US20060046089A1 - Metal based coating composition and related coated substrates - Google Patents

Metal based coating composition and related coated substrates Download PDF

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Publication number
US20060046089A1
US20060046089A1 US10/931,748 US93174804A US2006046089A1 US 20060046089 A1 US20060046089 A1 US 20060046089A1 US 93174804 A US93174804 A US 93174804A US 2006046089 A1 US2006046089 A1 US 2006046089A1
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Prior art keywords
coated substrate
over
layer
metal based
dielectric layer
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Abandoned
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US10/931,748
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English (en)
Inventor
Dennis O'Shaughnessy
James Finley
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Vitro SAB de CV
Vitro Flat Glass LLC
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Individual
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Priority to US10/931,748 priority Critical patent/US20060046089A1/en
Application filed by Individual filed Critical Individual
Assigned to PPG INDUSTRIES OHIO, INC. reassignment PPG INDUSTRIES OHIO, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: FINLEY, JAMES J., O'SHAUGHNESSY, DENNIS J.
Priority to CN2005800294396A priority patent/CN101010443B/zh
Priority to EP05792592.7A priority patent/EP1784522B1/en
Priority to RU2007111924/02A priority patent/RU2379377C2/ru
Priority to PCT/US2005/030375 priority patent/WO2006028729A1/en
Publication of US20060046089A1 publication Critical patent/US20060046089A1/en
Priority to US11/712,240 priority patent/US7923131B2/en
Priority to US13/053,478 priority patent/US8329318B2/en
Assigned to VITRO, S.A.B. DE C.V. reassignment VITRO, S.A.B. DE C.V. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: PPG INDUSTRIES OHIO, INC.
Assigned to VITRO, S.A.B. DE C.V. reassignment VITRO, S.A.B. DE C.V. CORRECTIVE ASSIGNMENT TO CORRECT THE ASSIGNEE ADDRESS PREVIOUSLY RECORDED AT REEL: 040473 FRAME: 0455. ASSIGNOR(S) HEREBY CONFIRMS THE ASSIGNMENT. Assignors: PPG INDUSTRIES OHIO, INC.
Assigned to VITRO FLAT GLASS LLC reassignment VITRO FLAT GLASS LLC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: VITRO, S.A.B. DE C.V.
Abandoned legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface 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
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface 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
    • C03C17/3602Surface 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
    • C03C17/3615Coatings of the type glass/metal/other inorganic layers, at least one layer being non-metallic
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface 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
    • C03C17/3602Surface 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
    • C03C17/3618Coatings of type glass/inorganic compound/other inorganic layers, at least one layer being metallic
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface 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
    • C03C17/3602Surface 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
    • C03C17/3626Surface 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 a nitride, oxynitride, boronitride or carbonitride
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface 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
    • C03C17/3602Surface 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
    • C03C17/3644Surface 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 metal being silver
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface 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
    • C03C17/3602Surface 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
    • C03C17/3649Surface 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
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface 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
    • C03C17/3602Surface 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
    • C03C17/3652Surface 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 coating stack containing at least one sacrificial layer to protect the metal from oxidation
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C2217/00Coatings on glass
    • C03C2217/70Properties of coatings
    • C03C2217/73Anti-reflective coatings with specific characteristics
    • C03C2217/734Anti-reflective coatings with specific characteristics comprising an alternation of high and low refractive indexes
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C2217/00Coatings on glass
    • C03C2217/70Properties of coatings
    • C03C2217/78Coatings specially designed to be durable, e.g. scratch-resistant
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/12All metal or with adjacent metals
    • Y10T428/12493Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/12All metal or with adjacent metals
    • Y10T428/12493Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/12All metal or with adjacent metals
    • Y10T428/12493Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12597Noncrystalline silica or noncrystalline plural-oxide component [e.g., glass, etc.]
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/12All metal or with adjacent metals
    • Y10T428/12493Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12597Noncrystalline silica or noncrystalline plural-oxide component [e.g., glass, etc.]
    • Y10T428/12604Film [e.g., glaze, etc.]
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/26Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263Coating layer not in excess of 5 mils thick or equivalent
    • Y10T428/264Up to 3 mils
    • Y10T428/2651 mil or less

Definitions

  • the present invention relates to novel functional coatings and substrates coated therewith.
  • Glass substrates are used for a variety of purposes, from automotive to architectural applications. Generally, glass manufacturers produce standard size glass sheets in large quantities and then cut the glass to size based on the customer requirements. Some of the glass will have to be bent into various shapes. Typically, glass is shaped using a bending process which requires heating the glass. In addition to bending, glass may be subjected to a heating operation for tempering or heat strengthening, as is well known in the art. The most efficient bending, tempering and heat strengthening processes take place at temperatures ranging between 1150° F. (621° C.) and 1450° F. (788° C.).
  • the glass will need to exhibit various performance properties such as emissivity, visible light reflectance, color, etc.
  • the glass substrates can be coated with a functional coating so that the substrate can achieve the desired performance properties.
  • Functional coatings such as photocatalytic coatings, solar management coatings, low emissivity coatings, conductive coatings, etc. are well known in the art.
  • a customer will need coated glass that has been heat treated and coated glass that has not been heat treated.
  • the heat treated, coated glass and the non-heat treated, coated glass will exhibit the same appearance and provide similar functional characteristics. This would be the simplest solution for both the glass manufacturer and the customer.
  • the present invention is a coated substrate comprising a substrate and a coating composition over the substrate comprising at least one metal based layer selected from tungsten, chromium, tantalum, molybdenum, aluminum, niobium, and mixtures and alloys thereof, and mixtures and alloys of cobalt and chromium; and at least one dielectric layer including a silicon nitride having a formula of Si x N y , where x/y ranges from 0.75 to 1.5, over the metal based layer.
  • the present invention is a coated substrate comprising a first dielectric layer including a silicon nitride having a formula of Si x N y , where x/y ranges from 0.75 to 1.5, over the substrate, a metal based layer selected from tungsten, chromium, aluminum, tantalum, molybdenum, and mixtures and alloys thereof, and mixtures and alloys of cobalt and chromium over the first dielectric layer; and a second dielectric layer including a silicon nitride having a formula of Si x N y , where x/y ranges from 0.75 to 1.5, over the metal based layer.
  • the present invention is a coated substrate comprising a first metal based layer selected from tungsten, chromium, tantalum, molybdenum, aluminum, niobium, and mixtures and alloys thereof, and alloys of cobalt and chromium over the substrate; an infrared reflective layer over the first metal based layer; and a second metal based layer selected from tungsten, chromium, tantalum, molybdenum, aluminum, niobium, and mixtures and alloys thereof; and mixtures and alloys of cobalt and chromium over the infrared reflective layer and a dielectric layer over the second metal based layer.
  • the present invention is a method for making a coated substrate comprising depositing a metal based layer selected from tungsten, chromium, tantalum, molybdenum, aluminum, niobium, and mixtures and alloys thereof; and mixtures and alloys of cobalt and chromium on a substrate; and depositing a dielectric layer including a layer of Si x N y , where x/y ranges from 0.75 to 1.5, over the metal based layer.
  • a metal based layer selected from tungsten, chromium, tantalum, molybdenum, aluminum, niobium, and mixtures and alloys thereof; and mixtures and alloys of cobalt and chromium on a substrate
  • a dielectric layer including a layer of Si x N y , where x/y ranges from 0.75 to 1.5, over the metal based layer.
  • the present invention is a method for modifying the R1 color of a coated substrate including a first dielectric layer including a silicon nitride having a formula of Si x N y over the substrate, a metal based layer selected from tungsten, tantalum, chromium, aluminum, molybdenum, and mixtures and alloys thereof; and mixtures and alloys of cobalt and chromium over the first dielectric layer and a second dielectric layer including a silicon nitride having a formula of Si x N y over the metal based layer, wherein x/y ranges from 0.75 to 1.5, comprising adjusting the thickness of the second dielectric layer.
  • the present invention is a method for modifying the R2 color of a coated substrate including a first dielectric layer including a silicon nitride having a formula of Si x N y over the substrate, a metal based layer selected from tungsten, tantalum, chromium, aluminum, molybdenum and mixtures and alloys thereof; and mixtures and alloys of cobalt and chromium over the first dielectric layer and a second dielectric layer including a silicon nitride having a formula of Si x N y over the metal based layer, where x/y ranges from 0.75 to 1.5, comprising adjusting the thickness of the first dielectric layer.
  • a stated range of “1 to 10” should be considered to include any and all subranges between (and inclusive of) the minimum value of 1 and the maximum value of 10; that is, all subranges beginning with a minimum value of 1 or more and ending with a maximum value of 10 or less, e.g., 1.0 to 7.8, 3.0 to 4.5, and 6.3 to 10.0.
  • the terms “on”, “applied on/over”, “formed on/over”, “deposited on/over”, “overlay” and “provided on/over” mean formed, overlay, deposited, or provided on but not necessarily in contact with the surface.
  • a coating layer “formed over” a substrate does not preclude the presence of one or more other coating layers of the same or different composition located between the formed coating layer and the substrate.
  • the substrate can include a conventional coating such as those known in the art for coating substrates, such as glass or ceramic.
  • aesthetic properties i.e., transmitted color, reflected color and brightness
  • R1 properties aesthetic properties as viewed from the coated side of the substrate
  • R2 properties aesthetic properties as viewed from the uncoated side of the substrate
  • a coated substrate is “color stable” if ⁇ E cmc(1.5:1) (T), ⁇ E cmc(1.5:1) (R1) and ⁇ E cmc(1.5:1) (R2) of the non-heat treated coated substrate compared to the heat treated, coated substrate are no greater than or equal to 8 units, for example, no greater than or equal to 5 units, or no greater than or equal to 1 unit.
  • Heat treated substrate refers to a coated substrate heated to a temperature of at least 1150° F. (621° C.). The method used to calculate ⁇ E per the CMC color difference equation can be found in the Principle of Color Technology by Roy S. Berns, Third Edition, John Wiley and Sons, 117-118, (2000) which is incorporated by reference.
  • the L*a*b* data used should be for a CIE standard illuminant D65 and a CIE standard observer angle of 10 degrees.
  • the present invention is a coated substrate comprising at least one metal based layer and at least one dielectric layer.
  • suitable substrates include glass, steel, ceramic, etc.
  • the glass is made via conventional float glass processes. Suitable float processes are described in U.S. Pat. Nos. 3,083,551; 3,220,816; and 3,843,346, which are hereby incorporated by reference.
  • the substrate is a glass float ribbon.
  • the metal based layer has a single film or multi-film configuration and overlays the substrate.
  • the metal based layer provides physical and chemical durability to the coated substrate and comprises a metal that is corrosion resistant, hard, and able to withstand heating for 20 minutes to a maximum temperature of 1200° F. (649° C.).
  • Suitable materials for the metal based layer include metals such as tungsten, chromium, tantalum, molybdenum, niobium, and mixtures and alloys thereof, as well as mixtures and alloys of cobalt and chromium, which are commercially available under the Stellite® family of products from Deloro Stellite in Geshan, Indiana.
  • the metal based layer is a highly reflective material such as aluminum.
  • the metal based layer can have any thickness.
  • the thickness of the metal based layer can range from 1 nm to 50 nm, for example, from 2 nm to 25 nm, or 3 nm to 20 nm.
  • the thickness of the metal based layer can affect the visible transmittance of the coated substrate. Generally, the thicker the metal based layer, the lower the visible light transmittance of the coated substrate.
  • the metal based layer of the present invention can be applied using conventional techniques such as magnetron sputtered vacuum deposition (“MSVD”). Suitable MSVD methods of deposition are described in the following references, which are hereby incorporated by reference: U.S. Pat. Nos. 4,379,040; 4,861,669; and 4,900,633.
  • a dielectric layer overlays the metal based layer.
  • the dielectric layer provides mechanical durability and impacts the aesthetic properties of the coated substrate.
  • the dielectric layer can be made up of a single film or multiple films.
  • the dielectric layer is a single film comprising Si x N y , where x/y ranges from 0.75 to 1.5, for example, Si 3 N 4 .
  • a layer of titanium nitride, chromium nitride or tungsten nitride as well as mixtures thereof can be over the dielectric layer.
  • the dielectric layer is made up of multiple films.
  • the multiple film configuration can comprise (i) a first dielectric film comprising Si x N y having an index of refraction; (ii) a second dielectric film over the first dielectric film having an index of refraction lower than the index of refraction of the first dielectric film; and (iii) a third dielectric film comprising Si x N y over the second film.
  • the second dielectric film has an index of refraction that is at least 0.25, for example, at least 0.2 or at least 1.8, less than the index of refraction of the first Si x N y film.
  • An example of a suitable material for the second dielectric film is silicon dioxide.
  • the dielectric layer can be any thickness.
  • the thickness of the dielectric layer can be at least 5 nm, for example, from 10 nm to 50 nm, or from 20 nm to 40 nm.
  • the thickness of the dielectric layer has a dominant effect on the R1 aesthetic properties of the coated substrate.
  • the strength of the effect depends on the thickness of the metal based layer. The effect is more pronounced for thicker metal based layers.
  • the thickness of the dielectric layer has a lesser effect on the R2 aesthetic properties of the coated substrate as compared to the R1 properties.
  • the dielectric layer of the present invention can be applied using MSVD as discussed above in reference to the metal based layer, as well as CVD and spray pyrolysis methods, which are well known in the art.
  • the metal based layer and the dielectric layer discussed above comprise the “basic coating stack” of the present invention and are referred to herein as the “basic metal based layer” and the “basic dielectric layer”, respectively.
  • layers of other materials can be incorporated into the basic coating stack to provide different performance properties.
  • the coating stack of the present invention comprises additional dielectric layers.
  • the coated substrate comprises a first dielectric layer over the substrate, a metal based layer over the first dielectric layer, and a second dielectric layer over the metal based layer.
  • the first and second dielectric layers have the same composition and thickness as described above in reference to the basic dielectric layer.
  • the R1 and R2 aesthetic properties can be controlled by varying the thickness of the dielectric layers.
  • the coated substrate of the present invention is used as a member of a multi-ply glazing unit, the coated surface typically faces the interior of the structure within which the window is installed so that the R2 properties are the properties viewed from the exterior of the structure.
  • the primary effect of adjusting the thickness of the second dielectric layer is modifying the R1 color of the coated substrate.
  • the primary effect of adjusting the thickness of the first dielectric layer is modifying the R2 color of the coated substrate.
  • the strength of the effect depends on the thickness of the metal based layer. The effect is more pronounced for thicker metal based layers.
  • Suitable materials for the metal based layer for this non-limiting embodiment include metals such as tungsten, chromium, tantalum, molybdenum, aluminum, and mixtures and alloys thereof; as well as mixtures and alloys of cobalt and chromium which are commercially available under the Stellite® family of products.
  • the metal based layer can be applied as described above.
  • the first and second dielectric layers can be applied using conventional techniques such as CVD, spray pyrolysis, and MSVD as discussed above.
  • an infrared reflective layer and a second metal based layer are included in the coating stack of the present invention. More particularly, the coated substrate of the present invention comprises a first metal based layer over the substrate, an infrared reflective layer over the first metal based layer, a second metal based layer over the infrared reflective layer and a dielectric layer over the second metal based layer.
  • Suitable materials for the infrared reflective layer include metals such as gold, copper, and silver as well as mixtures and alloys thereof.
  • composition and thickness of the first and second metal based layers are as discussed above for the basic metal based layer.
  • the metal based layers can be applied as discussed above.
  • composition and thickness of the dielectric layer is as discussed above for the basic dielectric layer.
  • the dielectric layer can be applied as discussed above.
  • the infrared reflective layer can be any thickness.
  • the thickness of the layer of infrared reflective material can range from 1 nm to 50 nm, for example, from 1 nm to 25 nm, or from 2 nm to 20 nm.
  • the thicker the infrared reflective layer the lower the emissivity of the coated substrate.
  • the infrared reflective layer of the present invention can be applied using conventional MSVD techniques as discussed above.
  • the various embodiments of the coated substrate exhibit the following performance properties: an emissivity of no greater than 0.8, for example, 0.3 to 0.7 or 0.3 to 0.6, a visible transmittance no greater than 90%, for example 2% to 85% or 5% to 60%, and an R2 visible reflectance of at least 4%, for example, 4% to 70% or 10% to 70%.
  • the coated substrate is also color stable.
  • all of the described embodiments of the present invention can include a protective overcoat as the last layer of the coating stack to provide improved chemical and/or mechanical durability.
  • suitable protective coatings include, but are not limited to, a layer of coating comprising silicon dioxide, zirconium dioxide, titanium dioxide, niobium dioxide, chromium dioxide and silicon oxynitride as well as mixtures thereof.
  • Coated substrates according to the present invention can be used in various applications such as automotive applications, architectural applications, etc.
  • the coated substrate of the present invention is included in an insulating glass unit.
  • the present invention also encompasses methods for making the coated substrates.
  • the method of the invention comprises depositing a metal based layer selected from tungsten, chromium, tantalum, molybdenum, aluminum, niobium, and mixtures and alloys thereof; and alloys of cobalt and chromium on a substrate; and depositing a dielectric layer comprising Si x N y , where x/y ranges from 0.75 to 1.5, over the metal based layer.
  • the present invention further encompasses methods for modifying the R1 and R2 color of a coated substrate by adjusting the thickness of the first or second dielectric layer.
  • Samples 1-12 were prepared in a conventional laboratory MSVD coater under standard coating conditions.
  • the substrate was a 6 mm thick piece of clear glass.
  • the various configurations of the coating stacks are shown in Table 1.
  • the described coating layers were applied over a substrate from left to right (i.e., the first dielectric layer was applied first, then the metal based layer was applied, etc.) as described in Table 1.
  • the first dielectric layer was a multiple film configuration comprised of a first film of silicon nitride, a film of silicon dioxide over the first film of silicon nitride and a second film of silicon nitride over the film of silicon dioxide. More particularly, in Samples 3 and 4, the first dielectric layer was comprised of a 24 nanometer (nm) thick first film of Si 3 N 4 , a 7 nm thick film of silicon dioxide over the first film of silicon nitride and a 24 nm thick second film of silicon nitride over the film of silicon dioxide.
  • the first dielectric layer was comprised of a 18 nm thick first film of silicon nitride, a 14 nm thick film of silicon dioxide over the first film of silicon nitride and a 18 nm thick second film of silicon nitride over the film of silicon dioxide.
  • the first dielectric layer was comprised of a 18 nm thick first film of silicon nitride, a 28 nm thick film of silicon dioxide over the first film of silicon nitride and a 18 nm thick second film of silicon nitride over the film of silicon dioxide.
  • the first dielectric layer was comprised of a 18 nm thick first film of silicon nitride, a 10 nm thick film of silicon dioxide over the first film of silicon nitride and a 18 nm thick second film of silicon nitride over the film of silicon dioxide.
  • the first dielectric layer was comprised of Si 3 N 4 .
  • the metal based layer for each sample was comprised of Stellite® 6B alloy, and the protective overcoat was comprised of silicon dioxide (if one was present).
  • TABLE 1 Description of the Coating Configurations for the Various Samples Thickness of Thickness of Thickness of the First the Metal the Second Thickness of Dielectric based layer Dielectric the Protective Sample Layer [nm] [nm] Layer [nm] Overcoat [nm] 1 47 18 38 10 2 47 17 38 3 55 18 38 10 4 55 17 38 5 12 15 37 10 6 12 14 37 7 50 17 37 10 8 50 16 37 9 64 17 37 10 10 64 16 37 11 46 19 43 10 12 46 18 43
  • the exemplary coated substrates were subjected to a Taber test to measure the durability of the coated substrates.
  • the Taber test involves imparting a standard level of mechanical exposure to each sample using a Gardner Taber Abraser commercially available from the Paul N. Gardner Company, Inc. in Pompano Beach, Fla.
  • the Taber test was performed as follows. First, a load of 500 grams was employed on both wheels of the Gardner Taber Abraser. The two abrasive wheels on the instrument were specified as Calibrase CS-10F having a specified durometer hardness of 72+5. Second, a 4 inch by 4 inch example was taped at two edges to a 5-7 ⁇ 8 inch diameter platen. Third, the sample was abraded 10 cycles, removed from then platen and cleaned using towels and 50/50 solution of isopropanol/deionized water.
  • the recorded Taber score is then calculated in the following manner: the diffuse reflectance, Y (CIE 1931 Y, x, y chromaticity space), was measured using a TCS Spectrogard calorimeter (commercially available from BYK-Gardner) at four positions around a circle that corresponded to the Taber abrasion track. The Spectrogard calorimeter was run in large aperture “specular-excluded” mode with an Illuminant D65, 2° observer. The average of the four diffuse reflectance measurements was recorded as the Taber score. A higher Taber score indicates more diffuse reflectance from the abrasion track and is interpreted as indicating a greater degree of damage.
  • Samples 13-16 were prepared in a conventional laboratory MSVD coater under standard coating conditions.
  • the substrate was 6 mm thick clear float glass.
  • the coating stack of Sample 13 comprised a 25 nm thick first dielectric layer of Si 3 N 4 over the substrate, a 16 nm thick metal based layer of Stellite®6B alloy over the first dielectric layer, a 35 nm second dielectric layer of Si 3 N 4 over the metal based layer and a 15 nm thick protective layer of silicon dioxide over the second dielectric layer.
  • the coating stack of Sample 14 comprised a multiple film first dielectric layer over the substrate made up of 16 nm of Si 3 N 4 , 31 nm of silicon oxide over the Si 3 N 4 and 16 nm of Si 3 N 4 over the silicon dioxide, a 16 nm thick metal based layer of Stellite®6B alloy over the first dielectric layer, a 35 nm second dielectric layer of Si 3 N 4 over the metal based layer and a 15 nm thick protective layer of silicon dioxide over the second dielectric layer.
  • the coating stack of Sample 15 comprised a multiple film first dielectric layer over the substrate made up of 70 nm of Si 3 N 4 , 19 nm of silicon oxide over the Si 3 N 4 and 16 nm of Si 3 N 4 over the silicon dioxide, a 16 nm thick metal based layer of Stellite®6B alloy over the first dielectric layer, a 35 nm second dielectric layer of Si 3 N 4 over the metal based layer and a 15 nm thick protective layer of silicon dioxide over the second dielectric layer.
  • the coating stack of Sample 15 comprised a multiple film first dielectric layer over the substrate made up of 70 nm of Si 3 N 4 , 19 nm of silicon oxide over the Si 3 N 4 and 19 nm of Si 3 N 4 over the silicon dioxide, a 16 nm thick metal based layer of Stellite®6B alloy over the first dielectric layer, a 35 nm second dielectric layer of Si 3 N 4 over the metal based layer and a 15 nm thick protective layer of silicon dioxide over the second dielectric layer.
  • Table 3 shows various performance properties of the samples in an insulating glass unit made up of two, 6 mm clear glass plies with a 12 mm air gap. A coating of the present invention was applied on the #2 surface (i.e., inboard surface of outboard ply). The performance properties were determined using Lawrence Berkeley National Lab's WINDOW 5.2.17 algorithm based on the measured spectrophotometric data.
  • a color stability test was also performed on the samples.
  • the chromaticity values (L*a*b* for a CIE standard illuminant D65 and a CIE standard observer angle of 10°) were measured using a Perkin-Elmer Lambda 9 UV/VIS/NIR spectrophotometer prior to heat treatment. Each sample was then heated to raise the temperature of the sample to 1150° F. (649° C.) for 20 minutes and the chromaticity values were measured again. The measured data was used to determine color stability via ⁇ E cmc(1.5:1) (T), ⁇ E cmc(1.5:1) (R1) and ⁇ E cmc(1.5:1) (R2) as described above.
  • coated substrate according to the present invention exhibits good durability as represented by a Taber score.
  • the exemplary coated substrates exhibited Taber scores of no greater than 0.09.
  • the tested samples also demonstrated excellent color stability as demonstrated by ⁇ E cmc(1.5:1) (T), ⁇ E cmc(1.5:1) (R1) and ⁇ E cmc(1.5:1) (R2).
  • the exemplary coated substrates exhibited a ⁇ E cmc(1.5:1) (T) of no greater than 2.07, a ⁇ E cmc(1.5:1) (R1) of no greater than 2.40 and a ⁇ E cmc(1.5:1) (R2) of no greater than 1.70.
  • a coated substrate is “color stable” if the ⁇ E cmc(1.5:1) (T), a ⁇ E cmc(1.5:1) (R1) and a ⁇ E cmc(1.51) (R2) of the non-heat treated coated substrate and the heat treated substrate are no greater than or equal to 8 units.
  • coated substrates according to the present invention can exhibit the following properties when incorporated into an insulating glass unit as described above: a visible light transmittance no greater than 22%, for example no greater than 19%, an R2 Reflectance no greater than 42%, for example, no greater than 39% or no greater than 35%, an R1 Reflectance no greater than 30%, for example, no greater than 28%, or no greater than 26%, a shading coefficient no greater than 0.30, for example, no greater than 0.28, or no greater than 0.25, a U-Value no greater than 0.45, for example, no greater than 0.42, or no greater than 0.41.
  • a visible light transmittance no greater than 22% for example no greater than 19%
  • an R2 Reflectance no greater than 42% for example, no greater than 39% or no greater than 35%
  • an R1 Reflectance no greater than 30% for example, no greater than 28%, or no greater than 26%
  • a shading coefficient no greater than 0.30 for example, no greater than 0.28, or no greater than 0.25
  • the color stability of these exemplary substrates is demonstrated by a ⁇ E cmc(1.5:1) (T) of no greater than 1.1, a ⁇ E cmc(1.5:1) (R1) of no greater than 1.0 and a ⁇ E cmc(1.5:1) (R2) of no greater than 1.9.
  • the substrates can also be produced in a variety of colors as demonstrated by the chromaticity values.

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  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Surface Treatment Of Glass (AREA)
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EP05792592.7A EP1784522B1 (en) 2004-09-01 2005-08-25 Metal based coating composition and related coated substrates
RU2007111924/02A RU2379377C2 (ru) 2004-09-01 2005-08-25 Композиция покрытия на основе металла и соответствующие подложки с нанесенным покрытием
PCT/US2005/030375 WO2006028729A1 (en) 2004-09-01 2005-08-25 Metal based coating composition and related coated substrates
US11/712,240 US7923131B2 (en) 2004-09-01 2007-06-01 Metal based coating composition and related coated substrates
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WO2012095380A1 (fr) * 2011-01-11 2012-07-19 Agc Glass Europe Vitrage de controle solaire
WO2014125081A1 (fr) * 2013-02-14 2014-08-21 Agc Glass Europe Vitrage de contrôle solaire
WO2014207171A1 (fr) * 2013-06-27 2014-12-31 Agc Glass Europe Vitrage antisolaire
TWI471443B (zh) * 2010-09-15 2015-02-01 Hon Hai Prec Ind Co Ltd 殼體之製作方法及由該方法製得之殼體
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HUE049451T2 (hu) * 2008-03-20 2020-09-28 Agc Glass Europe Vékony rétegekkel bevont üvegezés
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EA019368B1 (ru) * 2008-03-20 2014-03-31 Агк Гласс Юроп Остекление, обладающее солнцезащитными и низкоэмиссионными свойствами
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AU2014301013B2 (en) * 2013-06-27 2018-03-29 Agc Glass Europe Solar protection glazing
US9944553B2 (en) * 2013-06-27 2018-04-17 Agc Glass Europe Solar protection glazing
EA031932B1 (ru) * 2013-06-27 2019-03-29 Агк Гласс Юроп Секция солнцезащитного остекления
CN108081710A (zh) * 2017-12-11 2018-05-29 东莞南玻工程玻璃有限公司 镀膜夹层玻璃的制备工艺

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EP1784522A1 (en) 2007-05-16
RU2379377C2 (ru) 2010-01-20
US7923131B2 (en) 2011-04-12
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WO2006028729A1 (en) 2006-03-16
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US20070218311A1 (en) 2007-09-20

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