EP2162565A2 - Ultraharte kompositschichten auf metalloberflächen und verfahren zu ihrer herstellung - Google Patents
Ultraharte kompositschichten auf metalloberflächen und verfahren zu ihrer herstellungInfo
- Publication number
- EP2162565A2 EP2162565A2 EP08774318A EP08774318A EP2162565A2 EP 2162565 A2 EP2162565 A2 EP 2162565A2 EP 08774318 A EP08774318 A EP 08774318A EP 08774318 A EP08774318 A EP 08774318A EP 2162565 A2 EP2162565 A2 EP 2162565A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- composite layer
- metal substrate
- ultra
- filler
- abrasive
- 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
Classifications
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- 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
- C23C18/1279—Process of deposition of the inorganic material performed under reactive atmosphere, e.g. oxidising or reducing atmospheres
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- 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
- C23C18/1212—Zeolites, glasses
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- 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
- C23C18/1225—Deposition of multilayers of inorganic material
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- 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
- C23C18/1241—Metallic substrates
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- 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
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- 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
- C23C18/1262—Process of deposition of the inorganic material involving particles, e.g. carbon nanotubes [CNT], flakes
- C23C18/1266—Particles formed in situ
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- 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
- C23C18/1275—Process of deposition of the inorganic material performed under inert atmosphere
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
- Y10T428/24372—Particulate matter
- Y10T428/2438—Coated
- Y10T428/24388—Silicon containing coating
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/252—Glass or ceramic [i.e., fired or glazed clay, cement, etc.] [porcelain, quartz, etc.]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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- Y10T428/256—Heavy metal or aluminum or compound thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T428/258—Alkali metal or alkaline earth metal or compound thereof
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- Y10T428/259—Silicic material
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- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
- Y10T428/264—Up to 3 mils
- Y10T428/265—1 mil or less
Definitions
- Metal surfaces with the exception of hard metals or specially hardened metals, are generally relatively soft compared to ceramic materials. Therefore, they are very sensitive to abrasive media or scouring agents. This means that metal surfaces, especially when they are polished, are very sensitive to cleaning agents, steel wool, but also other scratching objects such. As zippers or paper clips are. The metal surfaces then very quickly lose their noble-looking surface and become dull and unsightly.
- hardened metal surfaces are also important in other areas.
- chromium-hardened steel surfaces are used in mechanical engineering and in the automotive industry to produce B. pistons or piston rods, cylinder liners and many other, standing under wear surfaces to harden in order to avoid or reduce wear and so extend the life.
- the surfaces are hardened by nitriding or carbonization to produce nitrides or carbides by the diffusion of nitrogen or carbon on the surface.
- CVD processes eg TiN, ZrN, glassy carbon
- hard coatings can be applied to surfaces.
- these layers are very thin and the associated methods are only conditionally suitable for large surfaces and / or complex geometries.
- CVD processes can only produce a very limited amount of colors.
- PVD processes are also used for surface layers, but as a rule these layers are mechanically and chemically not very stable due to the mostly columnar growth. Ceramic layers can be applied to metal surfaces by flame or plasma spraying. These layers are up to several 100 microns thick, usually very abrasion resistant, but not transparent and very brittle and usually not thermally shock resistant.
- Thin, transparent coatings based on sol-gel systems and nanoscale systems can be produced by wet coating techniques.
- DE-A-102004001097 (corresponding to WO-A-2005066388) describes a coating technology with which only a few ⁇ m thin layers on metal surfaces can be obtained. Despite these small thicknesses, the layers are very resistant to abrasion and, for example, can not be scratched with corundum scouring sponges. However, they can be massively damaged during long-term use of grinding and abrasion bodies based on corundum or silicon carbide.
- the object was therefore to provide a transparent, translucent or colored coating system for metal surfaces, which does not have the above-mentioned defects.
- it should have an extremely high abrasion resistance compared to the systems mentioned and can be applied by a wet-chemical coating method.
- it should be possible to impart any coloration to the metal substrate in addition to the formation of an ultra-hard protective layer.
- the object could be achieved by applying a coating composition comprising precursors for an inorganic, glassy matrix and fine, highly abrasion-resistant fillers to a metal surface of a substrate and thermally compacting it, the particle size of the abrasive fillers used being smaller than the one obtained Layer thickness of the layer obtained.
- the invention therefore relates to a metal substrate having an ultrahard composite layer of an inorganic, glassy matrix which comprises one or more abrasive fillers, wherein the diameter of the filler particles or, in the case of a platelet-shaped geometry of the filler particles, the thickness of the filler particles is smaller than the layer thickness of the composite layer, and a method for producing these composite layer coated metal substrates.
- these composite layers are characterized by enormously high scratch and abrasion resistance, so that one can speak of ultra-hard layers.
- the composite layer can be wet-chemically applied, manufacturing is easy and economical, and metal substrates of complex geometry can be provided with the composite layer.
- the composite layer can be made transparent and interlayers can be interposed between the metal substrate and the composite layer, color effects can be generated as needed by incorporating appropriate colorants in the composite layer itself or in an intermediate layer.
- the layers can be very thin.
- Suitable metal substrates to be coated according to the invention or metallic surfaces to be coated are all surfaces or surfaces comprising a metal or a metal alloy, eg substrates of another material provided with a metal layer on at least one surface.
- Metal always includes metal alloys in this application.
- the metal substrate can be, for example, semi-finished products such as plates, sheets, tubes, rods or wires, components or finished products.
- the metal substrate can be completely provided on the metal surface with the composite layer.
- suitable metals for the metal substrate are aluminum, titanium, tin, zinc, copper, chromium or nickel, including galvanized, chrome-plated or enamelled surfaces.
- suitable metal alloys are in particular steel or stainless steel, aluminum, magnesium and copper alloys such as brass and bronze. Particular preference is given to using metallic surfaces made of steel, stainless steel, galvanized, chromium-plated or enamelled steel or titanium.
- the metallic surface or the metallic substrate may have a planar or a structured surface.
- the geometry of the metal substrate may be simple, e.g. a simple sheet, but also complex, e.g. with edges, curves, elevations or depressions, be.
- the metallic surface is cleaned prior to application of the coating composition and freed of grease and dust.
- a surface treatment e.g. by corona discharge.
- the cured composite layer comprises an inorganic, glassy matrix containing one or more abrasive fillers.
- the layer is therefore a composite of the matrix and the filler, preferably a filler of hard material.
- the filler is made of an abrasive material, in particular a highly abrasion-resistant or highly abrasive material. Such materials are known to the person skilled in the art and are used, for example, as abrasives.
- the abrasive fillers used preferably have a Mohs hardness of at least 7 and more preferably> 7 based on the Mohs hardness scale.
- the one or more abrasive fillers used are preferably fillers of a hard material. Hard materials are generally known to the person skilled in the art, are commercially available and are used, for example, in the hard metal and abrasive industry.
- abrasive materials or hard materials suitable for the present invention can be found, for example, in Ullmanns Encyclopadie der ischen Chemie, 4th ed., Vol and abrasives ", pp. 449-455, and vol. 12," Hartstoffe (Einannon) ", pp. 523-524, Verlag Chemie, Weinheim New York, 1976.
- Abrasive materials in particular hard materials are characterized by their high hardness. Many different materials are known as abrasive or hard materials, especially as abrasives, all of which are useful for the purposes of the present invention. It can metallic or non-metallic abrasive fillers or hard materials are used, non-metallic are preferred. In a preferred embodiment, transparent abrasive fillers are used. An abrasive filler or mixtures of two or more abrasive fillers may be used. Mixtures of abrasive filler of the same material, e.g. in size and / or particle shape, can be used, of course also optionally with abrasive fillers of other materials.
- hard materials are carbides, nitrides, borides, oxycarbides or oxynitrides of transition metals or semimetals, such as Si, Ti, Ta, W and Mo, eg TiC, WC, TiN, TaN, TiB 2 , MoSi 2 , hard material mixed crystals, such as TiC-WC or TiC-TiN, double carbides and complex carbides, such as C03W3C and Ni 3 W 3 C, and intermetallic compounds, for example from the systems W-Co or Mo-Be, natural or synthetic diamond, corundum (Al 2 O 3 ), such as emery, fused corundum or sintered corundum, natural or synthetic gemstones such as sapphire, ruby or zirconium, boron, cubic boron nitride, boron carbide (B 4 C), silicon carbide (SiC) and silicon nitride (Si 3 N 4 ), quartz, glass or glass powder.
- abrasion-resistant fill
- hard materials are carbides, nitrides or borides of transition metals, natural or synthetic diamond, corundum and platelet corundum, natural or synthetic gemstones, boron, boron nitride, boron carbide, silicon carbide, silicon nitride and aluminum nitride, the non-metallic ones being preferred.
- Particularly suitable hard materials are corundum, silicon carbide and tungsten carbide.
- the amount of abrasive filler used in the composite layer may vary widely depending on the application.
- the proportion of abrasive fillers in the composite layer in the range of 1 to 10 wt .-%, preferably 1 to 5 wt .-% and particularly preferably 1, 5 to 3 wt .-% , based on the total weight of the finished composite layer.
- the fillers are particles.
- the particles can have any shape. You can e.g. be spherical, block-shaped or platelet-shaped. It is known to those skilled in the art that the particles can often have a more or less irregular shape, e.g. if they are available as aggregates. If there are no preferred directions, the shape of a sphere is often assumed to determine the size. In platelet or flaky particles are two preferred directions.
- At least one abrasive filler has a platelet-shaped geometry, an example being platelet-shaped corundum.
- the weight ratio of platelet-shaped abrasive filler to non-platelet abrasive fillers in the layer is preferably in the range of 1 to 10, more preferably 1 to 5 to 5, and more preferably 2 to 3.
- the finished composite layer after thermal densification can have, for example, a layer thickness of up to 20 ⁇ m, preferably up to 10 ⁇ m and particularly preferably up to 4 ⁇ m, without crack formation occurring during drying and compaction.
- the layer thickness is at least 1 ⁇ m, preferably at least 2 ⁇ m.
- the layer thickness of the composite layer may be, for example, in the range of 3 to 8 ⁇ m.
- the particle size of the hard material fillers used is smaller than the layer thickness of the composite layer obtained after thermal densification.
- the particle size is significantly smaller than the layer thickness of the composite layer, eg the particle size is at least 2 times smaller and preferably at least 5 times smaller (ie the particle size is preferably less than 14, more preferably less than 1/5 of the layer thickness).
- the particle size refers to the diameter for non-platelet-shaped particles, ie in particular particles without preferred directions.
- the diameter is understood to mean the average particle diameter, based on the volume average (d 5 o value). This value can be determined eg by laser optics with dynamic laser light scattering, eg with an UPA (Ultrafine Particle Analyzer, Leeds Northrup).
- the relevant particle size is not the diameter of the particles, but the thickness of the platelets.
- the thickness of the platelets must be smaller, preferably significantly smaller than the layer thickness of the composite layer.
- the relative to the two preferred directions diameter is not significant and may even be greater than the layer thickness. Since the thickness of platelets is inherently significantly smaller than the diameter, platelets with a relatively large diameter can thus be used.
- the particle sizes of platelet-shaped particles can be determined, for example, by means of optical microscopy by optical image analysis. Since they are platelet-shaped particles, diameter refers to the lateral diameter or the equivalent diameter of the projection-equivalent circle in a stable particle position. Thickness and diameter here also mean the average thickness or the mean diameter in relation to the volume average (d 5 o value). Since platelet-shaped abrasive fillers, such as platelet-shaped corundum, show particularly good results, the use of at least one platelet-shaped abrasive filler, in particular of hard material, is preferred.
- the thickness of the platelets is preferably less than 1 ⁇ m.
- Platelet-shaped fillers are preferably used with a thickness of 0.100 to 0.3 microns, wherein the diameter may be about 3 to 10 microns. Particularly preferably used platelet-shaped fillers have a thickness in the range of about 0.2 microns and a platelet diameter in the range of about 3 to 7 microns. Then very smooth surfaces are achieved in layers of a few microns thick.
- the composite layer comprises an inorganic, glassy matrix.
- the matrix preferably comprises an alkaline earth and / or alkali silicate.
- the preparation of such inorganic, glassy matrices or alkaline earth and / or alkali metal silicate-containing matrices is known to the person skilled in the art. Particularly preferred is a matrix which is prepared by the process and with the materials as described in DE-A-102004001097.
- a coating composition comprising a hydrolyzate or condensate of a hydrolyzable compound as a glass-forming matrix precursor and one or more abrasive fillers, preferably a hard material, is applied to a metal substrate and thermally densified to form the composite layer, the diameter of the filler particles or, in the case of platelet-shaped geometry of the filler particles, the thickness of the filler particles in the coating composition is smaller than the layer thickness of the composite layer. That is, the composite layer is applied wet-chemically.
- the hydrolyzate or condensate of hydrolyzable compounds is preferably a coating suspension or solution, more preferably a coating sol, which are preferably prepared by the sol-gel process or similar hydrolysis and condensation processes.
- the hydrolyzable compounds preferably comprise at least one organically modified hydrolyzable silane.
- the hydrolyzate or condensate is particularly preferably an alkali or alkaline earth silicate-containing coating suspension or solution, and preferably a coating sol containing alkaline earth or alkali silicate.
- a coating composition is preferably used which is obtained by hydrolysis and condensation of at least one organically modified hydrolyzable silane in the presence of alkali metal or alkaline earth metal oxides or hydroxides and optionally nanoscale SiO 2 particles.
- Such a coating composition is e.g. obtainable by hydrolysis and condensation of one or more silanes of the general formula (I)
- silanes of the formula (I) is at least one silane, in whose general formula n has the value 1 or 2.
- these silanes are preferably used in such a ratio that the average value of n (on a molar basis) is 0.2 to 1.5, preferably 0.5 to 1.0.
- Particularly preferred is an average value of n in the range of 0.6 to 0.8.
- the groups X which are the same or different from each other are hydrolyzable groups or hydroxyl groups.
- hydrolyzable groups X are halogen atoms (especially chlorine and bromine), alkoxy groups and acyloxy groups of up to 6 carbon atoms.
- alkoxy groups especially Ci -4 -Al koxy phenomenon as methoxy, ethoxy, n-propoxy and i-propoxy.
- the groups X are preferably identical in a silane, particular preference being given to using methoxy and in particular ethoxy groups.
- the groups may have conventional substituents, but preferably such groups do not bear a substituent.
- Preferred groups R are alkyl groups having 1 to 4 carbon atoms, especially methyl and ethyl, as well as phenyl.
- At least one alkyltrialkoxysilane of the formula (I) is preferably used, in particular methyltriethoxysilane (MTEOS), methylthmethoxysilane, ethylthmethoxysilane and ethylthethoxysilane.
- MTEOS methyltriethoxysilane
- TEOS tetraethoxysilane
- tetramethoxysilane tetramethoxysilane
- silane mixtures include, for example, at least one alkyltrialkoxysilane (eg, (M) ethyltri (m) ethoxysilane) and a tetraalkoxysilane (eg, tetra (m) ethoxysilane), which are preferably used in such a ratio that the average value of n in the preferred ranges given above.
- alkyltrialkoxysilane eg, (M) ethyltri (m) ethoxysilane
- tetraalkoxysilane eg, tetra (m) ethoxysilane
- a particularly preferred combination for the starting silanes of the formula (I) is methyltri (m) ethoxysilane and tetra (m) ethoxysilane.
- (M) ethoxy and (M) ethyl mean methoxy or ethoxy or methyl or ethyl.
- the hydrolysis and condensation or polycondensation of the silane (s) of the formula (I) is carried out in the presence of at least one compound from the group of oxides and hydroxides of the alkali metals and alkaline earth metals. These oxides and hydroxides are preferably those of Li, Na, K, Mg, Ca and / or Ba.
- Examples are Li 2 O, LiOH, Na 2 O, NaOH, KOH, Mg (OH) 2 , CaO, Ca (OH) 2 , CaO, Ca (OH) 2 , BaO and Ba (OH) 2 , the hydroxides being preferred are.
- an alkali metal oxide or hydroxide this is preferably used in an amount such that the atomic ratio Si: alkali metal in the range of 20: 1 to 7: 1, in particular from 15: 1 to 10: 1, wherein the Si Proportion of nanoscale SiO 2 particles, if used, is taken into account.
- the atomic ratio of silicon to alkaline earth metal and / or alkali metal is chosen so large that the resulting coating is not water-soluble (as in the case of water glass, for example).
- the nanoscale SiO 2 particles used in addition to the hydrolyzable silanes of the general formula (I) are preferably used in such an amount that the ratio of all Si atoms in the silanes of the general formula (I) to all Si atoms in the nanoscale SiO 2 particles in the range of 5: 1 to 1: 2, in particular 3: 1 to 1: 1, is located.
- Nanoscale SiO 2 particles are understood as meaning SiO 2 particles having an average particle diameter, based on the volume average (d 5 o value) of preferably not more than 100 nm, more preferably not more than 50 nm and in particular not more than 30 nm.
- the size can be determined by laser optics as described above for the fillers.
- Commercially available silicic acid products for example silica sols, such as the Levasils®, silica sols from Bayer AG, or fumed silicas, for example Aerosil products from Degussa, can also be used for this purpose.
- the particulate materials may be in the form of powders and sols be added. However, they can also be formed in situ during the hydrolysis and polycondensation of the silanes.
- one or more additional hydrolyzable compounds that do not contain silicon may be added.
- the compound is preferably a boron or metal compound.
- the metal or boron is incorporated into the matrix.
- the hydrolyzable compound preferably has the general formula (II)
- Such compounds are compounds of glass- or ceramic-forming elements, in particular compounds of at least one element M from the main groups III to V and / or the subgroups II to IV of the Periodic Table of the Elements.
- These are preferably hydrolyzable compounds of Al, B, Sn, Ti, Zr, V or Zn, in particular those of Al, Ti or Zr, or mixtures of two or more of these elements.
- hydrolyzable compounds of elements of main groups I and II of the Periodic Table e.g., Na, K, Ca, and Mg
- subgroups V to VIII of the Periodic Table e.g., Mn, Cr, Fe, and Ni
- hydrolyzable compounds of lanthanides such as Ce can be used. Preference is given to hydrolyzable compounds of the elements B, Ti, Zr and Al, with Ti being particularly preferred.
- Preferred compounds are, for. B. the alkoxides of B, Al, Zr and Ti.
- Suitable hydrolyzable compounds are, for. B. Al (OCH 3 ) 3, Al (OC 2 H 5 ) 3, Al (OnC 3 H 7 ) 3, Al (OiC 3 H 7 ) S, Al (OnC 4 H 9 ) 3 , Al (O -sek.-C 4 H 9 ) 3 , AICI 3 , AICI (OH) 2 , Al (OC 2 H 4 OC 4 Hg) 3 , TiCl 4 , Ti (OC 2 Hs) 4 , Ti (OnC 3 H 7 ) 4 , Ti (OiC 3 H 7 ) 4 , Ti (OC 4 Hg) 4 , Ti (2-ethylhexoxy) 4 , ZrCl 4 , Zr (OC 2 Hs) 4 , Zr (OnC 3 H 7 ) 4 , Zr (OiC 3 H 7 ) 4 , Zr (OC 4 H
- the hydrolysis and polycondensation of the silanes can be carried out in the absence or presence of an organic solvent. Preferably, no organic solvent is added. When using an organic solvent, the starting components are preferably soluble in the reaction medium. Moreover, the hydrolysis and polycondensation can be carried out according to the methods known to the person skilled in the art. For hydrolysis and condensation, water is added. Water can also be added in excess, if appropriate, some of the water is added thereto only after at least partial hydrolysis and / or condensation.
- Suitable organic solvents are, in particular, water-miscible solvents, for example monohydric or polyhydric aliphatic alcohols, such as methanol, ethanol, 1- or 2-propanol, glycols, such as butylglycols, ethers, such as diethers, esters, such as ethyl acetate, ketones, amides, Sulfoxides and sulfones or mixtures thereof, such as a mixture of ethanol, isopropanol and butyl glycol.
- the use of high boiling solvents is sometimes useful, examples being polyethers such as triethylene glycol, diethylene glycol diethyl ether, ethylene glycol monobutyl ether and tetraethylene glycol dimethyl ether. These examples are also suitable for the below-mentioned applications of organic solvents.
- an organic solvent or water can be added, for example, to adjust the viscosity or to add the fillers or other additives.
- the resulting coating composition may thus comprise an organic solvent and / or water.
- the abrasive fillers are preferably dispersed in this coating suspension or solution or the sol of the glass-forming matrix to form the coating composition.
- this filler may be added directly to the coating composition as a powder or as a suspension or slurry in an organic solvent.
- the coating composition used in the paint industry in the paint industry may contain conventional additives, such as the rheology and drying behavior controlling additives, wetting and flow control agents, defoamers, surfactants, solvents, dyes and pigments, in particular coloring pigments or effect pigments.
- conventional additives such as the rheology and drying behavior controlling additives, wetting and flow control agents, defoamers, surfactants, solvents, dyes and pigments, in particular coloring pigments or effect pigments.
- matting agents for example microscale SiO 2 or ceramic powders
- the hydrolysis and polycondensation of the silanes can be carried out in the presence of matting agents, for example microscale SiO 2 or ceramic powders. However, these can also be added later to the coating composition.
- the coating composition can be applied by the usual wet-chemical coating techniques, e.g. As dipping, pouring, spinning, spraying, roller application, brushing, knife coating or curtain coating. It can e.g. also printing methods, e.g. Screen printing, to be used.
- wet-chemical coating techniques e.g. As dipping, pouring, spinning, spraying, roller application, brushing, knife coating or curtain coating. It can e.g. also printing methods, e.g. Screen printing, to be used.
- the coating composition applied to the metallic surface is normally dried at room temperature or slightly elevated temperature, for example up to 100 ° C., in particular up to 80 ° C., before it is thermally compacted to a glassy layer.
- the thermal densification may optionally also be effected by IR or laser radiation.
- the densification temperatures can vary within wide limits and naturally also depend on the materials used. The skilled person is suitable areas known.
- the thermal densification is generally carried out in the range at a temperature in the range from 300 to 800 ° C., preferably from 350 to 700 ° C.
- the thermal densification also burns off any organics which may be present completely or to a desired, very low residual content. such that a glassy, inorganic layer is obtained.
- the coating composition can be converted to dense SiO 2 films, for example on stainless steel or steel surfaces, even at relatively low temperatures, generally from 400 ° C.
- the layers may be thermally densified under normal or oxidizing atmosphere, under inert gas or reducing atmosphere, or with portions of hydrogen.
- the thermal densification may also include two or more stages at different or successively changing conditions, which is usually preferred as well. Thus, in a first stage, the thermal densification may be in an oxidizing atmosphere and at relatively low temperatures to burn out the organics and then in a second stage in an inert atmosphere and at relatively high temperatures for final compaction.
- the final temperature can range from 100 to 500 0 C, preferably 150 to 450 ° C, are, inter alia, the precise temperatures chosen by the conditions and the desired further treatment depend.
- the furnace interior volume per hour of process gas is retracted, wherein the overpressure in the furnace interior is about 1 to 10 mbar, preferably 2 to 3 mbar.
- the water vapor partial pressure in the process gas can be adjusted by introducing water into the stream of compressed air before entering the furnace.
- the microporosity of the precompressed or also the finally compacted layer can be adjusted.
- a relative humidity of the process gas from 50 to 100% (amount of water based on the room temperature).
- the addition of water is stopped.
- the second heat treatment stage a further densification takes place to form a glassy layer.
- the second heat treatment step is preferably carried out to a final temperature in the range of 350 to 700 0 C, more preferably 400 to 600 ° C and particularly preferably 450 to 560 ° C. These temperature ranges are also preferred when the densification is performed in one step.
- the second stage is preferably carried out in an oxygen-poor atmosphere or oxygen-free atmosphere with only a very low oxygen content ( ⁇ 0.5% by volume). For example, it can be carried out under normal pressure or in vacuo.
- an inert gas such as nitrogen with an overpressure of 1 to 10 mbar, preferably 1 to 3 mbar, can be used.
- the thermal compression is usually carried out according to a controlled temperature program, wherein the temperature is increased at a certain speed up to a maximum end temperature.
- the above temperatures for compaction refer to this maximum final temperature.
- the residence times at the maximum temperatures in the compression stages are usually 5 to 75 minutes and preferably 20 to 65 minutes.
- This glassy layers can be obtained on metallic surfaces, which have a very high scratch and abrasion resistance. They also form a hermetically sealed layer which, even at higher temperatures, prevents material access to the metallic surface or drastically reduced and ensures excellent corrosion protection and also helps prevent contamination, for example by fingerprints, water, oil, grease, surfactants and dust. For example, ultra-hard coatings with anti-fingerprint function can be obtained.
- one or more intermediate layers may be provided between the metal substrate and the composite layer, e.g. to improve adhesion, to provide additional protection or to create additional optical effects.
- inorganic, glassy layers are also used for this purpose.
- the interlayers may also be wet-chemically or by other methods, e.g. CVD or PVD, wherein they can be compressed separately or preferably together with the composite layer.
- CVD chemical vapor deposition
- PVD physical vapor deposition
- the intermediate layers are also inorganic, glassy layers, which in a preferred embodiment are also the alkaline earth or alkali silicate-containing layers which have been described for the composite layer.
- the intermediate layer or the intermediate layers contain no abrasive fillers such as the composite layer. However, they may contain other additives depending on the purpose. Since the composite layer can be formed transparently, it is e.g. possible to incorporate color pigments or effect pigments in the intermediate layer (s) to produce desired decorative effects. However, it is also possible to incorporate directly into the composite layer color pigments or effect pigments in order to produce such decorative effects, wherein intermediate layers may or may not be present. If one or more intermediate layers are present in this case, this may optionally also contain colored or effect pigments.
- the metal substrate provided with the composite layer may be a semi-finished product such as plates, sheets, tubes, rods or wires, a component or a finished product. It can be used, for example, for systems, tools, household appliances, electrical components, machines, vehicle parts, in particular automotive components, production equipment, facades, conveying tools, light switch covers, irons, telephone cases or parts thereof.
- the coatings are particularly suitable for metal substrates such as metal housing of electronic devices, metallic components for optical devices, metallic parts of vehicles indoors and outdoors, metallic components in mechanical and plant engineering, motors, metallic components of medical devices, metallic components of household appliances, other electrical appliances, sports equipment, weapons, ammunition and turbines, household appliances, such as Containers, knives, metallic facade components, metallic components of elevators, parts of conveyors, metallic parts of furniture, garden tools, agricultural machinery, fittings, engine components and production equipment in general.
- metal substrates such as metal housing of electronic devices, metallic components for optical devices, metallic parts of vehicles indoors and outdoors, metallic components in mechanical and plant engineering, motors, metallic components of medical devices, metallic components of household appliances, other electrical appliances, sports equipment, weapons, ammunition and turbines, household appliances, such as Containers, knives, metallic facade components, metallic components of elevators, parts of conveyors, metallic parts of furniture, garden tools, agricultural machinery, fittings, engine components and production equipment in general.
- Example 1 Super scratch resistant, colorless coating for sandblasted stainless steel light switch covers
- MTEOS methyltriethoxysilane
- TEOS tetraethoxysilane
- a mixture of 50 wt.% F1000 Al 2 O 3 (jet corundum, crushed, particle size 1 to 10 microns) in 2-propanol is homogenized in a Dispermat for 10 minutes with cooling, then the content of the suspension by evaporation of a sample of the final product is determined (40 , 0% by weight).
- the coating varnish (4) 0.9 kg of the basecoat material (1) are initially introduced and then 100 g of ethylene glycol monobutyl ether are added and stirred. With stirring, 30 g of pigment suspension (2) and 45 g of pigment suspension (3) are added and stirring is continued for a further 20 minutes.
- the coating varnish (4) is sprayed in an industrial flat spray system to a wet film thickness of 11 .mu.m onto the pre-cleaned in a commercial alkaline cleaning stainless steel parts and then dried at room temperature in 15 minutes.
- the coated parts are placed in an evacuable furnace retort, then cured in a first heating step at 200 0 C in air and in pure nitrogen at 500 ° C in 1 h.
- the hardened glass layer has a layer thickness of 4 ⁇ m.
- Example 2 Super scratch resistant, gold pigmented coating on stainless steel
- the topcoat (5) For the preparation of the topcoat (5), 0.9 kg of the basecoat (1) from Example 1 are initially charged and 100 g of ethylene glycol monobutyl ether are added and mixed. Then, with stirring, 30 g of pigment suspension (2) and 45 g of pigment suspension (3) from Example 1 are added.
- the coating varnish (6) is sprayed in an industrial flat spray system to a wet film of 7 .mu.m thickness onto the blasted stainless steel soles prepurified in distilled water and then dried at room temperature in 15 minutes.
- a further coating with the topcoat (5) (wet film thickness 7 microns) is sprayed and also dried for 15 minutes.
- the coated parts are placed in a forced-air chamber furnace, cured in a first heating step to 350 0 C in air under the controlled addition of water and then in dry air to 475 ° C in 1 h.
- the cured glass layer has a layer thickness of 6 microns. 3.
- the coating varnish (7) is sprayed in an industrial flat spray system to a wet film of 12 .mu.m onto the pre-cleaned in a commercial alkaline cleaning stainless steel parts and then dried at room temperature in 15 minutes.
- the coated parts are placed in a convection oven, and in a three-stage program at 350 0 C with the addition of air and steam, then at 500 0 C in dry air for 1 hour and finally in a reducing atmosphere (95% N 2 + 5% H 2 ) at 400 ° C cured in 1 hour.
- the hardened glass layer has a layer thickness of 5 ⁇ m.
- a wet film of 8 .mu.m is applied to the coating layer in an industrial robot painting installation using coating varnish (8) pre-cleaned titanium substrates sprayed on alkaline cleaning bath and then dried at room temperature in 15 minutes.
- the coated parts are introduced into an evacuable retort oven, cured in a first heating step to 200 0 C in air and then in pure nitrogen at 530 0 C for 1 h.
- the cured glass layer has a layer thickness of 3 microns.
- the composite layers of Examples 1 to 4 are all characterized by a very high scratch and abrasion resistance. For example, they can not be damaged by scrubbing bodies made of polymer-bound corundum.
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE102007029668A DE102007029668A1 (de) | 2007-06-27 | 2007-06-27 | Ultraharte Kompositschichten auf Metalloberflächen und Verfahren zu ihrer Herstellung |
PCT/EP2008/058132 WO2009000874A2 (de) | 2007-06-27 | 2008-06-26 | Ultraharte kompositschichten auf metalloberflächen und verfahren zu ihrer herstellung |
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EP2162565A2 true EP2162565A2 (de) | 2010-03-17 |
EP2162565B1 EP2162565B1 (de) | 2012-04-18 |
EP2162565B8 EP2162565B8 (de) | 2012-05-23 |
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EP08774318A Active EP2162565B8 (de) | 2007-06-27 | 2008-06-26 | Ultraharte kompositschichten auf metalloberflächen und verfahren zu ihrer herstellung |
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US (1) | US8133579B2 (de) |
EP (1) | EP2162565B8 (de) |
JP (1) | JP5334968B2 (de) |
AT (1) | ATE554199T1 (de) |
DE (1) | DE102007029668A1 (de) |
ES (1) | ES2382761T3 (de) |
WO (1) | WO2009000874A2 (de) |
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EP2206801A1 (de) * | 2008-12-24 | 2010-07-14 | Seb Sa | Verbundstoff-Kochgeschirr mit einer glasartigen Schutzbeschichtung |
DE102010011185A1 (de) * | 2010-03-12 | 2011-09-15 | Epg (Engineered Nanoproducts Germany) Ag | Metallische Oberflächen mit dünner, glas- oder keramikartiger Schutzschicht mit hoher chemischer Beständigkeit und verbesserten Antihaft-Eigenschaften |
DE102011078066A1 (de) * | 2011-06-24 | 2012-12-27 | Oskar Frech Gmbh + Co. Kg | Gießtechnisches Bauteil und Verfahren zum Aufbringen einer Korrosionsschutzschicht |
WO2013164028A1 (en) * | 2012-05-03 | 2013-11-07 | Eksen Makine Sanayi Ve Ticaret A.S. | Low-friction, abrasion resistant and easy-to-clean composite iron sole plate |
ITRM20120291A1 (it) * | 2012-06-21 | 2013-12-22 | Agenzia Naz Per Le Nuove Tecn Ologie L Ener | Metodo per il trattamento di superfici metalliche per conferire alle stesse una elevata idrofobicita' ed oleofobicita' |
EP2803302B1 (de) * | 2013-05-14 | 2015-12-30 | Eksen Makine Sanayi ve Ticaret A.S. | Chemisch stabile, fleck-, abrieb- und temperaturbeständige, leicht zu reinigende Sol-Gel beschichtete Metallwaren zur Verwendung bei erhöhten Temperaturen |
BR102014025812A2 (pt) * | 2014-10-16 | 2016-04-19 | Mahle Int Gmbh | camisa de cilindro molhada para motores de combustão interna, processo para obtenção de camisa de cilindro molhada e motor de combustão interna |
JP6408722B2 (ja) * | 2015-06-12 | 2018-10-17 | マーレ インターナショナル ゲゼルシャフト ミット ベシュレンクテル ハフツングMAHLE International GmbH | 内燃エンジン用ピストンの環状クーリングチャンネルの表面を被覆する方法および当該方法によって製造可能なピストン |
DE102016205318A1 (de) * | 2016-03-31 | 2017-10-05 | BSH Hausgeräte GmbH | Oberflächenbeschichtung für hochwertige Weiß- und/oder Grauware |
US10782741B2 (en) | 2017-03-09 | 2020-09-22 | Apple Inc. | Abrasion-resistant surface finishes on metal enclosures |
CN109280887A (zh) * | 2017-07-20 | 2019-01-29 | 深圳市诺真空科技有限公司 | 一种防指纹膜的镀膜方法 |
JP7148237B2 (ja) * | 2017-11-02 | 2022-10-05 | 株式会社放電精密加工研究所 | アルマイト材の代替材料に用いることができる表面被覆基材、その基板表面にトップコート層を形成するための塗料組成物 |
DE102019102202A1 (de) * | 2019-01-29 | 2020-07-30 | Epg (Engineered Nanoproducts Germany) Ag | Dotierte alkalisilikat-schutzschichten auf metall |
DE102019127658A1 (de) * | 2019-10-15 | 2021-04-15 | Hueck Rheinische Gmbh | Presswerkzeug und Verfahren zum Herstellen eines Presswerkzeugs |
DE102019127655B4 (de) * | 2019-10-15 | 2023-01-19 | Hueck Rheinische Gmbh | Presswerkzeug und Verfahren zum Herstellen eines Presswerkzeugs |
CN115403943A (zh) * | 2022-08-15 | 2022-11-29 | 广东富多新材料股份有限公司 | 一种低温珐琅涂料及其制备方法和应用 |
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DE19714949A1 (de) * | 1997-04-10 | 1998-10-15 | Inst Neue Mat Gemein Gmbh | Verfahren zum Versehen einer metallischen Oberfläche mit einer glasartigen Schicht |
JP3047180U (ja) * | 1997-09-16 | 1998-03-31 | 株式会社リボール | 断熱屋根材 |
DE19952040A1 (de) * | 1999-10-28 | 2001-05-03 | Inst Neue Mat Gemein Gmbh | Substrat mit einem abriebfesten Diffusionssperrschichtsystem |
AU2002242025A1 (en) * | 2001-01-29 | 2002-08-12 | Olga Kachurina | Advanced composite ormosil coatings |
DE102006040385A1 (de) * | 2001-06-09 | 2007-01-18 | Esk Ceramics Gmbh & Co. Kg | Dauerhafte temperaturstabile BN-Formtrennschichten auf Basis von keramischen und glasartigen Bindern |
DE102004001097B4 (de) | 2004-01-05 | 2014-06-05 | Epg (Engineered Nanoproducts Germany) Ag | Metallische Substrate mit verformbarer glasartiger Beschichtung |
DE102005050593A1 (de) | 2005-10-21 | 2007-04-26 | Esk Ceramics Gmbh & Co. Kg | Dauerhafte siliciumnitridhaltige Hartbeschichtung |
DE102005059614A1 (de) | 2005-12-12 | 2007-06-14 | Nano-X Gmbh | Beschichtungsmaterial zum Schutz von Metallen, insbesondere Stahl, vor Korrosion und/oder Verzunderung, Verfahren zum Beschichten von Metallen und Metallelement |
-
2007
- 2007-06-27 DE DE102007029668A patent/DE102007029668A1/de not_active Withdrawn
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- 2008-06-26 JP JP2010513915A patent/JP5334968B2/ja active Active
- 2008-06-26 EP EP08774318A patent/EP2162565B8/de active Active
- 2008-06-26 AT AT08774318T patent/ATE554199T1/de active
- 2008-06-26 US US12/666,540 patent/US8133579B2/en active Active
- 2008-06-26 WO PCT/EP2008/058132 patent/WO2009000874A2/de active Application Filing
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DE102007029668A1 (de) | 2009-01-08 |
EP2162565B8 (de) | 2012-05-23 |
ATE554199T1 (de) | 2012-05-15 |
JP2010532722A (ja) | 2010-10-14 |
US20100178491A1 (en) | 2010-07-15 |
WO2009000874A2 (de) | 2008-12-31 |
ES2382761T3 (es) | 2012-06-13 |
JP5334968B2 (ja) | 2013-11-06 |
US8133579B2 (en) | 2012-03-13 |
EP2162565B1 (de) | 2012-04-18 |
WO2009000874A3 (de) | 2009-09-17 |
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