WO2024112425A1 - Articles en verre et leurs procédés de fabrication - Google Patents

Articles en verre et leurs procédés de fabrication Download PDF

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Publication number
WO2024112425A1
WO2024112425A1 PCT/US2023/036982 US2023036982W WO2024112425A1 WO 2024112425 A1 WO2024112425 A1 WO 2024112425A1 US 2023036982 W US2023036982 W US 2023036982W WO 2024112425 A1 WO2024112425 A1 WO 2024112425A1
Authority
WO
WIPO (PCT)
Prior art keywords
inorganic layer
porous inorganic
polymeric material
glass article
interlayer
Prior art date
Application number
PCT/US2023/036982
Other languages
English (en)
Inventor
Mickaël Berrebi
Jean-Francois Georges Bruneaux
Original Assignee
Corning Incorporated
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Corning Incorporated filed Critical Corning Incorporated
Publication of WO2024112425A1 publication Critical patent/WO2024112425A1/fr

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Classifications

    • 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
    • C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00—Layered products having a non-planar shape
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10036—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10082—Properties of the bulk of a glass sheet
    • B32B17/101—Properties of the bulk of a glass sheet having a predetermined coefficient of thermal expansion [CTE]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10082—Properties of the bulk of a glass sheet
    • B32B17/10119—Properties of the bulk of a glass sheet having a composition deviating from the basic composition of soda-lime glass, e.g. borosilicate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10165—Functional features of the laminated safety glass or glazing
    • B32B17/10247—Laminated safety glass or glazing containing decorations or patterns for aesthetic reasons
    • B32B17/10256—Laminated safety glass or glazing containing decorations or patterns for aesthetic reasons created by printing techniques
    • B32B17/10266—Laminated safety glass or glazing containing decorations or patterns for aesthetic reasons created by printing techniques on glass pane
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10165—Functional features of the laminated safety glass or glazing
    • B32B17/10293—Edge features, e.g. inserts or holes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10165—Functional features of the laminated safety glass or glazing
    • B32B17/10339—Specific parts of the laminated safety glass or glazing being colored or tinted
    • B32B17/10348—Specific parts of the laminated safety glass or glazing being colored or tinted comprising an obscuration band
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10605—Type of plasticiser
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10761—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing vinyl acetal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10788—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing ethylene vinylacetate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10807—Making laminated safety glass or glazing; Apparatus therefor
    • B32B17/10889—Making laminated safety glass or glazing; Apparatus therefor shaping the sheets, e.g. by using a mould
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10807—Making laminated safety glass or glazing; Apparatus therefor
    • B32B17/10899—Making laminated safety glass or glazing; Apparatus therefor by introducing interlayers of synthetic resin
    • B32B17/10935—Making laminated safety glass or glazing; Apparatus therefor by introducing interlayers of synthetic resin as a preformed layer, e.g. formed by extrusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10807—Making laminated safety glass or glazing; Apparatus therefor
    • B32B17/10981—Pre-treatment of the layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/22—Layered products comprising a layer of synthetic resin characterised by the use of special additives using plasticisers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/027—Thermal properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/402—Coloured
    • B32B2307/4023—Coloured on the layer surface, e.g. ink
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/41—Opaque
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B32B2307/737—Dimensions, e.g. volume or area
    • B32B2307/7375—Linear, e.g. length, distance or width
    • B32B2307/7376—Thickness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • B32B2605/08—Cars
    • 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
    • C03C2217/425—Coatings comprising at least one inhomogeneous layer consisting of a porous layer

Definitions

  • the present disclosure relates generally to glass articles and methods of making the same and, more particularly, to glass articles comprising a porous inorganic layer and methods of forming the same.
  • Enamel layers are commonly used as decorative and tinting elements for automotive glass such as windshields, sunroofs, and rear windows. As decorations, enamel typically takes the form of dot gradients and borders along the periphery of window glass. Decorative layers can serve both to enhance appearance and to protect underlying adhesives from ultraviolet degradation, for example.
  • Automotive glass has conventionally been formed from thermally tempered soda-lime silica glass. Thermal tempering induces surface compressive stress that strengthens the glass against mechanical failure. However, the stresses and inherent risks of the road require conventional automotive glass to be relatively thick and heavy for a desired level of durability. Because such soda-lime silica glasses tend to suffer from several drawbacks from a durability standpoint. Examples of such drawbacks of soda-lime silicates include poor chemical weathering performance, impact performance, and scratch performance.
  • Borosilicate glasses are being considered for automotive window applications because they have several advantages over soda-lime silica glass, including improved chemical weathering performance, improved scratch resistance, improved impact performance, and favorable low densities.
  • One complexity associated with borosilicate glasses is that such glasses tend to have coefficients of thermal expansion (CTEs) that are lower than those associated with soda-lime silica glasses or aluminosilicate glasses.
  • CTEs coefficients of thermal expansion
  • Such lower coefficients of thermal expansion associated with borosilicate glasses may be incompatible with commercially available ceramic enamels. CTE differences between borosilicate glasses and commercially available enamels may degrade mechanical performance of the windshield glass and prevent the windshield glass from having a desired appearance.
  • glass articles comprising a porous inorganic layer with a polymeric material positioned in a plurality of pores of the porous inorganic layer.
  • Providing the polymeric material with a low glass transition temperature e.g., about 85°C or less
  • Providing a polymeric material with a glass transition temperature of about 40°C or more can reduce changes in properties of the polymeric material during a range of temperatures commonly encountered during use of the glass article.
  • Providing a thickness of the polymeric material outside of the plurality of pores of about 30 pm or less can reduce the visibility of the polymeric material in portions of the glass article without the porous inorganic layer(s), which can simplify manufacturing since slight misalignments or overapplication of a precursor of the polymeric material may not need to be removed (e.g., cleaned) from the glass substrate(s).
  • Providing a polymeric thickness of about 1 pm or more outside of the plurality of pores can provide enough polymeric material that the polymeric material can also be positioned in the plurality of pores of the porous inorganic layer. Positioning the polymeric material in the plurality of pores can provide a substantially uniform appearance with a predetermined color.
  • the glass article can exhibit a low maximum AE value between portions of the glass article with a porous inorganic layer having the polymeric material in the plurality of pores and without the polymeric material can provide a substantially uniform color associated with the porous inorganic layer that may be visually imperceptible to a viewer.
  • the porous inorganic layer(s) may act as a decorative layer with a predetermined color appearance when incorporated into a laminate.
  • the porosity has been found to prevent the porous inorganic layer(s) from degrading the mechanical strength of the glass substrate(s). Without wishing to be bound by theory, it is believed that the porosity reduces the size of areas of continuous contact between the glass substrate and the decorative enamel, which reduces CTE-induced stress buildup caused during fabrication of the decorated glass article, thereby reducing or preventing flaw formation and propagation.
  • the porosity may also aid the porous inorganic layer in having a predetermined color appearance when incorporated into a laminate.
  • an interlayer is used to attach a glass substrate with a porous inorganic layer to another glass substrate.
  • a polymeric material can fdl a plurality of pores of the porous inorganic layer, which may darken the appearance of the portion of the glass article including the porous inorganic layer.
  • Providing the porous inorganic layer(s) on inner surfaces of the glass article can serve to protect the layers from mechanical degradation and/or oxidation. Moreover, placement of the porous inorganic layer(s) may also aid in concealing any additional components (e.g., conductive elements associated with a defogging system) embedded between the first glass substrate 200 and the second glass substrate 220. Also, multiple bands of the porous inorganic layer(s) can provide a predetermined aesthetic appearance when the first glass substrate and the second glass substrate are constructed of glasses with different compositions and/or thicknesses. In aspects, the porous inorganic layer(s) will have the dual function of offering an attractive appearance and acting as a shield to block visible and ultraviolet (UV) light.
  • UV visible and ultraviolet
  • the glass article may include additional functionality, for example, including an infrared reflective coating and/or an anti -reflective coating.
  • additional functionality for example, including an infrared reflective coating and/or an anti -reflective coating.
  • the first glass substrate can comprise a borosilicate glass composition, which can be particularly beneficial as the outside of an automotive glazing since the borosilicate glass may have greater thermal shock resistance and be more resistant to crack formation from impact events from road debris (e.g., rocks or the like) than soda-lime silicate glasses currently used as outer glass substrates in automotive glazings.
  • Such glasses have been found to exhibit a favorable ring cracking behavior preventing radial propagation of flaws from an impact point.
  • Such fusion-formed glasses may also exhibit superior chemical durability, scratch resistance, mechanical strength, and optical performance (e.g., from both an optical transmission and optical distortion perspective) than other borosilicate glasses.
  • Providing the polymeric material separate from the interlayer can enable the interlayer (or portions thereof) to have different compositions and/or properties.
  • a concentration of plasticizer can be greater in the polymeric material than in the interlayer (or portions thereof) and/or the polymeric material can have a lower glass transition temperature than the interlayer (or portions thereof) even when a polymer in the polymeric material is the same as a polymer in the interlayer.
  • Providing at least a portion of the interlayer with no plasticizer (or a reduced amount relative to the polymeric material) can reduce an incidence of damage (e.g., corrosion) to any wiring or electronic devices that may be positioned therein.
  • providing at least a portion of the interlayer with no plasticizer (or a reduced amount relative to the polymeric material) can reduce optical distortion and/or haze that may interfere with the operation of an optical device (e.g., camera) positioned within the interlayer or configured to view objects through the second portion of the glass article (e.g., a camera positioned inside an automobile configured to view the surroundings outside of the automobile).
  • an optical device e.g., camera
  • the second portion of the glass article e.g., a camera positioned inside an automobile configured to view the surroundings outside of the automobile.
  • the polymeric material can be provided by drying a polymeric solution or a polymeric emulsion.
  • Providing the polymeric solution or the polymeric emulsion with a low viscosity e.g., about 8,000 milliPascal-seconds or less
  • the polymeric material can be formed by drying the polymeric solution or the polymeric emulsion without any reactions (e.g., cross-linking or polymerization).
  • the polymer in the polymeric solution or the polymeric emulsion can be substantially the same as the polymer in the polymeric material.
  • the limited processing involved in disposing the polymeric material can simplify processing and/or reduce costs.
  • a glass article comprising: a first glass substrate comprising a first substrate thickness defined between a first major surface and a second major surface opposite the first major surface; a second glass substrate comprising a second substrate thickness defined between a third major surface and a fourth major surface opposite the third major surface; an interlayer positioned between the second major surface and the third major surface; a porous inorganic layer comprising a plurality of pores and adhered to the second major surface or the third major surface; and a polymeric material positioned in the plurality of pores, wherein a first glass transition temperature of the interlayer is greater than a second glass transition temperature of the polymeric material by about 10°C or more.
  • Aspect 2 The glass article of aspect 1, wherein the first glass transition temperature of the interlayer is greater than the second glass transition temperature of the polymeric material by from about 15°C to about 30°C.
  • Aspect 3 The glass article of any one of aspects 1-2, wherein a maximum AE value between a first portion of the glass article where the polymeric material is positioned within the plurality of pores of the porous inorganic layer and a second portion of the glass article including the porous inorganic layer where the porous inorganic layer is not filled with the polymeric material is about 2.0 or less when illuminated with a D65 illuminant from the first major surface.
  • a glass article comprising: a first glass substrate comprising a first substrate thickness defined between a first major surface and a second major surface opposite the first major surface; a second glass substrate comprising a second substrate thickness defined between a third major surface and a fourth major surface opposite the third major surface; an interlayer positioned between the second major surface and the third major surface; a porous inorganic layer comprising a plurality of pores and adhered to the second major surface or the third major surface; and a polymeric material positioned in the plurality of pores, wherein a maximum AE value between a first portion of the glass article where the polymeric material is positioned within the plurality of pores of the porous inorganic layer and a second portion of the glass article including the porous inorganic layer where the porous inorganic layer is not filled with the polymeric material is about 2.0 or less when illuminated with a D65 illuminant from the first major surface.
  • Aspect 5 The glass article of any one of aspects 3-4, wherein the maximum AE value is from about 0. 1 to about 1 .0.
  • Aspect 6 The glass article of any one of aspects 3-5, wherein an absolute value of a difference between a CIE L* value of the first portion and a CIE L* value of the second portion is about 1 or less.
  • Aspect 7 The glass article of aspect 6, wherein the absolute value of the difference between the CIE L* value of the first portion and the CIE L* value of the second portion is about 0.5 or less.
  • Aspect 8 The glass article of any one of aspects 3-7, wherein an absolute value of a difference between a CIE a* value of the first portion and a CIE a* value of the second portion is about 0.5 or less.
  • Aspect 9 The glass article of any one of aspects 3-8, wherein an absolute value of a difference between a CIE b* value of the first portion and a CIE b* value of the second portion is about 0.5 or less.
  • Aspect 10 The glass article of any one of aspects 1-9, wherein a polymer of the polymeric material is the same as a polymer of the interlayer.
  • Aspect 11 The glass article of any one of aspects 1-9, wherein a polymer of the polymeric material is different than a polymer of the interlayer.
  • Aspect 12 The glass article of aspect 11, wherein the polymeric material is semicrystalline, and a melting temperature of the polymeric material is about 100°C or less.
  • Aspect 13 The glass article of any one of aspects 1-12, wherein the interlayer comprises poly(vinyl butyral).
  • Aspect 14 The glass article of any one of aspects 1-13, wherein an absolute value of a difference between a refractive index of the polymeric material and a refractive index of either the first glass substrate or the second glass substrate is about 0.05 or less.
  • Aspect 15 The glass article of any one of aspects 1-14, wherein a portion of the glass article comprising the porous inorganic layer surrounds another portion of the glass article without the porous inorganic layer on at least two sides.
  • Aspect 16 The glass article of aspect 15, wherein at least part of the another portion of the glass article is free from the polymeric material, and at least a part of the portion of the glass article comprising the porous inorganic layer includes the polymeric material.
  • Aspect 17 The glass article of any one of aspects 15-16, wherein the interlayer is non-uniform with at least part of the interlayer in the another portion of the glass article contains a lower concentration of a plasticizer than a concentration of the plasticizer in the portion of the glass article comprising the porous inorganic layer includes the polymeric material.
  • Aspect 18 The glass article of any one of aspects 1-16, wherein a concentration of a plasticizer in the polymeric material is greater than a concentration of a plasticizer in the interlayer.
  • Aspect 19 The glass article of any one of aspects 1-16, wherein the polymeric material comprises a plasticizer in an amount from about 25 wt% to about 50 wt% of the polymeric material.
  • Aspect 20 The glass article of any one of aspects 1-19, wherein the glass article exhibits an integrated visible transmittance of about 2.0% or less for light from 400 nm to 700 nm that is normally incident on the first major surface in a portion of the glass article comprising the porous inorganic layer.
  • Aspect 21 The glass article of any one of aspects 1-20, wherein the polymeric material comprises substantially linear polymers.
  • Aspect 22 The glass article of any one of aspects 1-21, wherein a polymeric thickness of the polymeric material is about 30 micrometers or less.
  • Aspect 23 The glass article of any one of aspects 1-22, wherein the polymeric material is present at a periphery of the glass article covering the porous inorganic layer.
  • Aspect 24 The glass article of any one of aspects 1-23, wherein the porous inorganic layer comprises a porosity from about 10% to about 60% by volume.
  • Aspect 25 The glass article of any one of aspects 1-24, wherein a thickness of the porous inorganic layer is from about 10 micrometers to about 30 micrometers.
  • Aspect 26 The glass article of any one of aspects 1-25, further comprising a second porous inorganic layer adhered to the third major surface, wherein the porous inorganic layer is adhered to the second major surface, and the polymeric material is positioned within pores of the first porous inorganic layer and within pores of the second porous inorganic layer.
  • Aspect 27 The glass article of any one of aspects 1-26, further comprising wiring or an electronic component positioned between the first glass substrate and the second glass substrate.
  • Aspect 28 The glass article of any one of aspects 1-26, wherein the interlayer comprises a first interlayer and a second interlayer, the glass article further comprises: an additional polymeric layer positioned between the first interlayer and the second interlayer; and wiring or an electronic component positioned between the first interlayer and the second interlayer.
  • a method of forming a glass article comprising: filling a plurality of pores of a porous inorganic layer with a polymeric solution or a polymeric emulsion, the porous inorganic layer adhered to a first glass substrate; drying the polymeric solution or the polymeric emulsion at a temperature from about 20°C to about 80°C for about 10 minutes or more to form a polymeric material positioned within the plurality of pores; disposing an interlayer on the porous inorganic layer; and laminating the first glass substrate to a second glass substrate such that the porous inorganic layer and the interlayer are positioned between the first glass substrate and the second glass substrate.
  • Aspect 30 The method of aspect 29, wherein a viscosity of the polymeric solution or the polymeric emulsion is in a range from about 10 mPa-s to about 8,000 mPa-s.
  • Aspect 31 The method of any one of aspects 29-30, wherein filling the plurality of pores comprises disposing a layer of the polymeric solution or the polymeric emulsion comprising a thickness of about 30 micrometers or less.
  • Aspect 32 The method of aspect 31, wherein the polymeric solution or the polymeric emulsion is disposed by brushing, rolling, or spraying.
  • Aspect 33 The method of any one of aspects 29-32, further comprising, before drying the polymeric solution or the polymeric emulsion, covering a periphery of the porous inorganic layer with the polymeric solution or the polymeric emulsion.
  • Aspect 34 The method of any one of aspects 29-33, wherein a first glass transition temperature of the interlayer is greater than a second glass transition temperature of the polymeric material by about 10°C or more.
  • Aspect 35 The method of aspect 34, wherein the first glass transition temperature of the interlayer is greater than the second glass transition temperature of the polymeric material by from about 15°C to about 30°C.
  • Aspect 36 The method of any one of aspects 29-35, wherein a maximum AE value between a first portion of the glass article where the polymeric material is positioned within the plurality of pores of the porous inorganic layer and a second portion of the glass article where the porous inorganic layer is not filled with the polymeric material is about 2.0 or less when illuminated with a D65 illuminant from the first major surface.
  • Aspect 37 The method of aspect 36, wherein the maximum AE value is from about 0. 1 to about 1.0.
  • Aspect 38 The method of any one of aspects 36-37, wherein an absolute value of a difference between a CIE L* value of the first portion and a CIE L* value of the second portion is about 1 or less.
  • Aspect 39 The method of any one of aspects 36-38, wherein an absolute value of a difference between a CIE a* value of the first portion and a CIE a* value of the second portion is about 0.5 or less.
  • Aspect 40 The method of any one of aspects 36-39, wherein an absolute value of a difference between a CIE b* value of the first portion and a CIE b* value of the second portion is about 0.5 or less.
  • Aspect 41 The method of any one of aspects 29-40, wherein a polymer of the polymeric material is the same as a polymer of the interlayer.
  • Aspect 42 The method of any one of aspects 29-41, wherein a polymer of the polymeric material is different than a polymer of the interlayer.
  • Aspect 43 The method of aspect 42, wherein the polymeric material is semicrystalline, and a melting temperature of the polymeric material is about 100°C or less.
  • Aspect 44 The method of any one of aspects 29-43, wherein the interlayer comprises poly(vinyl butyral).
  • Aspect 45 The method of any one of aspects 29-44, wherein an absolute value of a difference between a refractive index of the polymeric material and a refractive index of either the first glass substrate or the second glass substrate is about 0.05 or less.
  • Aspect 46 The method of any one of aspects 29-45, wherein a portion of the glass article comprising the porous inorganic layer surrounds another portion of the glass article without the porous inorganic layer on at least two sides.
  • Aspect 47 The method of aspect 46, wherein at least part of the another portion of the glass article is free from the polymeric material, and at least a part of the portion of the glass article comprising the porous inorganic layer includes the polymeric material.
  • Aspect 48 The method of any one of aspects 46-47, wherein the interlayer is non-uniform with at least part of the interlayer in the another portion of the glass article contains a lower concentration of a plasticizer than a concentration of the plasticizer in the portion of the glass article comprising the porous inorganic layer includes the polymeric material.
  • Aspect 49 The method of any one of aspects 29-47, wherein a concentration of a plasticizer in the polymeric material is greater than a concentration of a plasticizer in the interlayer.
  • Aspect 50 The method of any one of aspects 29-47 or 49, wherein the polymeric material comprises a plasticizer in an amount from about 25 wt% to about 50 wt% of the polymeric material.
  • Aspect 51 The method of any one of aspects 29-50, wherein the glass article exhibits an integrated visible transmittance of about 2.0% or less for light from 400 nm to 700 nm in a portion of the glass article comprising the porous inorganic layer.
  • Aspect 52 The method of any one of aspects 29-51, wherein the polymeric material comprises substantially linear polymers.
  • Aspect 53 The method of any one of aspects 29-52, wherein the porous inorganic layer comprises a porosity from about 10% to about 60% by volume.
  • Aspect 54 The method of any one of aspects 29-53, wherein an inorganic thickness of the porous inorganic layer is from about 10 micrometers to about 30 micrometers.
  • Aspect 55 The method of any one of aspects 29-54, wherein the interlayer comprises a first interlayer and a second interlayer, the glass article further comprises: an additional polymeric layer positioned between the first interlayer and the second interlayer; and wiring or an electronic component positioned between the first interlayer and the second interlayer.
  • FIG. 1 is an illustration of a vehicle including a glass article (e.g., automotive glazing) according to aspects of the disclosure, where cross-sectional views taken along line 2-2 may appear as shown in FIGS. 2-6;
  • a glass article e.g., automotive glazing
  • FIG. 2 depicts a cross-sectional view of the glass article (e.g., automotive glazing) taken along line 2-2 of FIG. 1 with a single interlayer according to aspects of the disclosure, where view 7 can appear as shown in FIG. 7;
  • the glass article e.g., automotive glazing
  • FIG. 3 depicts a cross-sectional view of the glass article (e.g., automotive glazing) taken along line 2-2 of FIG. 1 showing a curved automotive glazing according to aspects of the disclosure;
  • the glass article e.g., automotive glazing
  • FIG. 4 depicts a cross-sectional view of the glass article (e.g., automotive glazing) taken along line 2-2 of FIG. 1 with a non-uniform interlayer according to aspects of the disclosure;
  • the glass article e.g., automotive glazing
  • FIG. 5 depicts a cross-sectional view of the glass article (e.g., automotive glazing) taken along line 2-2 of FIG. 1 with an electronic device in a non- uniform interlayer according to aspects of the disclosure;
  • the glass article e.g., automotive glazing
  • FIG. 6 depicts a cross-sectional view of the glass article (e.g., automotive glazing) taken along line 2-2 of FIG. 1 with multiple layers and an electronic device between the glass substrates according to aspects of the disclosure;
  • the glass article e.g., automotive glazing
  • FIG. 7 depicts an enlarged view 7 of FIG. 2 showing the porous inorganic layer and polymeric material
  • FIG. 8 depicts a glass article with a design corresponding to the porous inorganic layer suitable for automobile windshields;
  • FIG. 9 is a flow chart illustrating example methods of making a glass article in accordance with aspects of the disclosure.
  • FIG. 10 schematically illustrates a step in methods of making a glass article comprising filling a plurality of pores of the porous inorganic layer in accordance with the flow chart of FIG. 9;
  • FIG. 11 schematically illustrates a step in methods of making a glass article comprising drying the material within the pores to form a polymeric material in accordance with the flow chart of FIG. 9;
  • FIG. 12 schematically illustrates a step in methods of making a glass article comprising placing an interlayer between two glass substrates in accordance with the flow chart of FIG. 9;
  • FIG. 13 schematically illustrates a step in methods of making a glass article comprising laminating the first glass substrate to the second glass substrate with the interlayer and the porous inorganic layer positioned therebetween in accordance with the flow chart of FIG. 9;
  • FIG. 14 depicts a cross-sectional view of the glass article (e.g., automotive glazing) taken along line 2-2 of FIG. 1 with an electronic device between the glass substrates with a porous inorganic layer occupying a footprint of the electronic device according to aspects of the disclosure.
  • the glass article e.g., automotive glazing
  • FIG. 1 illustrates a vehicle 100 including a body 110 defining an interior and at least an opening 120 with a glass article 130 (e.g., automotive glazing) in accordance with aspects of the disclosure positioned in the opening 120.
  • the glass article 130 can be a windshield, although the glass article can also be used in at least one sidelight, rear window, side window, sunroof, or combinations thereof in further aspects.
  • the glass article 130 can be part of an interior display, an engine block cover, a headlight cover, a taillight cover, a door panel cover, a pillar cover, or a combination thereof.
  • a “vehicle” e.g., vehicle 100 includes automobiles (e.g., see FIG.
  • FIG. 2 schematically depicts a cross-sectional view of the glass article 130 (e.g., automotive glazing) taken along line 2-2 in FIG. 1 according to aspects of the disclosure.
  • the glass article(s) 130, 300, 400, 500, 600, or 1400 comprises a first glass substrate 200, a second glass substrate 220, and an interlayer 230, 430, 630, or 1430 positioned between the first glass substrate 200 and the second glass substrate 220.
  • FIGS. 1 the glass article(s) 130, 300, 400, 500, 600, or 1400 comprises a first glass substrate 200, a second glass substrate 220, and an interlayer 230, 430, 630, or 1430 positioned between the first glass substrate 200 and the second glass substrate 220.
  • the first glass substrate 200 comprises a first major surface 202, a second major surface 204 opposite the first major surface 202, and a first substrate thickness 206 defined as an average distance between the first major surface 202 and the second major surface 204.
  • the second glass substrate 220 comprises a third major surface 222, a fourth major surface 224 opposite the third major surface 222, and a second substrate thickness 226 defined as an average thickness between the third major surface 222 and the fourth major surface 224.
  • the interlayer 230, 430, 630, or 1430 is positioned between the second major surface 204 of the first glass substrate 200 and the third major surface 222 of the second glass substrate 220.
  • An interlayer thickness 236 or 636 is defined as an average distance between the second major surface 204 and the third major surface 222.
  • the interlayer serves to bond the second major surface 204 of the first glass substrate 200 and the third major surface 222 of the second glass substrate 220, which can be accomplished with one or more layers and/or portions of material positioned therebetween, as discussed below.
  • the first substrate thickness 206 is at least 0.5 millimeters (mm), at least 1 mm, at least 1.6 mm, at least 2 mm, at least 3 mm, at least 3.3 mm, or at least 3.8 mm.
  • the first substrate thickness 206 is in a range from about 0.1 mm to about 6 mm, from about 0.3 mm to about 6 mm, from about 0.5 mm to about 6 mm, from about 0.8 mm to about 6 mm, from about 1 mm to about 6 mm, from about 1.2 mm to about 6 mm, from about 1.4 mm to about 6 mm, from about 1.5 mm to about 6 mm, from about 1.6 mm to about 5.8 mm, from about 1.6 mm to about
  • 1.6 mm to about 4.8 mm from about 1.6 mm to about 4.6 mm, from about 1.6 mm to about 4.4 mm, from about 1.6 mm to about 4.2 mm, from about 1.6 mm to about 4 mm, from about 1.6 mm to about 3.9 mm, from about 1.6 mm to about 3.8 mm, from about 1.6 mm to about 3.7 mm, from about 1.6 mm to about 3.6 mm, from about 1.6 mm to about 3.5 mm, from about 1.6 mm to about 3.4 mm, from about 1.6 mm to about 3.3 mm, from about 1.6 mm to about 3.2 mm, from about 1.6 mm to about 3.1 mm, from about 1.6 mm to about 3 mm, from about 1.6 mm to about 2.8 mm, from about 1.6 mm to about 2.6 mm, from about 1.6 mm to about 2.4 mm, from about 1.6 mm to about 2.2 mm, from about 1.6 mm to about 2 mm,
  • the second substrate thickness 226 of the second glass substrate 220 is less than the first substrate thickness 206.
  • the second substrate thickness 226 can be about 2.0 mm or less, for example, from about 0.1 mm to about 2.0 mm, from about 0.1 mm to about 1.8 mm, from about 0.1 mm to about
  • a total glass thickness (i.e., the first substrate thickness 206 plus the second substrate thickness 226) can be 8 mm or less, 7 mm or less, 6.5 mm or less, 6 mm or less, 5.5 mm or less, 5 mm or less, or about 2 mm or more.
  • a coefficient of thermal expansion is measured in accordance with ASTM E831-19 to calculate the CTE between 25°C and 300°C, unless otherwise indicated.
  • a CTE of the first glass substrate 200 and/or the second glass substrate 220 can be about 55xl0' 7 K 1 or less, about 50xl0' 7 K 1 or less, about 45xl0' 7 K 1 or less, about 40xl0' 7 K 1 or less, about 35xl0' 7 K 1 or less, about 32.5xlO' 7 K' 1 or less.
  • the first glass substrate 200 can comprise, consist of, or consists essentially of a borosilicate glass composition.
  • the CTE of the first glass substrate 200 can be within one or more of the ranges mentioned above in this paragraph. Such a low CTE range may render the first glass substrate 200 incompatible with decoration via existing commercially available enamels.
  • the second glass substrate 220 can be a soda-lime silicate glass or a chemically- strengthenable alkali aluminosilicate glass composition having a CTE greater than the CTE of the first glass substrate 200 (e.g., borosilicate glass composition).
  • the first glass substrate 200 and the second glass substrate 220 can comprise different compositions.
  • the CTE of the second glass substrate 220 can be 60xl0' 7 K 1 about or more, for example, from about 60xl0' 7 K 1 to about 120xl0' 7 K’ 1 , from about 70xl0' 7 K 1 to about 120xl0' 7 K’ 1 , from about 80xl0' 7 K 1 to about 120xl0' 7 K’ 1 , or any range or subrange therebetween.
  • an absolute value of a difference between the CTE of the first glass substrate 200 and the CTE of the second glass substrate 220 can be at least 5xl0' 7 K’ 1 , at least lOxlO' 7 K’ 1 , at least 20xl0' 7 K’ 1 , at least 25xl0' 7 K’ 1 , at least 30xl0' 7 K’ 1 , at least 35xl0' 7 K’ 1 , at least 40xl0' 7 K’ 1 , at least 40xl0' 7 K’ 1 , at least 45xl0' 7 K’ 1 , or at least 50xl0' 7 K’ 1 .
  • first glass substrate 200 can have a first CTE of approximately 32xl0' 7 K 1 and the second glass substrate 220 can have a second CTE of approximately 90xl0' 7 K’ 1 .
  • first glass substrate 200 has a first CTE of approximately 45x1 O' 7 K 1 and the second glass substrate 220 has a second CTE of approximately 90xl0' 7 K’ 1 .
  • the first glass substrate 200 comprises a borosilicate glass composition comprising from 60 mol% to 90 mol% SiCh, from about 1 mol% to about 20 mol% AI2O3, from 7 mol% to 16 mol% B2O3, from 2 mol% to 20 mol% R2O, where R2O comprises a combined amount of Na2O, Li2O, and K2O.
  • An exemplary borosilicate glass composition comprises about 83.60 mol% SiCh, about 1.20 mol% AI2O3, about 11.60 mol% B2O3, about 3.00 mol% Na2O, and about 0.70 mol% K2O, and comprises a CTE of about 32x1 O' 7 K’ 1 .
  • Such borosilicate glasses may be particularly beneficial when the first glass substrate 200 is on the outside of an automotive glazing (e.g., glass article 130) such that the first major surface 202 is an outer surface of the automotive glazing, as the borosilicate glass may have greater thermal shock resistance and be more resistant to crack formation from impact events from road debris (e.g., rocks or the like) than soda-lime silicate glasses currently used as outer glass substrates in automotive glazings.
  • Borosilicate glasses are known to exhibit less anomalous cracking behavior and be less susceptible to the formation of cracks that radially propagate from a point of debris impact, which is particularly beneficial for automotive glazing durability.
  • the first glass substrate 200 particularly beneficially comprises one of the fusion-formable borosilicate glass compositions described in U.S. Provisional Patent Application No. 63/123863, entitled “Fusion Formable Borosilicate Glass Composition and Articles Formed Therefrom” filed on December 10, 2020, U.S. Provisional Patent Application No. 63/183271, entitled “Fusion Formable Borosilicate Glass Composition and Articles Formed Therefrom” filed on May 3, 2021, U.S. Provisional Patent Application No. 63/183292, entitled “Glass with Unique Fracture Behavior for Vehicle Windshield” filed on May 3, 2021, U.S. Patent Application No.
  • such a borosilicate glass composition comprises, in terms of constituent oxides, SiOa, B2O3, AI2O3, one or more alkali metal oxides, and one or more divalent cation oxides selected from the group consisting of MgO, CaO, SrO, BaO, and ZnO.
  • the borosilicate glass composition comprises from about 11 mol% to about 16 mol% B2O3, from about 2 mol % to about 6 mol% AI2O3, and a total amount of Na2O, K2O, MgO, and CaO of about 7.0 mol% or more.
  • the first glass substrate 200 comprises a fusion-formable borosilicate glass composition comprising from about 74 mol% to about 80 mol% SiO2, from about 2.5 mol% to about 6 mol% AI2O3, from about 11.5 mol% to about 14.5 mol% B2O3, from about 4.5 mol% to about 8 mol% Na2O, from about 0.5 mol% to about 3 mol% K2O, from about 0.5 mol% to about 2.5 mol% MgO, and from 0 mol% to about 4 mol% CaO (e.g., such that a combined amount of CaO and MgO is less than 5 mol%), and a CTE from about 32.5xl0' 7 K 1 to about 56xl0' 7 K’ 1 .
  • a fusion-formable borosilicate glass composition comprising from about 74 mol% to about 80 mol% SiO2, from about 2.5 mol% to about 6 mol% AI2O3, from about 11.5 mol% to about 1
  • the borosilicate glass composition can satisfy the relationships: (R2O + R'O) > Al, (R2O + RO) > (AI2O3 + 2), and/or 0.80 ⁇ (1 - [(2R 2 O + 2RO)/(SiO 2 + 2A1 2 O 3 + 2B 2 O 3 )]) ⁇ 0.93, where all concentrations are in mole percent on an oxide basis.
  • R2O is the sum of alkali metal oxides, namely, Li 3 O, Na 3 O. K2O, Rb 3 O. and CS2O.
  • R'O is the sum of alkali earth metal oxides including MgO, CaO, SrO, and BaO.
  • Such glasses have been found to exhibit a favorable ring cracking behavior preventing radial propagation of flaws from an impact point.
  • Such fusion-formed glasses may also exhibit superior chemical durability, scratch resistance, mechanical strength, and optical performance (e.g., from both an optical transmission and optical distortion perspective) than other borosilicate glasses.
  • the second glass substrate 220 can comprise, consist of, or consist essentially of a second glass composition that is different from the composition of glass used to form the first glass substrate 200.
  • the second glass substrate comprises a soda lime silicate composition, an aluminosilicate glass composition, an alkali aluminosilicate glass composition, an alkali containing borosilicate glass composition, an alkali aluminophosphosilicate glass composition, or an alkali aluminoboro silicate glass composition.
  • the second glass substrate 220 comprises one of the boroaluminosilicate glass compositions described in U.S. Provisional Patent Application No.
  • the second glass substrate 220 is formed of one of the glass compositions described in U.S. Patent Application No. 16/002276, entitled “Automotive Glass Compositions, Articles, and Hybrid Uaminates” filed on June 7, 2018” or U.S. Patent No. 10,125,044, entitled “Ion Exchangeable High Damage Resistance Glasses” filed on November 14, 2014.
  • the content of each of these patent applications is hereby incorporated by reference in their entireties.
  • neither of the first glass substrate 200 and the second glass substrate 220 are strengthened (e.g., chemically, thermally, or mechanically), although in other aspects, at least one of the first glass substrate 200 or the second glass substrate 220 is strengthened (e.g., chemically, thermally, or mechanically).
  • the second glass substrate 220 can be chemically strengthened (e.g., when constructed of a suitable alkali aluminosilicate glass composition) and the first glass substrate 200 is unstrengthened (but may optionally be annealed) and exhibits a surface compressive stress of less than about 3 MPa, or about 2.5 MPa or less, 2 MPa or less, 1.5 MPa or less, 1 MPa or less, or about 0.5 MPa or less.
  • a surface compressive stress of less than about 3 MPa, or about 2.5 MPa or less, 2 MPa or less, 1.5 MPa or less, 1 MPa or less, or about 0.5 MPa or less.
  • both the first glass substrate 200 and the second glass substrate 220 can be strengthened.
  • the second glass substrate 220 and/or the first glass substrate 200 can be strengthened with one or more compressive stress regions.
  • Chemically strengthening comprises an ion exchange process, where ions in a surface layer are replaced by-or exchanged with-larger ions having the same valence or oxidation state. Methods of chemically strengthening will be discussed later.
  • a compressive stress region can extend into a portion of the first portion and/or the second portion for a depth called the depth of compression.
  • depth of compression means the depth at which the stress in the chemically strengthened substrates and/or portions described herein changes from compressive stress to tensile stress.
  • Depth of compression is measured by a surface stress meter or a scattered light polariscope (SCALP, wherein values reported herein were made using SCALP-5 made by Glasstress Co., Estonia) depending on the ion exchange treatment and the thickness of the article being measured.
  • a surface stress meter for example, the FSM-6000 (Orihara Industrial Co., Ltd. (Japan)
  • compressive stress is measured by surface stress meter (FSM) using commercially available instruments, for example the FSM- 6000, manufactured by Orihara.
  • SOC stress optical coefficient
  • ASTM standard C770- 16(2020) entitled “Standard Test Method for Measurement of Glass Stress-Optical Coefficient,” the contents of which are incorporated herein by reference in their entirety.
  • SCALP is used to measure the depth of compression and central tension (CT).
  • the depth of compression and CT are measured by SCALP.
  • the exchange depth of sodium may indicate the depth of compression while the exchange depth of potassium ions may indicate a change in the magnitude of the compressive stress (but not the change in stress from compressive to tensile).
  • the refracted near-field (RNF; the RNF method is described in U.S. Patent No. 8,854,623, entitled “Systems and methods for measuring a profile characteristic of a glass sample”, which is incorporated herein by reference in its entirety) method also may be used to derive a graphical representation of the stress profile.
  • DOL depth of layer
  • the maximum central tension when the maximum central tension cannot be measured directly by SCALP (as when the article being measured is thinner than about 400 pm) the maximum central tension can be approximated by a product of a maximum compressive stress and a depth of compression divided by the difference between the thickness of the substrate and twice the depth of compression, wherein the compressive stress and depth of compression are measured by FSM.
  • a first compressive stress region can extend to a first depth of compression from the third major surface 222 of the second glass substrate 220, and/or a second compressive stress region can extend to a second depth of compression from the fourth major surface 224 of the second glass substrate 220.
  • the first depth of compression and/or the second depth of compression as a percentage of the second substrate thickness can be about 1% or more, about 5% or more, about 10% or more, about 30% or less, about 25% or less, or about 20% or less.
  • the first depth of compression and/or the second depth of compression as a percentage of the substrate thickness can be in a range from about 1% to about 30%, from about 5% to about 25%, from about 10% to about 20%, or any range or subrange therebetween.
  • the first depth of compression and/or the second depth of compression can be about 1 pm or more, about 10 pm or more, about 30 pm or more, about 50 pm or more, about 500 pm or less, about 2000 pm or less, about 100 pm or less, or about 60 pm or less.
  • the first depth of compression and/or the second depth of compression can be in a range from about 1 pm to about 500 pm, from about 10 pm to about 200 pm, from about 30 pm to about 100 pm, from about 50 pm to about 60 pm, or any range or subrange therebetween. In aspects, the first depth of compression can be substantially equal to the second depth of compression.
  • the first compressive stress region can comprise a maximum first compressive stress
  • the second compressive stress region can comprise a maximum second compressive stress.
  • the maximum first compressive stress and/or the maximum second compressive stress can be about 100 MegaPascals (MPa) or more, about 250 MPa or more, about 500 MPa or more, about 600 MPa or more, about 700 MPa or more, about 1,500 MPa or less, about 1,200 MPa or less, about 1,000 MPa or less, or about 800 MPa or less.
  • the maximum first compressive stress and/or the maximum second compressive stress can be in a range from about 100 MPa to about 1,500 MPa, from about 250 MPa to about 1,200 MPa, from about 500 MPa to about 1,000 MPa, from about 600 MPa to about 1,000 MPa, from about 700 MPa to about 800 MPa, or any range or subrange therebetween.
  • the first glass substrate 200 is chemically strengthened, it can comprise compressive stress region(s) with depth(s) of compression and/or maximum compressive stress values within one or more of the ranges discussed above for the first compressive stress region and/or the second compressive stress region.
  • the glass article 130, 300, 400, 500, 600, or 1400 comprises a first porous inorganic layer 240.
  • the glass article 130, 300, 400, 500, 600, or 1400 further comprises a second porous inorganic layer 250.
  • the first porous inorganic layer 240 is not porous but another suitable decorative coating (e.g., non- porous enamel, inorganic ink, organic ink, other suitable decorative material).
  • the first porous inorganic layer 240 may not be included, In aspects, the first porous inorganic layer 240 can be adhered to the third major surface 222, although the first porous inorganic layer 240 can be adhered to the second major surface 204 in other aspects. In further aspects, the second porous inorganic layer 250 can be adhered to the second major surface 204, and the first porous inorganic layer 240 can be adhered to the third major surface 222. Providing the first porous inorganic layer 240 and/or the second porous inorganic layer 250 on the inner surfaces of the glass article (e.g., second major surface 204, third major surface 222) can serve to protect the layers from mechanical degradation and/or oxidation.
  • the inner surfaces of the glass article e.g., second major surface 204, third major surface 222
  • first porous inorganic layer 240 and/or the second porous inorganic layer 250 on the second major surface 204 and the third major surface 222 may also aid in concealing any additional components (e.g., conductive elements associated with a defogging system) embedded between the first glass substrate 200 and the second glass substrate 220.
  • additional components e.g., conductive elements associated with a defogging system
  • multiple bands of the porous inorganic layer(s) can provide a predetermined aesthetic appearance when the first glass substrate 200 and the second glass substrate 220 are constructed of glasses with different compositions and/or thicknesses.
  • the first porous inorganic layer 240 can extend for a width substantially perpendicular to a direction of the first substrate thickness 206 that is different (e.g., less than) a width that the second porous inorganic layer 250 extends substantially perpendicular to the direction of the first substrate thickness 206.
  • the first porous inorganic layer 240 and the second porous inorganic layer 250 can extend for substantially the same width for a width substantially perpendicular to a direction of the first substrate thickness 206.
  • the glass article 130, 400, 500, 600, or 1400 comprises a first portion 294a including the first porous inorganic layer 240 and/or the second porous inorganic layer 250 and a second portion 292 free of the first porous inorganic layer 240 and the second porous inorganic layer 250, if present in the first portion 294a.
  • the first portion 294a and the second portion 292 each include a portion of the first glass substrate 200, a portion of the second glass substrate 220, and a portion of the interlayer 230, 430, 630, or 1430. Further, as shown in FIGS.
  • a cross-sectional view of the glass article 130, 400, 500, 600, or 1400 can appear to have another first portion 294b including the first porous inorganic layer 240 and/or the second porous inorganic layer 250 separated from the first portion 294a by the second portion 292. Consequently, the second portion 292 can be surrounded by the first portion 294a and 294b on at least two sides.
  • the structure 800 includes a glass article 820 surrounded by a border 810.
  • the glass article 8320 includes a first portion 894 including a decorative pattern including the porous inorganic layer 840 and a second portion 892 including the first glass substrate 830 but free of the porous inorganic layer 840.
  • the first portion 894 surrounds the second portion 892 on at least two sides (e.g., first portion 894 is surrounded by the second portion 892 on three sides, as shown in FIG. 8).
  • a portion of a surface of the glass article 130, 400, 500, 600, 800, or 1400 e.g., first major surface 202 of the first glass substrate 200
  • corresponding the first portion 294a, 294b, and/or 894 or corresponding to the porous inorganic layer can be less than 60%, 50%, 40%, 30%, 20%, 10%, 5%, 1%, 0.1%, or less than 0.01% of the total surface area of the surface of the glass article.
  • the porous inorganic layer(s) described herein can function as a decorative enamel.
  • Decorative enamels can serve an aesthetic purpose, a functional purpose, or both.
  • the porous inorganic layer(s) will have the dual function of offering an attractive appearance and acting as a shield to block visible and ultraviolet (UV) light.
  • the second porous inorganic layer 250 comprises an inorganic thickness 746 perpendicular to the second major surface 204.
  • the inorganic thickness 746 can correspond to a distance between a first surface 732 adhered to the second major surface 204 and a second surface 734 opposite the first surface 732.
  • the thickness of the first porous inorganic layer 240 and/or the second porous inorganic layer 250 is measured using a scanning electron microscope (SEM) image.
  • SEM scanning electron microscope
  • an inorganic thickness of the first porous inorganic layer 240 and/or the second porous inorganic layer 250 can be about 1 micrometer (pm) or more, about 10 pm or more, about 15 pm or more, about 20 pm or more, about 30 pm or less, about 25 pm or less, or about 20 pm or less.
  • the inorganic thickness of the first porous inorganic layer 240 and/or the second porous inorganic layer 250 can range from about 1 pm to about 30 pm, from about 10 pm to about 30 pm, from about 15 pm to about 25 pm, or any range or subrange therebetween.
  • a thickness of the second porous inorganic layer 250 can comprise a thickness within one or more of the ranges discussed above in this paragraph.
  • the first porous inorganic layer 240 and/or the second porous inorganic layer 250 comprises a plurality of pores. As shown in FIG. 7, the second porous inorganic layer 250 comprises a plurality of pores 760.
  • porosity of a material is calculated from an image taken at a major surface of the material using a scanning electron microscope (SEM), where the SEM image is analyzed using ImageJ with auto-thresholding to determine the fraction of the image corresponding to heights below the threshold.
  • SEM scanning electron microscope
  • a porosity (vol%) of the first porous inorganic layer 240 and/or the second porous inorganic layer 250 can be about 10% or more, about 15% or more, about 20% or more, about 25% or more, about 60% or less, about 50% or less, about 40% or less, or about 30% or less.
  • a porosity of the first porous inorganic layer 240 and/or the second porous inorganic layer 250 can range from about 10% to about 60%, from about 15% to about 50%, from about 20% to about 40%, from about 20% to about 30%, from about 25% to about 30%, or any range or subrange therebetween.
  • the porosity may also act as a decorative with a predetermined color appearance when incorporated into a laminate.
  • the porosity has been found to prevent the porous inorganic layer(s) from degrading the mechanical strength of the glass substrate(s). Without wishing to be bound by theory, it is believed that the porosity reduces the size of areas of continuous contact between the glass substrate and the decorative enamel, which reduces CTE-induced stress buildup caused during fabrication of the decorated glass article, thereby reducing or preventing flaw formation and propagation.
  • the porosity may also aid the porous inorganic layer in having a predetermined color appearance when incorporated into a laminate.
  • an interlayer is used to attach a glass substrate with a porous inorganic layer to another glass substrate.
  • a polymeric material can fdl a plurality of pores of the porous inorganic layer, which may darken the appearance of the portion of the glass article including the porous inorganic layer.
  • the first porous inorganic layer 240 and/or the second porous inorganic layer 250 can comprise a CTE that is within 15xl0’ 7 K’ 1 of the CTE of the glass substrate such that the decorative layer does not degrade a mechanical strength of the glass substrates despite being in contact with the glass substrate(s).
  • the porous inorganic layer(s) may be deposited onto the second major surface and/or the third major surface in a pattern suitable for decorative or concealment purposes.
  • the relatively low CTEs of the decorative layers described herein as compared with certain existing commercially available enamels e.g., with a CTE of approximately 80xl0’ 7 K’ 1 or more) enables use of various borosilicate glasses in automotive glass applications.
  • an absolute value of a difference between a CTE of the glass substrate(s) (CTE g ) and the CTE of the porous inorganic layer (CTE d ) can be about 15 xlO’ 7 K’ 1 or less, about lOxlO' 7 K’ 1 or less, about 9xlO' 7 K _1 or less, about 8xlO' 7 K _1 or less, about 7xl0’ 7 K’ 1 or less, about 6xl0’ 7 K’ 1 or less, about 5xl0’ 7 K’ 1 or less, about 4xl0’ 7 K’ 1 or less, about 3xl0’ 7 K’ 1 or less, about 2xl0’ 7 K’ 1 or less, about IxlO’ 7 K’ 1 or less, about 0.5xl0’ 7 K’ 1 or less, about 0.25xl0’ 7 K’ 1 or less, about 0.2xl0' 7 K’
  • lxlO' 7 K’ 1 or less about 0.05xl0' 7 K’ 1 or less.
  • 20xl0’ 7 K’ 1 ⁇ CTE d ⁇ 32.5xl0’ 7 K’ 1 or any range or subrange therebetween.
  • first porous inorganic layer 240 constructing the porous inorganic layer(s) to have a CTE that is approximately equal to the CTE of the first glass substrate 200 can prevent cracks from forming in the porous inorganic layer during fabrication of the glass article and also prevents the incorporation of the porous inorganic layer from degrading the mechanical strength of the first glass substrate and/or glass article.
  • the first porous inorganic layer 240 and/or the second porous inorganic layer 250 can include a low CTE additive component.
  • the low CTE additive component can be present in an amount of at least 5 wt%, at least 10 wt%, at least 12 wt%, at least 14 wt%, at least 16 wt%, at least 18 wt%, at least 20 wt%, at least 22 wt%, at least 24 wt%, at least 26 wt%, at least 28 wt%, or at least 30 wt%.
  • the low CTE additive component can be present in an amount from about 15 wt% to about 50 wt%, from about 15% to about 45 wt%, from about 20 wt% to about 45 wt%, from about 20 wt% to about 40 wt%, from about 25 wt% to 40 wt%, or any range or subrange therebetween.
  • the low CTE additive component can be present in an amount from about 40 wt% to about 85 wt%, from about 50 wt% to about 85 wt%, from about 50 wt% to about 80 wt%, from about 50 wt% to about 75 wt%, from about 50 wt% to about 70 wt%, or any range or subrange therebetween.
  • the low CTE additive component can be present, as wt% of the low CTE additive, of about 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, or 85 wt%.
  • the low CTE additive component can comprise a ceramic or glass-ceramic material having a CTE in any of the ranges described above.
  • Exemplary ceramics include a B-eucryptite ceramic developed by Coming® Incorporated with a CTE of approximately -10x1 O' 7 K 1 or an aluminum titanate ceramic with a CTE of less than -lOxlO' 7 K’ 1 .
  • An exemplary glass-ceramic material is Kerablack® Plus ceramic sold by Eurokera S.N.C. with a CTE of approximately OxlO' 7 K’ 1 .
  • the low CTE additive component comprises a negative CTE.
  • Such negative CTE materials may include Bi-Ni-Fe-oxides, Zr-W-oxides, and other suitable materials.
  • the low CTE additive component may be selected such that the resultant porous inorganic layer has a predetermined opacity.
  • the low CTE additive component may be selected to absorb light (e.g., at least 50% of light, at least 60% of light, at least 70% of light, at least 80% of light, at least 90% of light) in the visible spectrum (averaged).
  • the low CTE additive component is selected such that the first porous inorganic layer 240 and/or the second porous inorganic layer 250 exhibits a high blackness (e.g., a L* value of about 20 or less, about 18 or less, about 16 or less, about 14 or less, about 13 or less, about 12 or less, about 10 or less, about 8 or less, about 6 or less, about 5 or less) when illuminated by a D65 illuminant at a 0° illumination angle.
  • a high blackness e.g., a L* value of about 20 or less, about 18 or less, about 16 or less, about 14 or less, about 13 or less, about 12 or less, about 10 or less, about 8 or less, about 6 or less, about 5 or less
  • a precursor of the porous inorganic layer(s) may comprise a mixture of an enamel (e.g., frit) and particles of the low CTE additive component.
  • the low CTE additive component can be present in the porous inorganic layer(s) as a fdler.
  • a material of the low CTE additive component may have a melting point or a softening temperature greater than a corresponding temperature of the frit component in the enamel.
  • the particles of the low CTE additive component can comprise an average particle size that is about 100 pm or less, about 50 pm or less, about 40 pm or less, about 30 pm or less, or about 20 pm or less.
  • the size of the particles of the low CTE additive component influences the porosity of the resulting porous inorganic layer after curing, for example, by preventing densification of the enamel (e.g., frit) around the particles during sintering to produce the porous structure.
  • the porosity has been found to prevent the porous inorganic layer from reducing the strength of the glass substrate and/or the glass article or even increase the strength of the glass substrate and/or the glass article.
  • the low CTE additive component can comprise a CTE that is about lOxlO' 7 K 1 or less, about 5xl0' 7 K 1 or less, about OxlO' 7 K 1 or less, about -5xl0' 7 K 1 or less, about -lOxlO' 7 K 1 or less, about -50xl0' 7 K 1 or less, about - 100x1 O' 7 K 1 or less. It has been found that the CTE of the resulting porous inorganic layer after curing is roughly a weighted average of all of the constituent components (e.g., between the frit and the low CTE additive component).
  • the CTE of the low CTE additive can determine the weight percentage needed to achieve a predetermined CTE for a given frit.
  • a refractive index of the low CTE additive component can be about 1.5 or less or about 1.6 or less.
  • the refractive index of the low CTE additive component is greater than 1.6.
  • a higher refractive index may be preferred to maintain higher opacity of the decorative layer.
  • refractive index is measured in accordance with ASTM El 967- 19, where the first wavelength comprises 589 nm.
  • the porous inorganic layer(s) can be formed from a mixture of particles of the low CTE additive component and a commercially available enamel.
  • the commercially available enamel comprises a glass or ceramic enamel comprising a glass frit component, a stain component, and optionally an additive component.
  • the glass frit component determines various characteristics of the resulting porous inorganic layer, including the mechanical strength and required firing conditions.
  • the glass frit can comprise one or more Bi, B, Zn, or Si oxides.
  • the glass frit can be characterized by the presence of Bi, B, Zn, or Si oxides as main components.
  • the glass frit can comprise about 1 wt% or more, about 5 wt% or more, or about 10 wt% or more of Bi, B, Zn, or Si oxide. In further aspects, the glass frit can comprise less than 1 mol% Na2O, less than 10 mol% Fe2C>3, or less than 25 mol% P2O5. In further aspects, the glass frit is free of Na2O, Fe2C>3, or P2O5. In further aspects, the stain component is incorporated into the glass frit and comprises one or more Cu, Co, Fe, Ni, Mn, or Cr oxides. In even further aspects, the stain comprises a non-Fe oxide, or is free of Fe oxides.
  • suitable ceramic enamels are available from Ferro Corporation (Mayfield Heights, Ohio), including Product No. 14 316 (a bismuth- system based frit system, having a black, matte color, a wide firing range of from 570°C to 640°C at 6 minutes, and relatively high melting point) and Product No. VPS 4100 (a black enamel which may be fired at from 630°C to 650°C).
  • the enamel can be black, white, or any color, e.g., red, indigo, blue, green, brown, orange, violet, yellow.
  • the commercially available enamel may be dispersed in a suitable a medium to form a paste for application to a glass substrate, where the medium can comprise an oil or organic resin suitable for drying by an evaporation of solvents.
  • the first porous inorganic layer 240 and/or the second porous inorganic layer 250 can be formed of a commercially available ceramic enamel or glass frit (e.g., without the particles of the low CTE additive component discussed above).
  • the first porous inorganic layer 240 and/or the second porous inorganic layer 250 can be formed of a frit that is designed to be ion exchangeable.
  • the frit can be applied to an ion-exchangeable glass prior to undergoing an ion-exchange treatment. Such frit is configured to allow the exchange of ions between the glass and the treatment bath.
  • the frit can be a Bi-Si-B alkali system, a Zn-based Bi-system, a Bi-Zn-system, a Bi-system, an Si-Zn-B-Ti system with no or low Bi, an Si-Bi-Zn-B-alkali system, and/or an Si- Bi-Ti-B-Zn-alkali system, among others.
  • An exemplary ion-exchangeable frit, including colorant comprises 45.11 mol% Bi 2 O 3 , 20.61 mol% SiO 2 , 13.56 mol% Cr 2 O 3 , 5.11 mol% CuO, 3.48 mol% MnO, 3.07 mol% ZnO, 2.35 mol% B 2 O 3 , 1.68 mol% TiO 2 , 1.60 mol% Na 2 O, 1.50 mol% Li 2 O, 0.91 mol% K 2 O, 0.51 mol% A1 2 O 3 , 0.15 mol% P 2 O 5 , 0.079 mol% SO 3 , 0.076 mol% BaO, 0.062 mol% ZrO 2 , 0.060 mol% Fe 2 O 3 , 0.044 mol% MoO 3 , 0.048 mol% CaO, 0018 mol% Nb 2 O 5 , 0.006 mol% Cl, and 0.012 mol% SrO.
  • the first porous inorganic layer 240 and/or the second porous inorganic layer 250 can comprise (e.g., in addition to the enamel/frit-based components described in the preceding paragraph) a colorant coating comprised of an ink, such as an organic ink. Additionally or alternatively, in aspects, although not shown, a colorant coating may be applied to the third major surface 222 or the fourth major surface 224.
  • a colorant coating may be applied to the second glass substrate 220 while the second glass substrate 220 is in a planar configuration, and then the second glass substrate 220 can be cold formed to a curved configuration without disrupting the colorant coating (e.g., organic ink coating).
  • the colorant coating comprises at least one pigment, at least one mineral filler, and a binder comprising an alkoxysilane functionalized isocyanurate or an alkoxysilane functionalized biuret.
  • a binder comprising an alkoxysilane functionalized isocyanurate or an alkoxysilane functionalized biuret.
  • an infrared reflective (IRR) coating, frit, anti-reflective coating, or pigment coating can be disposed on the first glass substrate and/or the second glass substrate.
  • IRR coating can be disposed on the second major surface 204 of the first glass substrate 200 or the third major surface 222 of the second glass substrate 220 is coated with an infrared- reflective film and, optionally, one or more layers of a transparent dielectric film.
  • the infrared-reflecting film can comprise a conductive metal, such as silver, gold, or copper, that reduces the transmission of heat through the automotive glazing.
  • the optional dielectric film can be used to anti -reflect the infrared-reflecting film and to control other properties and characteristics of the coating, such as color and durability.
  • the dielectric film comprises one or more oxides of zinc, tin, indium, bismuth, and titanium, among others.
  • the IRR coating includes one or two silver layers each sandwiched between two layers of a transparent dielectric film. In embodiments, the IRR coating is applied using physical vapor deposition, chemical vapor deposition, or via lamination.
  • the precursor to the first porous inorganic layer 240 and/or the second porous inorganic layer 250 can include particles of a suitable pigment to provide a predetermined appearance.
  • the pigment particles can be added in an amount that is less than or equal to that of the low CTE additive component (discussed above) .
  • the pigment may also be incorporated into the base frit (e.g., ceramic enamel), for example, as a stain component.
  • the pigment if included, is added such that the pigment is present in an amount that is from greater than 0 wt% to about 50 wt% of the first porous inorganic layer 240 and/or the second porous inorganic layer 250, when cured (e.g., from greater than 0 wt% to about 40 wt%, from greater than 5 wt% to about 30 wt%, from greater than 5 wt% to about 20 wt%, or any range or subrange therebetween).
  • Suitable pigments include BIG pigment, 30C965 (a CuCr-based pigment), 20F944 (a MgFe- based pigment) from Shepherd (Cincinnati, Ohio) and V7709 (a CuCr-based pigment), and 240137 (a FeCrCoNi-based pigment) from Ferro Corporation (Mayfield Heights, Ohio).
  • Pigments can be selected to have the following primary- components in order to obtain a predetermined color, for example as follows: black (CuCrFe, CrFe, manganese ferrite spinel, FeCrCoNi), blue (Cobalt aluminate, cobalt chromite spinel, CoZnCrAl), green (Cobalt titanate green spinel), brown (Manganese antimony titanium buff rutile, zinc iron chromite brown spinel, iron titanium brown spinel), orange (Rutile tin zinc), violet (Cobalt phosphate), yellow (Nickel antimony titanium yellow rutile, niobium sulfur tin zinc oxide), and metallic aspect (Mica flakes covered with titanate, titanate and tin oxide, or iron oxide).
  • black CuCrFe, CrFe, manganese ferrite spinel, FeCrCoNi
  • blue Cobalt aluminate, cobalt chromite spinel, CoZnCrAl
  • green
  • Pigments can be black, blue, green, brown, orange, violet, yellow, or metallic variants thereof.
  • the pigments can be the same or similar color as the frit (e.g., enamel), for example, the pigment and enamel may exhibit CIE a* values and CIE b* values, when illuminated with a D65 illuminate at a 0° illumination angle, that differ from one another by less than 5.
  • the first porous inorganic layer 240 and/or the second porous inorganic layer 250 may also comprise optical properties that are favorable for decorative automotive applications.
  • the first porous inorganic layer 240 and/or the second porous inorganic layer 250 may exhibit a relatively high blackness (e.g., an L* value according to the CIE 1976 color space that is about 20 or less, about 15 or less, about 10 or less, about 5 or less, about 2.5 or less) at a thickness of about 30 pm or less.
  • the first porous inorganic layer 240 and/or the second porous inorganic layer 250 exhibits an integrated visible transmittance of about 2.0% or less (e.g., about 1.8% or less, about 1.6% or less, about 1.4% or less, about 1.2% or less, about 1.0% or less, about 0.8% or less, about 0.6% or less, about 0.4% or less, about 0.2% or less, about 0. 1% or less) for light from 400 nm to 700 nm that is normally incident on the glass article.
  • Such low optical transmittance aids in the decorative layer in performing various concealment and decorative functions in automotive applications.
  • optical transmission and “transmittance” are used interchangeably to refer to a percentage of light transmitted through an article over a wavelength range of interest.
  • An “integrated visible transmittance” for light in a particular wavelength range is determined using the following equation: where T( ) represents a transmittance spectra over the wavelength range, and cp(X) equals the transmission of the light source used to measure the transmission.
  • a portion (e.g., first portion 294a or 294b) of the glass article 130, 300, 400, 500, 600, or 1400 comprising a porous inorganic layer (e.g., the first porous inorganic layer 240 and/or the second porous inorganic layer 250) can comprise an integrated visible transmittance of about 2.0% or less (e.g., about 1.8% or less, about 1.6% or less, about 1.4% or less, about 1.2% or less, about 1.0% or less, about 0.8% or less, about 0.6% or less, about 0.4% or less, about 0.2% or less, about 0.1% or less) for light from 400 nm to 700 nm that is normally incident on the glass article.
  • a precursor of the porous inorganic layer can be compatible with the temperature requirements for bending and laminating the glass substrate(s) to form the glass article.
  • the precursor e.g., uncured modified enamel
  • the precursor may be capable of being cured before or during a heating phase associated with bending the glass substrate(s) into a shape suitable for a glazing application of the glass article.
  • the precursor e.g., modified enamel
  • the precursor may be cured during a heating cycle of the bending process to facilitate process efficiencies.
  • the precursor e.g., modified enamel
  • the glass softening temperature of precursor e.g., the modified enamel
  • the first porous inorganic layer 240, and/or the second porous inorganic layer 250 may be about 750°C or less (e.g., about 725°C or less, about 700°C or less, about 675°C or less, about 650°C or less, about 625°C or less, about 600°C or less, about 575°C or less, about 550°C or less) to facilitate such a simultaneous bending and curing action.
  • a polymeric material 750 can be positioned in a plurality of pores 760 in the second porous inorganic layer 250.
  • the polymeric material can be positioned in a plurality of pores in the second porous inorganic layer 250 without being positioned in all of the plurality of pores (e.g., see pores 762), although in other aspects substantially all of the plurality of pores can have the polymeric material positioned therein.
  • the polymeric material 750 can be positioned in the plurality of pores in a first portion 782 but not in the plurality of pores in a second portion 784.
  • a pore “filled” with the polymeric material means that the polymeric material positioned in a pore without requiring that 100% of a volume of the pore contains the polymeric material.
  • a portion of a material of the interlayer 230, 430, 630, or 1430 can be positioned in one or more of the plurality of pores of the second porous inorganic layer 250.
  • a “maximum” color shift or a “maximum” AE value is the largest value of any AE measured between a point in the first portion relative to a point in the second portion, wherein points in each portion are samples at least every 0.1 mm.
  • CIE values (and AE) is measured using a D65 illuminant incident on the first major surface of the first glass substrate of the glass article and assuming a 2° standard observer, unless otherwise indicated.
  • the maximum AE value between (1) the first portion 782 of the glass article 130 where the polymeric material 750 is positioned within the plurality of pores of the first porous inorganic layer 240 and (2) the second portion 784 of the glass article 130 where the first porous inorganic layer 240 is not filled with the polymeric material 750 when illuminated with a D65 illuminant from the first major surface 202 (see FIG.
  • Providing a low maximum AE value between these portions of the glass article with a porous inorganic layer can provide a substantially uniform color associated with the porous inorganic layer that may be visually imperceptible to a viewer.
  • a maximum absolute value of a difference between the L*i value and the L*2 value can be within or more of the ranges discussed above in this paragraph.
  • a maximum absolute value of a difference between the a*i value and the a* 2 value can be within or more of the ranges discussed above in this paragraph.
  • a maximum absolute value of a difference between the b*i value and the b*2 value can be within or more of the ranges discussed above in this paragraph.
  • the polymeric material can be present at the periphery of the glass article and covering the first porous inorganic layer 240 and/or the second porous inorganic layer 250.
  • the polymeric material 750 can be present at a periphery of the first glass substrate 200 corresponding to a periphery of the resulting glass article.
  • a portion 770 of the polymeric material 750 can cover the second porous inorganic layer 250.
  • the polymeric material covers the second porous inorganic layer if there is no path from outside of the glass article to the porous inorganic layer without going through the polymeric material, the interlayer, or the glass substrates.
  • Providing the polymeric material at the periphery of the glass article can ensure color uniformity of the glass article, including at the periphery of the glass article by filling the pores at the periphery. Also, providing the polymeric material covering the porous inorganic layer, oxygen and moisture can be prevented from entering the glass article, which can improve a longevity of the glass article, including the porous inorganic layer(s).
  • polymers of the polymeric material 750 can comprise substantially linear polymers.
  • substantially linear polymers are substantially free of cross-links that are branching points that connect between otherwise distinct polymeric chains.
  • thermoplastic means a polymeric material that can be reformed after an initial curing (e.g., polymerization) reaction by heating the material. A thermoplastic polymer is to be contrasted with a thermoset polymer, which cannot be reformed after an initial curing reaction.
  • the polymeric material 750 can comprise any of the polymers discussed above for the interlayer.
  • the polymeric material 750 can include poly( vinyl butyral) (PVB) (e.g., acoustic PVB (aPVB)), poly(vinyl chloride) (PVC), an ionomer, poly(ethylene-co-vinyl acetate) (EVA), polyurethane (e.g., thermoplastic polyurethane (TPU)), or combinations thereof and any of these polymers (or blends) can be combined with a plasticizer (discussed below) to form the polymeric material 750.
  • PVB poly(vinyral)
  • PVB poly(vinyl chloride)
  • EVA poly(ethylene-co-vinyl acetate)
  • TPU thermoplastic polyurethane
  • Exemplary aspects of the polymeric material 750 include EVA, plasticized PVB, and plasticized PVC.
  • a glass transition temperature (Tg) of a polymeric material is measured using digital scanning calorimetry (DSC).
  • a second glass transition temperature of the polymeric material 750 e.g., including any plasticizer, if present
  • the second glass transition temperature of the polymeric material 750 can be in a range from about -120°C to about 85°C, from about 40°C to about 80°C, from about 50°C to about 75°C, from about 60°C to about 70°C, or any range or subrange therebetween.
  • Providing a polymeric material with a low glass transition temperature can enable the polymeric material to readily be positioned in (e.g., fill) the plurality of pores of the porous inorganic layer(s).
  • Providing a polymeric material with a glass transition temperature of about 40°C or more can reduce changes in properties of the polymeric material during a range of temperatures commonly encountered during use of the glass article.
  • a polymer of the polymeric material 750 can be semicrystalline with a melting temperature of about 100°C or less, about 90°C or less, or about 80°C.
  • the polymeric material 750 can comprise a plasticizer in addition to a polymer, although the polymeric material can be substantially free of a plasticizer (e.g., consisting essentially of the polymer).
  • a plasticizer refers to a material combined with a polymer that reduces a glass transition temperature of the resulting polymeric material relative to the polymer alone.
  • the plasticizer can comprise fish oil, castor oil, tetraethtylene glycol- di-n-heptanoate, triethyleneglycol di(2-ethyl hexanoate), sebacates (e.g., dibutyl sebacate), adipates (e.g., dihexyl adipate, dioctyl adipate, hexyl cyclohexyl adipate), a phthalate, a trimellitate, an organophosphate.
  • plasticizers include fish oil and castor oil.
  • the polymeric material 750 can comprise, as a wt% of the polymeric material, the plasticizer in an amount of about 20 wt% or more, about 25 wt% or more, about 30 wt% or more, about 35 wt% or more, about 60 wt% or less, about 55 wt% or less, about 50 wt% or less, about 45 wt% , or about 40 wt% or less.
  • the polymeric material 750 can comprise, as a wt% of the polymeric material, the plasticizer in an amount from about 20 wt% to about 60 wt%, from about 20 wt% to about 55 wt%, from about 25 wt% to about 50 wt%, from about 30 wt% to about 45 wt%, from about 35 wt% to about 40 wt%, or any range or subrange therebetween.
  • the plasticizer can decrease the second glass transition temperature of the polymer in the polymeric material 750 relative to the glass transition temperature of the polymer alone by about 10°C or more, by about 15°C or more, about 18°C or more, about 20°C or more, about 40°C or less, about 30°C or less, about 25°C or less, or about 23°C or less.
  • the plasticizer can decrease the second glass transition temperature of the polymer in the polymeric material 750 relative to the glass transition temperature of the polymer alone by from about 10°C to about 40°C, from about 15 °C to about 30°C, from about 18°C to about 25°C, from about 20°C to about 23°C, or any range of subrange therebetween.
  • a plasticizer content (e.g., of the polymeric material 750 or a layer or portion of the interlayer) can be determined using spectroscopy (e.g., infrared (IR) spectroscopy).
  • plasticizers can produce distinctive absorption bands (e.g., compared to the polymers discussed above) and an intensity of the absorption can be correlated with a concentration of the plasticizer.
  • an absolute value of a difference between a refractive index of the polymeric material 750 and a refractive index of either the first glass substrate 200 or the second glass substrate 220 can be about 0.10 or less, about 0.05 or less, about 0.04 or less, about 0.03 or less, about 0.02 or less, or about 0.01 or less.
  • the polymeric material 750 can comprise an adhesion promoter, an ultraviolet (UV) absorber, an antioxidant, or a combination thereof.
  • the adhesion promoter, the UV absorber, and/or the antioxidant may have substantially no impact (e.g., about 1°C or less, 0°C) on the glass transition temperature of the polymeric material 750.
  • a weight of the adhesion promoter, the ultraviolet (UV) absorber, and/or the antioxidant can be about 0.01 wt% or more, about 0.1 wt% or more, about 0.2 wt% or more, about 2 wt% or less, about 1 wt% or less, about 0.5 wt% or less, about 0.4 wt% or less, or about 0.3 wt% or less.
  • a weight of the adhesion promoter, the ultraviolet (UV) absorber, and/or the antioxidant can be in a range from about 0.01 wt% to about 2 wt%, from about 0.1 wt% to about 1 wt%, from about 0.1 wt% to about 0.5 wt%, from about 0.2 wt% to about 0.3 wt%, or any range or subrange therebetween.
  • Adhesion promoters can increase an adhesion between the polymeric material 750 and the porous inorganic layer(s) 240 or 250, the first glass substrate 200, the second glass substrate 220, and/or the interlayer 230 or 430.
  • adhesion promoters include silane coupling agents, for example, amine-functionalized silanes or epoxy-fimctionalized silanes.
  • UV absorbers increase an absorption for one or more optical wavelengths from about 200 nm to about 380 nm.
  • Exemplary aspects of UV absorbers include the TINUVIN and CHIMASSORB product lines available from BASF, including benzotriazole, triazines, and hindered amine light stabilizers.
  • Antioxidants can comprise a phenolic-based compound or a phosphite-based compound.
  • antioxidants comprising phenolic-based compounds available include pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4- hydroxyphenyl)proprionate (e.g., Irganox 1010 (BASF)), thiodiethylene bis[3 -(3,5 -di- ter-butyl-4-hydroxy-phenyl)]propionate (e.g., Irganox 1035 (BASF)), octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl)propionate (e.g., Irganox 1076 (BASF)), benzenepropanoic acid (e.g., Irganox 1135 (BASF)), 3,3’,3’,5,5’,5’-hexa-tert-butyl- a,a’,a’-(mesitylene-2,4,6-triy
  • antioxidants comprising phosphite-based compounds include 2,2’ ,2” -nitrolo(triethyl-tris [3, 3 ’,5,5’ -terta-tert-butyl- 1,1’ -biphenyl -2, 2 ’ - diyl])phosphile (e.g., Irgafos 12 BASF), bis[2,4,-di-tert-butylphenol]pentalerthythiol diphosphate (e.g., Irgafos 126 (BASF), tris[2,4-ditert-butylphenyl]phosphite (e.g., Irgafos 168 (BASF)), bis[2,4-di-tert-butyl-6-methylphenyl]-ethyl-phosphite (e.g., Irgafos 38 (BASF)), trisnonylphenyl phos
  • the interlayer 230, 430, 630, or 1430 adheres the second major surface 204 of the first glass substrate 200 to the third major surface 222 of the second glass substrate 220.
  • the interlayer(s) 230 or 430 can comprise a single layer of a polymeric material with a first contact surface 232 or 432 contacting the second major surface 204 and a second contact surface 234 or 434 contacting the third major surface 222.
  • the interlayer 230 can comprise a substantially homogenous layer of material.
  • the interlayer can be non-uniform (e.g., heterogenous) with a first portion 431a and/or 431b and a second portion 433 having different compositions.
  • concentration of a plasticizer can be different between these portions, for example, with a greater concentration of the plasticizer in the first portion than in the second portion.
  • a polymer in the first portion can be different than a polymer in the second portion.
  • a boundary between the first portion 431a, 431b, 641a, 641b, 651a, and/or 651b and the second portion 433, 643, and/or 654 can be coincident with a boundary between the first portion 294a and/or 294b and the second portion 292 of the glass article, although the first portion 431a, 431b, 641a, 641b, 651a, and/or 651b of the interlayer can extend into a portion of the second portion 292 of the glass article in other aspects.
  • the interlayer 630 can comprise a first interlayer 640, a second interlayer 650, and an additional polymeric layer 660 positioned therebetween.
  • the first interlayer 640 comprises a first contact surface 642 that can contact the second major surface 204 of the first glass substrate 200 and a second contact surface 644 opposite the first contact surface 642 with a first interlayer thickness 646 defined therebetween.
  • the second interlayer 650 comprises a fourth contact surface 654 that can contact the third major surface 222 of the second glass substrate 220 and a third contact surface 652 opposite the fourth contact surface 654 with a second interlayer thickness 656 defined therebetween.
  • the first interlayer 640 and/or the second interlayer 650 can be non-uniform, for example, with a boundary between the first portion 641a, 641b, 651a, and/or 651b and the second portion 643 and/or 653 indicated by reference numbers 648a, 648b, 658a, and/or 658b.
  • the additional polymeric layer 660 can comprise a fifth contact surface 662 contacting the second contact surface 644 of the first interlayer 640 and a sixth contact surface 664 opposite the fifth contact surface 662, where the sixth contact surface can contact the third contact surface 652 of the second interlayer 650.
  • first porous inorganic layer and/or the second porous inorganic layer can include another portion (e.g., see another portion 1470 in FIG. 14) aligned with and/or covering a footprint of the electronic device 661 (as described below).
  • the interlayer 1403 can comprise a first interlayer 1433 and an additional polymeric layer 1460.
  • the first interlayer 1433 comprises a first contact surface 1432 that can contact the second major surface 204 of the first glass substrate 200 and a second contact surface 1434 opposite the first contact surface 1432 with a first interlayer thickness 236 defined therebetween.
  • the additional polymeric layer 1460 comprises a third contact surface 1462 that can contact the second major surface 204 of the first glass substrate 200 and a fourth contact surface 1464 opposite the third contact surface 1462.
  • the first contact surface 1432 of the first interlayer 1433 can contact the fourth contact surface 1464 of the additional polymeric layer 1460.
  • an electronic device 1401 can be disposed on and/or contact the second major surface 204 of the first glass substrate 200, and/or the electronic device 1401 can contact the second major surface 204 and be surrounded on the other sides by the third contact surface 1462 of the additional polymeric layer 1460.
  • the electronic device 1401 can be separated from the first interlayer 1433 by the additional polymeric layer 1460.
  • the first porous inorganic layer 240 can comprise an additional portion 1470 that can be aligned with the electronic device 1401 in a direction of the first substrate thickness 206. Further, the additional portion 1470 can cover a footprint of the electronic device 1401.
  • a first portion covers a footprint of a second portion, if a projection of the second portion in the direction of the first substrate thickness onto a plane including the first portion is completely within an area of the first portion (e.g., the footprint of the second portion can be coincident with the first portion).
  • Providing the additional portion 1470 covering the electronic device can obscure the electronic device when the glass article is viewed from one side while enabling the electronic device to function (e.g., to view the second side opposite the first side), which can provide an aesthetic benefit to a viewer.
  • the glass article 1400 can comprise another part of the first portion 294c that can be surrounded by the second portion 292 on at least two sides while the second portion 292 can be surrounded on at least two sides by the first portion 294a and 294b.
  • the electronic device can be disposed on the third major surface of the second glass substrate with another portion of the second porous inorganic layer covering a footprint of the electronic device. While FIG. 14 depicts a case where the electronic device 1401 is positioned in contact with the first glass substrate 200, aspects are also envisioned where the electronic device 1401 is positioned in contact with the second glass substrate 220 with the additional polymer layer 1460 being in contact with the electronic device 1460.
  • the second porous inorganic layer 250 can include an additional portion covering the electronic device 1401 and such an additional portion can overlap (or contact, or include the polymeric material 750 in pores thereof and in contact with) the additional polymeric layer 1460.
  • a plurality of electronic devices are disposed in direct contact with one of the first glass substrate 200 and/or the second glass substrate 220.
  • the additional polymeric layer 1460 can include a plurality of portions in which such electronic device is encapsulates.
  • a plurality of electronic devices are disposed in contact with the second glass substrate 220 and the additional polymeric layer 1460 can be disposed between such electronic devices and the first glass substrate 200.
  • the second porous inorganic layer 250 can overlap each electronic device.
  • the polymeric material 750 described herein may be incorporated into the pores of the second porous inorganic layer 250 in regions overlapping the additional polymeric layer 1460 to facilitate the glass article having a uniform appearance.
  • the additional polymeric layer 1460 extends an entirety of a distance between the electronic device 1401 and second porous inorganic layer 250 (and may contact the polymer material 750, for example, the additional polymeric layer 1460 can make up a portion of the interlayer 1430).
  • the interlayer 230, 430 (e.g., first portion 431a or 431b), 630 (e.g., first interlayer 640, second interlayer 650), or 1430 (e.g., first interlayer 1433) can comprise any of the polymers discussed above for the polymeric material 750.
  • a polymer of the interlayer 230, 430 e.g., first portion 431a or 431b), 630 (e.g., first interlayer 640, second interlayer 650), or 1430 (e.g., first interlayer 1433) can be the same as the polymer of the polymeric material 750, although a polymer of the interlayer can be different from the polymer of the polymeric material in further aspects.
  • interlayer 230, 430 e.g., first portion 431a or 431b
  • 630 e.g., first interlayer 640, second interlayer 650
  • 1430 e.g., first interlayer 1433
  • a plasticizer for example, any of the plasticizers discussed above for the polymeric material 750.
  • a concentration of the plasticizer in the polymeric material 750 can be greater than the concentration of plasticizer in the interlayer 230, 430 (e.g., first portion 431a or 431b), 630 (e.g., first interlayer 640, second interlayer 650, additional polymeric layer 660), or 1430 (e.g., first interlayer 1433, additional polymeric layer 1460).
  • the concentration of plasticizer in the interlayer 230, 430 e.g., first portion 431a or 431b
  • 630 e.g., first interlayer 640, second interlayer 650, additional polymeric layer 660
  • 1430 e.g., first interlayer 1433, additional polymeric layer 1460.
  • the second portion 433 of the interlayer 430 can comprise a lower concentration of the plasticizer than the first portion 431a and/or 431b of the interlayer 430, and the first portion 431a and/or 431b of the interlayer 430 can comprise a lower concentration of the plasticizer than the polymeric material 750 (see FIG. 7) (e.g., position in a plurality of pores of the first porous inorganic layer 240 and/or the second porous inorganic layer 250).
  • the second portion 433 of the interlayer 430, the additional polymeric layer 660 of the interlayer 630, and/or the additional polymeric layer 1460 of the interlayer 1430 can be substantially free of plasticizer.
  • a first Tg of the interlayer 230, 430 e.g., first portion 431a or 431b), 630 (e.g., first interlayer 640, second interlayer 650, additional polymeric layer 660), or 1430 (e.g., first interlayer 1433, additional polymeric layer 1460) can be greater than the second Tg of the polymeric material 750 by about 10°C or more, by about 15 °C or more, about 18°C or more, about 20°C or more, about 40°C or less, about 30°C or less, about 25°C or less, or about 23°C or less.
  • the first Tg of the interlayer 230, 430 (e.g., first portion 431a or 431b), 630 (e.g., first interlayer 640, second interlayer 650, additional polymeric layer 660), or 1430 (e.g., first interlayer 1433, additional polymeric layer 1460) can be greater than the second Tg of the polymeric material 750 by from about 10°C to about 40°C, from about 15°C to about 30°C, from about 18°C to about 25°C, from about 20°C to about 23°C, or any range of subrange therebetween. It is to be understood that a portion of the interlayer can comprise the first Tg greater than the second Tg of the polymeric material.
  • the second portion 433 of the interlayer 430 can comprise the first Tg that is greater than the second Tg of the polymeric material 750 (see FIG. 7) by one or more of the ranges discussed above in this paragraph while the rest of the interlayer 430, 630, or 1430 does not necessarily have a Tg greater than the second Tg.
  • the portion 770 of the polymeric material 750 can comprise a polymeric thickness 776 that excludes any portion of the polymeric material 750 positioned in a pore of the porous inorganic layer(s) (e.g., second porous inorganic layer 250).
  • the portion 770 of the polymeric material is shown in FIG. 7 as disposed on the second porous inorganic layer 250, it is to be understood that the portion 770 can additionally or alternatively be disposed on a major surface of the glass substrates (e.g., second major surface 204 of the first glass substrate 200, third major surface 222 of the second glass substrate 220).
  • the polymeric thickness 776 can be about 30 pm or less, about 20 pm or less, about 15 pm or less, about 10 pm or less, about 1 pm or more, about 3 pm or more, about 5 pm or more, about 8 pm or more, or about 10 pm or more. In aspects, the polymeric thickness 776 can be in a range from about 1 pm to about 30 pm, from about 3 pm to about 20 pm, from about 5 pm to about 15 pm, from about 8 pm to about 10 pm, or any range or subrange therebetween. In aspects, as shown in FIGS.
  • At least a portion of the second portion 292 of the glass article 130, 400, 500, 600, or 1400 can be free of the polymeric material 750.
  • a portion of the polymeric material can be present in at least a part of the second portion 292 of the glass article without the porous inorganic layer(s).
  • Providing the polymeric thickness 776 of about 30 pm or less can reduce the visibility of the polymeric material in portions of the glass article without the porous inorganic layer(s), which can simplify manufacturing since slight misalignments or overapplication of a precursor of the polymeric material may not need to be removed (e.g., cleaned) from the glass substrate(s).
  • Providing the polymeric thickness of about 1 pm or more can provide enough polymeric material that the polymeric material can also be positioned in the plurality of pores of the porous inorganic layer.
  • the interlayer 230, 430 (e.g., first portion 431a or 431b), 630 (e.g., first interlayer 640, second interlayer 650, additional polymeric layer 660), or 1430 (e.g., first interlayer 1433, additional polymeric layer 1460) comprises a thermoplastic polymer.
  • the interlayer can comprise any of the polymers discussed above for the polymeric material 750.
  • the interlayer 230, 430 e.g., first portion 431a or 431b), 630 (e.g., first interlayer 640, second interlayer 650, additional polymeric layer 660), or 1430 (e.g., first interlayer 1433, additional polymeric layer 1460) can comprise a polymer, such as at least one of polyvinyl butyral (PVB) (e.g., acoustic PVB (aPVB)), an ionomer, an ethylene-vinyl acetate (EVA) and a thermoplastic polyurethane (TPU), a polyester (PE), a polyethylene terephthalate (PET), or the like.
  • PVB polyvinyl butyral
  • EVA ethylene-vinyl acetate
  • TPU thermoplastic polyurethane
  • PET polyethylene terephthalate
  • the interlayer thickness 236, 646, or 656 can be about 0.5 mm or more, about 0.7 mm or more, about 2.5 mm or less, about 1.5 mm or less, for example, in a range from about 0.5 mm to about 2.5 mm, from about 0.7 mm to about 1.5 mm.
  • the interlayer(s) 430, 630, or 1430 may comprise multiple polymeric layers or films providing various functionalities.
  • wiring or an electronic device 501, 661, or 1401 can be positioned between the first glass substrate 200 and the second glass substrate 220.
  • FIG. 5-6 and 14 wiring or an electronic device 501, 661, or 1401 can be positioned between the first glass substrate 200 and the second glass substrate 220.
  • the additional polymeric layer 660 can be positioned between the first interlayer 640 and the second interlayer 650; the wiring or the electronic device 661 can be positioned between the first interlayer 640 and the second interlayer 650.
  • the wiring or the electronic device 661 can be positioned within the additional polymeric layer 660.
  • the electronic device 1401 can be disposed on and/or contact the second major surface 204 of the first glass substrate 200, and/or the electronic device 1401 can contact the second major surface 404 and be surrounded on the other sides by the third contact surface 1462 of the additional polymeric layer 1460.
  • the electronic device 1401 can be separated from the first interlayer 1433 by the additional polymeric layer 1460.
  • Providing at least a portion of the interlayer (e.g., second portion 433, additional polymeric layer 660, additional polymeric layer 1460) with no plasticizer (or a reduced amount relative to the polymeric material 750) can reduce an incidence of damage (e.g., corrosion) of the wiring or electronic device 501, 661, or 1401 that can be positioned therein.
  • providing at least the portion of the interlayer in the second portion 292 of the glass article with no plasticizer (or a reduced amount relative to the polymeric material 750) can reduce optical distortion and/or haze that may interfere with the operation of an optical device (e.g., camera) positioned within the interlayer (e.g., electronic device 501, 661, or 1401) or configured to view objects through the second portion 292 of the glass article (e.g., a camera positioned inside an automobile configured to view the surroundings outside of the automobile).
  • an optical device e.g., camera
  • the interlayer(s) 230, 430, 630, or 1430 may further incorporate at least one of solar insulation, sound dampening, an antenna, an anti-glare treatment, or an anti-reflective treatment, among others.
  • the interlayer 230, 430 e.g., first portion 431a or 431b
  • 630 e.g., first interlayer 640, second interlayer 650
  • 1430 e.g., first interlayer 1433
  • UV ultraviolet
  • IR infrared
  • the interlayer 230, 430 (e.g., first portion 431a or 431b), 630 (e.g., first interlayer 640, second interlayer 650), or 1430 (e.g., first interlayer 1433) can be modified by a suitable additive such as a dye, a pigment, a dopant, etc. to impart the predetermined property.
  • the interlayer 230, 430 e.g., first portion 431a or 431b), 630 (e.g., first interlayer 640, second interlayer 650), or 1430 (e.g., first interlayer 1433) can further comprise an adhesion promoter, a UV absorber, and/or an antioxidant.
  • the additive, the adhesion promoter, the UV absorber, and/or the antioxidant may have substantially no impact (e.g., about 1°C or less, 0°C) on the glass transition temperature of the interlayer 230, 430 (e.g., first portion 431a or 431b), 630 (e.g., first interlayer 640, second interlayer 650), or 1430 (e.g., first interlayer 1433).
  • FIGS. 2, 4-6, and 14 illustrate the glass article 130, 400, 500, 600, or 1400 as a flat structure (e.g., where the first glass substrate 200 and the second glass substrate 220 are planar), the glass article(s) 130, 400, 500, 600, or 1400 can comprise a curved shape.
  • the glass article 300 shown in FIG. 3 is curved.
  • the glass article 130 exhibits at least one curvature comprising a radius of curvature that is in the range of 300 mm to about 10 meters along at least a first axis.
  • the glass article 130 exhibits at least one curvature comprising a radius of curvature that is in the range of 300 mm to about 10 meters along a second axis that is transverse (e.g., perpendicular) to the first axis.
  • the second major surface 204 of the first glass substrate 200 has a first curvature depth 310 defined as the maximum depth from planar (dashed line) of the second major surface 204.
  • the fourth major surface 224 of the second glass substrate 220 has a second curvature depth 320 defined as the maximum depth from planar (dashed line) of the fourth major surface 224.
  • first curvature depth 310 or the second curvature depth 320 is about 2 mm or greater.
  • Curvature depth may be defined as maximum distance a surface is distanced orthogonally from a plane defined by points on a perimeter of that surface.
  • one or both the first curvature depth 310 or the second curvature depth 320 may be in a range from about 2 mm to about 30 mm.
  • the first curvature depth 310 and the second curvature depth 320 can be substantially equal.
  • the first curvature depth 310 is within 10% or within 5% of the second curvature depth 320.
  • the first curvature depth 310 may be range from about 13.5 mm to about 16.5 mm (to be within 10% of the second curvature depth 320).
  • first step 901 of methods of the disclosure methods can start with providing a first glass substrate 200 and a second glass substrate 220.
  • the first glass substrate 200 and/or the second glass substrate 220 may be provided by purchase or otherwise obtaining a substrate or by forming the first glass substrate 200 and/or the second glass substrate 220.
  • glass substrates can be provided by forming them with a variety of ribbon forming processes, for example, slot draw, down-draw, fusion down-draw, up-draw, press roll, redraw, or float.
  • the first glass substrate 200 and/or the second glass substrate 220 can be strengthened, for example, chemically strengthened and/or thermally strengthened, with one or more compressive stress regions, as discussed above.
  • the first substrate thickness 206 and/or the second substrate thickness 226 can be within one or more of the ranges discussed above.
  • one or more of the glass substrates can comprise a borosilicate glass.
  • the first glass substrate 200 and/or the second glass substrate 220 may be curved at the end of step 901, although curving can occur in a subsequent step or may be omitted entirely.
  • the first glass substrate 200 and/or the second glass substrate 220 can be chemically strengthened at the end of step 901, although chemically strengthening one or more of the glass substrates can occur in step 903 and/or one or more of the glass substrates may not be chemically strengthened.
  • a first porous inorganic layer 240 can be disposed on one of the glass substrates (e.g., second glass substrate 220) and/or a second porous inorganic layer 250 can be disposed on the other glass substrate (e.g., first glass substrate 200), although one or both porous inorganic layer(s) can be disposed in step 903.
  • the second porous inorganic layer 250 on the first glass substrate 200 are shown in FIGS. 10-11, it is to be understood that methods contemplate a second porous inorganic layer 250 disposed on the second glass substrate 220.
  • the first curvature depth 310 can be induced in the first glass substrate 200 by hot forming (e.g., the first glass substrate 200 may be bent by gravity sagging), and the second curvature depth 320 can be induced in the second glass substrate 220 by cold forming.
  • the first curvature depth 310 and second curvature depth 320 are induced by hot-bending the first glass substrate 200 and the second glass substrate 220 (e.g., in a co-bending process or in a process where the glass substrates are bent independently from one another).
  • curvature(s) are introduced into at least one of the first glass substrate 200 or the second glass substrate 220 through a thermal process.
  • the thermal process may include a sagging process that uses gravity to shape the first glass substrate 200 or both the first glass substrate 200 and the second glass substrate 220 when heated.
  • a glass substrate e.g., first glass substrate 200
  • a furnace e.g., a box furnace, or a lehr furnace
  • the thermal process may include a pressing process that uses a mold to shape the first glass substrate 200 or both the first glass substrate 200 and the second glass substrate 220 when heated or while heating.
  • two glass substrates are shaped together in a “pair-shaping” process.
  • one glass substrate is placed on top of another glass substrate to form a stack (which may also include an intervening release layer), which is placed on the mold.
  • the second glass substrate 220 used as an inner and/or thinner glass substrate in some aspects, has a pair-shaping temperature (e.g., at a viscosity of 10 11 Poise) that is greater than that of the first glass substrate 200.
  • the mold used during pair sagging may have an open interior for use in a sagging process.
  • the stack and mold are both heated by placing them in the furnace, and the stack is gradually heated to the bend or sag temperature of the glass substrates. During this process, the glass substrates are shaped together into a curved shape.
  • the viscosity curve for at least some of the borosilicate glass composition comprised herein at a viscosity of 10 11 Poise can be similar to that of the glass used for the second glass substrate 220, allowing for existing equipment and techniques to be utilized.
  • the heating time and the temperature are selected to obtain the desired degree of curvature and final shape. Subsequently, the glass substrate(s) are removed from the furnace and cooled.
  • the two glass substrates are separated before being reassembled at step 909 (discussed below) re-assembled with an interlayer (e.g., interlayer 230) between the glass substrates and heated (e.g., under vacuum to seal the glass substrates and interlayer together into a laminate), as discussed below with reference to step 911.
  • an interlayer e.g., interlayer 230
  • only one glass substrate e.g., the first glass substrate 200
  • the other glass substrate e.g., the second glass substrate 220
  • a cold-forming process by pressing the glass substrate to be curved into conformity with the already curved glass substrate at a temperature less than the softening temperature of the glass composition (in particular at a temperature of 200 °C or less, 100 °C or less, 50 °C or less, or at room temperature).
  • Pressure to cold-form one of the glass substrates against the other glass substrate may be provided by a vacuum, a mechanical press, or one or more clamps.
  • the cold-formed glass substrate may be held into conformity with the curved glass substrate via the interlayer and/or mechanically clamped thereto or otherwise coupled.
  • step 903 comprising disposing a porous inorganic layer (e.g., second porous inorganic layer 250) on one of the glass substrates (e.g., first glass substrate 200).
  • the second porous inorganic layer 250 can be disposed by applying a precursor (e.g., modified enamel) comprising a frit (e.g., enamel) that can be mixed with a pigment (e.g., inks, colorants, stains), and/or particles of a low CTE additive to the second major surface 204 of the first glass substrate 200.
  • a precursor e.g., modified enamel
  • a frit e.g., enamel
  • a pigment e.g., inks, colorants, stains
  • the precursor can be disposed using any suitable technique (e.g., screen printing, spraying, brushing, banding), with the understanding that viscosity adjustments may be needed (e.g., via additions of water or additional medium) depending on the deposition technique selected.
  • the precursor can be cured by heating at a suitable firing temperature, which can be at least the softening temperature associated with the enamel. Curing the precursor to form the porous inorganic layer can solidify the glass frit into a fused matrix surrounding the low CTE additive component and forming a plurality of pores.
  • the glass substrate e.g., first glass substrate 200
  • the glass substrate e.g., first glass substrate 200
  • the precursor can be cured to form the porous inorganic layer can occur simultaneously in step 903.
  • the porous inorganic layer can be disposed on a curved first glass substrate.
  • a porous inorganic layer can be disposed on the third major surface of the second glass substrate.
  • the second glass substrate can be shaped simultaneously with or after a precursor is cured to form the porous inorganic layer.
  • one or both of the glass substrates can be chemically strengthened in step 903 after depositing the porous inorganic layer(s), which can also be after the glass substrate(s) are shaped. At the end of step 903, as shown in FIG.
  • the second porous inorganic layer 250 comprises the inorganic thickness 746 discussed above.
  • the porosity of the second porous inorganic layer 250 can be within one or more of the corresponding ranges discussed above.
  • the second porous inorganic layer 250 is adhered to the first glass substrate 200, for example, with the first surface 732 of the second porous inorganic layer 250 contacting the second major surface 204 of the first glass substrate 200.
  • step 905 comprising filling a plurality of pores of the second porous inorganic layer 250 with a polymeric solution or a polymeric emulsion 1003.
  • the polymeric solution or a polymeric emulsion 1003 can be disposed on the second surface 734 of the second porous inorganic layer 250 by brushing with a brush 1001, although rolling or spraying can also be used.
  • the polymeric solution or the polymeric emulsion 1003 can flow into a plurality of pores of the second porous inorganic layer 250.
  • the polymeric solution or the polymeric emulsion 1003 can comprise a viscosity of about 8,000 milliPascal-seconds (mPa-s) or less, about 2,000 mPa-s or less, about 1,000 mPa-s or less, about 500 mPa-s or less, about 200 mPa-s or less, about 10 mPa-s or more, about 30 mPa-s or more, about 50 mPa-s or more, about 80 mPa-s or more, or about 100 mPa-s or more, for example, in a range from about 10 mPa-s to about 8,000 mPa-s, from about 30 mPa-s to about 2,000 mPa, from about 50 mPa-s to about 1,000 mPa-s, from about 80 mPa-s to about 500 mPa-s, from about 100 mPa-s to about 200 mPa-s, or any range or sub
  • Providing a viscosity within one of the ranges mentioned in the previous sentence can enable the polymeric solution to flow into a plurality of pores of the second porous inorganic layer 250.
  • providing a viscosity within one of the ranges mentioned above in this paragraph can enable the polymeric emulsion to form a continuous film on the second porous inorganic layer 250, which can be positioned in the plurality of pores, for example, after the lamination process (e.g., step 911 discussed below).
  • a “solution” means a substantially homogenous mixture of a polymer and a solvent, where the polymer has a non-zero solubility in the solvent.
  • an “emulsion” is a heterogenous mixture with at least two distinct phases, for example, with a droplet phase dispersed in a second, matrix phase.
  • an emulsion can comprise a solvent in the matrix phase that is immiscible with the polymer in the droplet phase.
  • the solvent of the polymeric solution or the polymeric emulsion can comprise water, alcohols (e.g., ethanol, methanol, butanol, isopropanol), toluene, ethers (e.g., dipropylene glycol butyl ether), acetates (e.g., ethyl acetate), ketones (e.g., methyl ethyl ketone, acetone, butanone), or combinations thereof.
  • An exemplary aspect of a solvent for the polymeric emulsion is water.
  • Exemplary aspects of a solvent for the polymeric solution include alcohols (e.g., ethanol, butanol, methanol), ethers (e.g., dipropylene glycol butyl ether), acetates (e.g., ethyl acetate), and ketones (e.g., methyl ethyl ketone, acetone, butanone).
  • alcohols e.g., ethanol, butanol, methanol
  • ethers e.g., dipropylene glycol butyl ether
  • acetates e.g., ethyl acetate
  • ketones e.g., methyl ethyl ketone, acetone, butanone
  • the polymeric solution or the polymeric emulsion 1003 comprises a polymer within one or more of the materials discussed above for the polymeric material 750.
  • the polymer in the polymeric emulsion can be a substantially linear polymer.
  • the polymeric solution or the polymeric emulsion 1003 can further comprise a plasticizer within one or more of the materials discussed above for the plasticizer of the polymeric material 750.
  • the polymeric solution of the polymeric emulsion 1003 can be disposed on and/or cover a periphery of the second porous inorganic layer 250.
  • a thickness 1006 of the polymeric solution of the polymeric emulsion 1003 can be about 30 pm or less, for example, within one or more of the ranges discussed above for the polymeric thickness 776.
  • step 907 comprising drying the polymeric solution of the polymeric emulsion 1003 (see FIG. 10) to form the polymeric material 750, including the polymeric material 750 positioned within the plurality of pores 760 (see FIG. 7).
  • drying the polymeric solution of the polymeric emulsion 1003 can comprise placing the second porous inorganic layer 250 and the polymeric solution of the polymeric emulsion 1003 in an oven 1101 maintained at a predetermined temperature for a predetermined period of time.
  • the polymeric solution of the polymeric emulsion 1003 can be dried at a temperature of about 20°C or more, about 30°C, about 40°C or more, about 50°C or more, about 80°C, about 70°C or less, about 65°C or less, or about 60°C or less.
  • the polymeric solution of the polymeric emulsion 1003 can be dried at a temperature from about 20°C to about 80°C, from about 30°C to about 70°C, from about 40°C to about 65°C, from about 50°C to about 60°C, or any range or subrange therebetween. Providing a temperature of about 80°C or less can reduce an incidence of bubbles in the resulting polymeric material 750.
  • the polymeric solution of the polymeric emulsion 1003 can be dried for a period of time of about 10 minutes or more, about 20 minutes or more, about 30 minutes or more, about 45 minutes or more, about 1 hour or more, about 168 hours or less, about 24 hours or less, about 8 hours or less, about 4 hours or less, about 2 hours or less, or about 1 hour or less.
  • no reactions may occur in step 905 such that the polymeric material 750 is substantially free of cross-linking and/or branching points, and the polymer of the polymeric material 750 can be substantially the same as the polymer of the polymeric solution of the polymeric emulsion 1003.
  • the polymeric material 750 can comprise one or more of the plasticizers discussed above and the plasticizer(s) can be present in an amount within one or more of the corresponding ranges discussed above.
  • the second glass transition temperature of the polymeric material 750 can be within one or more of the corresponding ranges discussed above.
  • the polymeric material 750 (including the portion 770) can be present (e.g., in a plurality of pores) in a first portion 782 but not present (e.g., in a plurality of pores) in a second portion 784.
  • an absolute value of a difference between a refractive index of the polymeric material 750 and a refractive index of either the first glass substrate 200 or the second glass substrate 220 can be about 0.10 or less, about 0.05 or less, about 0.04 or less, about 0.03 or less, about 0.02 or less, or about 0.01 or less.
  • step 909 comprising disposing an interlayer 230 or 430 on the porous inorganic layer (e.g., first porous inorganic layer 240, second porous inorganic layer 250).
  • a gap 1202 or 1204 can be formed between the interlayer 230 or 430 and the first glass substrate 200 or the second glass substrate 220, respectively, for example, due to the thickness of the porous inorganic layer(s).
  • the interlayer 430 can be non-uniform with the dashed lines labeled with reference numbers 448a and 448b indicating divisions between different portions of the interlayer 430 with different compositions (e.g., a first portion 431a and/or 431b, a second portion 433 - see FIG. 4).
  • the concentration of the plasticizer can be different between these portions (e.g., with a greater concentration of the plasticizer in the second 433 portion than in the first portion 431a and/or 431b).
  • a polymer in the first portion can be different than a polymer in the second portion (e.g., the second portion 433 can include or consist of PVB, whereas the first portion 431a and/or 431b can include PET or other suitable material having a relatively high Tg).
  • the interlayer can comprise a first interlayer, a second interlayer, and an additional polymeric layer positioned therebetween (see FIG. 6).
  • wiring or an electronic device can be positioned between the first glass substrate 200 and the second glass substrate 220 (e.g., within the interlayer or the additional polymeric layer, if present) (see FIGS. 5-6).
  • the first glass transition temperature of the interlayer can be less than the second glass transition temperature of the polymeric material 750 (see FIG. 7) by an amount within one or more of the corresponding ranges discussed above.
  • the concentration of the plasticizer in the polymeric material can be greater than the concentration of the plasticizer in the interlayer.
  • a polymer of the interlayer can be the same or different as the polymer of the polymeric material.
  • step 911 comprising laminating the first glass substrate 200 to the second glass substrate 220 such that the porous inorganic layer (e.g., first porous inorganic layer 240, second porous inorganic layer 250) and the interlayer(s) 230 or 430 are positioned therebetween.
  • the porous inorganic layer e.g., first porous inorganic layer 240, second porous inorganic layer 250
  • a first surface area 1319 of a first release liner 1317 can be disposed over and/or contact the first major surface 202 of the first glass substrate 200.
  • a third surface 1315 of the first support 1311 can be disposed over and/or contact the first release liner 1317.
  • a first surface area 1329 of a second release liner 1327 can be disposed over and/or contact the fourth major surface 224 of the second glass substrate 220.
  • a third surface 1323 of a second support 1321 can be disposed over and/or contact the second release liner 1327.
  • methods can comprise placing the assembly in a vacuum container 1303 (e.g., OBSJ/ABSJ vacuum bags available from Simtech).
  • the first support 1311 and/or the second support 1321 can comprise an elastic modulus of about 3 GPa or more and/or can comprise a glass-based material and/or a ceramic -based material.
  • Providing one or more release liners can reduce (e.g., prevent) adhesion of the glass article to undesired materials during methods and can reduce damage to the laminate during processing.
  • Providing one or more supports can decrease deformation (e.g., warp) of the substrate and/or film during processing.
  • Providing a vacuum container can protect the glass article from contamination during processing.
  • step 911 can further comprise heating the film and/or reducing a pressure of a chamber 1301 (e.g., relative to 101.325 kiloPascals) that the assembly is positioned in. Providing a reduced pressure can remove dissolved gases and/or gases between the elements of the assembly.
  • step 911 comprises (e.g., in addition to the previously discussed aspects), heating the assembly to a temperature greater than a glass transition temperature (and/or a melting temperature, if semicrystalline) of the interlayer 230, which can occur at an elevated pressure in the chamber 1301 (e.g., relative to 101.325 kiloPascals).
  • step 911 methods can proceed to step 913 comprising assembling the glass article 130, 300, 400, 500, 600, or 1400.
  • the article could be incorporated into any of the articles or applications discussed above.
  • the glass article could be attached to an automobile by attaching the glass article to a periphery of an opening in the automobile using an adhesive.
  • the glass article can comprise a maximum AE, an absolute value of a difference in L* value, an absolute value of a difference in a* value, and/or an absolute value of a difference in b* values between the first portion 782 with the polymeric material 750 positioned within the plurality of pores of the first porous inorganic layer 240 and the second portion 784 with the plurality of pores not filled by the polymeric material 750 (see FIG. 7) when illuminated with a D65 illuminant can be within one or more of the corresponding ranges discussed above.
  • an integrated visible transmittance of the first portion 294a or 294b of the glass article including the porous inorganic layer(s) can be within one or more of the corresponding ranges discussed above.
  • methods of making a glass article in accordance with aspects of the disclosure can proceed along steps 901, 903, 905, 907, 909, 911, and 913 of the flow chart in FIG. 9 sequentially, as discussed above.
  • arrow 902 can be followed from step 901 to step 905, for example, if the porous inorganic layer is already adhered to the glass substrate at the end of step 901.
  • arrow 904 can be followed from step 911 to step 915, for example, if the method is complete at the end of step 911. Any of the above options may be combined to make a coated article in accordance with aspects of the disclosure.
  • Examples A-C and Comparative Examples AA-BB comprised a borosilicate glass substrate (i.e., composition of 83.60 mol% SiCE, about 1.20 mol% AI2O3, about 11.60 mol% B2O3, about 3.00 mol% Na2O, and about 0.70 mol% K2O) with a CTE of 32xl0' 7 K 1 and a thickness of 3.8 mm.
  • the porous inorganic layer with a thickness of about 20 pm and a porosity of about 30% was formed on a second major surface of the borosilicate glass substrate by heating a precursor frit at about 600°C for about 8 minutes.
  • the porous inorganic layer had a dark gray appearance.
  • a polymeric solution was formed by dissolving plasticized PVB (RF41 available from Saflex) at 14 wt% in ethanol.
  • plasticized PVB RF41 available from Saflex
  • 100 pm thick polyethylene terephthalate) (PET) sheet was immersed in PET polymeric solution and then applied to the porous inorganic layer.
  • PET polyethylene terephthalate
  • Example B the polymeric solution was brushed on the porous inorganic layer and then the 100 pm thick PET sheet was applied thereon.
  • Comparative Example AA comprised the 100 pm thick PET sheet placed on the porous inorganic layer with no polymer.
  • Comparative Example BB comprised placing an already formed fdm of plasticized PVB (RF41 available from Saflex) on the porous inorganic layer and then pressing the 100 pm PET sheet into the film of plasticized PVB.
  • RF41 plasticized PVB
  • Comparative Example A had a light gray appearance.
  • Comparative Example B has a gray appearance that is lighter than the base porous inorganic layer but darker than Comparative Example A. Examples A and B appeared as dark gray or black other than a lighter border at the periphery of the PET sheets. It is believed that applying the polymeric solution covering the edges can remove this lighter border.
  • Example C the polymeric solution was brushed over a large area of the porous inorganic layer and the 100 pm thick sheet of PET was applied to a first portion of the porous inorganic layer leaving a second portion that is coated with the polymeric solution without the PET.
  • a 0.76 mm thick sheet of plasticized PVB RF41 available from Saflex
  • the assembly was laminated together in an autoclave to produce a glass article.
  • the autoclave treatment involved heating assembly at 110°C under vacuum for 45 minutes followed by heating at 140°C with an applied pressure of 1.3 MPa (gauge).
  • Comparative Example BB was prepared identical to Example C except that no polymeric solution was used.
  • the color of the glass article where the PET is (portion 1) looks virtually indistinguishable from the portion of the glass article including the polymeric material formed from the polymeric solution but without the PET (portion 2).
  • Table 1 presents the CIE color space coordinates for these portions of Example C.
  • the absolute value of the difference in CIE L* values is less than about 2.0, less than about 1.0, and less than about 0.5 (i.e., about 0.32).
  • the absolute value of the difference in CIE a* values is less than about 1, less than about 0.5, and less than about 0.3 (i.e., about 0.15).
  • the absolute value of the difference in CIE b* values is less than about 1, less than about 0.5, and less than about 0.3 (i.e., about 0.12).
  • AE e.g., maximum AE
  • Comparative Example BB appeared as a light gray (similar to Comparative Example A).
  • Table 1 CIE color space coordinates for Example C [00159]
  • the above observations can be combined to provide a glass article comprising a porous inorganic layer with a polymeric material positioned in a plurality of pores of the porous inorganic layer.
  • Providing the polymeric material with a low glass transition temperature e.g., about 85°C or less
  • Providing a polymeric material with a glass transition temperature of about 40°C or more can reduce changes in properties of the polymeric material during a range of temperatures commonly encountered during use of the glass article.
  • Providing a thickness of the polymeric material outside of the plurality of pores of about 30 pm or less can reduce the visibility of the polymeric material in portions of the glass article without the porous inorganic layer(s), which can simplify manufacturing since slight misalignments or overapplication of a precursor of the polymeric material may not need to be removed (e.g., cleaned) from the glass substrate(s).
  • Providing the polymeric thickness of about 1 pm or more outside of the plurality of pores can provide enough polymeric material that the polymeric material can also be positioned in the plurality of pores of the porous inorganic layer. Positioning the polymeric material in the plurality of pores can provide a substantially uniform appearance with a predetermined color.
  • the glass article can exhibit a low maximum AE value between portions of the glass article with a porous inorganic layer having the polymeric material in the plurality of pores and without the polymeric material can provide a substantially uniform color associated with the porous inorganic layer that may be visually imperceptible to a viewer.
  • the porous inorganic layer(s) may act as a decorative layer with a predetermined color appearance when incorporated into a laminate.
  • the porosity has been found to prevent the porous inorganic layer(s) from degrading the mechanical strength of the glass substrate(s). Without wishing to be bound by theory, it is believed that the porosity reduces the size of areas of continuous contact between the glass substrate and the decorative enamel, which reduces CTE-induced stress buildup caused during fabrication of the decorated glass article, thereby reducing or preventing flaw formation and propagation.
  • the porosity may also aid the porous inorganic layer in having a predetermined color appearance when incorporated into a laminate.
  • an interlayer is used to attach a glass substrate with a porous inorganic layer to another glass substrate.
  • a polymeric material can fill a plurality of pores of the porous inorganic layer, which may darken the appearance of the portion of the glass article including the porous inorganic layer.
  • Providing the porous inorganic layer(s) inner surfaces of the glass article can serve to protect the layers from mechanical degradation and/or oxidation. Moreover, placement of the porous inorganic layer(s) may also aid in concealing any additional components (e.g., conductive elements associated with a defogging system) embedded between the first glass substrate 200 and the second glass substrate 220. Also, multiple bands of the porous inorganic layer(s) can provide a predetermined aesthetic appearance when the first glass substrate and the second glass substrate are constructed of glasses with different compositions and/or thicknesses. In aspects, the porous inorganic layer(s) will have the dual function of offering an attractive appearance and acting as a shield to block visible and ultraviolet (UV) light. Additionally, the glass article may include additional functionality, for example, including an infrared reflective coating and/or an anti -reflective coating.
  • constructing the porous inorganic layer(s) to have a CTE that is approximately equal to the CTE of the first glass substrate can prevent cracks from forming in the porous inorganic layer during fabrication of the glass article and also prevents the incorporation of the porous inorganic layer from degrading the mechanical strength of the first glass substrate and/or glass article.
  • the first glass substrate can comprise a borosilicate glass composition, which can be particularly beneficial as the outside of an automotive glazing since the borosilicate glass may have greater thermal shock resistance and be more resistant to crack formation from impact events from road debris (e.g., rocks or the like) than soda-lime silicate glasses currently used as outer glass substrates in automotive glazings.
  • Such glasses have been found to exhibit a favorable ring cracking behavior preventing radial propagation of flaws from an impact point.
  • Such fusion-formed glasses may also exhibit superior chemical durability, scratch resistance, mechanical strength, and optical performance (e.g., from both an optical transmission and optical distortion perspective) than other borosilicate glasses.
  • Providing the polymeric material separate from the interlayer can enable the interlayer (or portions thereof) to have different compositions and/or properties.
  • a concentration of plasticizer can be greater in the polymeric material than in the interlayer (or portions thereof) and/or the polymeric material can have a lower glass transition temperature than the interlayer (or portions thereof) even when a polymer in the polymeric material is the same as a polymer in the interlayer.
  • Providing at least a portion of the interlayer with no plasticizer (or a reduced amount relative to the polymeric material) can reduce an incidence of damage (e.g., corrosion) to any wiring or electronic devices that may be positioned therein.
  • providing at least a portion of the interlayer with no plasticizer (or a reduced amount relative to the polymeric material) can reduce optical distortion and/or haze that may interfere with the operation of an optical device (e.g., camera) positioned within the interlayer or configured to view objects through the second portion of the glass article (e.g., a camera positioned inside an automobile configured to view the surroundings outside of the automobile).
  • an optical device e.g., camera
  • the second portion of the glass article e.g., a camera positioned inside an automobile configured to view the surroundings outside of the automobile.
  • the polymeric material can be provided by drying a polymeric solution or a polymeric emulsion.
  • Providing the polymeric solution or the polymeric emulsion with a low viscosity e.g., about 8,000 milliPascal-seconds or less
  • the polymeric material can be formed by drying the polymeric solution or the polymeric emulsion without any reactions (e.g., cross-linking or polymerization).
  • the polymer in the polymeric solution or the polymeric emulsion can be substantially the same as the polymer in the polymeric material.
  • the limited processing involved in disposing the polymeric material can simplify processing and/or reduce costs.
  • the term “about” means that amounts, sizes, formulations, parameters, and other quantities and characteristics are not and need not be exact, but may be approximate and/or larger or smaller, as desired, reflecting tolerances, conversion factors, rounding off, measurement error and the like, and other factors known to those of skill in the art. Ranges can be expressed herein as from “about” one particular value, and/or to “about” another particular value. When such a range is expressed, aspects include from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms another aspect.
  • substantially is intended to note that a described feature is equal or approximately equal to a value or description.
  • a “substantially planar” surface is intended to denote a surface that is planar or approximately planar.
  • substantially similar is intended to denote that two values are equal or approximately equal. In aspects, “substantially similar” may denote values within about 10% of each other, for example, within about 5% of each other, or within about 2% of each other.

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Abstract

Les articles en verre selon la présente invention comprennent une couche intermédiaire positionnée entre une deuxième surface principale d'un premier substrat en verre et une troisième surface principale d'un second substrat en verre. Les articles en verre comprennent une couche intermédiaire poreuse comprenant une pluralité de pores et adhérant à la deuxième surface principale ou à la troisième surface principale. Une matière polymère est positionnée dans les différents pores. Selon certains aspects, une première température de transition vitreuse de la couche intermédiaire est supérieure à une seconde température de transition vitreuse d'une matière polymère d'environ 10°C ou plus. Dans certains aspects, une valeur ΔE maximale est d'environ 2,0 ou moins. Les procédés comprennent le remplissage d'une pluralité de pores d'une couche inorganique poreuse sur un premier substrat en verre avec une solution polymère ou une émulsion polymère qui est ensuite séchée pour former une matière polymère. Une couche intermédiaire peut être utilisée pour laminer le premier substrat de verre sur un second substrat de verre.
PCT/US2023/036982 2022-11-22 2023-11-08 Articles en verre et leurs procédés de fabrication WO2024112425A1 (fr)

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US9724727B2 (en) 2014-02-13 2017-08-08 Corning Incorporated Methods for printing on glass
EP2617690B1 (fr) 2012-01-19 2017-11-22 Corning Incorporated Procédé de décoration de verre chimiquement renforcé
US10125044B2 (en) 2013-11-19 2018-11-13 Corning Incorporated Ion exchangeable high damage resistance glasses
US20200171800A1 (en) 2017-05-15 2020-06-04 Corning Incorporated Laminate having organic ink decoration and high impact resistance
WO2020214623A1 (fr) * 2019-04-16 2020-10-22 Corning Incorporated Couche décorative à pores remplis pour échange d'ions et verre d'automobile

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007046939A1 (fr) * 2005-10-18 2007-04-26 Cpfilms Inc. Revetements fonctionnels de pellicule et vitrage dotes d'une couche inorganique poreuse et d'un polymere de remplissage
EP2617690B1 (fr) 2012-01-19 2017-11-22 Corning Incorporated Procédé de décoration de verre chimiquement renforcé
US9346708B2 (en) 2012-05-04 2016-05-24 Corning Incorporated Strengthened glass substrates with glass frits and methods for making the same
US8854623B2 (en) 2012-10-25 2014-10-07 Corning Incorporated Systems and methods for measuring a profile characteristic of a glass sample
US20160002104A1 (en) 2013-02-26 2016-01-07 Corning Incorporated Decorative porous inorganic layer compatible with ion exchange processes
US10125044B2 (en) 2013-11-19 2018-11-13 Corning Incorporated Ion exchangeable high damage resistance glasses
US9724727B2 (en) 2014-02-13 2017-08-08 Corning Incorporated Methods for printing on glass
WO2016196546A1 (fr) * 2015-06-02 2016-12-08 Corning Incorporated Verre feuilleté comprenant une vitre ayant une structure feuilletée verre-verre
US20200171800A1 (en) 2017-05-15 2020-06-04 Corning Incorporated Laminate having organic ink decoration and high impact resistance
WO2020214623A1 (fr) * 2019-04-16 2020-10-22 Corning Incorporated Couche décorative à pores remplis pour échange d'ions et verre d'automobile

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