US20120295081A1 - Composite material and method for producing same - Google Patents
Composite material and method for producing same Download PDFInfo
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- US20120295081A1 US20120295081A1 US13/521,907 US201113521907A US2012295081A1 US 20120295081 A1 US20120295081 A1 US 20120295081A1 US 201113521907 A US201113521907 A US 201113521907A US 2012295081 A1 US2012295081 A1 US 2012295081A1
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3607—Coatings of the type glass/inorganic compound/metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44F—SPECIAL DESIGNS OR PICTURES
- B44F7/00—Designs imitating three-dimensional effects
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- 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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/006—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels to produce glass through wet route
- C03C1/008—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels to produce glass through wet route for the production of films or coatings
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3636—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer one layer at least containing silicon, hydrogenated silicon or a silicide
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3649—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer made of metals other than silver
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3684—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating being used for decoration purposes
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3686—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating being used for ovens
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
- C03C2217/44—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the composition of the continuous phase
- C03C2217/45—Inorganic continuous phases
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
- C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
- C03C2217/465—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase having a specific shape
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
- C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
- C03C2217/47—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase consisting of a specific material
- C03C2217/475—Inorganic materials
- C03C2217/478—Silica
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
- C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
- C03C2217/48—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase having a specific function
- C03C2217/485—Pigments
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/72—Decorative coatings
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/77—Coatings having a rough surface
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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.]
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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.]
- Y10T428/24479—Structurally defined web or sheet [e.g., overall dimension, etc.] including variation in thickness
- Y10T428/24521—Structurally defined web or sheet [e.g., overall dimension, etc.] including variation in thickness with component conforming to contour of nonplanar surface
- Y10T428/24545—Containing metal or metal compound
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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.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
- Y10T428/24851—Intermediate layer is discontinuous or differential
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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.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
- Y10T428/24893—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including particulate material
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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.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
- Y10T428/24926—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including ceramic, glass, porcelain or quartz layer
Definitions
- the invention relates to a composite material, in particular a composite material comprising a glass or glass-ceramic substrate and a coating.
- the substrate is at least partially transparent.
- the invention furthermore relates to a method for producing a composite material, in particular based on a glass or glass-ceramic substrate.
- the invention moreover relates to glass-ceramic articles having a decorative appearance, especially glass-ceramic cooktops, oven windows, architectural glazing, glass applications in consumer electronics, etc.
- Decorative coatings especially at the bottom face of transparent glass-ceramics such as cooktops, are known from practice.
- the coating may have a metallic appearance.
- a layer with a thickness of several microns has to be applied, whereby the coated area no longer exhibits a transparent appearance through which for example a backlight or a display would be visible.
- foils In the kitchen area, for example, surfaces are commonly used that have an appearance of brushed stainless steel.
- foils may be used, for example.
- such foils often fail to provide a high-quality appearance, and they are prone to delamination and discoloration, in particular when subjected to temperatures of more than 50° C.
- stainless steel sheets may be used.
- these are relatively expensive, and a seamless transition between a glass-ceramic substrate and a stainless steel surface is usually not possible.
- moisture and dirt may penetrate between the layers thereby considerably deteriorating the appearance thereof.
- An object of the invention therefore is to provide a simple and inexpensive method for applying decorative coatings with a high level of creative freedom, wherein such decorative coatings should in particularly exhibit a high temperature resistance.
- Another object of the invention is to provide decorative layers with good adhesion to the substrate and a high level of scratch resistance. Also, the applied layers should not impair the strength of the substrate.
- one embodiment of the invention is based on the object to provide layers with display and/or touch display capability.
- the object of the invention is already achieved by a method for producing a composite material having at least two layers, and by a composite material according to any of the independent claims.
- the invention relates to a method for producing a composite material having at least two layers.
- a glass or glass-ceramic composite material which resists to thermal shocks and has a coefficient of thermal expansion (CTE) of not more than 5*10 ⁇ 6 K ⁇ 1 , preferably not more than 4*10 ⁇ 6 K ⁇ 1 (at 20° C.), and which is at least partially transparent.
- CTE coefficient of thermal expansion
- This may be a material exhibiting high transmittance in the visible range as well as a nearly opaque material with only low transmittance.
- a plastic substrate in particular a transparent plastic substrate.
- a patterned sol-gel layer i.e. an at least partially inorganic layer, is applied using a liquid phase process.
- a further layer is deposited onto the patterned layer by a PVD or CVD deposition process, in particular by a PVD process.
- the inventors have found that by combining a pattern-defining sol-gel layer and a deposited, for example color-defining layer a virtually unlimited creational freedom may be provided.
- the deposited, further layer may be a colored layer or a layer having a metallic appearance, in particular a metal layer.
- a decor is applied to the substrate.
- a luster color which usually comprises dissolved metal resinates which at higher temperatures form a thin metal oxide layer with a colored or metallic appearance.
- the patterned sol-gel layer is preferably transparent and may for example be applied by a screen printing process.
- the sol-gel layer is patterned using an embossing tool, in particular an embossing stamp or a roller.
- An advantage of this embodiment of the method is that it permits to copy almost any texture from a master pattern, for example that of a brushed metal surface, and to transfer it to the sol-gel layer.
- the subsequently applied further layer follows the pattern of the patterned sol-gel layer or fills it.
- Such a method comprises for example the following steps:
- a stamp is produced for which a master is required.
- a master For a brushed stainless steel surface this may be a sheet metal or piece of metal having the desired pattern, for example.
- the master may be cleaned so as to be free of grease and lint.
- a polymer mass in particular a silicone molding compound
- Curing may be accomplished for example by polymerization, preferably under heating. Possibly occurring bubbles may be removed from the system by vacuum.
- the cured polymer stamps are then released from the master template and are now ready for the actual embossing process.
- the stamps can be used multiple times, i.e. after the embossing operation they may be cleaned, for example using a cleaning agent such as water, ethanol, or isopropanol, and can so be reused.
- the glass or glass-ceramic substrate is coated with a sol-gel layer.
- the sol-gel layer may comprise amorphous and/or hybrid and/or crystalline particles.
- the refractive index of the layer may be adapted to that of the substrate and/or to that of an overlying layer.
- Refractive indices that may be obtained for the patterned layer range from 1.2 to 1.8, preferably from 1.4 to 1.65.
- Adaptation of the refractive index is particularly important if the deposited layer serves for compensating a color cast of the substrate.
- An advantage of a sol-gel layer is that it may be applied by virtually any known liquid coating technique.
- the sol-gel layer is applied by a screen printing process.
- An advantage thereof is that areas which are not intended to be provided with a decorative layer may be excluded from being coated, and that a sophisticated inspection for layer roughnesses, inhomogeneities, and/or contaminations may be dispensed with in these areas.
- the sol may be precured prior to embossing, in particular using a photochemical process, for example by means of UV radiation, or thermally, or using IR radiation.
- the sol-gel layer may be embossed using the polymer embossing stamp, in continuous or static manner.
- the embossing stamp may likewise be provided with a sol-gel layer, as it is envisaged according to one embodiment of the invention.
- the arrangement Preferably under a defined pressure of the stamp, the arrangement may be cured thermally and/or photochemically, preferably photochemically.
- a sol is employed which is automatically drawn into the stamp, due to capillary forces.
- the embossing process may be a thixotropic process.
- a patterned layer is exhibited, especially having a layer thickness from 0.01 to 1 mm.
- the pattern is predefined by the pattern of the embossing stamp, and nearly any pattern is possible, for example periodic or random patterns.
- any surface profile may be copied, for example wooden surfaces, etched surfaces, etc.
- the pattern depth may vary within a range from 100 nm to 1 mm.
- the applied patterned layer defines the texture of the at least one subsequent further layer.
- the patterned layer is cured, for example at temperatures from 50 to 1000° C., preferably from 100 to 500° C., depending on the required temperature resistance of the final product.
- the pattern is maintained, even if the organic components of the sol are removed at least partially, i.e. the layers are either almost purely inorganic or partially organic and may in particular comprise high-temperature stable Si-methyl and/or Si-phenyl groups.
- the pattern depth decreases as compared to that of the master, depending on the temperature and the sol used, in particular depending on whether or not nanoparticles are added to the sol and in which amount. So a reduction of the pattern depth of up to 60% may result. This may be adjusted selectively to permit to produce different pattern depth with one master.
- the resultant patterned sol-gel layer may have a refractive index ranging from 1.2 to 1.8, preferably from 1.4 to 1.65.
- the layer may be porous, i.e. it has meso- and/or micropores with a pore radius of not more than 10 nm, preferably not more than 5 nm, more preferably 3 nm. Most of the pores are bottleneck-shaped, with the pore radius being larger than the outlet radius.
- the layers preferably exhibit a porosity of from 5 to 50%, more preferably from 15 to 30%. The pore radii and the total porosity can be determined by ellipsometric porosimetry or by nitrogen-sorption measurements.
- the porosity of the layer, through a mixture of the coating material and air, may also contribute to achieve an adaptation of the refractive index.
- Sol-gel precursors that may be used are in particular hydrolyzed and condensed epoxy- or methacrylate-functionalized alkoxysilanes which in particular comprise oxide nanoparticles such as SiO 2 .
- the nanoparticles are preferably added as a dispersion, in particular as an alcoholic dispersion. This allows to decrease shrinking to 25% or less.
- irregularly shaped fibrous particles may be used, especially silicon oxide particles.
- the diameter thereof may range from 5 to 15 nm, with a length from 5 to 150 nm.
- mixtures of spherical particles of different sizes are added, in particular sizes from 5 to 125 nm. Thereby, in particular when using larger and smaller particle fractions, it is possible to provoke self-assembly.
- a self-assembling sol-gel is used.
- This is a self-assembling layer for which different diffuser particles are added, especially of a size ranging from 0.1 to 1 ⁇ m, which due to the different particle sizes arrange themselves, at the latest during drying and condensation of the layer, such that a pattern with a defined roughness results, which may function for example as a diffusion layer or as a layer having an anti-slip effect.
- Coating using a so-called self-assembling sol also provides for a continuous cost-efficient and production-ready application process.
- the sol used therefor also preferably comprises amorphous and/or hybrid and/or crystalline nanoparticles. Additionally, it preferably comprises a proportion of texture-defining inorganic particles, in particular of a size ranging from 0.1 to 1 p.m. These particles may for example serve as scattering particles. Through the choice of different particle sizes, surface roughnesses and scattering properties of the layers may be adjusted.
- a self-assembling sol-gel layer may also be applied by a screen printing process, for example.
- Use of a self-assembling sol is particularly suitable for applications, especially decorative applications, which are desired to have a matted surface.
- the further layer is applied using a vapor based deposition process, preferably a PVD or CVD process, more preferably a sputtering process.
- This layer may be applied over the entire surface, or may be patterned in a sense of sub-sections. In the latter case techniques known in the art are employed, such as peel-off films or the like.
- PVD Physical Vapor Deposition
- CVD Chemical Vapor Deposition
- a target or precursor material onto the substrate in a particularly simple way.
- the material may be oxidized by supplying gaseous O 2 , where appropriate, and so an oxide layer may be applied.
- Such a process may also be achieved with other additives and is referred to as so-called reactive sputtering.
- nitrides or elementary layers may be used as well.
- the following elements or compounds may be used: Si, Ge, Al, Mn, Fe, Zn, Ni, Cr, Ti, Mo, Ag, NiCr, NiCrSi (so-called Thermax® stainless steel), and/or alloys or combinations thereof.
- metal clusters having a metallic appearance are introduced or embedded in the sputtered layer, in nanoparticulate form.
- At least one further layer applied by a deposition process may serve as a color adjusting layer, i.e. for example may compensate for the yellowness of the glass-ceramic substrate.
- a uniform transmittance without color appearance may be achieved, or a specific other color cast, such as a blue tint.
- a colorless or color-adjusted appearance is to be understood in particular as a transmission, wherein when transmitting white light, the transmitted, i.e. the passed light has an absolute value below 20, preferably below 10, on the a* axis and/or the b* axis in the L*a*b* color space.
- a preferred embodiment of the composite material does not exhibit any color cast, not greenish, nor reddish, or bluish, or yellowish.
- This may for example be achieved by an Si 3 N 4 layer or an SiO X N V layer with a thickness ranging for example from 40 to 500 nm, in particular ranging from 75 to 97 nm.
- two-layer or multilayer systems of the following materials may be used to reduce the intrinsic color of glass-ceramics: Si X N V , SiO X N V , TiO 2 , ZrO 2 , Y 2 O 3 , MgF 2 , Al 2 O 3 , Nb 2 O 5 , Ta 2 O 5 , CeO 2 , and/or SiO 2 .
- a combination of high refractive index layers and low refractive index layers such as titanium oxide and silicon oxide is likewise conceivable.
- the colored layer in particular if applied on a metallic-looking layer, in particular a metal or metal oxide layer, may serve as an additional gas barrier and so ensure thermal resistance up to 800° C.
- At least one further layer is sputtered with high ion energies, and the substrate is heated prior to sputtering.
- Typical ion energies here are greater than 10 eV, preferably greater than 20 eV, and the substrate heating temperatures range from 100 to 600° C., preferably from 200 to 400° C.
- this layer may be formed as a hard material coating.
- barrier layers may for example comprise silicon, aluminum, titanium, tin, zirconium, cerium or oxides or nitrides or oxynitrides thereof.
- silicon oxide, silicon oxynitride, and silicon nitride are envisaged for barrier layers.
- barrier layers with thicknesses ranging from 50 to 500, preferably from 100 to 250 nm are suitable.
- a further layer is provided between the glass-ceramic substrate and the sol-gel layer, this layer in particular also being applied by a PVD process, especially by a sputtering process.
- This layer preferably exhibits a CTE of less than 5*10 ⁇ 6 K ⁇ 1 .
- the layer serves as an adhesion promoting layer for the sol-gel layer and any further layers.
- This layer may also be colored and thus serve as a color adjusting layer, as envisaged according to one embodiment of the invention.
- a thin layer having a high resistivity is applied. Since pure metal layers typically would need to be made so thin that transparency would be too high for many applications, semiconductor materials such as silicon or germanium may be used for this purpose. In particular a semiconductor material is used which at room temperature exhibits a resistivity of more than 1*10 3 ⁇ mm 2 /m, preferably of 1*10 6 ⁇ mm 2 /m.
- a touch-enabled opaque layer with an appearance of stainless steel in particular brushed stainless steel may be provided, for example.
- Semiconductor materials in doped form are likewise conceivable, for example those including aluminum, boron, or phosphorus.
- a sealing coating may be applied, especially with one or more preferably temperature-stable sol-gel layers and/or glass flux and/or phenyl or methyl polysiloxane layers.
- the layer may be pigmented by inorganic fillers, in particular pyrogenic or precipitated inorganic materials, and/or by mica and/or graphite and/or inorganic pigments, in particular black pigments.
- a layer system with such a sealing coating may comply with a scratch resistance greater than 300 g, preferably greater than 500 g in the Bosch-Siemens home appliance test (BSH) known in the art.
- the at least partially inorganic layer or the deposited layer may serve to enhance the surface hardness of the composite material.
- the composite material is at least partially transparent, so that for example infrared sensors may be arranged behind the composite material. Preferably there is no sealing coating in this area.
- the invention is also suitable for transparent plastics, such as polycarbonates, polyacrylates, polyolefins, in particular cyclo-olefinic copolymers.
- transparent plastics such as polycarbonates, polyacrylates, polyolefins, in particular cyclo-olefinic copolymers.
- the composite material according to the invention may also be used indoors and for architectural glazing, and applications in consumer electronics are also conceivable.
- FIGS. 1 to 5 a method for producing a composite material with a metallic appearance will be described in more detail with reference to a schematically illustrated exemplary embodiment.
- FIG. 6 schematically shows a flow chart of one exemplary embodiment of a method for producing a composite material having an appearance of brushed stainless steel.
- FIGS. 7 and 8 show transmission curves of a composite material with and without a colored layer to compensate for the color cast of the substrate.
- FIGS. 9 and 10 show exemplary layer systems for a glass-ceramic coating with an appearance of stainless steel ( FIG. 9 ) and for a touch-enabled glass-ceramic coating with an appearance of stainless steel ( FIG. 10 ).
- FIG. 1 shows a composite material 1 which comprises a substrate 2 on which a sol-gel layer 3 is applied as the layer to be patterned in sections thereof.
- the sol-gel layer 3 is patterned using an embossing tool 4 that is pressed onto the layer.
- the patterned sol-gel layer 3 is illustrated in FIG. 3 .
- the embossed pattern is similar to the texture of a brushed stainless steel surface.
- a metal layer 5 is applied onto patterned sol-gel layer 3 using a sputtering process, and the result is a coating having a metallic appearance.
- another layer may be applied between the patterned layer and the metal layer, which leads to a substantially colorless transmittance and/or the desired color adjustment.
- an embossing stamp may be used, for example.
- the sol-gel layer may be applied onto a glass or glass-ceramic substrate by liquid coating, for example.
- the sol-gel layer comprises amorphous and/or hybrid and/or crystalline particles. Through the particles and the sol, an adaptation of the refractive index of the layer to that of the substrate 2 or to that of further overlying layers (not shown) may be provided.
- the sol-gel layer 3 is applied using a screen printing process. Therefore, areas which are not to be patterned may be excluded from being coated, and free areas which are for example required for a display or a control panel are not provided with the sol-gel layer, and a sophisticated inspection for layer roughnesses, inhomogeneities, and/or contaminations in these areas is eliminated.
- sol-gel layer 3 is precured, in particular using a photochemical process.
- the embossing tool 4 is preferably formed as an embossing stamp, which is continuously pressed onto the sol-gel layer under a defined pressure, in particular in form of a roller or a planar embossing stamp.
- the sol-gel layer 3 is cured during embossing, in particular thermally or photochemically.
- embossing stamp with particularly great force, rather the sol is drawn into the texture of the embossing stamp almost automatically. If bubbles arise between the embossing stamp and the sol, they may be removed using a roller, or assisted by vacuum.
- both periodic and random patterns may be used, in particular lines, brushed surfaces, light-scattering layers, etched surfaces, textures that serve to provide enhanced haptics, and simple geometric shapes such as pyramids, inverted pyramids, cubes, spheres, etc.
- the patterned sol-gel layer defines the texture of subsequently deposited layers, in particular that of the metal-containing layers deposited according to the invention, and optionally also that of subsequent further layers or intermediate layers.
- the patterned sol-gel layer 3 provided with a metal layer 5 is cured at temperatures from 50 to 1000° C., preferably from 100 to 800° C., depending, inter alia, on the required temperature resistance of the final product.
- the pattern is maintained, even if organic components of the sol-gel layer are completely burned off.
- the depth of the pattern decreases by 0 to 60% as compared to the pattern of the embossing tool, depending on the temperature and the sol-gel used which in particular includes particles. If necessary, this may be compensated for by using an embossing tool that has a greater pattern depth than the pattern depth that is actually desired.
- FIG. 6 shows a schematic flow chart of the essential method steps.
- a sol-gel layer is applied.
- the applied sol-gel layer is patterned using an embossing stamp and is simultaneously cured using UV light. Then, the embossing stamp is removed and subsequently the composite material is cured thermally.
- a stainless steel layer is applied by a sputtering process. If desired, additional layers may be applied.
- a composite material according to the invention may be produced as follows, for example:
- GPTES glycidyloxypropyltriethoxysilane
- TEOS tetraethoxysilane
- a patterned silicone stamp (PDMS) is applied, and then the layer is cured through the stamp using a UV lamp.
- PDMS patterned silicone stamp
- the layers may then be cured thermally at temperatures from 300 to 500° C.
- a preferred heating rate is 3 K/min, with a holding time of 1 h at 500° C.
- the final thickness of the layer ranges from 2 to 3 p.m.
- a stainless steel layer is applied by a sputtering process in a thickness of at least 100 nm.
- GPTES glycoloxypropyltriethoxysilane
- TEOS tetraethoxysilane
- MTEOS methyltriethoxysilane
- layers of this lacquer system may be applied to one face of transparent glass-ceramic substrates.
- a patterned silicone stamp (PDMS) is applied, and then curing is accomplished through the stamp using a UV lamp.
- PDMS patterned silicone stamp
- the layers may then be cured thermally at temperatures from 300 to 500° C.
- a preferred heating rate is 3 K/min, with a holding time of 1 h at 500° C.
- the final thickness of the layer is 1.5 p.m.
- a color-adjusting SiN layer is applied in a thickness of 80 nm, then a stainless steel layer in a minimum thickness of 100 nm, and then an SiO 2 barrier layer as the top layer.
- FIG. 7 shows the transmission curve of a known non-coated glass-ceramic substrate.
- the x-axis 8 indicates the wavelength in nm, and the y-axis 9 indicates the transmittance 7 in %.
- the transmittance continuously increases from slightly above 91.5% at 400 nm to 92.5% at 650 nm. Accordingly, the glass-ceramic material is yellowish.
- FIG. 8 similar to FIG. 7 , shows the transmission curve of a glass-ceramic substrate coated with a color adjusting layer.
- the transmission curve 7 in the wavelength range from 400 to 750 nm substantially extends at about 93%, that is, the composite material has no visible color appearance.
- color adjustment has been achieved by bringing the transmittance in the entire visible range to substantially the same level.
- FIG. 9 shows an exemplary layer structure of a composite material having a metallic appearance, especially an appearance of brushed stainless steel.
- a patterned sol-gel layer is applied, then followed by a layer for color compensation.
- a metal layer is disposed on this layer.
- This embodiment of the invention is particularly suitable for coating a bottom face or for use of the layer system on the side facing away from the viewer.
- the patterned sol-gel layer functions to define a pattern of the subsequent layers.
- the layer for color compensation of a yellowish tint of the glass or glass-ceramic substrate is arranged between the metal layer and the patterned layer.
- FIG. 10 shows an alternative layer structure which is in particular intended for a touch-enabled bottom face coating with an appearance of stainless steel. Also in this embodiment, first a patterned sol-gel layer is applied on the glass-ceramic substrate. It is followed by a silicon nitride layer which serves for color compensation.
- a semiconductor layer follows, in this embodiment a silicon layer, which due to its high electrical resistance also permits to attach capacitive switching elements behind the composite material.
- the table of FIG. 11 shows the color impression of several composite materials before and after temperature stress.
- Listed in the table are layer systems applied to a glass-ceramic substrate and having a metallic appearance, in which first a silicon nitride layer was applied in different thicknesses as a color adjusting layer, onto which then a stainless steel layer in a thickness of 300 nm and a silicon oxide layer in a thickness of 300 nm as a barrier layer were applied.
- the coordinates of the L*a*b* color space are indicated in the unstressed state and following a thermal stress of 490° C. It can be seen that with increasing thickness of the silicon nitride layer the brightness (L* axis) tends to increase slightly.
- the absolute values on the a* axis and on the b* axis are always less than 8, both for the unstressed samples and for the samples stressed at a temperature of 490° C.
- the maximum indicated level of a color change dE is about 2.5, i.e. the color appearance of the composite material has not or only hardly visibly changed, even after exposure to heat.
- the invention permits to produce temperature-resistant composite materials with virtual any visual appearance in a very simple way.
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PCT/EP2011/000141 WO2011085996A1 (de) | 2010-01-14 | 2011-01-14 | Verbundmaterial und verfahren zu dessen herstellung |
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2011
- 2011-01-14 WO PCT/EP2011/000140 patent/WO2011085995A1/de active Application Filing
- 2011-01-14 WO PCT/EP2011/000141 patent/WO2011085996A1/de active Application Filing
- 2011-01-14 EP EP11701198A patent/EP2523917A1/de not_active Withdrawn
- 2011-01-14 EP EP11700892.0A patent/EP2523916B1/de not_active Not-in-force
- 2011-01-14 CN CN201180006231.8A patent/CN102712518B/zh not_active Expired - Fee Related
- 2011-01-14 EP EP11700802.9A patent/EP2523915B1/de active Active
- 2011-01-14 CN CN2011800062303A patent/CN102712517A/zh active Pending
- 2011-01-14 JP JP2012548382A patent/JP2013517196A/ja active Pending
- 2011-01-14 US US13/521,824 patent/US20130040116A1/en not_active Abandoned
- 2011-01-14 US US13/522,052 patent/US8999445B2/en active Active
- 2011-01-14 ES ES11700802.9T patent/ES2613500T3/es active Active
- 2011-01-14 US US13/521,907 patent/US20120295081A1/en not_active Abandoned
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Cited By (12)
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US20150037507A1 (en) * | 2012-04-20 | 2015-02-05 | Schott Ag | Composite material with decorative coating and method for producing same |
US10308548B2 (en) * | 2012-04-20 | 2019-06-04 | Schott Ag | Glass or glass ceramic substrate provided with a decorative coating and method for producing same |
US10590036B2 (en) * | 2012-04-20 | 2020-03-17 | Schott Ag | Composite material with decorative coating and method for producing same |
US11713277B2 (en) | 2012-04-20 | 2023-08-01 | Schott Ag | Glass or glass ceramic substrate provided with a decorative coating and method for producing same |
US20150144613A1 (en) * | 2012-06-21 | 2015-05-28 | Eurokera S.N.C. | Glass-ceramic article and manufacturing process |
US11419187B2 (en) * | 2012-06-21 | 2022-08-16 | Eurokera S.N.C. | Glass-ceramic article and manufacturing process |
US10012362B2 (en) | 2012-08-14 | 2018-07-03 | Eurokera S.N.C. | Glass-ceramic article comprising a luminous color display |
US20160068431A1 (en) * | 2013-04-18 | 2016-03-10 | Agc Glass Europe | Process for enamelling a glass sheet |
US10543061B2 (en) | 2014-10-03 | 2020-01-28 | 3M Innovative Properties Company | Methods for managing the scattering of incident light and articles created therefrom |
US11130704B2 (en) * | 2016-06-17 | 2021-09-28 | Eurokera S.N.C. | Glass-ceramic glass article and method for obtaining same |
US10310141B2 (en) * | 2016-08-09 | 2019-06-04 | Electronics And Telecommunications Research Institute | Metamaterial structure and method of fabricating the same |
CN115210193A (zh) * | 2020-02-28 | 2022-10-18 | 松下知识产权经营株式会社 | 加热烹调器用顶板 |
Also Published As
Publication number | Publication date |
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CN102712518A (zh) | 2012-10-03 |
US20130183487A1 (en) | 2013-07-18 |
US8999445B2 (en) | 2015-04-07 |
JP2013517196A (ja) | 2013-05-16 |
US20130040116A1 (en) | 2013-02-14 |
EP2523916A1 (de) | 2012-11-21 |
WO2011085995A1 (de) | 2011-07-21 |
US9388070B2 (en) | 2016-07-12 |
ES2613500T3 (es) | 2017-05-24 |
DE102010004741B4 (de) | 2023-02-23 |
US20150191392A1 (en) | 2015-07-09 |
CN102712518B (zh) | 2016-08-03 |
DE102010004741A1 (de) | 2011-07-21 |
EP2523916B1 (de) | 2017-08-23 |
EP2523915B1 (de) | 2017-01-11 |
EP2523917A1 (de) | 2012-11-21 |
WO2011085996A1 (de) | 2011-07-21 |
CN102712517A (zh) | 2012-10-03 |
WO2011085997A1 (de) | 2011-07-21 |
EP2523915A1 (de) | 2012-11-21 |
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