EP2200947A2 - Materiau a proprietes photocatalytiques - Google Patents
Materiau a proprietes photocatalytiquesInfo
- Publication number
- EP2200947A2 EP2200947A2 EP08835279A EP08835279A EP2200947A2 EP 2200947 A2 EP2200947 A2 EP 2200947A2 EP 08835279 A EP08835279 A EP 08835279A EP 08835279 A EP08835279 A EP 08835279A EP 2200947 A2 EP2200947 A2 EP 2200947A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- coating
- material according
- titanium oxide
- substrate
- wavelength converting
- Prior art date
- Legal status (The legal status 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 status listed.)
- Withdrawn
Links
Classifications
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/16—Halogen containing crystalline phase
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
- C03C17/245—Oxides by deposition from the vapour phase
- C03C17/2456—Coating containing TiO2
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/12—Compositions for glass with special properties for luminescent glass; for fluorescent glass
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7756—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing neodynium
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7767—Chalcogenides
- C09K11/7769—Oxides
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7772—Halogenides
- C09K11/7773—Halogenides with alkali or alkaline earth metal
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/77744—Aluminosilicates
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/212—TiO2
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
- C03C2217/44—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the composition of the continuous phase
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
- C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
- C03C2217/47—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase consisting of a specific material
- C03C2217/475—Inorganic materials
- C03C2217/477—Titanium oxide
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/71—Photocatalytic coatings
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31—Surface property or characteristic of web, sheet or block
- Y10T428/315—Surface modified glass [e.g., tempered, strengthened, etc.]
Definitions
- the present invention relates to the field of photocatalytic materials, in particular materials having photocatalytic activity when subjected to low energy radiation.
- Titanium oxide in particular when it is crystallized in anatase form, has photocatalytic properties: excited by radiation whose wavelength is less than or equal to 380 nm, thus located in the ultraviolet range, it has the particularity of catalyzing radical oxidation reactions. Under the effect of the radiation, an electron-hole pair is created, which contributes to degrade the organic compounds possibly present on the surface of the titanium oxide.
- a material comprising a coating based on photocatalytic titanium oxide thus has self-cleaning properties, antibacterial, or purification of liquid or gaseous effluents polluted particularly appreciable. Such materials are known from, for example, EP-A-0 850 204.
- a disadvantage of titanium oxide is that its photocatalytic activity is mainly triggered by high energy radiation, in this case ultraviolet radiation.
- This disadvantage is not detrimental when the material is exposed to solar radiation, since the latter comprises components in the ultraviolet, but becomes when the material is located in a place little subject to ultraviolet radiation (part of a dwelling, passenger compartment, tunnel ).
- Most of the solar ultraviolet radiation is absorbed by the glazing, while artificial light sources emit only slightly in the ultraviolet. It is therefore desirable to develop photocatalytic layers whose activity can be high for wavelengths located in the visible range, or even the infrared. Solutions have been proposed to this problem, which consist in particular in doping the crystal lattice of titanium oxide with various atoms (for example nitrogen) in order to modify the gap between the valence and conduction bands of titanium oxide. Such solutions are for example described in application WO2005 / 102953.
- the object of the invention is to propose a titanium oxide-based photocatalytic material whose photocatalytic activity can be high even in the absence of ultraviolet radiation while being free of the above-mentioned drawbacks.
- the subject of the invention is a material comprising a substrate coated on at least a part of at least one of its faces with a coating comprising photocatalytic titanium oxide.
- the material is characterized in that said substrate and / or a coating disposed between said substrate and said coating comprising photocatalytic titanium oxide comprises at least one compound capable of converting radiation whose wavelength is within the range visible or infrared radiation whose wavelength is in the field of ultraviolet.
- the compound capable of converting a radiation whose wavelength is comprised in the visible or infrared range into a radiation whose wavelength is in the ultraviolet range will be called a "length converter compound". wave "throughout the text as well as in the claims. It is understood that this term can not be interpreted otherwise. In particular, it can not be interpreted as covering compounds that are not capable of emitting ultraviolet radiation, or as covering compounds capable of converting radiation included in the ultraviolet range into radiation included in the visible range or infrared.
- the ultraviolet range comprises wavelengths of between 100 and 400 nm.
- the visible domain includes wavelengths between 400 and 800 nm.
- the infrared range includes wavelengths between 800 nm and 12 micrometers.
- the fluorescent compounds have the particularity, when they are subjected to radiation of a given wavelength, to re-emit a second radiation of higher wavelength, and therefore of lower energy than that of the incident radiation.
- such a compound is present under the photocatalytic coating based on titanium oxide, either within an underlayer or within the substrate itself.
- the operating principle of the invention can be schematically presented in the following manner: the titanium oxide being transparent to most of the visible or infrared radiation, this radiation passes through the photocatalytic coating, then is partially absorbed by the converter compound of wavelengths. This compound then isotropically re-emits ultraviolet radiation, part of which is absorbed by the titanium oxide. Titanium oxide, excited by this ultraviolet radiation, then fully plays its role of photocatalyst. It is important that the wavelength converting compound is disposed under the coating photocatalytic and not above because the organic soils must be in contact with the titanium oxide.
- the substrate is preferably of glass (in particular of silico-soda-lime or borosilicate glass), ceramic, glass-ceramic or polymeric material. It is advantageously flat or curved.
- the substrate is preferably at least partially transparent.
- the substrate may also be fibrous, for example a mineral wool mat (glass wool or rock wool), a felt or fiberglass or silica cloth.
- the substrate is of polymeric material, it is preferably polycarbonate, polymethyl methacrylate (PMMA), polyvinyl chloride (PVC), polyethylene, polypropylene.
- the titanium oxide is preferably at least partially crystallized in the anatase form because it is the most active crystalline form.
- the rutile form, alone or mixed with the anatase form, is also interesting.
- the coating comprising titanium oxide may consist of titanium oxide: it may be for example a coating obtained by processes using organometallic precursors of titanium oxide in liquid, solid form. or gaseous, as sol-gel type processes or CVD (chemical vapor deposition, possibly assisted by plasma, preferably at atmospheric pressure). It may also be coatings obtained by physical vapor deposition (PVD) techniques such as cathode sputtering, in particular assisted by magnetic field (magnetron process), or evaporation. Techniques for deposition of titanium oxide by magnetron method are for example described in application WO 02/24971.
- sublayers promoting the epitaxial growth of TiO 2 anatase in particular BaTiO 3 or SrTiO 3 , may be previously deposited, as described in application WO 2005/040058.
- the coating comprising titanium oxide may also comprise particles of titanium oxide dispersed in an organic binder and / or mineral, especially a mineral binder obtained by sol-gel route.
- the particles are preferably of nanometric size (nanoparticles), in particular of average diameter between 0.5 and 100 nm, especially between 1 and 80 nm. They generally consist of clusters of grains or elemental crystallites of diameter between 0.5 and 10 nm.
- the particles are preferably at least partly crystallized in the anatase form.
- the binder is preferably inorganic so as not to be degraded by the photocatalytic activity of the titanium oxide.
- the coating comprising titanium oxide is advantageously obtained by sol-gel, for example by laminar coating, spin-coating, or cell-coating, solutions comprising a precursor of the binder (usually an organometallic compound) and particles. of titanium oxide.
- the binder is preferably a silica binder (SiO 2 ), which can be easily obtained sol-gel from silicon alkoxides (for example TEOS, tetraethoxysilane).
- This binder especially the silica binder, can advantageously be mesoporous, in the sense that it contains generally ordered pores whose size is between 2 and 50 nm.
- a binder is for example known from the application WO 03/087002, and makes it possible to obtain particularly high photocatalytic activities.
- the thickness of the photocatalytic coating is preferably greater than or equal to 5 nm, especially 10 nm and / or less than or equal to 1 micrometer, especially 50 nm when the coating is made of titanium oxide. Large thicknesses lead indeed to a reflection of the high visible radiation and therefore undesirable in some applications where the optical appearance is important (especially glazing). It is possible to insert under the photocatalytic coating at least one layer whose function is to reduce the luminous reflection of the material and / or to make the coloration in reflection more neutral. It may in particular be the layers or stacks of layers described in the application WO 02/24971. The photocatalytic coating may also itself be included in an antireflection stack, as described in application WO 2005/110937.
- the coating comprising the titanium oxide is preferably in contact with the air, therefore the only layer deposited on the substrate or the last layer of the stack.
- the coating comprising the titanium oxide may, however, itself be coated with a very thin, preferably non-covering, layer of an oxide comprising silicon, in particular and preferably based on silica (SiO 2 ). This layer makes it possible to confer photo hydrophilic properties. induced prolonged even in the dark and / or improve the abrasion resistance of the stack. Its thickness is preferably less than or equal to 5 nm.
- the application WO 2005/040056 describes such overlays.
- the coating comprising the titanium oxide may also be coated with a very thin metal layer, preferably non-covering (for example in the form of micro-grid), in particular based on metal chosen from silver, platinum, palladium.
- This electroconductive layer makes it possible to avoid recombinations of the electron-hole pairs produced during the activation of the titanium oxide.
- the or each wavelength converting compound preferably comprises at least one rare earth ion or a transition metal inserted in a mineral matrix. Mineral matrices have higher durability than organic matrices. Rare earth ions (lanthanides) are preferred because they have the highest conversion efficiencies.
- the ions of a rare earth or of a transition metal are preferably chosen among the ions Yb 3+ , Tb 3+ , Tm 3+ , Eu 3+ , Eu 2+ , Er 3+ , Pr 3+ , Nd 3+ , Dy 3+ , Ho 3+ , Ti 2+ , Ni 2+ , Mo 3+ , Os 4+ , Re 4+ , Mn 2+ , Cr 3+ . It may be preferable to use two different ions, one absorbing visible or infrared radiation, the other retransmitting ultraviolet radiation after energy transfer.
- the pairs formed by the Yb 3+ ion (which absorbs for wavelengths close to 980 nm) with Tb 3+ or Tm 3+ or Er 3+ make it possible, for example, to obtain high luminescence yields.
- the pair of ions Pr 3 VNd 3+ is also interesting. In the case where an ion of a single nature is used, the Pr 3+ or Er 3+ ions are preferred. It may be advantageous in applications of the glazing type to choose wavelength converting compounds which absorb infrared radiation and not visible radiation, which is the case, for example, of compounds containing a Yb 3+ / Tb 3+ couple. or Tm 3+ or Er 3+ described previously.
- the mineral matrix can be amorphous (it can for example be a glass), or crystallized.
- the advantage of choosing an amorphous matrix is that it can contain large amounts of ions.
- the crystallized matrices are however preferred because the environment of the ions (and therefore their emission / absorption spectrum) is perfectly controlled.
- the amorphous matrices generally contain more structural defects, which can lead to the creation of intermediate energy levels and thus facilitate deexcitations by non-radiative (for example by phonon emission) or radiative transfer, but low energy transfers.
- the active ion In the case where the matrix is crystallized, the active ion must be able to be inserted into the crystal lattice in place of an ion of the matrix.
- matrices containing yttrium (Y), lanthanum (La), gadolinium (Gd) or lutetium (Lu) atoms are preferred because it has been observed that rare earth ions can easily be substitute for these ions within a crystal lattice.
- the phonon frequency of the crystalline matrix is preferably at least four times lower than the emission frequency so as to avoid non-radiative transfer deexcitations.
- the preferred crystalline matrices are chosen from halides (in particular fluorides, but also bromides or chlorides) or oxides.
- the inorganic matrix is selected for example (non-limiting manner) from NaYF 4, Y 2 O 3, Y 2 SiO 5, LaPO 4, TeO 2, or Y 3 Al 5 O 2 (YAG).
- the quantity of doping ions is generally between 0.01 and 50% (in moles relative to the ions to which they substitute), more particularly between 5 and 50% when it is about Yb 3+ and between 0, 01 and 10% for the other doping ions mentioned above.
- wavelength-converting compounds proved to be particularly effective: doped TeO 2 Pr 3 VNd 3+ , doped Y 2 SiO 5 Pr 3+ , Y 3 Al 5 O 12 doped Er 3+ , CaF 2 doped Yb 3 VTb 3+ , Y 2 O 3 doped Yb 3 VTb 3+ , NaYF 4 doped Yb 3 VTb 3+ .
- doped is meant that the matrix comprises the ions mentioned, without necessarily prejudging the amount of ions present, which can be relatively high, as indicated above.
- the wavelength converter compound may be included in the substrate.
- the latter can thus be a glass-ceramic comprising crystals and an amorphous binder, at least a portion of said crystals constituting wavelength converting compounds.
- Vitro-ceramics based on SiO 2 / Al 2 O 3 / CaF 2 in which crystals of CaF 2 are formed, which crystals include in their crystal structure Yb 3+ and Tb 3+ ions are thus capable of absorbing radiation whose wavelength is 980 nm to re-emit radiation centered on the 380 nm wavelength.
- the wavelength converting compound may alternatively or cumulatively be included in a coating disposed between the substrate and the coating comprising photocatalytic titanium oxide. This coating is called in the following text "coating wavelength converter”.
- the wavelength converting compound can be included in the coating in the form of particles dispersed in a mineral or organic binder. These particles are preferably less than 500 nm in size, in particular 300 nm and even 200 nm or 100 nm so as not to generate spurious diffusions likely to affect the transparency of the material. Diffusion can also be avoided by choosing a binder whose refractive index is equal to that of the particles.
- the amount of particles of the energy converting compound within the binder is at least 1% (by weight) and preferably greater than 5%.
- the thickness of the coating is preferably at least equal to 100 nm, preferably greater than or equal to 500 nm and even greater than or equal to 1 ⁇ m and / or less than or equal to 10 ⁇ m, or even 5 ⁇ m.
- the organic binder can be, for example, acrylic, epoxy, cellulosic or silicone type, the latter type being preferred because it is less sensitive to possible degradation by photocatalytic titanium oxide.
- a barrier layer may be disposed between the wavelength converting coating and the photocatalytic coating to prevent degradation of the first coating by the second.
- the inorganic binder can be, for example, a binder made of a material chosen from silica (SiO 2 ), alumina (Al 2 O 3 ), zirconia (ZrO 2 ) or a mixture thereof.
- This binder may in particular be obtained by a decomposition method of organometallic precursors or halides, for example a sol-gel type process, or plasma-assisted chemical vapor deposition at atmospheric pressure (APPECVD).
- the binder can also be an enamel or a glaze, obtained by melting a glass frit deposited for example by screen printing.
- the wavelength converter coating may also consist of a wavelength converter compound. Unlike the mode of previously described embodiment, in which active particles were dispersed in a binder, the wavelength converting compound forms in itself the coating.
- CVD chemical vapor deposition
- sol-gel type techniques sol-gel type techniques
- physical vapor deposition techniques by example by sputtering, in particular assisted by magnetic field (magnetron process), or by evaporation.
- the coating when the wavelength converting compound comprises an amorphous mineral matrix, may also be an enamel or a glaze obtained by melting a glass frit deposited for example by screen printing.
- An underlayer or a stack of sub-layers reflecting at least a portion of the ultraviolet radiation is advantageously disposed between the wavelength converting coating and the substrate.
- the ultraviolet radiation emitted by the wavelength converting compound is indeed isotropic, so that a portion of this radiation is emitted towards the substrate and not towards the photocatalytic coating. Thanks to the underlayer reflecting at least a portion of the ultraviolet radiation, this portion of the emitted radiation is reflected to the photocatalytic coating, thereby increasing the activity of the latter.
- Stacks of sub-layers containing at least three layers having alternately low and high refractive indexes are preferred because they exhibit very low reflection in the visible range, but strong reflection in the ultraviolet range.
- a preferred embodiment consists of a transparent silica-soda-lime glass substrate coated with a silica layer obtained by a sol-gel type process comprising particle-length wavelength converting compounds, this layer being itself even surmounted by a silica layer also obtained by a sol-gel type process and comprising crystallized titanium oxide particles in anatase form.
- the substrate contains alkaline ions (especially in the case of silico-soda-lime glass, which contains about 13% by weight of sodium oxide), these are likely to migrate, especially under the effect of temperature, in the layers that surmount the substrate. Since this migration is likely to cause a decrease in the luminescence efficiency of the wavelength converting compound, it is preferable to have an underlayer acting as a barrier to migration between the substrate and the wavelength converting coating. alkaline ions.
- Such an underlayer which is otherwise known, may be, for example, SiO 2 , Al 2 O 3 , SiO x Cy, Si 3 N 4 , SnO 2 etc.
- the invention also relates to different products incorporating the material according to the invention.
- the material according to the invention can be incorporated into a glazing, for example single, multiple and / or laminated glazing, curved and / or tempered glazing, clear or tinted glazing.
- the material according to the invention can also be incorporated in a display screen, an aquarium, a greenhouse, indoor furniture, tiles, a mirror.
- the substrate may be a mirror comprising a transparent glass sheet on one side of which is deposited a layer of silver coated with a lacquer. The resulting mirror thus has self-cleaning and anti-fogging properties that are particularly appreciable, for example in a bathroom.
- the material according to the invention can also be used in eyewear.
- the material may also be used as tiling, in particular glass, for example as described in application FR-A-2868799.
- the material according to the invention in particular when the substrate is fibrous, may be incorporated into a filtration and purification structure for liquid or gaseous effluents.
- the material according to the invention can be used in a dwelling or vehicle interior to degrade organic soil deposited on its surface.
- the invention will be better understood in the light of the embodiments described below, which illustrate the present invention without limiting it.
- the wavelength converting compound is included in an enamel coating.
- Micrometric particles of yttrium oxide (Y 2 O 3 ) doped with 18% (in mol) of ytterbium Yb 3+ and 2% of terbium Tb 3+ are dispersed in a glass frit with a low melting point ( 600 0 C) based on silica and bismuth oxide.
- the paste obtained is deposited on a silico-soda-lime glass substrate by screen printing, then annealed for 6 minutes at a temperature of 680 ° C. After cooling, a layer of titanium oxide of 50 nm thick is deposited with known manner by chemical vapor deposition (CVD), using titanium tetraisopropylate as a precursor.
- CVD chemical vapor deposition
- the photocatalysis process is activated by excitation by a lamp emitting mainly between 900 and 1000 nm. Under these radiations, the wavelength converting material emits at 380 nm, wavelength which triggers the photocatalytic effect.
- This example illustrates an embodiment in which the wavelength converting compound is included in a coating by being dispersed in a sol-gel silica binder.
- sol-gel silica sol To 4 ml of a colloidal solution of nanoparticles of NaYF 4 : 20 mol% Yb 3+ , 2 mol% Er 3+ is added 1 ml of sol-gel silica sol.
- the diameter of the nanoparticles is 30 nm ⁇ 10 nm, the mass concentration of the colloidal solution in nanoparticles being 10%.
- the solution containing nanoparticles of NaYF 4 : 20% Yb, 2 mol% Er 3+ and silica sol-gel is then deposited by spin-coating on a sand-calcium-silicate glass substrate previously cleaned with the aid of a aqueous solution containing 2% by weight of RBS (surfactant).
- the coating obtained is then dried at 100 ° C. for 1 hour, then annealed at 450 ° C. for 3 hours.
- the thickness of the coating is 450 nm, its light transmission being greater than 80% over the entire visible spectrum.
- a photocatalytic coating based on TiO 2 nanoparticles dispersed in a mesoporous silica sol-gel binder is deposited.
- the photocatalysis process is activated by excitation by a lamp emitting mainly between 900 and 1000 nm. Under this radiation, the wavelength converting material emits at 380 nm, a wavelength that triggers the photocatalytic effect.
- the wavelength converting compound is included in the substrate itself.
- the substrate is a vitroceramic obtained by ceramizing a mother glass of molar composition SiO 2 (47%) / Al 2 O 3 (19%) / CaF 2 (28%) TbF 3 (2%) / YbF 3 (3%). It may be thought that the wavelength converting compound consists of a CaF 2 matrix doped with Tb 3+ and Yb 3+ ions.
- TiO 2 coating On this glass-ceramic substrate is deposited a TiO 2 coating with a thickness of 50 nm. This coating is deposited by chemical vapor deposition (CVD) using titanium tetraisopropoxide (TiPt) at 500 ° C.
- CVD chemical vapor deposition
- TiPt titanium tetraisopropoxide
- the photocatalysis process is activated by excitation by a lamp emitting mainly between 900 and 1000 nm. Under these radiations, the wavelength converting material emits at 380 nm, wavelength which triggers the photocatalytic effect.
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- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Inorganic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
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Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0757467A FR2920762B1 (fr) | 2007-09-10 | 2007-09-10 | Materiau a proprietes photocatalytiques |
PCT/FR2008/051602 WO2009044066A2 (fr) | 2007-09-10 | 2008-09-09 | Materiau a proprietes photocatalytiques |
Publications (1)
Publication Number | Publication Date |
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EP2200947A2 true EP2200947A2 (fr) | 2010-06-30 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP08835279A Withdrawn EP2200947A2 (fr) | 2007-09-10 | 2008-09-09 | Materiau a proprietes photocatalytiques |
Country Status (7)
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US (1) | US20100304059A1 (fr) |
EP (1) | EP2200947A2 (fr) |
JP (1) | JP2010538808A (fr) |
KR (1) | KR20100065322A (fr) |
CN (1) | CN101801868B (fr) |
FR (1) | FR2920762B1 (fr) |
WO (1) | WO2009044066A2 (fr) |
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KR20100126208A (ko) * | 2009-05-21 | 2010-12-01 | 조지아 테크 리서치 코포레이션 | 항미생물성 자외선 역변환 조성물 |
US20130000719A1 (en) * | 2010-03-15 | 2013-01-03 | Ocean's King Lighting Science & Technology Co. Ltd | Organic solar cell and method for manufacturing the same |
CN102064209B (zh) * | 2010-09-21 | 2013-04-10 | 南京工业大学 | 一种转光增强型光催化复合材料及其制备方法 |
CN102849946B (zh) * | 2011-07-01 | 2015-05-06 | 何森 | 自体发射类地紫外光谱玻璃陶瓷材料抗菌的新方法 |
DE102011118057A1 (de) * | 2011-11-09 | 2013-05-16 | Giesecke & Devrient Gmbh | Spektraler Lumineszenzstandard für den Nahinfrarotbereich |
IN2013DE00202A (fr) * | 2013-01-28 | 2015-06-05 | Rosario Cosmetics Pvt Ltd | |
NL2011242C2 (nl) * | 2013-07-31 | 2015-02-03 | Valk Systemen Bvvd | Flexibele folie, samenstel van een constructie en een dergelijke folie en werkwijze voor het vervaardigen van een dergelijke folie. |
US9663400B2 (en) * | 2013-11-08 | 2017-05-30 | Corning Incorporated | Scratch-resistant liquid based coatings for glass |
US9465273B2 (en) * | 2013-11-20 | 2016-10-11 | The Board Of Trustees Of The Leland Stanford Junior University | Photonic micro-structured vacuum-ultraviolet radiation source based on solid-state frequency conversion |
CN103951219B (zh) * | 2014-05-08 | 2016-02-10 | 宁波大学 | 稀土离子掺杂的K2LaI5微晶玻璃及其制备方法 |
CN104190455B (zh) * | 2014-09-26 | 2016-09-07 | 福州大学 | 光催化剂磷酸镧及其制备方法和应用 |
CN104923210A (zh) * | 2015-05-21 | 2015-09-23 | 南京理工大学 | 基于玻璃纤维滤膜载体的Pr3+:Y2SiO5/TiO2光催化复合薄膜、制备方法及其应用 |
JP6914927B2 (ja) * | 2015-10-21 | 2021-08-04 | トロノックス エルエルシー | NOxを低減するコーティング及び当該コーティングによってNOxを低減するための方法 |
CN106495474B (zh) * | 2016-10-11 | 2019-04-23 | 杭州电子科技大学 | 一种可用于温度探测的Eu2+/Eu3+双掺杂玻璃陶瓷复合材料及其制备方法和应用 |
BR112019023126A2 (pt) * | 2017-05-04 | 2020-05-26 | Agc Glass Europe | Substrato revestido |
CN108107490A (zh) * | 2018-01-04 | 2018-06-01 | 中国电子科技集团公司第二十六研究所 | 一种钇铝石榴石晶体镜片及其加工方法 |
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CN114351142A (zh) * | 2021-11-26 | 2022-04-15 | 格力电器(武汉)有限公司 | 抗菌搪瓷内胆的制备方法、抗菌搪瓷内胆及含其的热水器 |
CN114315156B (zh) * | 2021-11-30 | 2023-12-29 | 无锡极电光能科技有限公司 | 钙钛矿量子点釉料、光伏玻璃及其制备方法和光伏组件 |
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2007
- 2007-09-10 FR FR0757467A patent/FR2920762B1/fr not_active Expired - Fee Related
-
2008
- 2008-09-09 JP JP2010523576A patent/JP2010538808A/ja active Pending
- 2008-09-09 EP EP08835279A patent/EP2200947A2/fr not_active Withdrawn
- 2008-09-09 US US12/676,619 patent/US20100304059A1/en not_active Abandoned
- 2008-09-09 KR KR1020107005179A patent/KR20100065322A/ko not_active Application Discontinuation
- 2008-09-09 WO PCT/FR2008/051602 patent/WO2009044066A2/fr active Application Filing
- 2008-09-09 CN CN200880106450.1A patent/CN101801868B/zh not_active Expired - Fee Related
Non-Patent Citations (1)
Title |
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See references of WO2009044066A3 * |
Also Published As
Publication number | Publication date |
---|---|
US20100304059A1 (en) | 2010-12-02 |
FR2920762B1 (fr) | 2009-10-23 |
FR2920762A1 (fr) | 2009-03-13 |
CN101801868A (zh) | 2010-08-11 |
JP2010538808A (ja) | 2010-12-16 |
CN101801868B (zh) | 2012-10-10 |
WO2009044066A3 (fr) | 2009-05-28 |
KR20100065322A (ko) | 2010-06-16 |
WO2009044066A2 (fr) | 2009-04-09 |
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