US20050170098A1 - Glass, ceramic and metal substrates with a self-cleaning surface, method of making them and their use - Google Patents
Glass, ceramic and metal substrates with a self-cleaning surface, method of making them and their use Download PDFInfo
- Publication number
- US20050170098A1 US20050170098A1 US11/059,713 US5971305A US2005170098A1 US 20050170098 A1 US20050170098 A1 US 20050170098A1 US 5971305 A US5971305 A US 5971305A US 2005170098 A1 US2005170098 A1 US 2005170098A1
- Authority
- US
- United States
- Prior art keywords
- range
- forming particles
- glass
- substrate
- layer
- 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.)
- Abandoned
Links
- 239000011521 glass Substances 0.000 title claims abstract description 95
- 239000000758 substrate Substances 0.000 title claims abstract description 71
- 238000004140 cleaning Methods 0.000 title claims abstract description 41
- 239000000919 ceramic Substances 0.000 title claims abstract description 14
- 239000002184 metal Substances 0.000 title claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000002245 particle Substances 0.000 claims abstract description 84
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 47
- 230000004907 flux Effects 0.000 claims abstract description 38
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims description 40
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 238000007639 printing Methods 0.000 claims description 15
- 238000000576 coating method Methods 0.000 claims description 11
- -1 zirconium silicates Chemical class 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 7
- 239000010457 zeolite Substances 0.000 claims description 6
- 239000011449 brick Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 4
- 230000002902 bimodal effect Effects 0.000 claims description 3
- 239000004927 clay Substances 0.000 claims description 3
- 229910052573 porcelain Inorganic materials 0.000 claims description 3
- 229910052572 stoneware Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 238000009826 distribution Methods 0.000 claims 2
- 229920002554 vinyl polymer Polymers 0.000 claims 1
- 239000010410 layer Substances 0.000 description 23
- 230000000694 effects Effects 0.000 description 19
- 239000000463 material Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000005299 abrasion Methods 0.000 description 8
- 239000002609 medium Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000007650 screen-printing Methods 0.000 description 5
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- 229910010293 ceramic material Inorganic materials 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 4
- 238000009503 electrostatic coating Methods 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- 150000004756 silanes Chemical class 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 240000002853 Nelumbo nucifera Species 0.000 description 3
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 3
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- QXJJQWWVWRCVQT-UHFFFAOYSA-K calcium;sodium;phosphate Chemical compound [Na+].[Ca+2].[O-]P([O-])([O-])=O QXJJQWWVWRCVQT-UHFFFAOYSA-K 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 210000003298 dental enamel Anatomy 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011254 layer-forming composition Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000005661 hydrophobic surface Effects 0.000 description 2
- 239000004922 lacquer Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 125000005372 silanol group Chemical group 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000012815 thermoplastic material Substances 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- NDUKHFILUDZSHZ-UHFFFAOYSA-N [Fe].[Zr] Chemical compound [Fe].[Zr] NDUKHFILUDZSHZ-UHFFFAOYSA-N 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002152 aqueous-organic solution Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 238000010017 direct printing Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000005329 float glass Substances 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000002241 glass-ceramic Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000003075 superhydrophobic effect Effects 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000010023 transfer printing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B17/00—Methods preventing fouling
- B08B17/02—Preventing deposition of fouling or of dust
- B08B17/06—Preventing deposition of fouling or of dust by giving articles subject to fouling a special shape or arrangement
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B17/00—Methods preventing fouling
- B08B17/02—Preventing deposition of fouling or of dust
- B08B17/06—Preventing deposition of fouling or of dust by giving articles subject to fouling a special shape or arrangement
- B08B17/065—Preventing deposition of fouling or of dust by giving articles subject to fouling a special shape or arrangement the surface having a microscopic surface pattern to achieve the same effect as a lotus flower
-
- 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
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
- C03C17/008—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
- C03C17/009—Mixtures of organic and inorganic materials, e.g. ormosils and ormocers
-
- 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
- C03C17/42—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating of an organic material and at least one non-metal coating
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
-
- 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
- C23C24/00—Coating starting from inorganic powder
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
-
- 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
- C23C24/00—Coating starting from inorganic powder
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
- C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
-
- 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
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
-
- 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
- C03C2217/45—Inorganic continuous phases
- C03C2217/452—Glass
-
- 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
- C03C2217/465—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase having a specific shape
-
- 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
-
- 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
- C03C2217/77—Coatings having a rough surface
-
- 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
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
-
- 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
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
- Y10T428/24364—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.] with transparent or protective coating
-
- 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
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24479—Structurally defined web or sheet [e.g., overall dimension, etc.] including variation in thickness
-
- 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
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31609—Particulate metal or metal compound-containing
- Y10T428/31612—As silicone, silane or siloxane
-
- 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
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31652—Of asbestos
- Y10T428/31663—As siloxane, silicone or silane
Definitions
- the invention relates to glass, ceramic and metal substrates with at least one structured hydrophobic surface that provides a good self-cleaning effect.
- Another subject of the invention is a method of making said substrates with a self-cleaning surface, the method comprising forming a structured surface then making it hydrophobic.
- a further subject is use of the glass, ceramic and metal substrates with a surface according to the invention having a self-cleaning effect.
- a surface with a self-cleaning effect may be applied to ceramic bricks or to glass by coating the substrate with a suspension containing glass spheres with a diameter within the 3-12 ⁇ m range and a glass sphere (diameter 3-12 ⁇ m) and a fluorocarbon wax based on a fluoroalkylethoxy methacrylate polymer.
- a disadvantage of such coatings with a self-cleaning effect is their poor resistance to abrasion. As established by the inventors involved in this patent application, glass spheres do indeed form a structure but their self-cleaning effect is only moderate.
- EP 0 909 747 A1 teaches a method of producing self-cleaning properties in surfaces, particularly roof tiles.
- the surface has hydrophobic elevations 5 to 200 ⁇ m high.
- a surface of this type is formed by applying a dispersion of powder particles of an inert material in a siloxane solution then letting it harden. As in the previously assessed method the structure-forming particles are not fixed on the surface of the substrate in an abrasion-resistant manner.
- EP 0 772 514 B1 and EP 0 933 388 A2 teach of self-cleaning surfaces on articles with an artificial surface structure comprising elevations and depressions, the distance between the elevations being within the 5 to 200 ⁇ m range (EP 0 772 514 B1) or the 50 nm to 10 ⁇ m range (EP 0 933 388 A2) and the height of the elevations being within the 5 to 100 ⁇ m range or the 50 nm to 10 ⁇ m range respectively and the structure being made of hydrophobic polymers or materials made durably hydrophobic.
- Methods suitable for forming the structures are etching and embossing processes, coating processes for sticking on a structure-forming powder and shaping processes using appropriately structured female molds.
- the formation of the structure is followed by treatment to make it hydrophobic, particularly by silanising it.
- self-cleaning surfaces according to EP 0 772 514 B1 may also be applied to glazing or roofs the process is very expensive and the surface forming the structure, like that in the documents assessed above, has little resistance to abrasion, so the self-cleaning effect declines rapidly under quite strong mechanical stress.
- the object of the invention is to indicate substrates of glass, a ceramic material or metal with a structured and hydrophobic surface having a good self-cleaning effect.
- a further object is that the structured surface should have higher abrasion resistance than known surfaces in which structure-forming particles were fixed to the surface by means of an organic polymer.
- a further object of the invention is that substrates with the self-cleaning surface according to the invention should be obtainable by a simple method. It should be possible to carry out the structure-forming method using stages in the process and industrial apparatus normal for surface treatment, such as decoration, of said substrates.
- a substrate of glass, a ceramic material or metal is coated with a composition containing a material producing a glass flux such as a glass frit and structure-forming particles, and the coated substrate is fired at a temperature adapted to the substrate and the material forming the glass flux then made hydrophobic, the substrate being made hydrophobic preferably using a fluoroalkylsilane or fluoroalkylsiloxane.
- the subject of the invention is accordingly a glass, ceramic or metal substrate with at least one self-cleaning surface comprising a layer with a micro-rough surface structure which is arranged on the substrate and made at least partly hydrophobic, characterized in that the layer contains a glass flux and structure-forming particles with a mean particle diameter within the 0.1 to 50 ⁇ m range, the glass flux and structure-forming particles are present in a volume ratio within the 0.1 to 5 range, and the micro-rough surface structure has a ratio of mean profile height to mean distance between adjacent profile tips within the 0.3 to 10 range.
- FIG. 1 is a scanning electron microscope photograph of a self-cleaning surface according to the invention.
- the substrates in question are ones that are resistant to ceramic burning under temperature conditions adapted to the substrate. They are accordingly glass of any chemical composition including glass-ceramics, any ceramic materials such as bricks, clinker, architecturally applied ceramics, stoneware, vitrified clay, hard and soft porcelain, oxide and special ceramics and metals, in particular steels.
- the substrates may also be coated with colored slip, glazed or enameled before the self-cleaning surface is applied.
- self-cleaning surface is used in the same sense as in prior art.
- the surface is virtually unwettable by water and preferably by other liquids, so rapid drop formation becomes possible and dirt particles deposited are washed away in a simple manner with the drops running down.
- Substrates with a self-cleaning surface produced according to the invention are substantially dry when water has run off the surface.
- the self-cleaning surface has a micro-rough structure, i.e. a structure with elevations and depressions in a geometrical or random, preferably random arrangement.
- the elevations and depressions are distributed substantially over the whole self-cleaning surface.
- a surface with a coarse and a fine structure has been found to allow a particularly good self-cleaning effect.
- the mean profile height of the surface roughness is normally within the 0.2 to 10 ⁇ m range although values outside those limits are not excluded. Roughness with a profile height within the range from approx. 1 ⁇ m to approximately 10 ⁇ m is preferred. If the surface has both a coarse and a fine structure the mean profile height of the fine structure is generally within the range from 0.2 to approx. 4 ⁇ m, particularly 0.5 to 3 ⁇ m and that of the coarse structure within the range from 1 to 10 ⁇ m but above the height of the fine structure.
- a feature of the surface structure that is important for a good self-cleaning effect is the ratio of the mean profile height to the mean distance between adjacent profile tips.
- This aspect ratio is desirably within the 0.3 to 10 range, preferably within the 1 to 5 range and particularly preferably within the 1 to 2 range. Said aspect ratios apply to both the coarse and the fine structure.
- the micro-rough surface structure is formed from particles anchored in a glass flux and/or particle aggregates bonded together by glass flux.
- the glass flux is thus the binder for the structure-forming particles and gives the surface structure considerably higher abrasion resistance than was possible using known resins.
- the layer forming a micro-rough surface structure substantially comprises a glass flux and the structure-forming particles. A fraction of the particles may be completely enveloped in glass flux but another fraction, namely the fraction forming the structure, projects out of the flux.
- the micro-rough layer may contain other constituents, for example pigments to give the system a decorative appearance or metallic powders providing electrical conductivity. Said categories of material may themselves be a component of the structure-forming particles.
- the layer with the micro-rough surface structure located on the substrate contains glass flux and structure-forming particles in a volume ratio desirably within the 0.1 to 5 range, preferably within the 0.2 to 2 range and particularly preferably within the 0.3 to 1 range. As the proportion of glass flux increases, given the same particle spectrum, the degree of roughness and thus the effectiveness is diminished.
- the volume ratio of glass flux to structure-forming particles that is particularly suitable for the intended purpose also depends to a certain extent on the particle spectrum of the structure-forming particles. The optimum ratio can be determined by carrying out simple tests.
- the mean particle diameter of the structure-forming particles may be within a range from 0.1 to 50 ⁇ m, although it is preferably within the range from 0.2 to 20 ⁇ m and particularly preferably within the range from 0.5 to 15 ⁇ m. As the mean particle diameter of the structure-forming particles and the thickness of the micro-rough layer increase the layer becomes more opaque.
- a layer with the above-mentioned preferred bimodal structure contains a spectrum of structure-forming particles with an adequate proportion of fine particles, preferably within the range from 0.2 to 3 ⁇ m, and an adequate proportion of coarse particles of a diameter within the range from 3 to 15 ⁇ m, particularly from 5 to 10 ⁇ m.
- the particles used to form the micro-rough structure are those with a melting point above the firing temperature and thus above the deformation point of the glass flux. Particularly effective surface structures can be obtained when the structure-forming particles are idiomorphic, i.e. when they have pronounced edges and faces. Although particles with a rather spherical morphology or even glass spheres enable a micro-rough surface structure to be formed, its self-cleaning effect is only moderate or unsatisfactory.
- structure-forming particles Any products may be present as structure-forming particles; their melting point is above the firing temperature and the structure is preferably idiomorphic.
- Some examples of structure-forming particles are oxides and silicates such as zirconium silicates, zeolites, SiO 2 , TiO 2 , ZrO 2 , SnO 2 and Al 2 O 3 .
- the glass flux may be of very different compositions. Numerous glass compositions are known to those having skill in the art that have a deformation range from approximately 500° C. to over 1000° C. Glass compositions of the flux for a micro-rough surface structure on glass understandably have a deformation temperature below that of the glass substrate. Micro-rough surface structures on for example ceramic substrates generally have a substantially higher deformation point.
- the thickness of the micro-rough layer is variable, generally within the range from 5 to 100 ⁇ m, preferably from 10 to 20 ⁇ m.
- the given thickness covers the height of the layer including the mean profile height of the elevations.
- the surface of the micro-rough layer is at least partly made hydrophobic, especially the tips of the elevations. However the whole surface is preferably made hydrophobic.
- a very thin coating for example 1 to 10 nm thick, which adheres firmly to the surface below it.
- the adhesion results from the coating material forming a film after application.
- Preferred agents for making the surface hydrophobic are chemically bonded to the substrate for example by a Si—O—Si bridge. Such bridges result from the reaction of a silanol group of a silicate substrate with an alkoxysilane or alkoxysiloxane.
- Preferred substrates according to the invention with a self-cleaning surface have a coating, often only very few atomic layers thick, based on an alkyltrialkoxysilane and preferably a longer-chain fluoroalkyl trialkoxysilane or oligomers of those silanes.
- FIG. 1 shows a scanning electron microscope photograph of a self-cleaning surface according to the invention, where the substrate is glass and the structure-forming particles are a zeolite of the Pentasil type (ZSM 5) bonded to the substrate by a glass flux.
- the volume ratio of zeolite to glass flux is 1 to 1; a printing paste containing zeolite and glass frit in said volume ratio has been applied to the substrate by screen printing and burnt in at 650° C.
- the surface thus produced had an extremely good self-cleaning effect and high abrasion resistance.
- Substrates according to the invention with a self-cleaning surface can be produced by a method comprising applying a hydrophobic, micro-rough layer to the substrate and characterized by the steps of coating the substrate with a composition containing a glass frit which forms a glass flux and structure-forming particles with a mean particle diameter within the 0.1 to 50 ⁇ m range, the composition containing glass frit and structure-forming particles in a volume ratio within the 0.1 to 5 range, burning in the layer at a temperature above the deformation temperature of the glass frit, and making the burnt-in layer at least partly hydrophobic by applying an agent to make it hydrophobic.
- the choice of material, the structure and the spectrum of structure-forming particles used in the composition forming the layer can be found in the above description.
- the glass frit forming the glass flux may be one frit or a mixture of different glass frits.
- the composition may also contain one or more inorganic pigments and/or metallic powders such as silver for conductivity purposes and/or processing aids to improve the preparation of the composition and/or its application to the substrate to be coated.
- composition to be used for forming the micro-rough layer may be applied in a known manner to at least one surface of the substrate to be coated. Suitable methods of doing so are direct and indirect printing processes including screen printing and pad transfer printing processes, also dipping and spraying methods and electrostatic coating processes.
- the composition contains, in addition to the above-mentioned inorganic constituents, a liquid printing medium in which the inorganic constituents are made into a paste.
- Aqueous and/or organic or organic-aqueous media may be used, containing one or more organic binders and possibly normal processing aids such as viscosity regulators in addition to one or more solvents.
- Appropriate media are those known in the art for producing printing pastes for making ceramic decorations which are burnt-in in a decorative baking process.
- the layer-forming composition is applied to the substrate to be coated by a known electrostatic coating process.
- the composition should desirably also contain a few percent of a thermoplastic material, in particular 1 to 8% by weight of a polyethylene wax, and the substrate should be heated to a temperature above the deformation point of the thermoplastic material before or immediately after the electrostatic coating. Details of electrostatic coating of glass and ceramic materials can be found in WO 94/26679 and WO 98/58889.
- the layer-forming composition to the substrate is followed by normal baking. At a temperature above the deformation point of at least one glass frit, the frit fuses together into a glass flux.
- the structure-forming particles near the surface surprisingly form the required micro-rough surface structure with the aspect ratio claimed.
- the particles located at the surface are securely anchored in the glass flux.
- the micro-rough layer is printed by means of a printing paste containing a glass frit which forms a glass flux, and the structure-forming particles are applied to the still moist printing surface for example by powdering or dripping on, possibly followed by partial pressing of the particles into the printed surface.
- the substrate thus treated is then burnt and made hydrophobic in a known manner.
- the whole surface is made hydrophobic.
- the agents for making the surface hydrophobic are products normally used in the art. They are either polymers with that action or preferably monomeric or oligomeric compounds containing a fairly long-chain alkyl or preferably fluoroalkyl radical with that action and also a functional group whereby the compounds with a hydrophobising action can be cross-linked and thus form a film and/or whereby a reaction with functional groups at the surface of the micro-rough layer is enabled.
- the micro-rough surface may be made hydrophobic by applying a lacquer or by polymerizing monomers on the surface.
- Some suitable polymeric lacquers are solutions or dispersions for example of polyvinylidene fluoride.
- the surface may be made hydrophobic by plasma polymerisation of fully or partly fluorinated vinyl compounds.
- the surface is particularly desirable for the surface to be made hydrophobic using reactive alkyl or preferably fluoroalkyl silanes and oligomeric alkyl or fluoroalkyl siloxanes.
- the silanes or siloxanes preferably contain one or more alkoxy groups such as ethoxy groups as the reactive group.
- the agent for making the surface hydrophobic may be cross-linked and also chemically bound to a silicate surface containing silanol groups by these alkoxy groups.
- Particularly preferred silanising agents are tridecafluoroctyltriethoxy silane and oligomers thereof (Dynasilanes® produced by Sivento Chemie Rheinfelden GmbH). Products of this type may be applied to the surface to be made hydrophobic in the form of dilute organic, in particular alcoholic, aqueous-organic and aqueous solutions for example by dipping, spraying or painting.
- the substrate is dried and hardened preferably at a temperature up to 500° C., for example for 10-15 minutes at 250° C. to 300° C. or 1 minute at about 500° C. or 30-60 minutes at about 150° C.
- the optimum thermal post-treatment for maximum abrasion resistance is at a temperature in the range from 200° C. to 300° C.
- Hydrophobic layers which can be obtained by using reactive fluoroalkyl silanes or siloxanes are characterized by equally good hydrophobic and oleophobic properties, so even substrates according to the invention which are soiled with hydrophobic dirt particles can easily be cleaned with water.
- Substrates with a self-cleaning surface according to the invention may be used wherever the surface (a) is exposed to a constant danger of soiling and (b) must be cleanable in an extremely simple manner with water.
- Glass substrates with a self-cleaning surface according to the invention can appropriately be used for glazing vehicles and trains and for glass bricks.
- Ceramic substrates with a self-cleaning surface according to the invention are suitable for use as a building material such as roof tiles, clinker and floor tiles.
- the advantages of the invention are that self-cleaning surfaces of glass, ceramic and metal substrates are easily accessible and have a good self-cleaning effect.
- the structure-forming layer has high abrasion resistance.
- Preferred surfaces have “super-hydrophobic properties”, causing water drops to run down them almost without friction.
- substrates with a structured surface made hydrophobic according to the invention are also suitable for chemical engineering apparatus such as coated pipes and heat exchanger plates.
- Direct printing Glass frit and structure-forming particles were made into a paste in a known manner with a printing medium which can be diluted with water (No. 80858 from dmc 2 AG) or a purely organic one (No. 80820 from dmc 2 AG), and the printing paste was applied to the substrate by screen printing.
- a printing medium which can be diluted with water (No. 80858 from dmc 2 AG) or a purely organic one (No. 80820 from dmc 2 AG), and the printing paste was applied to the substrate by screen printing.
- Indirect printing Glass frit and structure-forming particles were made into a paste with a screen printing oil (No. 80820 from dmc 2 AG). The printing method was screen printing on transfer paper; after drying a covering film was formed. The printed image was applied in known manner to the substrate to be decorated.
- Electrostatic application Glass frit and structure-forming particles mixed with Siloxane H68 (Weinstock & Siebert) were treated (first mixed then tempered) to raise the specific resistance of the powder to >10 14 ⁇ m.
- the powder mixture of the glass frit thus siliconised and structure-forming particles was applied using an electrostatic gun at 90 kV.
- the coatings applied to the substrate by direct or indirect printing or electrostatically were burnt-in in a known manner; heating-up time 200 K/h, T max and holding time are given in the Table.
- the substrate was 4 mm float glass in all the examples.
- the glass frits were a low melting point glass frit with a high Pb content, a d 50 value of 3.3 ⁇ m and a d 90 value of 10 ⁇ m (No. 10022 from dmc 2 AG), another glass frit (No. 10157 from dmc 2 AG) and a glass frit for electrostatic glazing (VNR 9316 F) with a d 50 value of 3.7 ⁇ m and a d 90 value of 6.8 ⁇ m.
- the structure-forming particles used were zirconium dye pigments, namely zirconium iron rose (FK 27357 from dmc 2 AG), and a hydrophobic zeolite of the Pentasil type (Wessalith® DAZ).
- the structured burnt-in surface was made hydrophobic using a fluoroalkyl silane formulation, namely Dynasilan®) F8262 (Degussa-Huls AG) (a solution of tridecafluoroctyltriethoxy silane in ethanol). The solution was poured over the surface then hardened at an elevated temperature.
- a fluoroalkyl silane formulation namely Dynasilan®
- F8262 Degussa-Huls AG
- the solution was poured over the surface then hardened at an elevated temperature.
Abstract
The invention relates to glass, ceramic and metal substrates with at least one self-cleaning surface, comprising a layer with a micro-rough surface structure that is arranged on the substrate and made at least partly hydrophobic. The layer contains a glass flux and structure-forming particles with a mean particle diameter within the 0.1 to 50 μm range; the glass flux and structure-forming particles are present in a volume ratio within the 0.1 to 5 range, and the micro-rough surface structure has a ratio of mean profile height to mean distance between adjacent profile tips within the 0.3 to 10 range. To produce the subject of the invention the substrate is coated with a composition containing a glass flux and structure-forming particles, and the layer is burnt in and made hydrophobic.
Description
- This application is a division of application Ser. No. 10/239,066, filed Jan. 16, 2003, which was a U.S. National Stage Application of PCT/EP01/02790, filed Mar. 13, 2001, and claims priority to DE 10016585.4, filed Apr. 1, 2000.
- 1. Field of Invention
- The invention relates to glass, ceramic and metal substrates with at least one structured hydrophobic surface that provides a good self-cleaning effect. Another subject of the invention is a method of making said substrates with a self-cleaning surface, the method comprising forming a structured surface then making it hydrophobic. A further subject is use of the glass, ceramic and metal substrates with a surface according to the invention having a self-cleaning effect.
- 2. Description of Related Art
- It is known that in order to obtain a good self-cleaning effect a surface needs to have not only good hydrophobic properties but also a micro-rough surface structure. Both features are present in nature, for example in the lotus leaf; the surface, formed from a hydrophobic material, has pyramidal elevations a few micrometers away from each other. Drops of water substantially come into contact only with these tips, so the contact area is minute, resulting in very low adhesion. These relationships and the theoretical possibility of applying the “lotus effect” to industrial surfaces are taught by A. A. Abramzon, Khimia i Zhizn (1982), No. 11, pp. 38-40.
- Without reference to the lotus effect, water-repellent surfaces are known from U.S. Pat. No. 3,354,022, where the surface has a micro-rough structure with elevations and depressions and is formed from a hydrophobic material in particular a fluorine-containing polymer. In one embodiment a surface with a self-cleaning effect may be applied to ceramic bricks or to glass by coating the substrate with a suspension containing glass spheres with a diameter within the 3-12 μm range and a glass sphere (diameter 3-12 μm) and a fluorocarbon wax based on a fluoroalkylethoxy methacrylate polymer. A disadvantage of such coatings with a self-cleaning effect is their poor resistance to abrasion. As established by the inventors involved in this patent application, glass spheres do indeed form a structure but their self-cleaning effect is only moderate.
- EP 0 909 747 A1 teaches a method of producing self-cleaning properties in surfaces, particularly roof tiles. The surface has hydrophobic elevations 5 to 200 μm high. A surface of this type is formed by applying a dispersion of powder particles of an inert material in a siloxane solution then letting it harden. As in the previously assessed method the structure-forming particles are not fixed on the surface of the substrate in an abrasion-resistant manner.
- EP 0 772 514 B1 and EP 0 933 388 A2 teach of self-cleaning surfaces on articles with an artificial surface structure comprising elevations and depressions, the distance between the elevations being within the 5 to 200 μm range (EP 0 772 514 B1) or the 50 nm to 10 μm range (EP 0 933 388 A2) and the height of the elevations being within the 5 to 100 μm range or the 50 nm to 10 μm range respectively and the structure being made of hydrophobic polymers or materials made durably hydrophobic. Methods suitable for forming the structures are etching and embossing processes, coating processes for sticking on a structure-forming powder and shaping processes using appropriately structured female molds. If the material forming the structure is not itself hydrophobic the formation of the structure is followed by treatment to make it hydrophobic, particularly by silanising it. Although self-cleaning surfaces according to EP 0 772 514 B1 may also be applied to glazing or roofs the process is very expensive and the surface forming the structure, like that in the documents assessed above, has little resistance to abrasion, so the self-cleaning effect declines rapidly under quite strong mechanical stress.
- The object of the invention is to indicate substrates of glass, a ceramic material or metal with a structured and hydrophobic surface having a good self-cleaning effect. A further object is that the structured surface should have higher abrasion resistance than known surfaces in which structure-forming particles were fixed to the surface by means of an organic polymer. A further object of the invention is that substrates with the self-cleaning surface according to the invention should be obtainable by a simple method. It should be possible to carry out the structure-forming method using stages in the process and industrial apparatus normal for surface treatment, such as decoration, of said substrates.
- It has been found that the above objects and other objects revealed in the following description can be achieved, in that a substrate of glass, a ceramic material or metal is coated with a composition containing a material producing a glass flux such as a glass frit and structure-forming particles, and the coated substrate is fired at a temperature adapted to the substrate and the material forming the glass flux then made hydrophobic, the substrate being made hydrophobic preferably using a fluoroalkylsilane or fluoroalkylsiloxane.
- The subject of the invention is accordingly a glass, ceramic or metal substrate with at least one self-cleaning surface comprising a layer with a micro-rough surface structure which is arranged on the substrate and made at least partly hydrophobic, characterized in that the layer contains a glass flux and structure-forming particles with a mean particle diameter within the 0.1 to 50 μm range, the glass flux and structure-forming particles are present in a volume ratio within the 0.1 to 5 range, and the micro-rough surface structure has a ratio of mean profile height to mean distance between adjacent profile tips within the 0.3 to 10 range.
- The foregoing and other features of the invention are hereinafter more fully described and particularly pointed out in the claims, the following description setting forth in detail certain illustrative embodiments of the invention, these being indicative, however, of but a few of the various ways in which the principles of the present invention may be employed.
-
FIG. 1 is a scanning electron microscope photograph of a self-cleaning surface according to the invention. - The substrates in question are ones that are resistant to ceramic burning under temperature conditions adapted to the substrate. They are accordingly glass of any chemical composition including glass-ceramics, any ceramic materials such as bricks, clinker, architecturally applied ceramics, stoneware, vitrified clay, hard and soft porcelain, oxide and special ceramics and metals, in particular steels. The substrates may also be coated with colored slip, glazed or enameled before the self-cleaning surface is applied.
- The term “self-cleaning surface” is used in the same sense as in prior art. The surface is virtually unwettable by water and preferably by other liquids, so rapid drop formation becomes possible and dirt particles deposited are washed away in a simple manner with the drops running down. Substrates with a self-cleaning surface produced according to the invention are substantially dry when water has run off the surface.
- The self-cleaning surface has a micro-rough structure, i.e. a structure with elevations and depressions in a geometrical or random, preferably random arrangement. The elevations and depressions are distributed substantially over the whole self-cleaning surface. There may be a simple structure of elevations and depressions; alternatively the micro-roughness may comprise a coarse structure and a fine structure, with the elevations and depressions of the fine structure located on a coarse structure (=superstructure) having depressions and elevations. A surface with a coarse and a fine structure has been found to allow a particularly good self-cleaning effect.
- The mean profile height of the surface roughness is normally within the 0.2 to 10 μm range although values outside those limits are not excluded. Roughness with a profile height within the range from approx. 1 μm to approximately 10 μm is preferred. If the surface has both a coarse and a fine structure the mean profile height of the fine structure is generally within the range from 0.2 to approx. 4 μm, particularly 0.5 to 3 μm and that of the coarse structure within the range from 1 to 10 μm but above the height of the fine structure.
- A feature of the surface structure that is important for a good self-cleaning effect is the ratio of the mean profile height to the mean distance between adjacent profile tips. This aspect ratio is desirably within the 0.3 to 10 range, preferably within the 1 to 5 range and particularly preferably within the 1 to 2 range. Said aspect ratios apply to both the coarse and the fine structure.
- The micro-rough surface structure is formed from particles anchored in a glass flux and/or particle aggregates bonded together by glass flux. The glass flux is thus the binder for the structure-forming particles and gives the surface structure considerably higher abrasion resistance than was possible using known resins. The layer forming a micro-rough surface structure substantially comprises a glass flux and the structure-forming particles. A fraction of the particles may be completely enveloped in glass flux but another fraction, namely the fraction forming the structure, projects out of the flux. In addition to the glass flux and structure-forming particles the micro-rough layer may contain other constituents, for example pigments to give the system a decorative appearance or metallic powders providing electrical conductivity. Said categories of material may themselves be a component of the structure-forming particles.
- The layer with the micro-rough surface structure located on the substrate contains glass flux and structure-forming particles in a volume ratio desirably within the 0.1 to 5 range, preferably within the 0.2 to 2 range and particularly preferably within the 0.3 to 1 range. As the proportion of glass flux increases, given the same particle spectrum, the degree of roughness and thus the effectiveness is diminished.
- Conversely if the quantity of glass flux is too small, abrasion-proof fixing of the structure-forming particles on the substrate surface can no longer be guaranteed. The volume ratio of glass flux to structure-forming particles that is particularly suitable for the intended purpose also depends to a certain extent on the particle spectrum of the structure-forming particles. The optimum ratio can be determined by carrying out simple tests.
- The mean particle diameter of the structure-forming particles may be within a range from 0.1 to 50 μm, although it is preferably within the range from 0.2 to 20 μm and particularly preferably within the range from 0.5 to 15 μm. As the mean particle diameter of the structure-forming particles and the thickness of the micro-rough layer increase the layer becomes more opaque. A layer with the above-mentioned preferred bimodal structure (fine structure on a superstructure) contains a spectrum of structure-forming particles with an adequate proportion of fine particles, preferably within the range from 0.2 to 3 μm, and an adequate proportion of coarse particles of a diameter within the range from 3 to 15 μm, particularly from 5 to 10 μm.
- The particles used to form the micro-rough structure are those with a melting point above the firing temperature and thus above the deformation point of the glass flux. Particularly effective surface structures can be obtained when the structure-forming particles are idiomorphic, i.e. when they have pronounced edges and faces. Although particles with a rather spherical morphology or even glass spheres enable a micro-rough surface structure to be formed, its self-cleaning effect is only moderate or unsatisfactory.
- Any products may be present as structure-forming particles; their melting point is above the firing temperature and the structure is preferably idiomorphic. Some examples of structure-forming particles are oxides and silicates such as zirconium silicates, zeolites, SiO2, TiO2, ZrO2, SnO2 and Al2O3.
- The glass flux may be of very different compositions. Numerous glass compositions are known to those having skill in the art that have a deformation range from approximately 500° C. to over 1000° C. Glass compositions of the flux for a micro-rough surface structure on glass understandably have a deformation temperature below that of the glass substrate. Micro-rough surface structures on for example ceramic substrates generally have a substantially higher deformation point.
- The thickness of the micro-rough layer is variable, generally within the range from 5 to 100 μm, preferably from 10 to 20 μm. The given thickness covers the height of the layer including the mean profile height of the elevations.
- The surface of the micro-rough layer is at least partly made hydrophobic, especially the tips of the elevations. However the whole surface is preferably made hydrophobic.
- This is done substantially by a very thin coating, for example 1 to 10 nm thick, which adheres firmly to the surface below it. The adhesion results from the coating material forming a film after application. Preferred agents for making the surface hydrophobic are chemically bonded to the substrate for example by a Si—O—Si bridge. Such bridges result from the reaction of a silanol group of a silicate substrate with an alkoxysilane or alkoxysiloxane. Preferred substrates according to the invention with a self-cleaning surface have a coating, often only very few atomic layers thick, based on an alkyltrialkoxysilane and preferably a longer-chain fluoroalkyl trialkoxysilane or oligomers of those silanes.
-
FIG. 1 shows a scanning electron microscope photograph of a self-cleaning surface according to the invention, where the substrate is glass and the structure-forming particles are a zeolite of the Pentasil type (ZSM 5) bonded to the substrate by a glass flux. The volume ratio of zeolite to glass flux is 1 to 1; a printing paste containing zeolite and glass frit in said volume ratio has been applied to the substrate by screen printing and burnt in at 650° C. The surface thus produced had an extremely good self-cleaning effect and high abrasion resistance. - Substrates according to the invention with a self-cleaning surface can be produced by a method comprising applying a hydrophobic, micro-rough layer to the substrate and characterized by the steps of coating the substrate with a composition containing a glass frit which forms a glass flux and structure-forming particles with a mean particle diameter within the 0.1 to 50 μm range, the composition containing glass frit and structure-forming particles in a volume ratio within the 0.1 to 5 range, burning in the layer at a temperature above the deformation temperature of the glass frit, and making the burnt-in layer at least partly hydrophobic by applying an agent to make it hydrophobic.
- The choice of material, the structure and the spectrum of structure-forming particles used in the composition forming the layer can be found in the above description. The same applies to the volume ratio of glass frit forming glass flux to structure-forming particles to be used; glass flux and glass frit have the same volume, so the said ratio is also the same. The glass frit forming the glass flux may be one frit or a mixture of different glass frits. In addition to the one or more glass frits and the structure-forming particles the composition may also contain one or more inorganic pigments and/or metallic powders such as silver for conductivity purposes and/or processing aids to improve the preparation of the composition and/or its application to the substrate to be coated.
- To produce a metallic substrate with a self-cleaning surface it is desirable to select the usual glass frits for making enamels on metallic substrates. It may be desirable, in order to improve adhesion, first to provide the metallic substrate with a base enamel and only then to apply the composition for forming a layer with a micro-rough surface structure to the enamel.
- The composition to be used for forming the micro-rough layer may be applied in a known manner to at least one surface of the substrate to be coated. Suitable methods of doing so are direct and indirect printing processes including screen printing and pad transfer printing processes, also dipping and spraying methods and electrostatic coating processes.
- To enable the layer-forming composition to be applied in a normal printing process the composition contains, in addition to the above-mentioned inorganic constituents, a liquid printing medium in which the inorganic constituents are made into a paste. Aqueous and/or organic or organic-aqueous media may be used, containing one or more organic binders and possibly normal processing aids such as viscosity regulators in addition to one or more solvents. Appropriate media are those known in the art for producing printing pastes for making ceramic decorations which are burnt-in in a decorative baking process.
- In an alternative embodiment the layer-forming composition is applied to the substrate to be coated by a known electrostatic coating process. For this purpose the composition should desirably also contain a few percent of a thermoplastic material, in particular 1 to 8% by weight of a polyethylene wax, and the substrate should be heated to a temperature above the deformation point of the thermoplastic material before or immediately after the electrostatic coating. Details of electrostatic coating of glass and ceramic materials can be found in WO 94/26679 and WO 98/58889.
- Application of the layer-forming composition to the substrate is followed by normal baking. At a temperature above the deformation point of at least one glass frit, the frit fuses together into a glass flux. The structure-forming particles near the surface surprisingly form the required micro-rough surface structure with the aspect ratio claimed. The particles located at the surface are securely anchored in the glass flux.
- In a further embodiment the micro-rough layer is printed by means of a printing paste containing a glass frit which forms a glass flux, and the structure-forming particles are applied to the still moist printing surface for example by powdering or dripping on, possibly followed by partial pressing of the particles into the printed surface. The substrate thus treated is then burnt and made hydrophobic in a known manner.
- After the baking at least part of the micro-rough surface, particularly the tips of the elevations, preferably the whole surface is made hydrophobic. The agents for making the surface hydrophobic are products normally used in the art. They are either polymers with that action or preferably monomeric or oligomeric compounds containing a fairly long-chain alkyl or preferably fluoroalkyl radical with that action and also a functional group whereby the compounds with a hydrophobising action can be cross-linked and thus form a film and/or whereby a reaction with functional groups at the surface of the micro-rough layer is enabled.
- The micro-rough surface may be made hydrophobic by applying a lacquer or by polymerizing monomers on the surface. Some suitable polymeric lacquers are solutions or dispersions for example of polyvinylidene fluoride.
- As an alternative to the use of fluorine-containing silanes and siloxanes, the surface may be made hydrophobic by plasma polymerisation of fully or partly fluorinated vinyl compounds.
- It is particularly desirable for the surface to be made hydrophobic using reactive alkyl or preferably fluoroalkyl silanes and oligomeric alkyl or fluoroalkyl siloxanes. The silanes or siloxanes preferably contain one or more alkoxy groups such as ethoxy groups as the reactive group. The agent for making the surface hydrophobic may be cross-linked and also chemically bound to a silicate surface containing silanol groups by these alkoxy groups. Particularly preferred silanising agents are tridecafluoroctyltriethoxy silane and oligomers thereof (Dynasilanes® produced by Sivento Chemie Rheinfelden GmbH). Products of this type may be applied to the surface to be made hydrophobic in the form of dilute organic, in particular alcoholic, aqueous-organic and aqueous solutions for example by dipping, spraying or painting.
- When a solution containing a fluorine-containing silane or siloxane has been applied to it, the substrate is dried and hardened preferably at a temperature up to 500° C., for example for 10-15 minutes at 250° C. to 300° C. or 1 minute at about 500° C. or 30-60 minutes at about 150° C. The optimum thermal post-treatment for maximum abrasion resistance is at a temperature in the range from 200° C. to 300° C.
- By using dilute solutions of said silanes or siloxanes chemically and mechanically very resistant layers only a few nm thick are obtained, which are 2- and 3-dimensional siloxane networks.
- Hydrophobic layers which can be obtained by using reactive fluoroalkyl silanes or siloxanes are characterized by equally good hydrophobic and oleophobic properties, so even substrates according to the invention which are soiled with hydrophobic dirt particles can easily be cleaned with water.
- Substrates with a self-cleaning surface according to the invention may be used wherever the surface (a) is exposed to a constant danger of soiling and (b) must be cleanable in an extremely simple manner with water. Glass substrates with a self-cleaning surface according to the invention can appropriately be used for glazing vehicles and trains and for glass bricks. Ceramic substrates with a self-cleaning surface according to the invention are suitable for use as a building material such as roof tiles, clinker and floor tiles.
- The advantages of the invention are that self-cleaning surfaces of glass, ceramic and metal substrates are easily accessible and have a good self-cleaning effect. The structure-forming layer has high abrasion resistance. Preferred surfaces have “super-hydrophobic properties”, causing water drops to run down them almost without friction. In addition to surfaces where a self-cleaning effect is important, substrates with a structured surface made hydrophobic according to the invention are also suitable for chemical engineering apparatus such as coated pipes and heat exchanger plates.
- The following examples are intended only to illustrate the invention and should not be construed as imposing limitations upon the claims.
- General information on the production of substrates with a self-cleaning surface follows. Details such as the products used, relative quantities and baking conditions to obtain the structured surface and conditions to make it hydrophobic can be found in the Tables.
- Direct printing: Glass frit and structure-forming particles were made into a paste in a known manner with a printing medium which can be diluted with water (No. 80858 from dmc2 AG) or a purely organic one (No. 80820 from dmc2 AG), and the printing paste was applied to the substrate by screen printing.
- Indirect printing: Glass frit and structure-forming particles were made into a paste with a screen printing oil (No. 80820 from dmc2 AG). The printing method was screen printing on transfer paper; after drying a covering film was formed. The printed image was applied in known manner to the substrate to be decorated.
- Electrostatic application: Glass frit and structure-forming particles mixed with Siloxane H68 (Weinstock & Siebert) were treated (first mixed then tempered) to raise the specific resistance of the powder to >1014 Ωm. The powder mixture of the glass frit thus siliconised and structure-forming particles was applied using an electrostatic gun at 90 kV.
- The coatings applied to the substrate by direct or indirect printing or electrostatically were burnt-in in a known manner; heating-up time 200 K/h, Tmax and holding time are given in the Table.
- The substrate was 4 mm float glass in all the examples.
- The glass frits were a low melting point glass frit with a high Pb content, a d50 value of 3.3 μm and a d90 value of 10 μm (No. 10022 from dmc2 AG), another glass frit (No. 10157 from dmc2 AG) and a glass frit for electrostatic glazing (VNR 9316 F) with a d50 value of 3.7 μm and a d90 value of 6.8 μm.
- The structure-forming particles used were zirconium dye pigments, namely zirconium iron rose (FK 27357 from dmc2 AG), and a hydrophobic zeolite of the Pentasil type (Wessalith® DAZ).
- The structured burnt-in surface was made hydrophobic using a fluoroalkyl silane formulation, namely Dynasilan®) F8262 (Degussa-Huls AG) (a solution of tridecafluoroctyltriethoxy silane in ethanol). The solution was poured over the surface then hardened at an elevated temperature.
- The self-cleaning effect was evaluated by a test with drops of water running down a slightly inclined surface:
-
- +++ very good, ++ good, + moderate, ∘ poor
- Tables 1a and 1b below give the detailed conditions and results.
TABLE 1a 1 2 3 4 5 6 Glass frit* 10022 10022 10022 10022 10022 10022 Structure-forming FK 22389 FK 22389 FK 22389 FK 27357 FK 27357 FK 27357 particles Glass frit/particles 50:50 80:20 50:50 50:50 50:50 50:50 (volume ratio) Printing medium* 80858 80858 80820 80858 80820 80820 (ratio of frit + particles: 10:3 10:3 10:10 10:6 10:10 10:10 medium) Application method direct direct indirect direct direct direct Screen fabric 100 180 100 100 180 100 Baking condition: 560/4 560/4 560/4 560/4 560/4 660/4 (° C./min) Making 150° C./60 min 150° C./60 min 150° C./60 min 300° C./60 min 300° C./60 min 300° C./60 min hydrophobic/hardening conditions Drop of water running +++ + +++ +++ ++ ++ down effect
*Numbers given are product numbers of commercially available products of dmc2 AG.
-
TABLE 1b 7 8 9 10 11 Glass frit* 10157 10022 10022 10022 VNR 9316F Structure-forming FK 22389 DAZ DAZ DAZ ** particles Glass frit/particles 50:50 50:50 50:50 50:50 — (volume ratio) Printing medium* 80858 80858 80858 — 80858 (ratio of frit + particles: 10:6 10:7 10:7 — 10:8 medium) Application method direct direct direct electrostatic direct Screen fabric 100 100 180 — 100 Baking condition: 560/4 560/4 560/4 650/4 630/4 (° C./min) Making 150° C./60 min 150° C./60 min 150° C./60 min 150° C./60 min 150° C./60 min hydrophobic/hardening conditions Drop of water running ++ ++ ++ ++ ◯ down effect
*Numbers given are product numbers of commercially available products of dmc2 AG;
**The glass frit fuses incompletely and is thus structure-forming; surface like matt glass; micro-structure differs from that in Examples 1-10, in that the elevations are rounded.
- Additional advantages and modifications will readily occur to those skilled in the art. Therefore, the invention in its broader aspects is not limited to the specific details and illustrative examples shown and described herein. Accordingly, various modifications may be made without departing from the spirit or scope of the general inventive concept as defined by the appended claims and their equivalents.
Claims (22)
1. A method of making a substrate with a self-cleaning surface having a hydrophobic, micro-rough layer comprising the steps of:
(a) coating the substrate with a composition containing a glass frit which forms a glass flux and structure-forming particles with a mean particle diameter within the range of from 0.1 to 50 μm, the composition containing glass frit and structure-forming particles in a volume ratio within the range of 0.1 to 5;
(b) burning in the substrate at a temperature above the deformation temperature of the glass frit thereby forming a burnt-in layer; and
(c) making the burnt-in layer at least partially hydrophobic by applying an agent to make it hydrophobic.
2. The method according to claim 1 wherein the composition containing the glass frit which forms a glass flux and structure-forming particles is applied to the substrate in the form of a printable paste by a direct or indirect printing process.
3. The method according to claim 1 , wherein the composition containing the glass frit which forms a glass flux and structure-forming particles is applied to the substrate electrostatically in the form of a mixture of powders.
4. The method according to claim 1 , wherein the burnt-in layer has a micro-rough surface structure having a ratio of mean profile height to mean distance between adjacent profile tips within the 0.3 to 10 range.
5. The method according to claim 4 , wherein the substrate is selected from the group consisting of glass, porcelain, vitrified clay, stoneware, clinker and brick substrates.
6. The method according to claim 4 , wherein the volume ratio of glass flux to structure-forming particles is within the range of from 0.2 to 2.
7. The method according to claim 4 , wherein the micro-rough surface structure has an aspect ratio within the range of from 1 to 5.
8. The method according to claim 4 , wherein the structure-forming particles have a mean diameter within the range of from 0.5 to 15 μm.
9. The method according to claim 4 , wherein the structure-forming particles are idiomorphic.
10. The method according to claim 4 , wherein the layer that makes the burnt-in layer hydrophobic is based on a fluoroalkyl alkoxysilane or a fluoroalkyl alkoxysiloxane.
11. A method of making a substrate with at least one self-cleaning surface that is at least partially hydrophobic, comprising the steps of:
(a) coating the substrate with a composition containing a glass frit which forms a glass flux and structure-forming particles having a bimodal size distribution, wherein a first portion of the structure-forming particles has a mean particle diameter within the range of from 0.2 to 3 μm and a second portion of the structure-forming particles has a mean particle diameter within the range of from 3 to 15 μm, and the glass frit and structure-forming particles are present in a volume ratio within the range of 0.1 to 5;
(b) burning in the substrate at a temperature above the deformation temperature of the glass frit thereby forming a burnt-in layer having a micro-rough surface structure having a ratio of mean profile height to mean distance between adjacent profile tips within the 0.3 to 10 range; and
(c) making the burnt-in layer at least partially hydrophobic by applying an agent to make it hydrophobic.
12. The method according to claim 11 , wherein the second portion of the structure-forming particles has a mean diameter of 5 to 10 μm.
13. The method according to claim 11 , wherein the glass flux and structure-forming particles are present in a volume ratio within the 0.2 to 2 range.
14. The method according to claim 11 , wherein the micro-rough surface structure has a ratio of mean profile height to mean distance between adjacent profile tips within the 1 to 5 range.
15. The method according to claim 11 , wherein the burnt-in layer is made at least partially hydrophobic by application of a substance selected from the group consisting of fluroalkyl alkoxysilane, fluoroalkyl alkoxysiloxane, and partly fluorinated vinyl polymer.
16. The method according to claim 11 , wherein the substrate is selected from the group consisting of metal, glass, porcelain, vitrified clay, stoneware, clinker and brick substrates.
17. The method according to claim 11 , wherein the volume ratio of glass flux to structure-forming particles is within the range of from 0.3 to 1.
18. The method according to claim 11 , wherein the micro-rough surface structure has an aspect ratio within the range of from 1 to 2.
19. The method according to claim 11 , wherein the structure-forming particles have a mean diameter within the range of from 1 to 2 μm.
20. The method according to claim 11 , wherein the structure-forming particles are idiomorphic.
21. A method of making a glass, ceramic or metal substrate with at least one self-cleaning surface that is at least partially hydrophobic, comprising the steps of:
(a) coating the substrate with a composition containing a glass frit which forms a glass flux and structure-forming particles having a bimodal size distribution, wherein a first portion of the structure-forming particles has a mean particle diameter within the range of from 0.2 to 3 μm and a second portion of the structure-forming particles has a mean particle diameter within the range of from 5 to 10 μm, and the glass frit and structure-forming particles are present in a volume ratio within the range of 0.2 to 2;
(b) burning in the substrate at a temperature above the deformation temperature of the glass frit thereby forming a burnt-in layer having a micro-rough surface structure having a ratio of mean profile height to mean distance between adjacent profile tips within the 0.3 to 10 range; and
(c) making the burnt-in layer at least partially hydrophobic by applying an agent to make it hydrophobic.
22. The method according to claim 21 , wherein the structure-forming particles are selected from the group consisting of SiO2, TiO2, ZrO2, SnO2, Al2O3, zirconium silicates and zeolites.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/059,713 US20050170098A1 (en) | 2000-04-01 | 2005-02-16 | Glass, ceramic and metal substrates with a self-cleaning surface, method of making them and their use |
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10016485A DE10016485A1 (en) | 2000-04-01 | 2000-04-01 | Glass, ceramic and metal substrates with a self-cleaning surface, process for their production and their use |
DE10016485.4 | 2000-04-01 | ||
US10/239,066 US6872441B2 (en) | 2000-04-01 | 2001-03-13 | Glass ceramic and metal substrates with a self-cleaning surface, method for the production and use thereof |
PCT/EP2001/002790 WO2001074739A1 (en) | 2000-04-01 | 2001-03-13 | Glass ceramic and metal substrates with a self-cleaning surface, method for the production and use thereof |
US11/059,713 US20050170098A1 (en) | 2000-04-01 | 2005-02-16 | Glass, ceramic and metal substrates with a self-cleaning surface, method of making them and their use |
Related Parent Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2001/002790 Division WO2001074739A1 (en) | 2000-04-01 | 2001-03-13 | Glass ceramic and metal substrates with a self-cleaning surface, method for the production and use thereof |
US10/239,066 Division US6872441B2 (en) | 2000-04-01 | 2001-03-13 | Glass ceramic and metal substrates with a self-cleaning surface, method for the production and use thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
US20050170098A1 true US20050170098A1 (en) | 2005-08-04 |
Family
ID=7637408
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/239,066 Expired - Fee Related US6872441B2 (en) | 2000-04-01 | 2001-03-13 | Glass ceramic and metal substrates with a self-cleaning surface, method for the production and use thereof |
US11/059,713 Abandoned US20050170098A1 (en) | 2000-04-01 | 2005-02-16 | Glass, ceramic and metal substrates with a self-cleaning surface, method of making them and their use |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/239,066 Expired - Fee Related US6872441B2 (en) | 2000-04-01 | 2001-03-13 | Glass ceramic and metal substrates with a self-cleaning surface, method for the production and use thereof |
Country Status (6)
Country | Link |
---|---|
US (2) | US6872441B2 (en) |
EP (1) | EP1272442B1 (en) |
AT (1) | ATE308490T1 (en) |
DE (2) | DE10016485A1 (en) |
ES (1) | ES2251478T3 (en) |
WO (1) | WO2001074739A1 (en) |
Cited By (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060051561A1 (en) * | 2002-03-23 | 2006-03-09 | University Of Durham | Method and apparatus for the formation of hydrophobic surfaces |
US20060134554A1 (en) * | 2003-02-28 | 2006-06-22 | Ferro Gmbh | Radiationhardenable printing media, transfer pictures produced therewith, and method for producing ceramic decorations |
FR2928642A1 (en) * | 2008-03-11 | 2009-09-18 | Saint Gobain | Durable hydrophobic and/or oleophobic glass substrate, useful e.g. as oven door interior glass, cooking plate and vitroceramic cooking plate, comprises a monomolecular layer of hydrophobic and/or oleophobic silane on a surface rugosity |
US20100008101A1 (en) * | 2008-06-09 | 2010-01-14 | Lloyd Keith Bucher | Head lamp assembly and accent lighting therefor |
WO2010147738A1 (en) | 2009-05-29 | 2010-12-23 | Corning Incorporated | Super non-wetting, anti-fingerprint coatings for glass |
WO2012004337A1 (en) * | 2010-07-09 | 2012-01-12 | Agc Glass Europe | Glass article coated with an enamel layer |
WO2012061240A1 (en) * | 2010-11-01 | 2012-05-10 | Corning Incorporated | Transparent substrate having durable hydrophobic/oleophobic surface |
US8286561B2 (en) | 2008-06-27 | 2012-10-16 | Ssw Holding Company, Inc. | Spill containing refrigerator shelf assembly |
WO2013014393A1 (en) | 2011-07-25 | 2013-01-31 | Seb Sa | Heating article comprising a microstructured heat-stable coating and method of manufacturing such an article. |
US20130149514A1 (en) * | 2010-07-30 | 2013-06-13 | Kyocera Corporation | Insulating sheet, method of manufacturing the same, and method of manufacturing structure using the insulating sheet |
US20150144613A1 (en) * | 2012-06-21 | 2015-05-28 | Eurokera S.N.C. | Glass-ceramic article and manufacturing process |
US9067821B2 (en) | 2008-10-07 | 2015-06-30 | Ross Technology Corporation | Highly durable superhydrophobic, oleophobic and anti-icing coatings and methods and compositions for their preparation |
US9074778B2 (en) | 2009-11-04 | 2015-07-07 | Ssw Holding Company, Inc. | Cooking appliance surfaces having spill containment pattern |
US9139744B2 (en) | 2011-12-15 | 2015-09-22 | Ross Technology Corporation | Composition and coating for hydrophobic performance |
US9388325B2 (en) | 2012-06-25 | 2016-07-12 | Ross Technology Corporation | Elastomeric coatings having hydrophobic and/or oleophobic properties |
US9546299B2 (en) | 2011-02-21 | 2017-01-17 | Ross Technology Corporation | Superhydrophobic and oleophobic coatings with low VOC binder systems |
US20170273360A1 (en) * | 2017-05-17 | 2017-09-28 | Rai Strategic Holdings, Inc. | Aerosol delivery device |
US20170273356A1 (en) * | 2016-03-25 | 2017-09-28 | Rai Strategic Holdings, Inc. | Aerosol production assembly including surface with micro-pattern |
US9914849B2 (en) | 2010-03-15 | 2018-03-13 | Ross Technology Corporation | Plunger and methods of producing hydrophobic surfaces |
US10317578B2 (en) | 2014-07-01 | 2019-06-11 | Honeywell International Inc. | Self-cleaning smudge-resistant structure and related fabrication methods |
US10317129B2 (en) | 2011-10-28 | 2019-06-11 | Schott Ag | Refrigerator shelf with overflow protection system including hydrophobic layer |
US11412781B2 (en) * | 2016-02-12 | 2022-08-16 | Rai Strategic Holdings, Inc. | Adapters for refilling an aerosol delivery device |
US11506526B2 (en) | 2014-04-17 | 2022-11-22 | Heraeus Nexensos Gmbh | Sensor element, sensor module, measuring assembly and exhaust-gas re-circulation system comprising a sensor element of this type, and production method |
US11786036B2 (en) | 2008-06-27 | 2023-10-17 | Ssw Advanced Technologies, Llc | Spill containing refrigerator shelf assembly |
Families Citing this family (63)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10016485A1 (en) | 2000-04-01 | 2001-10-11 | Dmc2 Degussa Metals Catalysts | Glass, ceramic and metal substrates with a self-cleaning surface, process for their production and their use |
DE10063739B4 (en) | 2000-12-21 | 2009-04-02 | Ferro Gmbh | Substrates with self-cleaning surface, process for their preparation and their use |
DE10106213A1 (en) | 2001-02-10 | 2002-08-22 | Dmc2 Degussa Metals Catalysts Cerdec Ag | Self-cleaning paint coatings and methods and means of making the same |
DE10159767A1 (en) * | 2001-12-05 | 2003-06-18 | Degussa | Process for the manufacture of articles with anti-allergic surfaces |
DE10164389A1 (en) * | 2001-12-28 | 2003-07-10 | Knorr Bremse Systeme | Contactless measuring device used for vehicles, especially rail vehicles, has elements having surfaces partially provided with a self-cleaning coating |
DE10210673A1 (en) * | 2002-03-12 | 2003-09-25 | Creavis Tech & Innovation Gmbh | Injection molded body with self-cleaning properties and method for producing such injection molded body |
DE10210667A1 (en) * | 2002-03-12 | 2003-09-25 | Creavis Tech & Innovation Gmbh | Production of web products with self-cleaning surfaces by means of a calendering process, web products themselves and the use of these |
DE10218820B4 (en) * | 2002-04-26 | 2006-05-11 | Fritz Reupsch | Exterior mirrors for motor vehicles |
DE10224385A1 (en) * | 2002-06-01 | 2003-12-18 | Kuesters Eduard Maschf | Device for treating a textile web |
DE10233829A1 (en) * | 2002-07-25 | 2004-02-12 | Creavis Gesellschaft Für Technologie Und Innovation Mbh | Process for preparation of surfaces with selfcleaning properties by application of nano particles with production of a lotus effect useful for coating objects subjected to high soiling and water loads, e.g. in outdoor sports |
DE10246840A1 (en) * | 2002-10-08 | 2004-04-29 | Daimlerchrysler Ag | Production of a transparent cover for a vehicle windscreen comprises applying an electrode layer on the surface of a substrate, applying an aluminum intermediate layer, oxidizing the aluminum and forming a transparent oxide layer |
DE10246841A1 (en) * | 2002-10-08 | 2004-04-29 | Daimlerchrysler Ag | Production of a windscreen for a vehicle comprises forming recesses in a substrate, and introducing functional material of a functional layer into the recesses |
DE10247278B3 (en) | 2002-10-10 | 2004-01-29 | Schollglass Holding- und Geschäftführungsgesellschaft mbH | Substrate with a self-cleaning surface |
DE10306582A1 (en) * | 2003-02-17 | 2004-08-26 | BSH Bosch und Siemens Hausgeräte GmbH | Surface coating for a cooker or oven comprises a vitreous enamel layer with embedded crystal zones that provide both coarse and fine surface roughness |
DE10321851A1 (en) * | 2003-05-15 | 2004-12-02 | Creavis Gesellschaft Für Technologie Und Innovation Mbh | Use of particles hydrophobized with fluorosilanes for the production of self-cleaning surfaces with lipophobic, oleophobic, lactophobic and hydrophobic properties |
US6997018B2 (en) * | 2003-06-02 | 2006-02-14 | Ferro Corporation | Method of micro and nano texturing glass |
DE602005003234T2 (en) | 2004-07-12 | 2008-08-28 | Cardinal Cg Co., Eden Prairie | MAINTENANCE-FREE COATINGS |
US7722951B2 (en) * | 2004-10-15 | 2010-05-25 | Georgia Tech Research Corporation | Insulator coating and method for forming same |
JP3965480B2 (en) * | 2004-12-16 | 2007-08-29 | Toto株式会社 | COMPOSITE MATERIAL, COATING LIQUID AND METHOD FOR PRODUCING COMPOSITE MATERIAL |
US20060216476A1 (en) * | 2005-03-28 | 2006-09-28 | General Electric Company | Articles having a surface with low wettability and method of making |
US7524531B2 (en) * | 2005-04-27 | 2009-04-28 | Ferro Corporation | Structured self-cleaning surfaces and method of forming same |
US7527832B2 (en) * | 2005-04-27 | 2009-05-05 | Ferro Corporation | Process for structuring self-cleaning glass surfaces |
US20060292345A1 (en) * | 2005-06-14 | 2006-12-28 | Dave Bakul C | Micropatterned superhydrophobic silica based sol-gel surfaces |
DE102005037338A1 (en) * | 2005-08-04 | 2007-02-08 | Starnberger Beschichtungen Gmbh | Producing a nonstick coating on a substrate comprises applying a primer coat having inclusions, applying a top coat and heat-treating the top coat |
US8092911B2 (en) * | 2005-09-14 | 2012-01-10 | Ferro Corporation | Extended firing range enamels to produce frost effects |
US20090011222A1 (en) * | 2006-03-27 | 2009-01-08 | Georgia Tech Research Corporation | Superhydrophobic surface and method for forming same |
US20070231542A1 (en) * | 2006-04-03 | 2007-10-04 | General Electric Company | Articles having low wettability and high light transmission |
CN101466649B (en) | 2006-04-11 | 2013-12-11 | 卡迪奈尔镀膜玻璃公司 | Photocatalytic coatings having improved low-maintenance properties |
US20080011599A1 (en) | 2006-07-12 | 2008-01-17 | Brabender Dennis M | Sputtering apparatus including novel target mounting and/or control |
DE102006040007B3 (en) * | 2006-08-25 | 2008-05-15 | Saint-Gobain Glass Deutschland Gmbh | Slip-resistant glass element |
US7919151B2 (en) | 2006-12-14 | 2011-04-05 | General Electric Company | Methods of preparing wetting-resistant surfaces and articles incorporating the same |
AT504995B1 (en) * | 2007-03-02 | 2011-12-15 | Fabian Ferdinand Dipl Ing Dr | DEVICE FOR PREPARING WATER |
JP2008282751A (en) * | 2007-05-14 | 2008-11-20 | Kagawa Gakusei Venture:Kk | Ice-accretion and snow-accretion preventive insulator and electric wire, antenna, their manufacturing method, and power transmission steel tower using them |
US8741158B2 (en) | 2010-10-08 | 2014-06-03 | Ut-Battelle, Llc | Superhydrophobic transparent glass (STG) thin film articles |
EP2261186B1 (en) | 2007-09-14 | 2017-11-22 | Cardinal CG Company | Low maintenance coating technology |
FI123691B (en) * | 2007-12-10 | 2013-09-30 | Beneq Oy | A method for producing a highly hydrophobic surface |
WO2009094416A1 (en) * | 2008-01-22 | 2009-07-30 | Brad Barrett | System and device for grilling foods |
US7754279B2 (en) * | 2008-02-05 | 2010-07-13 | Ut-Battelle, Llc | Article coated with flash bonded superhydrophobic particles |
MX345941B (en) | 2008-06-27 | 2017-02-27 | Ssw Holding Co Inc | Method for spill containment and shelves or the like therefore. |
US20100009188A1 (en) * | 2008-07-11 | 2010-01-14 | John Haozhong Xin | Nano-structured surface and an in situ method for forming the same |
US20100028604A1 (en) * | 2008-08-01 | 2010-02-04 | The Ohio State University | Hierarchical structures for superhydrophobic surfaces and methods of making |
US8545994B2 (en) * | 2009-06-02 | 2013-10-01 | Integran Technologies Inc. | Electrodeposited metallic materials comprising cobalt |
US8486319B2 (en) | 2010-05-24 | 2013-07-16 | Integran Technologies Inc. | Articles with super-hydrophobic and/or self-cleaning surfaces and method of making same |
US9303322B2 (en) | 2010-05-24 | 2016-04-05 | Integran Technologies Inc. | Metallic articles with hydrophobic surfaces |
US11292919B2 (en) | 2010-10-08 | 2022-04-05 | Ut-Battelle, Llc | Anti-fingerprint coatings |
FR2967995B1 (en) * | 2010-11-26 | 2018-01-19 | Saint-Gobain Glass France | NON-SLIP GLASS PANEL AND METHOD OF MANUFACTURE |
US20120258853A1 (en) * | 2011-04-11 | 2012-10-11 | 3M Innovative Property Company | Porous particles with masking powder and methods of making and using the same |
US10155361B2 (en) | 2011-11-09 | 2018-12-18 | Corning Incorporated | Method of binding nanoparticles to glass |
GB201111439D0 (en) | 2011-07-04 | 2011-08-17 | Syngenta Ltd | Formulation |
DE102011115379B4 (en) | 2011-10-10 | 2018-09-27 | Schott Ag | Coated glass or glass ceramic substrate with haptic properties and glass ceramic hob |
US20150298165A1 (en) * | 2012-03-26 | 2015-10-22 | Silcotek Corp. | Coated article and chemical vapor deposition process |
DE202012012372U1 (en) | 2012-12-20 | 2013-01-16 | Schott Ag | Coated glass or glass-ceramic substrate with haptic properties |
US20150239773A1 (en) | 2014-02-21 | 2015-08-27 | Ut-Battelle, Llc | Transparent omniphobic thin film articles |
CN106536441B (en) | 2014-07-16 | 2020-03-06 | 肖特股份有限公司 | Method for producing a coated substrate, planar substrate comprising at least two layers applied by heating, and use of a coated substrate |
DE102014220457B4 (en) | 2014-10-09 | 2020-07-30 | Schott Ag | Process for producing a coated substrate |
JP6370488B2 (en) | 2014-10-28 | 2018-08-08 | サン−ゴバン グラス フランスSaint−Gobain Glass France | Walkable safety laminated glass with non-slip surface |
DE102015101332A1 (en) | 2015-01-29 | 2016-08-04 | Schott Ag | Glass ceramic with a specially designed surface and method for its production |
BE1023402B1 (en) * | 2016-01-14 | 2017-03-08 | Polyvision, Naamloze Vennootschap | A TILE WITH TEXTURE |
EP3541762B1 (en) | 2016-11-17 | 2022-03-02 | Cardinal CG Company | Static-dissipative coating technology |
EP3630691A1 (en) | 2017-06-02 | 2020-04-08 | Guardian Glass, LLC | Glass article containing a coating with an interpenetrating polymer network |
US20210403748A1 (en) * | 2018-12-18 | 2021-12-30 | 3M Innovative Properties Company | Impervious Coatings for Making Metal, Metal Oxide, and Silicon Oxide Surfaces Resistant to Graffiti |
WO2020159534A1 (en) * | 2019-02-01 | 2020-08-06 | Hewlett-Packard Development Company, L.P. | Hinges for electronic devices |
CN113211610A (en) * | 2021-07-08 | 2021-08-06 | 佛山市东鹏陶瓷有限公司 | Glazed tile capable of forming positioning crystallization effect and preparation process thereof |
Citations (35)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3279937A (en) * | 1962-11-08 | 1966-10-18 | Westinghouse Electric Corp | Method and apparatus for coating electric lamp bulbs |
US3354022A (en) * | 1964-03-31 | 1967-11-21 | Du Pont | Water-repellant surface |
US3931428A (en) * | 1974-01-04 | 1976-01-06 | Michael Ebert | Substrate coated with super-hydrophobic layers |
US3951633A (en) * | 1974-12-23 | 1976-04-20 | Combustion Engineering, Inc. | Method for producing patterned glass on a float ribbon |
US3958073A (en) * | 1970-01-29 | 1976-05-18 | Fidenza S.A. Vetraria S.P.A. | Properties of glass surfaces |
US3998643A (en) * | 1975-03-31 | 1976-12-21 | General Electric Company | Composition and methods for protecting and rendering non-porous surfaces water and soil repellent |
US4343641A (en) * | 1981-03-02 | 1982-08-10 | Ball Corporation | Article having a scratch resistant lubricated glass surface and its method of manufacture |
US4377608A (en) * | 1979-09-24 | 1983-03-22 | Dow Corning Corporation | Method of modifying a substrate |
US4387195A (en) * | 1981-07-20 | 1983-06-07 | Tully Paul R | Hydrophobic ceramic wares |
US4410563A (en) * | 1982-02-22 | 1983-10-18 | The United States Of America As Represented By The Secretary Of The Navy | Repellent coatings for optical surfaces |
US4482656A (en) * | 1983-09-29 | 1984-11-13 | Battelle Development Corporation | Method for manufacturing a composition for coating substrates with an abrasion-resistant transparent and translucent film |
US4687707A (en) * | 1984-06-26 | 1987-08-18 | Asahi Glass Company Ltd. | Low reflectance transparent material having antisoiling properties |
US5240774A (en) * | 1990-10-25 | 1993-08-31 | Matsushita Electric Industrial Co., Ltd. | Fluorocarbon-based coating film and method of manufacturing the same |
US5324566A (en) * | 1991-01-23 | 1994-06-28 | Matsushita Electric Industrial Co., Ltd. | Water and oil repelling film having surface irregularities and method of manufacturing the same |
US5424130A (en) * | 1991-05-13 | 1995-06-13 | Toyota Jidosha Kabushiki Kaisha | Water repellent glass and process for producing the same |
US5466486A (en) * | 1990-10-25 | 1995-11-14 | Matsushita Electric Industrial Co., Ltd. | Chemically adsorbed monomolecular lamination film |
US5478651A (en) * | 1994-10-31 | 1995-12-26 | E. I. Du Pont De Nemours And Company | Process for making fluoropolymer finish composition |
US5599489A (en) * | 1993-01-18 | 1997-02-04 | Onoda Cement Co., Ltd. | Preparing molded articles of fluorine-containing polymer with increased water-repellency |
US5674625A (en) * | 1993-11-10 | 1997-10-07 | Central Glass Company, Limited | Multilayered water-repellent film and method of forming same on glass substrate |
US5800918A (en) * | 1994-07-13 | 1998-09-01 | Saint-Gobain Vitrage | Multilayered hydrophobic window glass |
US5808125A (en) * | 1996-12-03 | 1998-09-15 | Huels Aktiengesellschaft | Fluoroalkyl-functional organopolysiloxane-containing compositions based on water, a process for their preparation and their use |
US5853894A (en) * | 1997-02-03 | 1998-12-29 | Cytonix Corporation | Laboratory vessel having hydrophobic coating and process for manufacturing same |
US5874197A (en) * | 1997-09-18 | 1999-02-23 | E. I. Du Pont De Nemours And Company | Thermal assisted photosensitive composition and method thereof |
US6048910A (en) * | 1997-02-06 | 2000-04-11 | Shin-Etsu Chemical Co., Ltd. | Coating compositions, hydrophilic films, and hydrophilic film-coated articles |
US6156409A (en) * | 1996-12-09 | 2000-12-05 | Nippon Sheet Glass Co., Ltd. | Non-fogging article and process for the production thereof |
US6159409A (en) * | 1994-02-03 | 2000-12-12 | Rolco, Inc. | Method of molding |
US6235383B1 (en) * | 1997-01-24 | 2001-05-22 | Samsung Corning Co., Ltd. | Glass article having a durable water repellent surface |
US6403213B1 (en) * | 1999-05-14 | 2002-06-11 | E. I. Du Pont De Nemours And Company | Highly filled undercoat for non-stick finish |
US6447919B1 (en) * | 1997-02-03 | 2002-09-10 | Cytonix Corporation | Hydrophobic coating compositions, articles coated with said compositions, and processes for manufacturing same |
US6461670B2 (en) * | 1998-02-13 | 2002-10-08 | Central Glass Company, Ltd. | Water-repellent solution and method of forming water-repellent film on substrate by using the solution |
US20020150725A1 (en) * | 2001-04-12 | 2002-10-17 | Creavis Gesellschaft Fuer Techn. Und Innov. Mbh | Surfaces rendered self-cleaning by hydrophobic structures, and process for their production |
US6471761B2 (en) * | 2000-04-21 | 2002-10-29 | University Of New Mexico | Prototyping of patterned functional nanostructures |
US20020164443A1 (en) * | 2001-03-06 | 2002-11-07 | Creavis Gesellschaft Fuer Tech. Und Innovation Mbh | Geometyrical shaping of surfaces with a lotus effect |
US6485838B1 (en) * | 1999-05-21 | 2002-11-26 | Jsr Corporation | Coating composition, and a coated film and glass each having a coating layer comprised thereof |
US6511753B1 (en) * | 1998-06-04 | 2003-01-28 | Nippon Sheet Glass Co., Ltd. | Process for producing article coated with water-repellent film article coated with water-repellent film and liquid composition for water-repellent film, article coated |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4377808A (en) * | 1980-07-28 | 1983-03-22 | Sound Engineering (Far East) Limited | Infrared intrusion alarm system |
EP0867490A3 (en) * | 1991-01-23 | 1999-02-03 | Matsushita Electric Industrial Co., Ltd. | Water- and oil- repellant article |
GB9309295D0 (en) | 1993-05-06 | 1993-06-16 | British Ceramic Res Ltd | Firable material |
DE69432348T8 (en) | 1993-12-10 | 2004-08-26 | Toto Ltd., Kita-Kyushu | MULTIFUNCTIONAL MATERIAL WITH PHOTOCATALYTIC FUNCTION AND METHOD FOR THE PRODUCTION THEREOF |
DE59504640D1 (en) | 1994-07-29 | 1999-02-04 | Wilhelm Prof Dr Barthlott | SELF-CLEANING SURFACES OF OBJECTS AND METHOD FOR THE PRODUCTION THEREOF |
EP0748775A3 (en) | 1995-05-30 | 1998-11-25 | Central Glass Company, Limited | Water-repellent glass plate having minutely roughed metal-oxide base film |
DE19726778A1 (en) | 1997-06-24 | 1999-01-14 | Cerdec Ag | Process for the production of ceramic and glassy coatings, electrostatically applicable coating powder therefor and its use |
DE19746053B4 (en) | 1997-10-17 | 2006-11-16 | Erlus Aktiengesellschaft | Process for producing a self-cleaning property of surfaces, in particular roofing tiles, and ceramic bodies with a self-cleaning surface |
DE19803787A1 (en) | 1998-01-30 | 1999-08-05 | Creavis Tech & Innovation Gmbh | Structured surfaces with hydrophobic properties |
CN1278759C (en) | 1998-04-02 | 2006-10-11 | 东陶机器株式会社 | Humidity-controlling functional material and process for production thereof |
US6461870B2 (en) * | 1998-05-06 | 2002-10-08 | Isotechnika Inc. | 13C glucose breath test for the diagnosis of diabetic indications and monitoring glycemic control |
DE19941753A1 (en) | 1999-09-02 | 2001-05-10 | Nanogate Gmbh | Processes and substances |
DE10018223A1 (en) | 1999-09-23 | 2001-04-19 | Nanogate Gmbh | Process for altering the surface properties of an object useful for providing a self-cleaning coating on glass, comprises formation of a stochastic surface structure and coating |
DE10016485A1 (en) | 2000-04-01 | 2001-10-11 | Dmc2 Degussa Metals Catalysts | Glass, ceramic and metal substrates with a self-cleaning surface, process for their production and their use |
DE10059487A1 (en) | 2000-11-30 | 2002-06-06 | Inst Neue Mat Gemein Gmbh | Use of coating compositions for protective vitreous coatings on metal involves using compositions obtained by hydrolysis and polycondensation of organosilane in presence of nano-scale silica particles and alkali hydroxide |
DE10063739B4 (en) | 2000-12-21 | 2009-04-02 | Ferro Gmbh | Substrates with self-cleaning surface, process for their preparation and their use |
DE10106213A1 (en) | 2001-02-10 | 2002-08-22 | Dmc2 Degussa Metals Catalysts Cerdec Ag | Self-cleaning paint coatings and methods and means of making the same |
DE10138036A1 (en) | 2001-08-03 | 2003-02-20 | Creavis Tech & Innovation Gmbh | Structured self-cleaning surface is hydrophobic, and has a pattern of raised surfaces with lower burrs linking neighboring projections |
-
2000
- 2000-04-01 DE DE10016485A patent/DE10016485A1/en not_active Ceased
-
2001
- 2001-03-13 ES ES01925431T patent/ES2251478T3/en not_active Expired - Lifetime
- 2001-03-13 WO PCT/EP2001/002790 patent/WO2001074739A1/en active IP Right Grant
- 2001-03-13 DE DE50107908T patent/DE50107908D1/en not_active Expired - Lifetime
- 2001-03-13 US US10/239,066 patent/US6872441B2/en not_active Expired - Fee Related
- 2001-03-13 AT AT01925431T patent/ATE308490T1/en not_active IP Right Cessation
- 2001-03-13 EP EP01925431A patent/EP1272442B1/en not_active Expired - Lifetime
-
2005
- 2005-02-16 US US11/059,713 patent/US20050170098A1/en not_active Abandoned
Patent Citations (36)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3279937A (en) * | 1962-11-08 | 1966-10-18 | Westinghouse Electric Corp | Method and apparatus for coating electric lamp bulbs |
US3354022A (en) * | 1964-03-31 | 1967-11-21 | Du Pont | Water-repellant surface |
US3958073A (en) * | 1970-01-29 | 1976-05-18 | Fidenza S.A. Vetraria S.P.A. | Properties of glass surfaces |
US3931428A (en) * | 1974-01-04 | 1976-01-06 | Michael Ebert | Substrate coated with super-hydrophobic layers |
US3951633A (en) * | 1974-12-23 | 1976-04-20 | Combustion Engineering, Inc. | Method for producing patterned glass on a float ribbon |
US3998643A (en) * | 1975-03-31 | 1976-12-21 | General Electric Company | Composition and methods for protecting and rendering non-porous surfaces water and soil repellent |
US4377608A (en) * | 1979-09-24 | 1983-03-22 | Dow Corning Corporation | Method of modifying a substrate |
US4343641A (en) * | 1981-03-02 | 1982-08-10 | Ball Corporation | Article having a scratch resistant lubricated glass surface and its method of manufacture |
US4387195A (en) * | 1981-07-20 | 1983-06-07 | Tully Paul R | Hydrophobic ceramic wares |
US4410563A (en) * | 1982-02-22 | 1983-10-18 | The United States Of America As Represented By The Secretary Of The Navy | Repellent coatings for optical surfaces |
US4482656A (en) * | 1983-09-29 | 1984-11-13 | Battelle Development Corporation | Method for manufacturing a composition for coating substrates with an abrasion-resistant transparent and translucent film |
US4687707A (en) * | 1984-06-26 | 1987-08-18 | Asahi Glass Company Ltd. | Low reflectance transparent material having antisoiling properties |
US5240774A (en) * | 1990-10-25 | 1993-08-31 | Matsushita Electric Industrial Co., Ltd. | Fluorocarbon-based coating film and method of manufacturing the same |
US5466486A (en) * | 1990-10-25 | 1995-11-14 | Matsushita Electric Industrial Co., Ltd. | Chemically adsorbed monomolecular lamination film |
US5324566A (en) * | 1991-01-23 | 1994-06-28 | Matsushita Electric Industrial Co., Ltd. | Water and oil repelling film having surface irregularities and method of manufacturing the same |
US5437894A (en) * | 1991-01-23 | 1995-08-01 | Matsushita Electric Industrial Co., Ltd. | Method of manufacturing a water- and oil-repelling film having surface irregularities |
US5424130A (en) * | 1991-05-13 | 1995-06-13 | Toyota Jidosha Kabushiki Kaisha | Water repellent glass and process for producing the same |
US5599489A (en) * | 1993-01-18 | 1997-02-04 | Onoda Cement Co., Ltd. | Preparing molded articles of fluorine-containing polymer with increased water-repellency |
US5674625A (en) * | 1993-11-10 | 1997-10-07 | Central Glass Company, Limited | Multilayered water-repellent film and method of forming same on glass substrate |
US6159409A (en) * | 1994-02-03 | 2000-12-12 | Rolco, Inc. | Method of molding |
US5800918A (en) * | 1994-07-13 | 1998-09-01 | Saint-Gobain Vitrage | Multilayered hydrophobic window glass |
US5478651A (en) * | 1994-10-31 | 1995-12-26 | E. I. Du Pont De Nemours And Company | Process for making fluoropolymer finish composition |
US5808125A (en) * | 1996-12-03 | 1998-09-15 | Huels Aktiengesellschaft | Fluoroalkyl-functional organopolysiloxane-containing compositions based on water, a process for their preparation and their use |
US6156409A (en) * | 1996-12-09 | 2000-12-05 | Nippon Sheet Glass Co., Ltd. | Non-fogging article and process for the production thereof |
US6235383B1 (en) * | 1997-01-24 | 2001-05-22 | Samsung Corning Co., Ltd. | Glass article having a durable water repellent surface |
US5853894A (en) * | 1997-02-03 | 1998-12-29 | Cytonix Corporation | Laboratory vessel having hydrophobic coating and process for manufacturing same |
US6447919B1 (en) * | 1997-02-03 | 2002-09-10 | Cytonix Corporation | Hydrophobic coating compositions, articles coated with said compositions, and processes for manufacturing same |
US6048910A (en) * | 1997-02-06 | 2000-04-11 | Shin-Etsu Chemical Co., Ltd. | Coating compositions, hydrophilic films, and hydrophilic film-coated articles |
US5874197A (en) * | 1997-09-18 | 1999-02-23 | E. I. Du Pont De Nemours And Company | Thermal assisted photosensitive composition and method thereof |
US6461670B2 (en) * | 1998-02-13 | 2002-10-08 | Central Glass Company, Ltd. | Water-repellent solution and method of forming water-repellent film on substrate by using the solution |
US6511753B1 (en) * | 1998-06-04 | 2003-01-28 | Nippon Sheet Glass Co., Ltd. | Process for producing article coated with water-repellent film article coated with water-repellent film and liquid composition for water-repellent film, article coated |
US6403213B1 (en) * | 1999-05-14 | 2002-06-11 | E. I. Du Pont De Nemours And Company | Highly filled undercoat for non-stick finish |
US6485838B1 (en) * | 1999-05-21 | 2002-11-26 | Jsr Corporation | Coating composition, and a coated film and glass each having a coating layer comprised thereof |
US6471761B2 (en) * | 2000-04-21 | 2002-10-29 | University Of New Mexico | Prototyping of patterned functional nanostructures |
US20020164443A1 (en) * | 2001-03-06 | 2002-11-07 | Creavis Gesellschaft Fuer Tech. Und Innovation Mbh | Geometyrical shaping of surfaces with a lotus effect |
US20020150725A1 (en) * | 2001-04-12 | 2002-10-17 | Creavis Gesellschaft Fuer Techn. Und Innov. Mbh | Surfaces rendered self-cleaning by hydrophobic structures, and process for their production |
Cited By (48)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9056332B2 (en) | 2002-03-23 | 2015-06-16 | P2I Limited | Method and apparatus for the formation of hydrophobic surfaces |
US10029278B2 (en) | 2002-03-23 | 2018-07-24 | Surface Innovations Limited | Method and apparatus for the formation of hydrophobic surfaces |
US20060051561A1 (en) * | 2002-03-23 | 2006-03-09 | University Of Durham | Method and apparatus for the formation of hydrophobic surfaces |
US20060134554A1 (en) * | 2003-02-28 | 2006-06-22 | Ferro Gmbh | Radiationhardenable printing media, transfer pictures produced therewith, and method for producing ceramic decorations |
US7968175B2 (en) | 2003-02-28 | 2011-06-28 | Ferro Gmbh | Radiation curable printing media, transfers produced therewith and process for the production of ceramic decoration |
FR2928642A1 (en) * | 2008-03-11 | 2009-09-18 | Saint Gobain | Durable hydrophobic and/or oleophobic glass substrate, useful e.g. as oven door interior glass, cooking plate and vitroceramic cooking plate, comprises a monomolecular layer of hydrophobic and/or oleophobic silane on a surface rugosity |
US20100008101A1 (en) * | 2008-06-09 | 2010-01-14 | Lloyd Keith Bucher | Head lamp assembly and accent lighting therefor |
US9207012B2 (en) | 2008-06-27 | 2015-12-08 | Ssw Holding Company, Inc. | Spill containing refrigerator shelf assembly |
US10827837B2 (en) | 2008-06-27 | 2020-11-10 | Ssw Holding Company, Llc | Spill containing refrigerator shelf assembly |
US8286561B2 (en) | 2008-06-27 | 2012-10-16 | Ssw Holding Company, Inc. | Spill containing refrigerator shelf assembly |
US11786036B2 (en) | 2008-06-27 | 2023-10-17 | Ssw Advanced Technologies, Llc | Spill containing refrigerator shelf assembly |
US9532649B2 (en) | 2008-06-27 | 2017-01-03 | Ssw Holding Company, Inc. | Spill containing refrigerator shelf assembly |
US8596205B2 (en) | 2008-06-27 | 2013-12-03 | Ssw Holding Company, Inc. | Spill containing refrigerator shelf assembly |
US11191358B2 (en) | 2008-06-27 | 2021-12-07 | Ssw Advanced Technologies, Llc | Spill containing refrigerator shelf assembly |
US10130176B2 (en) | 2008-06-27 | 2018-11-20 | Ssw Holding Company, Llc | Spill containing refrigerator shelf assembly |
US9179773B2 (en) | 2008-06-27 | 2015-11-10 | Ssw Holding Company, Inc. | Spill containing refrigerator shelf assembly |
US9279073B2 (en) | 2008-10-07 | 2016-03-08 | Ross Technology Corporation | Methods of making highly durable superhydrophobic, oleophobic and anti-icing coatings |
US9243175B2 (en) | 2008-10-07 | 2016-01-26 | Ross Technology Corporation | Spill resistant surfaces having hydrophobic and oleophobic borders |
US9926478B2 (en) | 2008-10-07 | 2018-03-27 | Ross Technology Corporation | Highly durable superhydrophobic, oleophobic and anti-icing coatings and methods and compositions for their preparation |
US9096786B2 (en) | 2008-10-07 | 2015-08-04 | Ross Technology Corporation | Spill resistant surfaces having hydrophobic and oleophobic borders |
US9067821B2 (en) | 2008-10-07 | 2015-06-30 | Ross Technology Corporation | Highly durable superhydrophobic, oleophobic and anti-icing coatings and methods and compositions for their preparation |
WO2010147738A1 (en) | 2009-05-29 | 2010-12-23 | Corning Incorporated | Super non-wetting, anti-fingerprint coatings for glass |
US9074778B2 (en) | 2009-11-04 | 2015-07-07 | Ssw Holding Company, Inc. | Cooking appliance surfaces having spill containment pattern |
US20150260412A1 (en) * | 2009-11-04 | 2015-09-17 | Ssw Holding Company, Inc. | Cooking appliance surfaces having spill containment pattern and methods of making the same |
US9914849B2 (en) | 2010-03-15 | 2018-03-13 | Ross Technology Corporation | Plunger and methods of producing hydrophobic surfaces |
EA028624B1 (en) * | 2010-07-09 | 2017-12-29 | Агк Гласс Юроп | Glass article coated with an enamel layer |
BE1019413A3 (en) * | 2010-07-09 | 2012-07-03 | Agc Glass Europe | GLASS ARTICLE COATED WITH A LAYER BASED ON EMAIL. |
WO2012004337A1 (en) * | 2010-07-09 | 2012-01-12 | Agc Glass Europe | Glass article coated with an enamel layer |
US20130149514A1 (en) * | 2010-07-30 | 2013-06-13 | Kyocera Corporation | Insulating sheet, method of manufacturing the same, and method of manufacturing structure using the insulating sheet |
WO2012061240A1 (en) * | 2010-11-01 | 2012-05-10 | Corning Incorporated | Transparent substrate having durable hydrophobic/oleophobic surface |
US10240049B2 (en) | 2011-02-21 | 2019-03-26 | Ross Technology Corporation | Superhydrophobic and oleophobic coatings with low VOC binder systems |
US9546299B2 (en) | 2011-02-21 | 2017-01-17 | Ross Technology Corporation | Superhydrophobic and oleophobic coatings with low VOC binder systems |
RU2598085C2 (en) * | 2011-07-25 | 2016-09-20 | Себ Са | Heating article comprising a microstructured heat-stable coating and method of manufacturing such an article |
WO2013014393A1 (en) | 2011-07-25 | 2013-01-31 | Seb Sa | Heating article comprising a microstructured heat-stable coating and method of manufacturing such an article. |
US10317129B2 (en) | 2011-10-28 | 2019-06-11 | Schott Ag | Refrigerator shelf with overflow protection system including hydrophobic layer |
US9139744B2 (en) | 2011-12-15 | 2015-09-22 | Ross Technology Corporation | Composition and coating for hydrophobic performance |
US9528022B2 (en) | 2011-12-15 | 2016-12-27 | Ross Technology Corporation | Composition and coating for hydrophobic performance |
US20150144613A1 (en) * | 2012-06-21 | 2015-05-28 | Eurokera S.N.C. | Glass-ceramic article and manufacturing process |
US11419187B2 (en) * | 2012-06-21 | 2022-08-16 | Eurokera S.N.C. | Glass-ceramic article and manufacturing process |
US9388325B2 (en) | 2012-06-25 | 2016-07-12 | Ross Technology Corporation | Elastomeric coatings having hydrophobic and/or oleophobic properties |
US11506526B2 (en) | 2014-04-17 | 2022-11-22 | Heraeus Nexensos Gmbh | Sensor element, sensor module, measuring assembly and exhaust-gas re-circulation system comprising a sensor element of this type, and production method |
US10317578B2 (en) | 2014-07-01 | 2019-06-11 | Honeywell International Inc. | Self-cleaning smudge-resistant structure and related fabrication methods |
US11412781B2 (en) * | 2016-02-12 | 2022-08-16 | Rai Strategic Holdings, Inc. | Adapters for refilling an aerosol delivery device |
US20170273356A1 (en) * | 2016-03-25 | 2017-09-28 | Rai Strategic Holdings, Inc. | Aerosol production assembly including surface with micro-pattern |
US11207478B2 (en) * | 2016-03-25 | 2021-12-28 | Rai Strategic Holdings, Inc. | Aerosol production assembly including surface with micro-pattern |
US11911561B2 (en) | 2016-03-25 | 2024-02-27 | Rai Strategic Holdings, Inc. | Aerosol production assembly including surface with micro-pattern |
US11297876B2 (en) * | 2017-05-17 | 2022-04-12 | Rai Strategic Holdings, Inc. | Aerosol delivery device |
US20170273360A1 (en) * | 2017-05-17 | 2017-09-28 | Rai Strategic Holdings, Inc. | Aerosol delivery device |
Also Published As
Publication number | Publication date |
---|---|
ATE308490T1 (en) | 2005-11-15 |
US6872441B2 (en) | 2005-03-29 |
US20030152780A1 (en) | 2003-08-14 |
EP1272442A1 (en) | 2003-01-08 |
ES2251478T3 (en) | 2006-05-01 |
DE50107908D1 (en) | 2005-12-08 |
EP1272442B1 (en) | 2005-11-02 |
DE10016485A1 (en) | 2001-10-11 |
WO2001074739A1 (en) | 2001-10-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6872441B2 (en) | Glass ceramic and metal substrates with a self-cleaning surface, method for the production and use thereof | |
US6800354B2 (en) | Substrates with a self-cleaning surface, a process for their production and their use | |
CA1049337A (en) | Coated-ceramic powder and electrostatic deposition thereof | |
US7879449B2 (en) | Non-stick ceramic coating composition and process | |
EP1835002B1 (en) | Non-stick ceramic coating composition and process | |
JP5149249B2 (en) | Decorative coating of glass or glass ceramic products | |
JP2002519300A (en) | Supply of organic paint on glass | |
JP3306603B2 (en) | Layer of decorative ceramic colorant applied to glass or glass ceramic substrate | |
EP0644860B1 (en) | Luster pigment application methods and article having luster pigment coating | |
AU2012227320B2 (en) | Non-stick ceramic coating composition and process | |
JP2002336768A (en) | Method for forming antifouling coating film | |
JP2001072893A (en) | Structure having hydrophilic microporous antifouling layer and coating liquid for forming the same antifouling layer, and production of the structure | |
CZ252393A3 (en) | Method of applying a glaze to non-metallic substrates | |
KR100408756B1 (en) | Dressing body composition used for clay bricks | |
JP2006152221A (en) | Product with inorganic film and inorganic coatings therefor, and manufacturing method thereof | |
JPH05305691A (en) | Hydrophilic film and formation thereof | |
JP2002003282A (en) | Water-repellent ceramics | |
JPH0616455A (en) | Water-repellent oxide film and its formation | |
JP2003128481A (en) | Method for manufacturing stain-resistant building material | |
JPH0647510B2 (en) | Method for generating ceramic-like decoration on the surface of ceramic products | |
Voges et al. | Properties of porcelain enamel, products utilizing porcelain enamel and basic processing procedures for porcelain enamel | |
AU2007224853B2 (en) | Non-stick ceramic coating composition and process | |
JPS63291886A (en) | Production of ceramic building material having tortoise pattern | |
JP2005126277A (en) | Water-repellent/oil-repellent ceramic | |
JPS63291885A (en) | Production of ceramic building material having tortoiseshell pattern |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: FERRO GMBH, GERMANY Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:BAUMANN, MARTIN;FRITSCHE, KLAUS-DIETER;KORBELARZ, DAGMAR;AND OTHERS;REEL/FRAME:016190/0577;SIGNING DATES FROM 20021213 TO 20021216 |
|
AS | Assignment |
Owner name: FERRO GMBH, GERMANY Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:BAUMANN, MARTIN;FRITSCHE, KLAUS-DIETER;KORBELARZ, DAGMAR;AND OTHERS;REEL/FRAME:016416/0042;SIGNING DATES FROM 20021213 TO 20021216 |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |