EP1507746A2 - Substrat comportant une couche de protection oxyde de titane/oxyde cerique - Google Patents

Substrat comportant une couche de protection oxyde de titane/oxyde cerique

Info

Publication number
EP1507746A2
EP1507746A2 EP03755136A EP03755136A EP1507746A2 EP 1507746 A2 EP1507746 A2 EP 1507746A2 EP 03755136 A EP03755136 A EP 03755136A EP 03755136 A EP03755136 A EP 03755136A EP 1507746 A2 EP1507746 A2 EP 1507746A2
Authority
EP
European Patent Office
Prior art keywords
protective layer
glass
alkali
substrate
resistant protective
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP03755136A
Other languages
German (de)
English (en)
Inventor
Martin Amlung
Klaus Endres
Martin Mennig
Helmut Schmidt
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
LEIBNIZ-INSTITUT fur NEUE MATERIALIEN GEMEINNUETZ
Original Assignee
Leibniz Institut fuer Neue Materialien Gemeinnuetzige GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Leibniz Institut fuer Neue Materialien Gemeinnuetzige GmbH filed Critical Leibniz Institut fuer Neue Materialien Gemeinnuetzige GmbH
Publication of EP1507746A2 publication Critical patent/EP1507746A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208—Oxides, e.g. ceramics
    • C23C18/1216—Metal oxides
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • C03C17/25—Oxides by deposition from the liquid phase
    • C03C17/256—Coating containing TiO2
    • 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
    • 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
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
    • C04B41/5045—Rare-earth oxides
    • 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
    • C04B41/85—Coating or impregnation with inorganic materials
    • C04B41/87—Ceramics
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1229—Composition of the substrate
    • C23C18/1245—Inorganic substrates other than metallic
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1254—Sol or sol-gel processing
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/212—TiO2
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/23—Mixtures
    • 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
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions
    • C03C2218/113—Deposition methods from solutions or suspensions by sol-gel processes

Definitions

  • the present invention relates to a substrate with an alkali-resistant protective layer based on titanium oxide / cerium oxide, the substrate or at least one surface layer of the substrate consisting of an inorganic non-metallic matrix material.
  • Substrates or coatings made of glass, glass ceramics and ceramics are often attacked by bases.
  • high-energy radiation such as UV radiation, high temperatures or a combination of these factors can also cause damage.
  • chemical and pharmaceutical industry e.g. The dissolution and aging of glass in production machines, laboratory equipment and also in windows is a major problem.
  • the aging or dissolution process of the glass network can, e.g. can be represented by the following equation:
  • Some high-temperature resistant materials such as Ti-sputtered BN layers are extremely durable. However, the production of these layers is technically complex and therefore very expensive. In addition, they are not transparent and cannot be applied to geometrically sophisticated glasses.
  • JP-A-2002036427, EP-A-1050603 and EP-A-696624 describe coatings made of metal oxides such as Zr0 2 , Al 2 0 3 , Y 2 0 3 and La 2 0 3 , which are also Ce0 2 - and / or Ti0 2 additives can contain, described as protection for metals and metal alloys against corrosion.
  • metal oxides such as Zr0 2 , Al 2 0 3 , Y 2 0 3 and La 2 0 3 , which are also Ce0 2 - and / or Ti0 2 additives can contain, described as protection for metals and metal alloys against corrosion.
  • the object of the present invention was to protect inorganic non-metallic materials from attack by alkaline media.
  • the protective layer should also have high heat resistance, be stable against UV light and not impair the optical effects of the material.
  • the manufacture should be simple and inexpensive.
  • a protective layer based on titanium oxide / cerium oxide which is obtainable by applying a coating composition comprising titanium oxide and cerium oxide precursors to a substrate with a surface made of an inorganic non-metallic matrix material and compacting the coating composition at a temperature of at least 500 ° C. Astonishingly, when compaction takes place at a temperature of at least 500 ° C., there is a layer whose permeability to alkaline media is severely restricted, so that alkali and OH " ions can no longer attack the underlying substrate or its coating
  • the barrier or protective layer used according to the invention provides excellent protection for inorganic non-metallic materials, in particular glass, glass ceramic and ceramic, against attack by alkaline media.
  • the alkali-resistant protective layer is also resistant to high temperatures, stable against UV radiation and transparent.
  • the protective layer can be coated by conventional wet chemical coating processes, e.g. Spraying or dipping can be applied in one step. The production is therefore simple and inexpensive.
  • the titanium oxide / cerium oxide layer is therefore suitable as an alkali-resistant, high-temperature-resistant, UV-stable and transparent protective layer for inorganic non-metallic materials.
  • the substrate can have different geometries.
  • An advantage of the invention is that even objects with more complex geometries can be coated easily.
  • the substrate can also only be partially provided with the protective layer. For example, it is possible to only coat the inside of glass jars.
  • Coated or uncoated substrates are suitable as substrates, part or all of the surface consisting of an inorganic non-metallic matrix material. Coated substrates can also have more than one layer. If there is a coating of an inorganic non-metallic matrix material, the substrate can be made of any other material.
  • the inorganic matrix may also contain organic groups, e.g. Methyl groups.
  • the inorganic non-metallic materials for the substrate itself or the coating are, for example, glass, glass ceramic or ceramic. This closes also oxide ceramics and enamel.
  • Oxide ceramics are usually understood to mean ceramics that are not based on silica as the main component.
  • semiconductors such as optionally doped Si or Ge, are also suitable as inorganic non-metallic matrix materials.
  • Glass substrates such as e.g. B. borosilicate glass, soda-lime glass or silica glass. It can be flat glass, hollow glass such as container glass, or laboratory equipment glass.
  • ceramics are ceramics based on the oxides Si0 2 , Al 2 0 3 , Zr0 2 or MgO or the corresponding mixed oxides.
  • additional components can be contained in the matrix made of glass, glass ceramic or ceramic, which serve, for example, as function carriers.
  • the matrix can contain, for example, pigments or metal colloids as coloring components.
  • Substrates can have a functional coating, for example made of glass, glass ceramic or ceramic, which, for example, has a decorative effect or has electrical conductivity or optoelectronic effects.
  • the substrates can, for example, be coated with indium tin oxide (ITO), antimony tin oxide (ATO) or fluorine-doped tin oxide (FTO) in order to achieve optoelectronic effects.
  • Metals can be coated with a layer of glass or an enamel before the protective layer is applied. An example of such a Si0 2 coating of metal surfaces is described in DE-A-19714949.
  • the inorganic non-metallic materials for the substrate itself or the coating can optionally also be organically modified inorganic polycondensates (for example made from tetraalkoxysilanes and methyltrialkoxysilanes), which are usually glass-like.
  • These glass-like materials are glasses that can contain organic groups in the inorganic matrix structure. It is known that organic groups such as methyl may remain in the matrix even at the high temperatures required to compact the protective layer.
  • the alkali-resistant protective layer is preferably applied directly to glass, glass ceramic or ceramic substrates, to glass-coated metals or to glass substrates provided with at least one functional layer.
  • a coating composition comprising titanium oxide and cerium oxide precursors is applied to the surface of the substrate.
  • the coating composition is usually obtained from cerium and titanium compounds in a solvent, preferably by the so-called sol-gel process.
  • At least one cerium salt and at least one hydrolyzable titanium compound are preferably converted in a solvent according to the sol-gel process into the titanium oxide and cerium oxide precursors, usually in the form of a sol.
  • hydrolyzable compounds are usually hydrolyzed with water, if appropriate with acidic or basic catalysis, and, if appropriate, at least partially condensed.
  • the reaction of the cerium salts with water is also regarded here as hydrolysis.
  • the hydrolysis and / or condensation reactions lead to the formation of compounds or condensates with hydroxyl, oxo groups and / or oxo bridges, which serve as titanium oxide and cerium oxide precursors, which precursors can also consist of condensates which contain both elements (Ce, Ti ) contain.
  • Stoichiometric amounts of water but also smaller or larger amounts can be used.
  • the sol that forms can be adjusted by suitable parameters, e.g.
  • Cerium (III) salts are preferably used as cerium compounds.
  • Cerium (III) salts which are found at room temperature in dissolving an alcohol are, for example, the nitrate and the chloride, the nitrate being particularly preferred.
  • the titanium compound is in particular a hydrolyzable compound of the formula TiX 4 , where the hydrolyzable groups X are, for example, hydrogen, halogen (F, Cl, Br or I, in particular Cl and Br), alkoxy (preferably C.sub.14-alkoxy, in particular C. ⁇ alkoxy, such as methoxy, ethoxy, n-propoxy, i- propoxy, butoxy, i-butoxy, sec-butoxy and tert-butoxy), aryloxy (preferably C6. 10, aryloxy, such as phenoxy), acyloxy (preferably C ⁇ acyloxy, such as acetoxy or propionyloxy) or alkylcarbonyl (preferably C 2.
  • the hydrolyzable groups X are, for example, hydrogen, halogen (F, Cl, Br or I, in particular Cl and Br), alkoxy (preferably C.sub.14-alkoxy, in particular C. ⁇ alkoxy, such as methoxy, ethoxy,
  • alkylcarbonyl such as acetyl
  • Preferred hydrolyzable radicals are alkoxy groups, in particular C 1-4 alkoxy.
  • Specific and preferably used titanates are Ti (OCH 3 ) 4 , Ti (OC 2 H 5 ) 4 and Ti (n- or i-OC 3 H 7 ) 4 .
  • an organic solvent in which the cerium and titanium compounds used are soluble is used as the solvent.
  • alcohols are used, preferably an alcohol having 1 to 4 carbon atoms, e.g. Methanol, ethanol, propanol and isopropanol, or a mixture thereof.
  • the resulting solution is in the presence of water, for example under reflux, at room temperature (about 20 ° C.) or at a slightly elevated temperature for a time-dependent period, for example from 1 min to several days ( for example up to 8 days), in order to obtain the coating composition comprising the titanium oxide and cerium oxide precursors, in particular in the form of a sol.
  • the treatment can, for example, take place under reflux for 1 minute to 24 hours or at 30 ° C. for 10 hours to 5 days.
  • the amounts of the titanium and cerium starting compounds are preferably chosen so that the molar ratio, based on Ti: Ce, is 1: 2 to 2: 1.
  • brine by dissolving cerium (III) salt eg cerium (III) nitrate hexahydrate
  • cerium (III) salt eg cerium (III) nitrate hexahydrate
  • a titanium tetraalkoxide in concentrations of 0.05 to 0.5 mol per liter, preferably 0.2 to 0.3 mol per liter
  • heating the clear solution under reflux or at a slightly elevated temperature 25 to 40 ° C
  • Prehydrolysis and / or condensation takes place, forming a sol and increasing the viscosity.
  • These brines can be stored for several weeks, especially when stored at temperatures around -20 ° C.
  • the coating composition may optionally contain other components, e.g. B. hydrolyzable compounds or salts of other elements for the matrix or other additives such as sintering aids.
  • the hydrolyzable compounds of other elements which can optionally be incorporated into the oxide matrix are, in particular, compounds of glass- or ceramic-forming elements, for example compounds of at least one element M from the main groups IM to V and / or the subgroups II to IV of the periodic table of the elements. These can be hydrolyzable compounds of Si, Al, B, Sn, Ti, Zr, V or Zn.
  • hydrolyzable compounds can also be used, such as those of elements of main groups I and II of the periodic table (for example Na, K, Ca and Mg) and subgroups V to VIII of the periodic table (for example Mn, Cr, Fe and Ni) or hydrolyzable compounds other lanthanides.
  • such other components based on the solids content of the finished protective layer, make up no more than 20% by weight, preferably no more than 5% by weight and in particular no more than 2% by weight.
  • the protective layer is particularly preferably formed only from the titanium oxide / cerium oxide.
  • the coating composition is applied to the substrates to be coated using the usual coating methods after the viscosity has been adjusted, if appropriate, by adding or removing solvent.
  • the coating can be done, for example, by spraying, dipping, brushing or spin coating.
  • the substrates are generally dried at room temperature or at elevated temperature (for example up to 100 ° C.). This is followed by compaction of the applied layer at temperatures in the range from 500 ° C. to just below the softening point of the substrate or coating material. Temperatures are preferably chosen just below the softening point of the material to be coated (Tg of the glass), which of course depends on the type of substrate or coating.
  • the coating composition can be compacted into crack-free, transparent and homogeneous coatings despite the possibly present organic components.
  • the heat treatment for compression can e.g. in the oven, by means of IR radiation or by flaming.
  • the protective layer is annealed by the heat treatment.
  • a matrix of oxides or mixed oxides (double oxides) of titanium and cerium (TiOj / CeO ;,) is obtained, here referred to as titanium oxide / cerium oxide, the stoichiometry depending on the molar ratio of the starting compounds used.
  • the protective layer obtained offers extremely good protection against attack by alkaline media.
  • the coating was able to achieve exceptional alkali resistance. In this way, a 30% sodium hydroxide solution could be heated to 80 ° C. in the reactor coated in this way without damage to the reactor being observed.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Structural Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Dispersion Chemistry (AREA)
  • Surface Treatment Of Glass (AREA)

Abstract

L'invention concerne un substrat comportant une surface réalisée dans un matériau matriciel non métallique, anorganique. Ledit substrat présente une couche de protection à base d'oxyde de titane/oxyde cérique pouvant être obtenue par application d'une composition de revêtement contenant des précurseurs d'oxyde de titane et d'oxyde cérique sur la surface du substrat, et compression de ladite composition de revêtement à une température de 500 °C. Ledit revêtement peut servir de protection thermorésistante, stable aux U.V. et transparente, de matériaux non métalliques anorganiques, notamment de verre, de vitrocéramique, contre l'attaque par des substances alcalines.
EP03755136A 2002-05-27 2003-05-26 Substrat comportant une couche de protection oxyde de titane/oxyde cerique Withdrawn EP1507746A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE2002123531 DE10223531A1 (de) 2002-05-27 2002-05-27 Substrat mit einer Titanoxid/Ceroxid-Schutzschicht
DE10223531 2002-05-27
PCT/EP2003/005502 WO2003099735A2 (fr) 2002-05-27 2003-05-26 Substrat comportant une couche de protection oxyde de titane/oxyde cerique

Publications (1)

Publication Number Publication Date
EP1507746A2 true EP1507746A2 (fr) 2005-02-23

Family

ID=29432345

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03755136A Withdrawn EP1507746A2 (fr) 2002-05-27 2003-05-26 Substrat comportant une couche de protection oxyde de titane/oxyde cerique

Country Status (3)

Country Link
EP (1) EP1507746A2 (fr)
DE (1) DE10223531A1 (fr)
WO (1) WO2003099735A2 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10324583B4 (de) * 2003-05-30 2005-08-11 Schott Ag Sol-Gel-Beschichtungslösung zur späteren Herstellung Li-Ionen transparenter Speicherschichten für Lithium-Ionen, Verfahren zur Herstellung der Sol-Gel-Beschichtungslösung sowie Verfahren zur Herstellung einer transparenten Li-Ionen-Speicherschicht
DE102005018246A1 (de) 2005-04-19 2006-10-26 Schott Ag Glas- oder Glaskeramik-Artikel mit dekorativer Beschichtung
US7744951B2 (en) 2006-04-13 2010-06-29 Guardian Industries Corp. Coated glass substrate with infrared and ultraviolet blocking characteristics
US8322754B2 (en) 2006-12-01 2012-12-04 Tenaris Connections Limited Nanocomposite coatings for threaded connections
DE102008062881B4 (de) 2008-12-16 2021-04-08 Schott Ag Verfahren zur Herstellung eines hohlen Glasformkörpers
AR100953A1 (es) 2014-02-19 2016-11-16 Tenaris Connections Bv Empalme roscado para una tubería de pozo de petróleo
GB2614722A (en) * 2022-01-13 2023-07-19 Pilkington Group Ltd Corrosion-resistant and/or cleanable coated glass substrate

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Publication number Priority date Publication date Assignee Title
KR0168710B1 (ko) 1994-08-11 1999-01-15 후지이 히로시 내식성 음극전착도료
DE69712194T2 (de) * 1996-12-25 2002-11-14 Nippon Sheet Glass Co Ltd Dünnschicht für optik, zusammensetzung zu deren herstellung und damit hergestelltes uv-absorbierendes und wärmereflektierendes glas
DE19714949A1 (de) 1997-04-10 1998-10-15 Inst Neue Mat Gemein Gmbh Verfahren zum Versehen einer metallischen Oberfläche mit einer glasartigen Schicht
WO2000028109A1 (fr) 1998-11-08 2000-05-18 Nkk Corporation Feuille d'acier traitee en surface presentant une excellente resistance a la corrosion et son procede de production
JP4532690B2 (ja) 2000-07-24 2010-08-25 新日本製鐵株式会社 樹脂系耐食性層を有する金属材

Non-Patent Citations (2)

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Title
None *
See also references of WO03099735A3 *

Also Published As

Publication number Publication date
WO2003099735A2 (fr) 2003-12-04
DE10223531A1 (de) 2003-12-11
WO2003099735A3 (fr) 2004-12-09

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