EP1835051A2 - Self-cleaning surface - Google Patents
Self-cleaning surface Download PDFInfo
- Publication number
- EP1835051A2 EP1835051A2 EP07003184A EP07003184A EP1835051A2 EP 1835051 A2 EP1835051 A2 EP 1835051A2 EP 07003184 A EP07003184 A EP 07003184A EP 07003184 A EP07003184 A EP 07003184A EP 1835051 A2 EP1835051 A2 EP 1835051A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- titanium dioxide
- dioxide particles
- metal matrix
- surface according
- self
- 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.)
- Granted
Links
- 238000004140 cleaning Methods 0.000 title claims abstract description 27
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 122
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 57
- 239000002245 particle Substances 0.000 claims abstract description 53
- 229910052751 metal Inorganic materials 0.000 claims abstract description 36
- 239000002184 metal Substances 0.000 claims abstract description 36
- 239000011159 matrix material Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 29
- 229910052759 nickel Inorganic materials 0.000 claims description 15
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 13
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 12
- 229910052804 chromium Inorganic materials 0.000 claims description 12
- 239000011651 chromium Substances 0.000 claims description 12
- 229910052709 silver Inorganic materials 0.000 claims description 12
- 239000004332 silver Substances 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims 1
- 239000006185 dispersion Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 229910052946 acanthite Inorganic materials 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 description 2
- 229940056910 silver sulfide Drugs 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 241000238631 Hexapoda Species 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- CWVZGJORVTZXFW-UHFFFAOYSA-N [benzyl(dimethyl)silyl]methyl carbamate Chemical compound NC(=O)OC[Si](C)(C)CC1=CC=CC=C1 CWVZGJORVTZXFW-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004512 die casting Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- LFAGQMCIGQNPJG-UHFFFAOYSA-N silver cyanide Chemical compound [Ag+].N#[C-] LFAGQMCIGQNPJG-UHFFFAOYSA-N 0.000 description 1
- 229940098221 silver cyanide Drugs 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Substances [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000005494 tarnishing Methods 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
- C25D15/02—Combined electrolytic and electrophoretic processes with charged materials
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1646—Characteristics of the product obtained
- C23C18/165—Multilayered product
- C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1655—Process features
- C23C18/1662—Use of incorporated material in the solution or dispersion, e.g. particles, whiskers, wires
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/08—Electroplating with moving electrolyte e.g. jet electroplating
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/623—Porosity of the layers
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
Definitions
- the invention relates to a self-cleaning surface with photocatalytically active titanium dioxide and a process for their preparation.
- titanium dioxide as a photocatalyst for decomposing organic compounds under the action of light is known. Due to the semiconductor properties of titanium dioxide according to equation (1), charge separation in the titanium dioxide particle occurs in the first step, forming an electron e - in the conduction band and a positive hole p + in the valence band.
- the hole oxidizes according to equation (2) a hydroxyl anion formed from water adsorbed on the TiO 2 surface to form a hydroxyl radical.
- hydroperoxyl radicals are formed from oxygen adsorbed on the TiO 2 surface which, together with the hydroxyl radical, degrade the organic compound as in Jochen Winkler "Titanium Dioxide", Ed. Ulrich Zorll - Hannover: Vincentz, 2003 (Coating Technology), pages 71 to 74 described in detail.
- the object of the invention is to provide a self-cleaning surface with photocatalytically active titanium dioxide, which can be prepared in a simple manner, leads to a firm adhesion to metallic surfaces and can also be applied to temperature-sensitive substrates.
- claim 11 is a preferred method for producing the self-cleaning surface according to the invention specified, and in claim 12, a preferred embodiment of this method.
- the self-cleaning surface consists of a metal matrix in which photocatalytically active titanium dioxide particles are incorporated.
- the self-cleaning effect is carried out by individual spaced titanium dioxide particles on the surface of the metal matrix, which surprisingly produces the same self-cleaning effect.
- the part to be provided with the self-cleaning surface is placed in a bath consisting of e.g. aqueous solution of a salt of the metal from which the metal matrix is formed.
- a bath consisting of e.g. aqueous solution of a salt of the metal from which the metal matrix is formed.
- the photocatalytically active titanium dioxide particles are formed by movement of the bath, e.g. Stirring or air injection, dispersed and then the metal matrix deposited with the titanium dioxide particles deposited by reduction of the salt on the part.
- the reduction can be carried out without electricity by adding a reducing agent.
- the metal matrix with the incorporated titanium dioxide particles is preferably electrodeposited.
- photocatalytically active titanium dioxide particles can be used to produce the self-cleaning surface according to the invention. From such particles, for example, porous sintered bodies are produced, which are used in wastewater treatment for UV sterilization.
- the titanium dioxide particles may be in the anatase or brookite crystal form. While titanium dioxide particles in the anatase form require light with a high UV content in order to be self-cleaning, the brookite form also leads to a self-cleaning effect in the visible light range.
- the particle size of the titanium dioxide particles is preferably 0.01 ⁇ m to 10 ⁇ m, in particular 0.1 ⁇ m to 1 ⁇ m.
- the proportion of titanium dioxide particles in the metal matrix is preferably 1 to 40% by volume, in particular 5 to 20% by volume, based on the total volume of metal matrix and titanium dioxide particles.
- the minimum layer thickness of the metal matrix in which the titanium dioxide particles are embedded depends on the particle size of the titanium dioxide particles. That is, the layer thickness of the metal matrix must be at least large enough to securely fix the titanium dioxide particles therein. It is therefore preferably at least one third, in particular at least two thirds of the average particle size of the titanium dioxide particles. On the other hand, the layer thickness of the metal matrix should not be too large, since only the proportion of titanium dioxide particles on the surface of the metal matrix has a self-cleaning effect.
- the layer thickness of the metal matrix is preferably between 0.5 ⁇ m and 30 ⁇ m, in particular 5 ⁇ m to 20 ⁇ m.
- the metal matrix may consist of any metal. Preferably, however, it is formed from nickel, chromium, copper, silver or gold.
- a silver matrix is achieved by the titanium dioxide particles in addition to the self-cleaning effect in addition that the silver surface does not start.
- the start of the silver is known to be due to oxidation of the silver at the surface by sulfur compounds from the environment to form silver sulfide.
- titanium dioxide is also a photo-semiconductor, whereby electrons are formed upon incidence of light. By draining these electrons into the silver matrix, reducing properties are imparted to the silver matrix, thereby preventing the formation of silver sulfide.
- a silver surface formed according to the invention therefore retains its luster, since not only does it not start when exposed to light, but organic impurities, for example traces of grease caused by fingerprints, are removed by self-cleaning.
- the electron surplus formed by the semiconductor properties of the titanium dioxide upon incidence of light not only prevents the silver from tarnishing, but generally causes a cathodic corrosion protection of the metal matrix.
- a further thin metal layer can be deposited on the metal matrix, in which the titanium dioxide particles are embedded.
- the lower layer may be formed by nickel, copper or silver and titanium dioxide particles and the upper layer may be formed by chromium or noble metals such as gold, platinum or ruthenium, in which even particle incorporation is not possible or difficult.
- the thin upper layer is deposited with a layer thickness of preferably at most 0.8 .mu.m, in particular 0.1 .mu.m to 0.5 .mu.m. It is important that the particles are not covered but present as open pores.
- the titanium dioxide particles can be deposited, for example, with the lower thick nickel layer, whereupon the chromium layer is deposited.
- This can be up the part first, for example, galvanically deposited a nickel layer with the embedded therein titanium dioxide particles having a layer thickness of, for example, 5 microns to 20 microns. Since chromium shines only in a thin layer and particle deposition is not possible, then a thin chromium layer of eg 0.1 .mu.m to 0.6 .mu.m is deposited on the nickel layer with the titanium dioxide particles.
- the part on which the nickel layer is galvanically deposited with the titanium dioxide particles incorporated therein may be e.g. be nickel plated steel sheet.
- the self-cleaning surface according to the invention can be applied to metal and any other substrate in a simple manner. Since the substrate according to the invention need not be subjected to heating, the self-cleaning surface according to the invention can also be formed on substrates with low temperature stability, that is, for example, plastic, aluminum or zinc die casting. If a galvanic deposition of the metal matrix takes place with the titanium dioxide particles embedded therein, the coating according to the invention can be produced on all substrates with an electrically conductive surface, e.g. also on galvanized plastic.
- the surface coating according to the invention is particularly suitable for chromed vehicle exterior surfaces that are exposed to heavy pollution by insects, such as flies, or other organic material, such as
- the self-cleaning surface according to the invention can also be used in the vehicle interior, especially when the brookite form of the titanium dioxide is used.
- the self-cleaning surface according to the invention for example, permanently high-gloss silver surfaces of high quality can be produced in the interior of a vehicle.
- a double-nickel plated steel sheet part after a conventional degreasing treatment as a cathode in an electrolyte bath containing as solution components 300 g / l nickel sulfate, 60 g / l nickel chloride and conventional amounts of a commercially available nickel luster carrier, a commercial nickel wetting agent, a also contains 15 g / l titanium dioxide particles of the anatase form with an average particle size of 0.5 microns.
- the bath is kept in motion by air injection. It is electrodeposited a nickel layer with a thickness of 2 microns, in which the titanium dioxide particles are embedded.
- a chromium layer with a layer thickness of 0.3 .mu.m is deposited from a commercially available chromium electrolyte in a conventional manner.
- the bath is kept moving. It is electrodeposited a silver layer with a layer thickness of 10 microns, in which the titanium dioxide particles are embedded.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Dispersion Chemistry (AREA)
- Catalysts (AREA)
Abstract
Description
Die Erfindung bezieht sich auf eine selbstreinigende Oberfläche mit photokatalytisch aktivem Titandioxid und ein Verfahren zu deren Herstellung.The invention relates to a self-cleaning surface with photocatalytically active titanium dioxide and a process for their preparation.
Die Verwendung von Titandioxid als Photokatalysator zum Abbau organischer Verbindungen unter Lichteinwirkung ist bekannt. Dabei kommt es aufgrund der Halbleitereigenschaften des Titandioxids gemäß der Gleichung (1) in einem ersten Schritt zu einer Ladungstrennung im Titandioxid-Partikel unter Bildung eines Elektrons e- im Leitungsband und einem positiven Loch p+ im Valenzband.
Im nächsten Schritt oxidiert das Loch gemäß der Gleichung (2) ein aus an der TiO2-Oberfläche adsorbierten Wasser gebildetes Hydroxyl-Anion, wobei ein Hydroxyl-Radikal entsteht.
Zudem werden aus an der TiO2-Oberfläche adsorbierten Sauerstoff Hydroperoxyl-Radikale gebildet, die zusammen mit dem Hydroxyl-Radikal die organische Verbindung abbauen, wie in
Es ist bekannt, photokatalytisch aktive Titandioxid-Beschichtungen durch chemische Dampfabscheidung (CVD), mittels Vakuumverfahren wie physikalische Dampfabscheidung (PVD) oder Plasmadampfabscheidung (PaCVD) oder mit dem Sol-Gel-Verfahren herzustellen, bei dem ein aus einer hydrolysierten Titanverbindung gebildetes Titandioxid-Sol auf dem Substrat in ein Gel und dann thermisch in kristallisiertes Titandioxid übergeführt wird. Die dabei gebildeten zusammenhängenden Schichten werden vorwiegend auf keramische oder metallische Substrate aufgetragen.It is known to produce photocatalytically active titanium dioxide coatings by chemical vapor deposition (CVD), by vacuum processes such as physical vapor deposition (PVD) or plasma vapor deposition (PaCVD) or by the sol-gel process, in which a titanium dioxide sol formed from a hydrolyzed titanium compound on the substrate into a gel and then thermally converted into crystallized titanium dioxide. The coherent layers formed are mainly applied to ceramic or metallic substrates.
Die bekannten Verfahren sind aufwändig und kostspielig. Zudem können nur temperaturstabile Substrate beschichtet werden. Des weiteren ist die Haftung z.B. beim Sol-Gel-Verfahren auf metallischen Oberflächen schwierig und oft nicht ausreichend.The known methods are complicated and expensive. In addition, only temperature-stable substrates can be coated. Furthermore, the adhesion is e.g. difficult and often insufficient in the sol-gel process on metallic surfaces.
Aufgabe der Erfindung ist es, eine selbstreinigende Oberfläche mit photokatalytisch aktivem Titandioxid bereitzustellen, die auf einfache Weise herstellbar ist, zu einer festen Haftung auf metallischen Oberflächen führt und auch auf temperaturempfindliche Substrate aufgetragen werden kann.The object of the invention is to provide a self-cleaning surface with photocatalytically active titanium dioxide, which can be prepared in a simple manner, leads to a firm adhesion to metallic surfaces and can also be applied to temperature-sensitive substrates.
Dies wird erfindungsgemäß mit der im Anspruch 1 gekennzeichneten selbstreinigenden Oberfläche erreicht, die durch die Merkmale der Ansprüche 2 bis 10 in vorteilhafter Weise ausgestaltet wird. Im Anspruch 11 ist ein bevorzugtes Verfahren zur Herstellung der erfindungsgemäßen selbstreinigenden Oberfläche angegeben, und im Anspruch 12 eine bevorzugte Ausführungsform dieses Verfahrens.This is achieved according to the invention with the characterized in claim 1 self-cleaning surface, which is configured by the features of claims 2 to 10 in an advantageous manner. In claim 11 is a preferred method for producing the self-cleaning surface according to the invention specified, and in claim 12, a preferred embodiment of this method.
Erfindungsgemäß besteht die selbstreinigende Oberfläche aus einer Metallmatrix, in die photokatalytisch aktive Titandioxid-Partikel eingelagert sind. Es liegt also keine zusammenhängende Titandioxid-Beschichtung vor, vielmehr erfolgt die selbstreinigende Wirkung durch einzelne im Abstand angeordnete Titandioxid-Partikel an der Oberfläche der Metallmatrix, wodurch überraschenderweise der gleiche selbstreinigende Effekt hervorgebracht wird.According to the invention, the self-cleaning surface consists of a metal matrix in which photocatalytically active titanium dioxide particles are incorporated. Thus, there is no contiguous titanium dioxide coating, but the self-cleaning effect is carried out by individual spaced titanium dioxide particles on the surface of the metal matrix, which surprisingly produces the same self-cleaning effect.
Zur Herstellung der selbstreinigenden Oberfläche wird erfindungsgemäß das Teil, das mit der selbstreinigenden Oberfläche versehen werden soll, in ein Bad gegeben, das aus einer z.B. wässerigen Lösung eines Salzes des Metalls besteht, aus dem die Metallmatrix gebildet wird. In der Lösung werden die photokatalytisch aktiven Titandioxid-Partikel durch Bewegung des Bades, also z.B. Rühren oder Lufteinblasung, dispergiert und dann die Metallmatrix mit den darin eingelagerten Titandioxid-Partikeln durch Reduktion des Salzes auf dem Teil abgeschieden.To produce the self-cleaning surface, according to the invention, the part to be provided with the self-cleaning surface is placed in a bath consisting of e.g. aqueous solution of a salt of the metal from which the metal matrix is formed. In the solution, the photocatalytically active titanium dioxide particles are formed by movement of the bath, e.g. Stirring or air injection, dispersed and then the metal matrix deposited with the titanium dioxide particles deposited by reduction of the salt on the part.
Die Reduktion kann stromlos durch Zugabe eines Reduktionsmittels erfolgen. Bei Teilen mit elektrisch leitfähiger Oberfläche wird die Metallmatrix mit den eingelagerten Titandioxid-Partikeln jedoch vorzugsweise galvanisch abgeschieden.The reduction can be carried out without electricity by adding a reducing agent. For parts with an electrically conductive surface, however, the metal matrix with the incorporated titanium dioxide particles is preferably electrodeposited.
Zur Herstellung der erfindungsgemäßen selbstreinigenden Oberfläche können im Handel erhältliche photokatalytisch aktive Titandioxid-Partikel verwendet werden. Aus solchen Partikeln werden beispielsweise poröse Sinterkörper hergestellt, die in der Abwasserbehandlung zur UV-Entkeimung verwendet werden.Commercially available photocatalytically active titanium dioxide particles can be used to produce the self-cleaning surface according to the invention. From such particles, for example, porous sintered bodies are produced, which are used in wastewater treatment for UV sterilization.
Die Titandioxid-Partikel können in der Anatas- oder Brookit-Kristallform vorliegen. Während Titandioxid-Partikel in der Anatas-Form Licht mit einem hohen UV-Anteil voraussetzen, um selbstreinigend zu wirken, führt die Brookit-Form auch im sichtbaren Lichtbereich zu einer selbstreinigenden Wirkung.The titanium dioxide particles may be in the anatase or brookite crystal form. While titanium dioxide particles in the anatase form require light with a high UV content in order to be self-cleaning, the brookite form also leads to a self-cleaning effect in the visible light range.
Die Teilchengröße der Titandioxid-Partikel beträgt vorzugsweise 0,01 µm bis 10 µm, insbesondere 0,1 µm bis 1 µm. Der Anteil der Titandioxid-Partikel in der Metallmatrix beträgt vorzugsweise 1 bis 40 Vol.-%, insbesondere 5 bis 20 Vol.-%, bezogen auf das Gesamtvolumen aus Metallmatrix und Titandioxid-Partikeln.The particle size of the titanium dioxide particles is preferably 0.01 μm to 10 μm, in particular 0.1 μm to 1 μm. The proportion of titanium dioxide particles in the metal matrix is preferably 1 to 40% by volume, in particular 5 to 20% by volume, based on the total volume of metal matrix and titanium dioxide particles.
Die Mindestschichtdicke der Metallmatrix, in der die Titandioxid-Partikel eingelagert sind, ist von der Teilchengröße der Titandioxid-Partikel abhängig. D.h., die Schichtdicke der Metallmatrix muss mindestens so groß sein, dass die Titandioxid-Partikel darin sicher fixiert werden. Sie beträgt daher vorzugsweise mindestens ein Drittel, insbesondere mindestens zwei Drittel der mittleren Teilchengröße der Titandioxid-Partikel. Andererseits soll die Schichtdicke der Metallmatrix nicht zu groß sein, da nur der Anteil der Titandioxid-Partikel an der Oberfläche der Metallmatrix eine selbstreinigende Wirkung besitzt. Vorzugsweise liegt die Schichtdicke der Metallmatrix zwischen 0,5 µm und 30 µm, insbesondere 5 µm bis 20 µm.The minimum layer thickness of the metal matrix in which the titanium dioxide particles are embedded depends on the particle size of the titanium dioxide particles. That is, the layer thickness of the metal matrix must be at least large enough to securely fix the titanium dioxide particles therein. It is therefore preferably at least one third, in particular at least two thirds of the average particle size of the titanium dioxide particles. On the other hand, the layer thickness of the metal matrix should not be too large, since only the proportion of titanium dioxide particles on the surface of the metal matrix has a self-cleaning effect. The layer thickness of the metal matrix is preferably between 0.5 μm and 30 μm, in particular 5 μm to 20 μm.
Die Metallmatrix kann aus einem beliebigen Metall bestehen. Vorzugsweise wird sie jedoch aus Nickel, Chrom, Kupfer, Silber oder Gold gebildet.The metal matrix may consist of any metal. Preferably, however, it is formed from nickel, chromium, copper, silver or gold.
In einer Silbermatrix wird durch die Titandioxid-Partikel neben der selbstreinigenden Wirkung zusätzlich erreicht, dass die Silberoberfläche nicht anläuft. Das Anlaufen des Silbers ist bekanntlich darauf zurückzuführen, dass eine Oxidation des Silbers an der Oberfläche durch Schwefelverbindungen aus der Umgebung unter Bildung von Silbersulfid erfolgt. Wie eingangs anhand der Gleichung (1) erläutert, stellt Titandioxid zugleich einen Photohalbleiter dar, wodurch bei Lichteinfall Elektronen gebildet werden. Durch Abfluss dieser Elektronen in die Silbermatrix werden der Silbermatrix reduzierende Eigenschaften verliehen, wodurch die Bildung von Silbersulfid verhindert wird. Eine erfindungsgemäß ausgebildete Silberoberfläche behält daher ihren Glanz, da sie bei Lichteinwirkung nicht nur nicht anläuft, sondern organische Verunreinigungen, beispielsweise Fettspuren durch Fingerabdrücke, selbstreinigend entfernt werden.In a silver matrix is achieved by the titanium dioxide particles in addition to the self-cleaning effect in addition that the silver surface does not start. The start of the silver is known to be due to oxidation of the silver at the surface by sulfur compounds from the environment to form silver sulfide. As explained above with reference to equation (1), titanium dioxide is also a photo-semiconductor, whereby electrons are formed upon incidence of light. By draining these electrons into the silver matrix, reducing properties are imparted to the silver matrix, thereby preventing the formation of silver sulfide. A silver surface formed according to the invention therefore retains its luster, since not only does it not start when exposed to light, but organic impurities, for example traces of grease caused by fingerprints, are removed by self-cleaning.
Der durch die Halbleitereigenschaften des Titandioxids bei Lichteinfall gebildete Elektronenüberschuss verhindert jedoch nicht nur ein Anlaufen des Silbers, sondern bewirkt generell einen kathodischen Korrosionsschutz der Metallmatrix.However, the electron surplus formed by the semiconductor properties of the titanium dioxide upon incidence of light not only prevents the silver from tarnishing, but generally causes a cathodic corrosion protection of the metal matrix.
Auf der Metallmatrix, in die die Titandioxid-Partikel eingelagert sind, kann eine weitere dünne Metallschicht abgeschieden werden. Beispielsweise kann die untere Schicht durch Nickel, Kupfer oder Silber und Titandioxid-Partikel und die obere Schicht durch Chrom oder Edelmetalle wie Gold, Platin oder Ruthenium gebildet sein, in denen selbst eine Partikeleinlagerung nicht möglich oder schwierig ist. Die dünne obere Schicht wird mit einer Schichtdicke von vorzugsweise maximal 0,8 µm, insbesondere 0,1 µm bis 0,5 µm, abgeschieden. Wichtig hierbei ist, dass die Partikel nicht zugedeckt werden, sondern als offene Poren vorliegen.On the metal matrix, in which the titanium dioxide particles are embedded, a further thin metal layer can be deposited. For example, the lower layer may be formed by nickel, copper or silver and titanium dioxide particles and the upper layer may be formed by chromium or noble metals such as gold, platinum or ruthenium, in which even particle incorporation is not possible or difficult. The thin upper layer is deposited with a layer thickness of preferably at most 0.8 .mu.m, in particular 0.1 .mu.m to 0.5 .mu.m. It is important that the particles are not covered but present as open pores.
Um ein Teil zu verchromen, können die Titandioxid-Partikel z.B. mit der unteren dicken Nickelschicht abgeschieden werden, worauf die Chromschicht abgeschieden wird. Dazu kann auf dem Teil zunächst beispielsweise galvanisch eine Nickelschicht mit den darin eingelagerten Titandioxid-Partikeln mit einer Schichtdicke von beispielsweise 5 µm bis 20 µm abgeschieden werden. Da Chrom nur in dünner Schicht glänzt und eine Partikeleinlagerung nicht möglich ist, wird dann auf der Nickelschicht mit den Titandioxid-Partikeln eine dünne Chromschicht von z.B. 0,1 µm bis 0,6 µm abgeschieden.To chromium a part, the titanium dioxide particles can be deposited, for example, with the lower thick nickel layer, whereupon the chromium layer is deposited. This can be up the part first, for example, galvanically deposited a nickel layer with the embedded therein titanium dioxide particles having a layer thickness of, for example, 5 microns to 20 microns. Since chromium shines only in a thin layer and particle deposition is not possible, then a thin chromium layer of eg 0.1 .mu.m to 0.6 .mu.m is deposited on the nickel layer with the titanium dioxide particles.
Wie sich gezeigt hat, findet dabei auf den aus der Oberfläche der Nickelschicht ragenden Titandioxid-Partikeln keine Chromabscheidung statt. In der Chromschicht werden vielmehr Poren gebildet, die einen Lichteinfall auf die Titandioxid-Partikel an der Oberfläche der Nickelschicht ermöglichen. Das Teil, auf dem die Nickelschicht mit den darin eingelagerten Titandioxid-Partikeln galvanisch abgeschieden wird, kann z.B. vernickeltes Stahlblech sein.As has been shown, no chromium deposition takes place on the titanium dioxide particles projecting from the surface of the nickel layer. On the contrary, pores are formed in the chromium layer which allow light to strike the titanium dioxide particles on the surface of the nickel layer. The part on which the nickel layer is galvanically deposited with the titanium dioxide particles incorporated therein may be e.g. be nickel plated steel sheet.
Die erfindungsgemäße selbstreinigende Oberfläche kann auf Metall und jedes andere Substrat auf einfache Weise aufgebracht werden. Da das Substrat erfindungsgemäß keiner Erwärmung unterworfen zu werden braucht, kann die erfindungsgemäße selbstreinigende Oberfläche auch auf Substrate mit geringer Temperaturstabilität, also beispielsweise Kunststoff, Aluminium oder Zinkdruckguss gebildet werden. Sofern eine galvanische Abscheidung der Metallmatrix mit den darin eingelagerten Titandioxid-Partikeln erfolgt, kann die erfindungsgemäße Beschichtung auf allen Substraten mit elektrisch leitfähiger Oberfläche hergestellt werden, also z.B. auch auf galvanisiertem Kunststoff.The self-cleaning surface according to the invention can be applied to metal and any other substrate in a simple manner. Since the substrate according to the invention need not be subjected to heating, the self-cleaning surface according to the invention can also be formed on substrates with low temperature stability, that is, for example, plastic, aluminum or zinc die casting. If a galvanic deposition of the metal matrix takes place with the titanium dioxide particles embedded therein, the coating according to the invention can be produced on all substrates with an electrically conductive surface, e.g. also on galvanized plastic.
Die erfindungsgemäße Oberflächenbeschichtung ist insbesondere für verchromte Fahrzeugaußenflächen geeignet, die einer starken Verschmutzung durch Insekten, wie Fliegen, oder anderes organisches Material ausgesetzt sind, beispielsweise die Spiegelkappe der Außenspiegel, die Scheinwerferringe, der Kühlergrill, usw. Die erfindungsgemäße selbstreinigende Oberfläche kann jedoch auch im Fahrzeuginnenraum eingesetzt werden, insbesondere wenn die Brookit-Form des Titandioxid verwendet wird. So können mit der erfindungsgemäßen selbstreinigenden Oberfläche beispielsweise dauerhaft hochglänzende Silberoberflächen hoher Wertigkeit im Innenraum eines Fahrzeugs hergestellt werden.The surface coating according to the invention is particularly suitable for chromed vehicle exterior surfaces that are exposed to heavy pollution by insects, such as flies, or other organic material, such as However, the self-cleaning surface according to the invention can also be used in the vehicle interior, especially when the brookite form of the titanium dioxide is used. Thus, with the self-cleaning surface according to the invention, for example, permanently high-gloss silver surfaces of high quality can be produced in the interior of a vehicle.
Um hochglanzverchromtes Stahlblech mit selbstreinigender Oberfläche herzustellen, wird ein zweifach vernickeltes Stahlblechteil nach einer herkömmlichen Entfettungsbehandlung als Kathode in ein Elektrolytbad gegeben, das als Lösungsbestandteile 300 g/l Nickelsulfat, 60 g/l Nickelchlorid sowie herkömmliche Mengen eines handelsüblichen Nickelglanzträgers, eines handelsüblichen Nickelnetzmittels, eines handelsüblichen Nickelglanzzusatzes und eines handelsüblichen Nickeleinebners enthält, außerdem 15 g/l Titandioxid-Partikel der Anatas-Form mit einer mittleren Teilchengröße von 0,5 µm. Das Bad wird durch Lufteinblasung in Bewegung gehalten. Es wird eine Nickelschicht mit einer Schichtdicke von 2 µm galvanisch abgeschieden, in die die Titandioxid-Partikel eingelagert sind.In order to produce high-gloss chrome-plated steel sheet with self-cleaning surface, a double-nickel plated steel sheet part after a conventional degreasing treatment as a cathode in an electrolyte bath containing as solution components 300 g / l nickel sulfate, 60 g / l nickel chloride and conventional amounts of a commercially available nickel luster carrier, a commercial nickel wetting agent, a also contains 15 g / l titanium dioxide particles of the anatase form with an average particle size of 0.5 microns. The bath is kept in motion by air injection. It is electrodeposited a nickel layer with a thickness of 2 microns, in which the titanium dioxide particles are embedded.
Darauf wird auf herkömmliche Weise eine Chromschicht mit einer Schichtdicke von 0,3 µm aus einem handelsüblichen Chromelektrolyten abgeschieden.Then, a chromium layer with a layer thickness of 0.3 .mu.m is deposited from a commercially available chromium electrolyte in a conventional manner.
Ein Stahlteil wird nach einer herkömmlichen Entfettungsbehandlung als Kathode in ein Elektrolytbad gegeben, das 50 g/l Silbercyanid, 70 g/l Calciumcyanid, 10 g/l Kaliumhydroxid und 20 g/l Kaliumcarbonat als Lösungsbestandteile sowie 15 g/l Titandioxid-Partikel der Anatas-Form mit einer mittleren Teilchengröße von 0,5 µm enthält. Das Bad wird in Bewegung gehalten. Es wird eine Silberschicht mit einer Schichtdicke von 10 µm galvanisch abgeschieden, in die die Titandioxid-Partikel eingelagert sind.A steel part, after a conventional degreasing treatment, is placed as a cathode in an electrolyte bath which is 50 g / l Silver cyanide, 70 g / l calcium cyanide, 10 g / l potassium hydroxide and 20 g / l potassium carbonate as solution components and 15 g / l anatase titanium dioxide particles having a mean particle size of 0.5 microns. The bath is kept moving. It is electrodeposited a silver layer with a layer thickness of 10 microns, in which the titanium dioxide particles are embedded.
Claims (12)
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| Application Number | Priority Date | Filing Date | Title |
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| DE102006011848A DE102006011848A1 (en) | 2006-03-15 | 2006-03-15 | Self-cleaning surface |
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| EP1835051A2 true EP1835051A2 (en) | 2007-09-19 |
| EP1835051A3 EP1835051A3 (en) | 2008-06-25 |
| EP1835051B1 EP1835051B1 (en) | 2018-10-17 |
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| DE102009012461A1 (en) | 2009-03-12 | 2010-09-16 | Kme Germany Ag & Co. Kg | Metallic carrier body such as metal sheet or strip useful as pollutant-reducing component in building construction and civil engineering, comprises patina layer applied on the carrier body, where the patina layer contains metal compounds |
| WO2016065449A1 (en) * | 2014-10-29 | 2016-05-06 | Docol Metais Sanitários Ltda. | A galvanic process, a chromed material with silver anoparticles and use of said material |
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| DE102009051439A1 (en) | 2009-10-30 | 2011-05-05 | Gottfried Wilhelm Leibniz Universität Hannover | Producing metallic conductive coating or partial coating made of metal on coated substrate, comprises applying metal coating made of an ionic solution at coated region on semiconductor surface of substrate, using light irradiation |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4960653A (en) | 1988-06-09 | 1990-10-02 | Kanto Kasei Co., Ltd. | Method of copper-nickel-cromium bright electroplating which provides excellent corrosion resistance and plating film obtained by the method |
| JPH11158694A (en) | 1997-11-27 | 1999-06-15 | Toto Ltd | Article with hydrophilic coating, and coating method |
| EP1369504A1 (en) | 2002-06-05 | 2003-12-10 | Hille & Müller | Metal strip for the manufacture of components for electrical connectors |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5595813A (en) * | 1992-09-22 | 1997-01-21 | Takenaka Corporation | Architectural material using metal oxide exhibiting photocatalytic activity |
| EP1304366B2 (en) * | 1995-03-20 | 2012-10-03 | Toto Ltd. | Use of a photocatalytically rendered superhydrophilic surface with antifogging properties |
| TW473575B (en) * | 1997-05-23 | 2002-01-21 | Kyorasha Co Ltd | Natural fibers containing titanium oxide and process for producing the same |
| DE10118763A1 (en) * | 2001-04-11 | 2002-10-17 | Univ Schiller Jena | Production of ceramic (mixed) metal oxide layers on substrate made from glass, ceramic, glass-ceramic, iron or other metals comprise coating substrate with an intermediate layer, applying ceramic (mixed) metal oxide layers using anodization |
| JP2004066218A (en) * | 2002-06-12 | 2004-03-04 | Toshiba Lighting & Technology Corp | Photocatalyst body |
| JP2005058900A (en) * | 2003-08-12 | 2005-03-10 | Nobuyuki Koura | Composite material of metal and photocatalyst particle, and manufacturing method therefor |
-
2006
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-
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4960653A (en) | 1988-06-09 | 1990-10-02 | Kanto Kasei Co., Ltd. | Method of copper-nickel-cromium bright electroplating which provides excellent corrosion resistance and plating film obtained by the method |
| JPH11158694A (en) | 1997-11-27 | 1999-06-15 | Toto Ltd | Article with hydrophilic coating, and coating method |
| EP1369504A1 (en) | 2002-06-05 | 2003-12-10 | Hille & Müller | Metal strip for the manufacture of components for electrical connectors |
Non-Patent Citations (1)
| Title |
|---|
| VINCENTZ, TECHNOLOGIE DES BESCHICHTENS, 2003, pages 71 - 74 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102009012461A1 (en) | 2009-03-12 | 2010-09-16 | Kme Germany Ag & Co. Kg | Metallic carrier body such as metal sheet or strip useful as pollutant-reducing component in building construction and civil engineering, comprises patina layer applied on the carrier body, where the patina layer contains metal compounds |
| WO2016065449A1 (en) * | 2014-10-29 | 2016-05-06 | Docol Metais Sanitários Ltda. | A galvanic process, a chromed material with silver anoparticles and use of said material |
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| DE102006011848A1 (en) | 2007-09-20 |
| EP1835051A3 (en) | 2008-06-25 |
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