applied coating will not flow such as by slumping, running, or dripping after application due to the effects of gravity.
  • the coating will flow if it is subjected to a mechanical shear stress, allowing it to be worked, if so desired.
  • the ability to work the coating will be gradually diminished during the curing period, which is dependent on the curing of the binder, up until curing is complete.
  • the photocatalytic coating solution is easy to apply using conventional coating apparatus, since it is provided as a mixture of ingredients suspended in an organic solvent.
  • the preferred embodiment of the coating formulation is provided as a mixture of NCPP, polyalkylphenylsiloxane; IABP, and nano densified hydrophilic fumed silica, all suspended in a fast-drying organic solvent.
  • the NCPP includes Ti ⁇ 2 as the photocatalytic agent to promote catalytic oxidation to degrade volatile organic compounds into carbon dioxide and water.
  • Polyalkylphenylsiloxane serves as the inorganic binder, IABP provides additional photocatalytic properties, as well as antibacterial properties and natural anti-microbial properties of noble metals such as silver and silver oxides.
  • Xylene is the preferred organic solvent and has been shown to provide excellent dispersion characteristics, as well as fast drying to yield a self-curing coating at ambient room temperature.
  • Densified hydrophilic fumed silica provides additional favorable coating characteristics, as discussed above, such as anti-settling, thickening and anti-sagging so that the coating can be applied to yield a uniformly thick, flexible, and adherent film on plastics, metals, and other complex geometric surfaces.
  • the photocatalytic coating can be applied to an organic or inorganic surface, and is self-curing, requiring no post-deposition catalyst reaction or other post-application treatment curing treatment (such as a gas or combustion related treatment or electrical furnace, microwave, plasma, light or infrared ray treatment).
  • post-application treatment curing treatment such as a gas or combustion related treatment or electrical furnace, microwave, plasma, light or infrared ray treatment.
  • the coating Upon application and curing, the coating exhibits excellent long-acting oxidation protection of the underlying substrate, as well as excellent resistance to moisture and other environmental conditions which can commence within about 15 minutes of coating, depending upon the amount of solvent used for the application.
  • the photocatalytic agent in the coating acts as a catalyst when exposed to UV by promoting photocatalytic oxidation to convert organic pollutants into harmless carbon dioxide and water vapor, and further creating free radicals that disrupt the life cycle of airborne pathogens such as bacteria, viruses, dust mites, molds, spores and fungi.
  • nano-size particles provides particular advantages over other known TiO 2 coatings.
  • the use of nano-sized particles for the active ingredient and fillers additionally provides a coating superior oxidation resistance and heat resistance due to the large specific surface area, high surface activity, good adhesion and dispersion, anti- skinning/coalescent properties, uniform thickness distribution, fast curing, and good adhesion to metals, plastics, fabrics, glass, composites, ceramics, paper, inorganic paints, etc.
  • known inorganic coatings such as sol gels that are comprised primarily of inorganic materials exhibit very limited working time before the coatings are cured, and must be rolled, brushed or sprayed. Due to this limitation in working time and application methods, known coatings are not suitable for continuous use in production plants.
  • the present coating exhibits a pot life of up to 12 hours at room temperature, yet dries to the touch in about in 30 seconds once applied to the substrate, although complete drying typically takes longer.
  • the present coating can be applied by spray, brush, roller, dipping, spin coating, capillary processes, flow coating, and various other methods. Thus, the present coating is particularly suitable for mass-production applications.
  • This formulation is to make a preferred embodiment of a primer coat for use on organic polymer substrates.
  • the recommended applications of primer coat are spray coating techniques, rolling and brushing teclmiques, and dip coating techniques.
  • the fumed silica is mixed with xylene and then stirred until the silica is substantially uniformly distributed.
  • the polyalkylphenylsiloxane is added to the mixture and stirred homogenously. While the primer coat is utilized on substrates comprising organic polymer materials, its use is not restricted to application on organic polymer substrates, and may be used on any type of substrate if adhesion is a concern.
  • NCPP is mixed with xylene and stirred. While stirring the mixture, IABP is added, followed by fumed silica. The mixture is stirred until it is properly mixed. Then the polyalkylphenylsiloxane is added to the mixture, which is stirred until a substantially homogenous mixture is obtained.
  • Drying time at room temperatur ⁇ s 30 seconds Dry to touch: 30 seconds
  • the most desirable coating properties are retained when the percentage by weight content of the NCCP and IABP individually does not exceed about 15% of the weight content of polyalkylphenylsiloxane in the formulation, and the percentage by weight of the densified hydrophilic fumed silica should not exceed about 5% of the weight content of polyalkylphenylsiloxane.
  • the percentage by weight content of xylene desirably should not exceed about 70% of the weight content of polyalkylphenylsiloxane.
  • the coatings of the present invention can be applied to a wide variety of substrates, including both organic and inorganic substrates, using a wide variety of coating teclmiques and apparatus.
  • the primer and photocatalytic coatings are exceptionally oxidation-resistant because of extremely low oxygen diffusivity, thereby providing oxidation protection to the underlying substrate.
  • the photocatalytic coating dries to fonn a very thin coating that provides significant protection by promoting the growth of dense, stable oxide scale. It forms a hermetic nano composite coating through very simple coating techniques and processes.
  • the weight gain is much greater when the coatings are applied to rough surface substrates as opposed to highly polished substrates.
  • All surfaces of the substrates should be clean, dry, and free of dirt, grease, oil, rust and other contaminants. Contaminated surfaces can be cleaned mechanically, if porous, or with a solvent, if non-porous. Glass can be cleaned with either water containing surfactant or a solvent. In latter case, the solvent should be applied with a clean oil free, lint free cloth. Residual solvent should be removed with a fresh, clean, dry cloth before it evaporates.
  • Inorganic substrates such as ceramic tiles, enamels, glass and a wide variety of metals do not require priming.
  • use of the primer of the present invention is recommended for organic substrates that cannot stand photocatalytic oxidation.
  • Masking such as with masking tapes, affords a simple and effective means of protecting critical areas from undesired contact with the coatings. Masking tapes should not be allowed to touch the clean faces of the joints, and should be removed immediately after the application and before the coating is dry.
  • the nano composite photocatalytic coating should be mixed or agitated by an agitation means that produces a smooth and homogeneous mixture, such as a power mixer. No straining with wire mesh is needed before use.
  • the mixture can be applied by dip coating techniques, spray coating techniques, flow coating process, spin coating process, rolling and brushing techniques and capillary coating process.
  • the preferred thickness will be from 1 to 5 ⁇ m (micron), although some methods will produce greater thicknesses, up to about 5 mils (0.005 mils). However, as the coating acts as a catalyst, greater thicknesses provide no advantage and only add weight and cost.
  • the nano composite coating will dry to the touch at a room temperature at about 30 seconds, although complete drying by solvent evaporation will take longer, up to 12 hours. Some curing may occur as the solvent evaporates. The coating will further cure as it is exposed to ultra violet by way of photocatalytic reaction of leftover xylene, which is oxidizes to CO 2 and H 2 O.
  • Dip coating technique is a process where subsfrate to be coated is immersed in the coating.
  • the substrate is then withdrawn with a well-defined withdrawal speed under controlled temperature and atmospheric conditions.
  • the thickness of the coating is determined by the withdrawal speed, the solid content and viscosity of the coating.
  • the gelation of the coating depends on solvent evaporation. Therefore, it is important to have a controlled atmosphere where destabilization of the coating by solvent evaporation leads to a gelation process and the formation of a transparent film due to the nano size particles in the coating.
  • a thixotropic coating will be produced on the substrate as it is withdrawn. If thicker coatings are desired, a multiple dipping process may be used, with each successive dip occurring after curing of the underlying layer.
  • Spray coating techniques are widely used in industry for organic coatings.
  • the coating of the present invention can be applied by preferably using spraying equipment with HVLP (high volume, low pressure) nozzles.
  • HVLP high volume, low pressure
  • ultra fine droplets or atomizers are produced that lead to very homogeneous coatings on substrates.
  • the coating material will hit on the substrates in the almost dried small particles in the nanometer range.
  • the preparation of coating by spraying offers several advantages compared to dip coating: it is a faster process producing less waste; and it can be apply on large substrates and is suitable for in-line process in the plant.
  • spraying can be controlled to provide various thicknesses in different areas, or no coating in preselected areas, if desired.
  • the viscosity can be controlled to vary the thickness of the coating, and a plurality of coatings can also be applied to vary the coating thickness.
  • a flow coating process is a process wherein the coating is poured over the substrate.
  • the thickness of the coating will depend on the angle of the inclination of the substrate with respect to the coating, the coating acting under the influence of gravity, the viscosity of the coating, the surrounding temperature and the solvent evaporation rate.
  • the advantages of this process are that non-planar large substrates can be coated easily.
  • a spin coat process is a process wherein the substrate spins around an axis that is perpendicular to the area to be coated, thereby providing a rotational symmetry.
  • the thickness of the coating will depend on the angular speed, the viscosity, the surrounding temperature and the solvent evaporation rate.
  • Rolling and brushing techniques are not state-of-the-art process. These processes require manual application and quite labor intensive. Such applications are recommended for large substrates that cannot be easily transported to a production plant environment.
  • the thickness of the coating will depend on the skill of the workers, the speed of the workers, the type of applicator (such as roller and brush), the coating viscosity, the sunounding temperature and atmosphere, and the solvent evaporation rate.
  • brushing processes are still effective with the coating of the present invention due to the thixotropic nature of the coating.
  • Capillary coating process or laminar flow coating process is a combination of dip coating technique with the advantage that all of the coating can be used without much waste.
  • a tubular dispenser containing the coating is moved under the substrate surface without physically contacting the surface.
  • a spontaneous meniscus is created between the top of a cylinder and the substrate surface.
  • a laminar deposition is accomplished whereby the coating is deposited homogeneously on the substrate.
  • the thickness of the coating will depend on the deposition rate, the viscosity, the surrounding temperature and the solvent evaporation rate.
  • the nano coating film of the present invention facilitates photocatalytic oxidation as an effective approach to cope with wastewater treatment and exhaust gas since it enables the effective photocatalytic reaction of all types of organic substances, pathogens, and pollutants.
  • photocatalytic coating and ultraviolet light with wave length of 340 to 400 nm can be used for photocatalytic oxidation inside electrical appliances and other dark areas for deodorizing, cleaning, repelling micro organism and sterilizing of air.
  • This application can further be used for air conditioners, dehumidifiers, refrigerators, deodorizer, heater, coolers, air purifiers, deodorizers, ventilation fans and germicidal equipment.
  • the coatings can be applied on the surface concrete, gypsum, tiles, roofing, ceramic tiles, cultured stones, paints, ceilings, timbers, plastics, blinders, signage, furniture and grills.
  • the coated substrates and products when exposed to sun light or ultra violet light will deodorize, clean, repel micro-organisms, and sterilize whatever organic compound stains might exist on its surfaces.
  • the nano composite photocatalytic coating can also be used to make substrates bacteria proof. The photocatalytic action non-selectively kills viruses and bacteria having a chemical composition of protein and nucleic acid.
  • the coating of the present invention is particularly suited for use in HVACR applications in which water is present.
  • the presence of water in these applications provides an environment which breed viruses and bacteria. Other chemicals may also be present.
  • the present invention inhibits the growth of viruses and bacteria, as it is applied to surfaces, which are in contact with water and other chemicals.
  • the coating of the present invention is applied to surfaces of HVACR equipment, which may come in contact with water, such as condensers, evaporators, chillers, and air handing systems.
  • the invention may further be used in components such as air handling systems and air filtration systems, which have minimal contact with water, but do experience contaminants such as dust mites, mold spore and fungi. Frequently, this equipment is enclosed in spaces, which is not accessible to sunlight.
  • the source should provide at least UVA, for which the coating acts as a catalyst, and, most preferably, also UVC, which individually affects bacteria and viruses.
  • the UV light should be focused on the equipments coated with the present invention so that all fluids passing over the coated surfaces are simultaneously irradiated by the UV light sources.

Abstract

L'invention concerne une composition de revêtement photocatalytique et un procédé de revêtement d'articles, ladite composition contenant : des solvants permettant une évaporation rapide à température ambiante, du polyalkylphénylsiloxane, du xylène, de la silice sublimée hydrophile nanodensifiée, de la poudre de photocatalyseur composite nanostructurée et de la poudre antibactérienne nano-inorganique. Ledit revêtement peut être appliqué par des procédés de revêtement classiques sur des surfaces structurées organiques ou inorganiques pour lesquelles une activité photocatalytique est souhaitée, tel que dans un environnement à circulation d'air forcée. Une fois appliqué, le revêtement sèche rapidement pour laisser un revêtement photocatalytique adhérent, souple, durable et de longue durée présentant une surface active importante et présentant une activité de surface élevée dirigée contre des agents pathogènes et des agents polluants tels que bactéries, virus, moisissures, champignons et composés organiques volatils.
PCT/US2003/032110 2003-10-09 2003-10-09 Revetement photocatalytique nanocomposite WO2005044446A1 (fr)

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US10/557,011 US20070000407A1 (en) 2003-10-09 2003-10-09 Nano composite photocatalytic coating
CNA2003801105142A CN1838993A (zh) 2003-10-09 2003-10-09 纳米复合光催化涂料
PCT/US2003/032110 WO2005044446A1 (fr) 2003-10-09 2003-10-09 Revetement photocatalytique nanocomposite
AU2003282559A AU2003282559A1 (en) 2003-10-09 2003-10-09 Nano composite photocatalytic coating
MYPI20041125A MY178950A (en) 2003-10-09 2004-03-29 Nano composite photocatalytic coating
TW093108740A TWI304085B (en) 2003-10-09 2004-03-30 Nano composite photocatalytic coating

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WO2008024174A1 (fr) * 2006-08-22 2008-02-28 Northrock Distribution, Inc. Photocatalyseur, procédés de desodorisation, et procédés permettant de fabriquer un système désodorisant
WO2009074120A3 (fr) * 2007-12-11 2009-08-06 Advanced Materials Jtj S R O Peintures multifonctionnelles photocatalytiques et hygiéniques et leur procédé d'application
WO2009103578A1 (fr) 2008-02-19 2009-08-27 Ebm-Papst Mulfingen Gmbh & Co. Kg Roue de ventilateur ou de soufflante ayant un revêtement antibactérien
EP2110145A1 (fr) * 2008-04-16 2009-10-21 Baraldi Srl Système de purification d'air et procédé en particulier d'un environnement domestique
WO2011147420A1 (fr) * 2010-05-26 2011-12-01 Airvention Aps Procédé et dispositif pour régler la formation et la propagation de cultures bactériennes, cultures virales, fongiques, moisissures et micro-organismes, etc., sur la bobine de condenseur dans des systèmes de réfrigération plus grands.
ITBO20120317A1 (it) * 2012-06-07 2013-12-08 Next Technology Tecnotessile Societ A Naz D Metodo di realizzazione di un pannello antibatterico.
DE102012110319A1 (de) * 2012-10-29 2014-04-30 Endress + Hauser Gmbh + Co. Kg Vorrichtung der Automatisierungstechnik mit Umweltfreundlichem Gehäuse
US9309164B2 (en) 2005-12-28 2016-04-12 Osaka University Method for purification of substances contaminated with organic chemicals
CN107961803A (zh) * 2017-12-12 2018-04-27 成都育芽科技有限公司 一种用于环境污染净化的有机无机复合光催化剂
IT201700117827A1 (it) * 2017-10-18 2019-04-18 Maria Sagula Unità di purificazione di aria ambientale
CN113599562A (zh) * 2019-01-18 2021-11-05 艾洁弗环境集团公司 用于使用光氢离子化的高级氧化过程的设备、系统和方法
CN115254197A (zh) * 2022-06-28 2022-11-01 天津城建大学 一种SR-TiO2-BaTiO3柔性半导体光电催化材料的制备方法
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US11224860B2 (en) * 2019-02-28 2022-01-18 The Hong Kong Polytechnic University Nanofiber surfaces

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US9309164B2 (en) 2005-12-28 2016-04-12 Osaka University Method for purification of substances contaminated with organic chemicals
US7914733B2 (en) 2006-08-22 2011-03-29 Northrock Distribution, Inc. Photocatalyst, methods for deodorizing, and methods for making a deodorizer system
WO2008024174A1 (fr) * 2006-08-22 2008-02-28 Northrock Distribution, Inc. Photocatalyseur, procédés de desodorisation, et procédés permettant de fabriquer un système désodorisant
EP2235118B1 (fr) 2007-12-11 2017-04-26 Advanced Materials - JTJ s.r.o. Procédé d'application de peintures multifonctionnelles photocatalytiques et hygiéniques
WO2009074120A3 (fr) * 2007-12-11 2009-08-06 Advanced Materials Jtj S R O Peintures multifonctionnelles photocatalytiques et hygiéniques et leur procédé d'application
CN101896559A (zh) * 2007-12-11 2010-11-24 高级材料-Jtj公司 多功能光催化卫生涂料及其施用方法
US8647565B2 (en) 2007-12-11 2014-02-11 Advanced Materials—JTJ S.R.O. Multifunctional photocatalytic paint coat and method of preparation thereof
WO2009103578A1 (fr) 2008-02-19 2009-08-27 Ebm-Papst Mulfingen Gmbh & Co. Kg Roue de ventilateur ou de soufflante ayant un revêtement antibactérien
EP2110145A1 (fr) * 2008-04-16 2009-10-21 Baraldi Srl Système de purification d'air et procédé en particulier d'un environnement domestique
WO2011147420A1 (fr) * 2010-05-26 2011-12-01 Airvention Aps Procédé et dispositif pour régler la formation et la propagation de cultures bactériennes, cultures virales, fongiques, moisissures et micro-organismes, etc., sur la bobine de condenseur dans des systèmes de réfrigération plus grands.
CN103096942A (zh) * 2010-05-26 2013-05-08 埃尔维申公司 用于在较大制冷系统中对抗细菌培养物、病毒、真菌培养物、霉菌和微生物等在冷凝器盘管上形成和传播的方法和装置
ITBO20120317A1 (it) * 2012-06-07 2013-12-08 Next Technology Tecnotessile Societ A Naz D Metodo di realizzazione di un pannello antibatterico.
DE102012110319A1 (de) * 2012-10-29 2014-04-30 Endress + Hauser Gmbh + Co. Kg Vorrichtung der Automatisierungstechnik mit Umweltfreundlichem Gehäuse
IT201700117827A1 (it) * 2017-10-18 2019-04-18 Maria Sagula Unità di purificazione di aria ambientale
EP3473941A1 (fr) * 2017-10-18 2019-04-24 Sagula, Maria Unité de purification de l'air ambiant
CN107961803A (zh) * 2017-12-12 2018-04-27 成都育芽科技有限公司 一种用于环境污染净化的有机无机复合光催化剂
CN107961803B (zh) * 2017-12-12 2020-10-09 北京众智创新科技开发有限公司 一种用于环境污染净化的有机无机复合光催化剂
CN113599562A (zh) * 2019-01-18 2021-11-05 艾洁弗环境集团公司 用于使用光氢离子化的高级氧化过程的设备、系统和方法
CN113599562B (zh) * 2019-01-18 2024-03-12 艾洁弗环境集团公司 用于使用光氢离子化的高级氧化过程的设备、系统和方法
US11629872B2 (en) 2021-04-12 2023-04-18 NQ Industries, Inc. Single pass kill air purifier system and process of operation
CN115254197A (zh) * 2022-06-28 2022-11-01 天津城建大学 一种SR-TiO2-BaTiO3柔性半导体光电催化材料的制备方法

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