EP1507746A2 - Substrate comprising a titanium oxide/cerium oxide protective layer - Google Patents

Substrate comprising a titanium oxide/cerium oxide protective layer

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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Withdrawn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)
French (fr)
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/en
Withdrawn legal-status Critical Current

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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.

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  • 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

A substrate having a surface consisting of an inorganic non-metallic matrix material comprises a protective layer based on titanium oxide/cerium oxide. This protective layer can be obtained by applying a coating composition, which comprises precursors of both titanium oxide and cerium oxide, onto the surface of the substrate and by compacting the coating composition at a temperature of at least 500 DEG C. The coating is suited for use as a heat-resistant, UV stable, and transparent protection for inorganic non-metallic materials, particularly glass, glass ceramics and ceramics, against corrosion caused by alkaline media.

Description

SUBSTRAT MIT EINER TITANOXID/CEROXID-SCHUTZSCHICHT SUBSTRATE WITH A TITANOXIDE / CEROXIDE PROTECTIVE LAYER
Die vorliegende Erfindung betrifft ein Substrat mit einer alkalibeständigeπ Schutzschicht auf Basis von Titanoxid/Ceroxid, wobei das Substrat oder zumindest eine Oberflächenschicht des Substrats aus einem anorganischen nichtmetallischen Matrixmaterial bestehen.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.
Substrate oder Beschichtungen aus Glas, Glaskeramik und Keramik werden häufig durch Basen angegriffen. Aber auch energiereiche Strahlung wie UV-Strahlung, hohe Temperaturen oder eine Kombination dieser Faktoren können zu Schädigungen führen. In der chemischen und pharmazeutischen Industrie stellt daher z.B. die Auflösung und die Alterung von Glas in Produktionsmaschinen, Laborausrüstungen und auch in Fenstern ein großes Problem dar.Substrates or coatings made of glass, glass ceramics and ceramics are often attacked by bases. However, high-energy radiation such as UV radiation, high temperatures or a combination of these factors can also cause damage. In the 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.
Der Alterungs- bzw. Auflösungsprozess des Glasnetzwerkes kann bei alkalischem Angriff z.B. durch die folgende Gleichung wiedergegeben werden:The aging or dissolution process of the glass network can, e.g. can be represented by the following equation:
R3Si-0-SiR3 + ROH → R3Si-0-R' + HO-SiR3 R = Glasnetzwerk, R' = ü, Na, KR 3 Si-0-SiR 3 + ROH → R 3 Si-0-R ' + HO-SiR 3 R = glass network, R' = ü, Na, K
Die Forschung zur Vermeidung dieser Schädigungen beschäftigt sich nahezu ausnahmslos mit einer hermetischen Versiegelung der zu schützenden Glasoberfläche mit Schichten, die gegen den alkalischen Angriff stabil sind. Häufig ist eine transparente Versiegelung wünschenswert, z.B. um die optischen Effekte des Substrats oder der darauf befindlichen Beschichtungen nicht zu beeinträchtigen oder um eine freie Sicht durch den Gegenstand zu gewährleisten.Research to avoid this damage deals almost exclusively with hermetic sealing of the glass surface to be protected with layers that are stable against the alkaline attack. A transparent seal is often desirable, e.g. in order not to impair the optical effects of the substrate or the coatings thereon or to ensure a clear view through the object.
Die meisten Schutzbeschichtungen, die bisher für solche Substrate vorgeschlagen worden sind, zeigen eine geringe Wärmebeständigkeit und/oder sie sind nicht transparent. Schutzbeschichtungen aus Polyethylen, Polystyrol oder Polypropylen zeigen eine gute Transparenz, sind aber auf Temperaturen bis maximal 150°C begrenzt, weswegen sie für viele Anwendungen ungeeignet sind. Auch Polyurethane und Polyester werden häufig verwendet, der Temperaturbereich, in dem sie eingesetzt werden können, ist aber ebenfalls begrenzt.Most protective coatings that have been proposed for such substrates have poor heat resistance and / or are not transparent. Protective coatings made of polyethylene, polystyrene or polypropylene show good transparency, but are limited to temperatures of up to 150 ° C, which is why they are unsuitable for many applications. Even polyurethanes and polyesters are widely used, but the temperature range in which they can be used is also limited.
Einige hochtemperaturbeständige Materialien wie Ti-besputterte BN-Schichten sind extrem beständig. Die Herstellung dieser Schichten ist jedoch technisch aufwendig und damit sehr teuer. Überdies sind sie nicht transparent und können nicht auf geometrisch anspruchsvolle Gläser appliziert werden.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.
Weitere gebräuchliche Methoden zum Schutz vor alkalischen Medien sind spezielle Glasmischungen, die z.B. B203, BaO, CaO und Al203 enthalten, oder synthetische Saphir-Gläser. Diese Gläser sind aber für Massenprodukte in der chemischen Industrie aufgrund ihres hohen Preises ebenfalls ungeeignet.Other common methods of protection against alkaline media are special glass mixtures which contain, for example, B 2 0 3 , BaO, CaO and Al 2 0 3 , or synthetic sapphire glasses. However, these glasses are also unsuitable for mass products in the chemical industry because of their high price.
In JP-A-2002036427, EP-A-1050603 und EP-A-696624 werden Beschichtungen aus Metalloxiden wie z.B. Zr02, Al203, Y203 und La203, die auch Ce02- und/oder Ti02- Zusätze enthalten können, als Schutz für Metalle und Metalllegierungen vor Korrosion beschrieben.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.
Die Aufgabe der vorliegenden Erfindung bestand darin, anorganische nichtmetallische Materialen vor dem Angriff durch alkalische Medien zu schützen. Die Schutzschicht sollte überdies eine hohe Wärmebeständigkeit aufweisen, stabil gegen UV-Licht sein und optische Effekte des Materials nicht beeinträchtigen. Außerdem sollte die Herstellung einfach und preiswert sein.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. In addition, the manufacture should be simple and inexpensive.
Überraschenderweise konnte dies durch eine Schutzschicht auf Basis von Titanoxid/Ceroxid erreicht werden, die erhältlich ist durch Aufbringen einer Titanoxid- und Ceroxid-Vorstufen umfassenden Beschichtungszusammensetzung auf ein Substrat mit einer Oberfläche aus einem anorganischen nichtmetallischen Matrixmaterial und Verdichten der Beschichtungszusammensetzung bei einer Temperatur von mindestens 500°C. Erstauniicherweise ergibt sich bei einer Verdichtung bei einer Temperatur von mindestens 500°C eine Schicht, deren Durchlässigkeit gegenüber alkalischen Medien stark eingeschränkt ist, so dass Alkali- und OH"-lonen das darunter liegende Substrat oder dessen Beschichtung nicht mehr angreifen können. Daher bietet die erfindungsgemäß verwendete Sperr- oder Schutzschicht einen ausgezeichneten Schutz für anorganische nichtmetallische Materialien, insbesondere Glas, Glaskeramik und Keramik, gegen Angriff durch alkalische Medien.Surprisingly, this could be achieved by 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.
Die alkalibeständige Schutzschicht ist ferner hochtemperaturbeständig, stabil gegen UV-Strahlung und transparent. Außerdem kann die Schutzschicht durch gängige nasschemische Beschichtungsverfahren, z.B. Sprühen oder Tauchen, in einem Schritt aufgebracht werden. Die Herstellung ist daher einfach und preisgünstig. Die Titanoxid/Ceroxid-Schicht eignet sich somit als alkalibeständige, hochtemperaturbeständige, UV-stabile und transparente Schutzschicht für anorganische nichtmetallische Materialien.The alkali-resistant protective layer is also resistant to high temperatures, stable against UV radiation and transparent. In addition, 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.
Das Substrat kann verschiedene Geometrien aufweisen. Ein Vorteil der Erfindung besteht darin, dass auch Gegenstände mit komplexeren Geometrien ohne weiteres beschichtet werden können. Das Substrat kann auch nur teilweise mit der Schutzschicht versehen werden. So besteht zum Beispiel die Möglichkeit, nur das Innere von Glasgefäßen zu beschichten.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.
Als Substrate kommen beschichtete oder unbeschichtete Substrate in Betracht, wobei ein Teil der Oberfläche oder die ganze Oberfläche aus einem anorganischen nichtmetallischen Matrixmaterial besteht. Bei beschichteten Substraten kann auch mehr als eine Schicht vorhanden sein. Sofern eine Beschichtung aus einem anorganischen nichtmetallischen Matrixmaterial vorliegt, kann das Substrat aus einem beliebigen anderen Material bestehen. Die anorganische Matrix kann gegebenenfalls auch organische Gruppen enthalten, z.B. Methylgruppen.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.
Bei den anorganischen nichtmetallischen Materialien für das Substrat selbst oder die Beschichtung handelt es sich z.B. um Glas, Glaskeramik oder Keramik. Dies schließt auch Oxidkeramik und Email ein. Unter Oxidkeramik wird gewöhnlich eine Keramik verstanden, die nicht auf Kieselsäure als Hauptbestandteil basiert. Aber auch Halbleiter, wie gegebenenfalls dotiertes Si oder Ge, sind als anorganische nichtmetallische Matrixmaterialien geeignet. Besonders bevorzugt sind Glassubstrate, wie z. B. Borosilicatglas, Natronkalkglas oder Kieselglas. Es kann sich um Flachglas, Hohlglas wie Behälterglas, oder um Laborgeräteglas handeln. Beispiele für Keramiken sind Keramiken auf Basis der Oxide Si02, Al203, Zr02 oder MgO oder der entsprechenden Mischoxide.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. However, 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. Examples of ceramics are ceramics based on the oxides Si0 2 , Al 2 0 3 , Zr0 2 or MgO or the corresponding mixed oxides.
Selbstverständlich können in der Matrix aus Glas, Glaskeramik oder Keramik zusätzliche Komponenten enthalten sein, die z.B. als Funktionsträger dienen. Die Matrix kann z.B. Pigmente oder Metallkolloide als farbgebende Komponenten enthalten. Substrate können eine Funktionsbeschichtung, z.B. aus Glas, Glaskeramik oder Keramik, aufweisen, die z.B. eine dekorative Wirkung hat oder elektrische Leitfähigkeit oder optoelektronische Effekte bewirkt. Die Substrate können z.B. mit Indium-Zinn-Oxid (ITO), Antimon-Zinn-Oxid (ATO) oder fluor-dotiertem Zinnoxid (FTO) beschichtet sein, um optoelektronische Effekte zu erzielen. Metalle können vor Aufbringen der Schutzschicht mit einer Glasschicht oder einem Email versehen werden. Ein Beispiel für eine derartige Si02-Beschichtung von Metalloberflächen ist in DE-A-19714949 beschrieben.Of course, 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.
Bei den anorganischen nichtmetallischen Materialien für das Substrat selbst oder die Beschichtung kann es sich gegebenenfalls auch um organisch modifizierte anorganische Polykondensate (z.B. hergestellt aus Tetraalkoxysilanen und Methyltri- alkoxysilanen) handeln, die meist glasartig sind. Bei diesen glasartigen Materialien handelt es sich um Gläser, die organische Gruppen im anorganischen Matrixgerüst enthalten können. Es ist bekannt, dass organische Gruppen wie Methyl gegebenenfalls auch bei den hohen Temperaturen, die für das Verdichten der Schutzschicht erforderlich sind, in der Matrix verbleiben können. Die alkalibeständige Schutzschicht wird bevorzugt unmittelbar auf Glas-, Glaskeramik- oder Keramiksubstrate, auf glasbeschichtete Metalle oder auf mit mindestens einer Funktionsschicht versehene Glassubstrate aufgebracht.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.
Zur Herstellung der Schutzschicht wird eine Titanoxid- und Ceroxid-Vorstufen umfassende Beschichtungszusammensetzung auf die Oberfläche des Substrats aufgebracht. Die Beschichtungszusammensetzung wird gewöhnlich aus Cer- und Titanverbindungen in einem Lösungsmittel erhalten, vorzugsweise nach dem sogenannten Sol-Gel-Verfahren. Bevorzugt werden mindestens ein Cersalz und mindestens eine hydrolysierbare Titanverbindung in einem Lösungsmittel nach dem Sol-Gel-Verfahren in die Titanoxid- und Ceroxid-Vorstufen, gewöhnlich in Form eines Sols, überführt.To produce the protective 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.
Beim Sol-Gel-Verfahren werden gewöhnlich hydrolysierbare Verbindungen mit Wasser, gegebenenfalls unter saurer oder basischer Katalyse, hydrolysiert und gegebenenfalls zumindest teilweise kondensiert. Dabei wird hier auch die Reaktion der Cersalze mit Wasser als Hydrolyse angesehen. Die Hydrolyse- und/oder Kondensationsreaktionen führen zur Bildung von Verbindungen oder Kondensaten mit Hydroxy-, Oxogruppen und/oder Oxobrücken, die als Titanoxid- und Ceroxid-Vorstufen dienen, wobei diese Vorstufen auch aus Kondensaten bestehen können, die beide Elemente (Ce, Ti) enthalten. Es können stöchiometrische Wassermengen, aber auch geringere oder größere Mengen verwendet werden. Das sich bildende Sol kann durch geeignete Parameter, z.B. Kondensationsgrad, Lösungsmittel oder pH- Wert, auf die für die Beschichtungszusammensetzung gewünschte Viskosität eingestellt werden. Weitere Einzelheiten des Sol-Gel-Verfahrens sind z.B. bei C.J. Brinker, G.W. Scherer: "Sol-Gel Science - The Physics and Chemistry of Sol-Gel- Processing", Academic Press, Boston, San Diego, New York, Sydney (1990) beschrieben.In the sol-gel process, 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. Degree of condensation, solvent or pH, are adjusted to the viscosity desired for the coating composition. Further details of the sol-gel process are e.g. at C.J. Brinker, G.W. Scherer: "Sol-Gel Science - The Physics and Chemistry of Sol-Gel-Processing", Academic Press, Boston, San Diego, New York, Sydney (1990).
Als Cerverbindungen werden bevorzugt in Alkohol lösliche Verbindungen, insbesondere Cer(lll)-Salze, eingesetzt. Cer(lll)-Salze, die sich bei Raumtemperatur in einem Alkohol lösen, sind z.B. das Nitrat und das Chlorid, wobei das Nitrat besonders bevorzugt wird. Erfindungsgemäß ist es auch bevorzugt, ein Kristallwasser-haltiges Cer(lll)-Salz (wie z.B. Cernitrat-hexahydrat) einzusetzen, so dass zumindest ein Teil des Wassers (vorzugsweise das gesamte Wasser), das im Verfahren eingesetzt wird, durch dieses Kristallwasser bereitgestellt wird.Alcohol-soluble compounds, in particular 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. According to the invention, it is also preferred to use a cerium (III) salt containing water of crystallization (such as, for example, cerium nitrate hexahydrate), so that at least some of the water (preferably all of the water) used in the process is provided by this water of crystallization ,
Bei der Titanverbindung handelt es sich insbesondere um eine hydrolysierbare Verbindung der Formel TiX4, wobei die hydrolysierbaren Gruppen X beispielsweise Wasserstoff, Halogen (F, Cl, Br oder I, insbesondere Cl und Br), Alkoxy (vorzugsweise C^-Alkoxy, insbesondere C^-Alkoxy, wie z.B. Methoxy, Ethoxy, n-Propoxy, i- Propoxy, Butoxy, i-Butoxy, sek.-Butoxy und tert.-Butoxy), Aryloxy (vorzugsweise C6.10-Aryloxy, wie z.B. Phenoxy), Acyloxy (vorzugsweise C^-Acyloxy, wie z.B. Acetoxy oder Propionyloxy) oder Alkylcarbonyl (vorzugsweise C2.7-Alkylcarbonyl, wie z.B. Acetyl) sind. Bevorzugte hydrolysierbare Reste sind Alkoxygruppen, insbesondere C^-Alkoxy. Konkrete und bevorzugt eingesetzte Titanate sind Ti(OCH3)4, Ti(OC2H5)4 und Ti(n- oder i-OC3H7)4.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. 7 alkylcarbonyl, such as acetyl), respectively. 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 .
Als Lösungsmittel wird insbesondere ein organisches Lösungsmittel verwendet, in dem die eingesetzten Cer- und Titanverbindungen löslich sind. Am zweckmäßigsten werden Alkohole verwendet, vorzugsweise ein Alkohol mit 1 bis 4 Kohlenstoffatomen, wie z.B. Methanol, Ethanol, Propanol und Isopropanol, oder eine Mischung davon.In particular, an organic solvent in which the cerium and titanium compounds used are soluble is used as the solvent. Most conveniently alcohols are used, preferably an alcohol having 1 to 4 carbon atoms, e.g. Methanol, ethanol, propanol and isopropanol, or a mixture thereof.
Nach Zugabe der Titan- und Cerverbindungen in das Lösungsmittel wird die resultierende Lösung in Anwesenheit von Wasser z.B. unter Rückfluss, bei Raumtemperatur (etwa 20°C) oder bei leicht erhöhter Temperatur über einen von der Temperatur abhängigen Zeitraum, z.B. 1 min bis mehrere Tage (z.B. bis zu 8 Tage), gerührt, um die Titanoxid- und Ceroxid-Vorstufen umfassende Beschichtungszusammensetzung, insbesondere in Form eines Sols, zu erhalten. Die Behandlung kann z.B. 1 min bis 24 Stunden unter Rückfluss oder über 10 h bis 5 Tage bei 30°C erfolgen. Die Mengen der Titan- und Cer-Ausgangsverbindungen werden bevorzugt so gewählt, dass das molare Verhältnis, bezogen auf Ti: Ce, 1 :2 bis 2:1 beträgt.After the titanium and cerium compounds have been added to the solvent, 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.
Es kann z.B. so vorgegangen werden, daß Sole durch Auflösung von Cer(lll)-Salz (z.B. Cer(lll)nitrat-hexahydrat) in einem kurzkettigen Alkohol in Konzentrationen von 0,05 bis 0,5 Mol pro Liter, vorzugsweise 0,2 bis 0,3 Mol pro Liter, portionierte Zugabe eines Titantetraalkoxids in Konzentrationen von 0,05 bis 0,5 Mol pro Liter, vorzugsweise 0,2 bis 0,3 Mol pro Liter, und Erhitzen der klaren Lösung unter Rückfluss oder bei leicht erhöhter Temperatur (25 bis 40°C) für eine bestimmte Zeit erzeugt werden. Dabei erfolgt eine Vorhydrolyse und/oder -kondensation unter Bildung eines Sols und Zunahme der Viskosität. Diese Sole sind, insbesondere bei Aufbewahrung bei Temperaturen um -20°C, über mehrere Wochen haltbar.For example, so that brine by dissolving cerium (III) salt (eg cerium (III) nitrate hexahydrate) in a short-chain alcohol in concentrations of 0.05 to 0.5 mol per liter, preferably 0.2 to 0, 3 mol per liter, portioned addition of a titanium tetraalkoxide in concentrations of 0.05 to 0.5 mol per liter, preferably 0.2 to 0.3 mol per liter, and heating the clear solution under reflux or at a slightly elevated temperature (25 to 40 ° C) can be generated for a certain time. 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.
Die Beschichtungszusammensetzung kann gegebenenfalls weitere Komponenten enthalten, z. B. hydrolysierbare Verbindungen oder Salze anderer Elemente für die Matrix oder andere Zusätze wie Sinterhilfsmittel. Bei den hydrolysierbaren Verbindungen von anderen Elementen, die gegebenenfalls in die Oxidmatrix eingebaut werden können, handelt es sich insbesondere um Verbindungen von glas- oder keramikbildenden Elementen, z.B. Verbindungen mindestens eines Elements M aus den Hauptgruppen IM bis V und/oder den Nebengruppen II bis IV des Periodensystems der Elemente. Dies können hydrolysierbare Verbindungen von Si, AI, B, Sn, Ti, Zr, V oder Zn sein. Auch andere hydrolysierbare Verbindungen können eingesetzt werden, wie solche von Elementen der Hauptgruppen I und II des Periodensystems (z.B. Na, K, Ca und Mg) und der Nebengruppen V bis VIII des Periodensystems (z.B. Mn, Cr, Fe und Ni) oder hydrolysierbare Verbindungen anderer Lanthaniden. Im allgemeinen machen solche andere Komponenten aber, bezogen auf den Feststoffgehalt der fertigen Schutzschicht, nicht mehr als 20 Gew.-%, bevorzugt nicht mehr als 5 Gew.-% und insbesondere nicht mehr als 2 Gew.-% aus. Besonders bevorzugt wird die Schutzschicht aber, abgesehen von möglichen Verunreinigungen (unter 1 Gew.-%), nur aus dem Titanoxid/Ceroxid gebildet. Die Beschichtungszusammensetzung wird, nachdem gegebenenfalls die Viskosität durch Zugabe oder Entfernen von Lösungsmittel eingestellt wurde, mit den üblichen Beschichtungsverfahren auf die zu beschichtenden Substrate aufgebracht. Die Beschichtung kann z.B. durch Sprühen, Tauchen, Aufstreichen oder Schleuderbeschichten erfolgen.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. Other 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. In general, however, 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. However, apart from possible impurities (below 1% 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.
Nach erfolgter Beschichtung werden die Substrate im allgemeinen bei Raumtemperatur oder erhöhter Temperatur (beispielsweise bis zu 100 °C) getrocknet. Daran schließt sich eine Verdichtung der aufgebrachten Schicht bei Temperaturen im Bereich von 500 °C bis kurz unter den Erweichungspunkt des Substrat- bzw. des Beschichtungsmaterials an. Vorzugsweise werden Temperaturen knapp unterhalb des Erweichungspunktes des zu beschichtenden Materials (Tg des Glases) gewählt, der naturgemäß von der Art des Substrats bzw. der Beschichtung abhängt. Die Beschichtungszusammensetzung kann trotz der eventuell vorhandenen organischen Bestandteile zu rissfreien, transparenten und homogenen Beschichtungen verdichtet werden.After 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.
Die Wärmebehandlung zum Verdichten kann z.B. im Ofen, mittels IR-Bestrahlung oder durch Beflammen erfolgen. Durch die Wärmebehandlung wird die Schutzschicht getempert.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.
Es wird eine Matrix aus Oxiden bzw. Mischoxiden (Doppeloxiden) von Titan und Cer (TiOj/CeO;,) erhalten, hier als Titanoxid/Ceroxid bezeichnet, wobei die Stöchiometrie vom molaren Verhältnis der eingesetzten Ausgangsverbindungen abhängt. Die erhaltene Schutzschicht bietet einen außerordentlich guten Schutz gegen einen Angriff durch alkalische Medien.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.
Die folgenden Beispiele erläutern die Erfindung. Beispie! 1The following examples illustrate the invention. Step Example! 1
48,85 g Cer(lll)nitrat-hexahydrat werden in 450 ml abs. Ethanol gelöst. Nach Zugabe von 32,00 g Tetraisopropylorthotitanat wird das Gemisch 1 h unter Rückfluß gekocht. Das so hergestellte Sol kann eisgekühlt mehrere Wochen gelagert werden. Das Beschichtungssol wird mittels Tauchbeschichtung (z. B. mit 4 mm/s) auf eine zuvor intensiv gereinigte Natronkalkscheibe appliziert, bei 100°C getrocknet und bei 500°C verdichtet.48.85 g of cerium (III) nitrate hexahydrate are dissolved in 450 ml of abs. Ethanol dissolved. After adding 32.00 g of tetraisopropyl orthotitanate, the mixture is boiled under reflux for 1 h. The sol produced in this way can be stored ice-cooled for several weeks. The coating sol is applied by means of dip coating (e.g. at 4 mm / s) to a previously intensively cleaned soda lime slice, dried at 100 ° C and compressed at 500 ° C.
Beispiel 2Example 2
48,85 g Cer(lll)nitrat-hexahydrat werden in 450 ml abs. Ethanol gelöst. Nach Zugabe von 32,00 g Tetraisopropylorthotitanat wird das Gemisch 4 d bei 30 °C gerührt. Das so hergestellte Sol kann eisgekühlt mehrere Wochen gelagert werden. Als Substrat wird ein Laborreaktor aus Borosilicatglas verwendet, der einen ITO-Primer als Beschichtung aufweist. Das Beschichtungssol wird mittels Sprühbeschichtung (z. B. mit einer kommerziell erhältlichen Lackierpistole) auf den Laborreaktor aufgebracht, bei 100 °C getrocknet und bei 600 °C verdichtet.48.85 g of cerium (III) nitrate hexahydrate are dissolved in 450 ml of abs. Ethanol dissolved. After adding 32.00 g of tetraisopropyl orthotitanate, the mixture is stirred at 30 ° C. for 4 d. The sol produced in this way can be stored ice-cooled for several weeks. A laboratory reactor made of borosilicate glass is used as the substrate, which has an ITO primer as a coating. The coating sol is applied to the laboratory reactor by means of spray coating (for example using a commercially available spray gun), dried at 100 ° C. and compressed at 600 ° C.
Durch die Beschichtung konnte eine außerordentliche Alkalibeständigkeit erzielt werden. So konnte eine 30%ige Natronlauge 500 h in dem so beschichteten Reaktor auf 80°C erwärmt werden, ohne dass eine Schädigung des Reaktors zu beobachten war. 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.

Claims

PATENTANSPRÜCHE
1. Mit einer alkalibeständigen Schutzschicht auf Basis von Titanoxid/Ceroxid versehenes Substrat mit einer Oberfläche aus einem anorganischen nicht- metallischen Matrixmaterial, erhältlich durch Aufbringen einer Titanoxid- und Ceroxid-Vorstufen umfassenden Beschichtungszusammensetzung auf die Oberfläche des Substrats und Verdichten der Beschichtungszusammensetzung bei einer Temperatur von mindestens 500°C.1. Provided with an alkali-resistant protective layer based on titanium oxide / cerium oxide with a surface made of an inorganic non-metallic matrix material, obtainable by applying a coating composition comprising titanium oxide and cerium oxide precursors to the surface of the substrate and compacting the coating composition at a temperature of at least 500 ° C.
2. Mit einer alkalibeständigen Schutzschicht versehenes Substrat nach Anspruch 1 , dadurch gekennzeichnet, dass das gesamte Substrat, eine Oberfläche des Substrats oder einer Beschichtung auf dem Substrat aus dem anorganischen nicht-metallischen Matrixmaterial gebildet sind.2. Provided with an alkali-resistant protective layer according to claim 1, characterized in that the entire substrate, a surface of the substrate or a coating on the substrate are formed from the inorganic non-metallic matrix material.
3. Mit einer alkalibeständigen Schutzschicht versehenes Substrat nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass das anorganische nicht-metallische Matrixmaterial ausgewählt ist aus Glas, Glaskeramik oder Keramik, einschließlich Oxidkeramik.3. Provided with an alkali-resistant protective layer according to claim 1 or 2, characterized in that the inorganic non-metallic matrix material is selected from glass, glass ceramic or ceramic, including oxide ceramic.
4. Mit einer alkalibeständigen Schutzschicht versehenes Substrat nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die Schutzschicht auf ein Glas-, Glaskeramik- oder Keramiksubstrat, ein mit mindestens einer Funktionsschicht beschichtetes Glas-, Glaskeramik- oder Keramiksubstrat oder ein mit einer Glas-, Glaskeramik- oder Keramikschicht beschichtetes Metall aufgebracht ist.4. Provided with an alkali-resistant protective layer according to one of claims 1 to 3, characterized in that the protective layer on a glass, glass ceramic or ceramic substrate, a glass, glass ceramic or ceramic substrate coated with at least one functional layer or a with a glass -, Glass ceramic or ceramic layer coated metal is applied.
5. Mit einer alkalibeständigen Schutzschicht versehenes Substrat nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass das anorganische Matrixmaterial durch organische Gruppen modifiziert ist. 5. Provided with an alkali-resistant protective layer according to one of claims 1 to 4, characterized in that the inorganic matrix material is modified by organic groups.
6. Mit einer alkalibeständigen Schutzschicht versehenes Substrat nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass die Schutzschicht transparent ist.6. Provided with an alkali-resistant protective layer according to one of claims 1 to 5, characterized in that the protective layer is transparent.
7. Mit einer alkalibeständigen Schutzschicht versehenes Substrat nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass die Schutzschicht im wesentlichen aus Titanoxid/Ceroxid besteht.7. Provided with an alkali-resistant protective layer according to one of claims 1 to 6, characterized in that the protective layer consists essentially of titanium oxide / cerium oxide.
8. Mit einer alkalibeständigen Schutzschicht versehenes Substrat nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass die aufgebrachte Beschichtungszusammensetzung vor dem Verdichten zur Entfernung des Lösungsmittels getrocknet wird.8. Provided with an alkali-resistant protective layer according to any one of claims 1 to 7, characterized in that the applied coating composition is dried before compaction to remove the solvent.
9. Mit einer alkalibeständigen Schutzschicht versehenes Substrat nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass das molare Verhältnis von Ti:Ce in der Beschichtungszusammensetzung im Bereich von 2:1 bis 1 :2 liegt.9. Provided with an alkali-resistant protective layer according to one of claims 1 to 8, characterized in that the molar ratio of Ti: Ce in the coating composition is in the range from 2: 1 to 1: 2.
10. Mit einer alkalibeständigen Schutzschicht versehenes Substrat nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass die Titanoxid- und Ceroxid- Vorstufen umfassende Beschichtungszusammensetzung aus mindestens einem Cersalz und mindestens einer hydrolysierbaren Titanverbindung in einem Lösungsmittel nach dem Sol-Gel-Verfahren unter Bildung eines Sols erhalten wird.10. Provided with an alkali-resistant protective layer according to one of claims 1 to 9, characterized in that the titanium oxide and cerium oxide precursors comprising coating composition of at least one cerium salt and at least one hydrolyzable titanium compound in a solvent by the sol-gel process with formation of a sol.
11. Mit einer alkalibeständigen Schutzschicht versehenes Substrat nach Anspruch 10, dadurch gekennzeichnet, dass die hydrolysierbare Titanverbindung eine Tetraalkoxytitanverbindung ist. 11. Provided with an alkali-resistant protective layer according to claim 10, characterized in that the hydrolyzable titanium compound is a tetraalkoxy titanium compound.
EP03755136A 2002-05-27 2003-05-26 Substrate comprising a titanium oxide/cerium oxide protective layer Withdrawn EP1507746A2 (en)

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DE2002123531 DE10223531A1 (en) 2002-05-27 2002-05-27 Substrate with a titanium oxide / cerium oxide protective layer
DE10223531 2002-05-27
PCT/EP2003/005502 WO2003099735A2 (en) 2002-05-27 2003-05-26 Substrate comprising a titanium oxide/cerium oxide protective layer

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DE102005018246A1 (en) 2005-04-19 2006-10-26 Schott Ag Glass or glass ceramic articles with decorative coating
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 (en) 2008-12-16 2021-04-08 Schott Ag Process for the production of a hollow molded glass body
AR100953A1 (en) 2014-02-19 2016-11-16 Tenaris Connections Bv THREADED PIPE FOR AN OIL WELL PIPING
GB2614722A (en) * 2022-01-13 2023-07-19 Pilkington Group Ltd Corrosion-resistant and/or cleanable coated glass substrate

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