TW202428536A - Glass articles and methods of making the same - Google Patents

Abstract

Glass articles include an interlayer positioned between a second major surface of a first glass substrate and a third major surface of a second glass substrate. Glass articles include a porous interlayer including a plurality of pores and adhered to the second major surface or the third major surface. A polymeric material is positioned in the plurality of pores. In aspects, first glass transition temperature of the interlayer is greater than a second glass transitions temperature of a polymeric material by about 10℃ or more. In aspects, a maximum ΔE value is about 2.0 or less. Methods include filling a plurality of pores of a porous inorganic layer on a first glass substrate with a polymeric solution or a polymeric emulsion that is then dried to form a polymeric material. An interlayer can be used to laminate the first glass substrate to a second glass substrate.

Description

Glass product and manufacturing method thereof

This application claims the benefit of priority under patent law to U.S. provisional application serial number 63/427167 filed on November 22, 2022, the contents of which are relied upon and incorporated herein by reference in their entirety.

The present disclosure relates generally to glass articles and methods of making the same, and more particularly to glass articles including porous inorganic layers and methods of forming the same.

Glazes are often used as decorative and tinted elements on automotive glass, such as windshields, sunroofs, and rear windows. As a decoration, glazes are usually in the form of dot gradients and edges along the perimeter of the window glass. Decorative layers can be used to enhance the appearance and protect the underlying adhesive from UV degradation, for example.

As is known, automotive glass is formed from heat-strengthened sodium calcium silicate glass. Heat strengthening induces surface compressive stresses, which in turn enhance the glass's ability to resist mechanical failure. However, the stresses and inherent risks of roads require that conventional automotive glass be relatively thick and heavy to achieve the desired durability level. Because such sodium calcium silicate glass often has several disadvantages from a durability point of view. Examples of such disadvantages of sodium calcium silicate include poor chemical weathering resistance, impact resistance, and scratch resistance.

Borosilicate glasses are being considered for automotive window applications because they have several advantages over sodium calcium silicate glasses, including improved chemical weathering performance, improved scratch resistance, improved impact performance, and advantageously low density. One complexity associated with borosilicate glasses is that the coefficient of thermal expansion (CTE) of such glasses is often lower than those CTEs associated with sodium calcium silicate glasses or aluminosilicate glasses. Such lower coefficients of thermal expansion associated with borosilicate glasses may be incompatible with commercial ceramic glazes. The difference in CTE between borosilicate glasses and commercial glazes may reduce the mechanical performance of the windshield and prevent the windshield from having a desired appearance.

Providing a polymer interlayer between glass substrates is known in automotive glazing applications. The properties of the interlayer used to bond the components in automotive glazing applications may conflict with optical clarity or other properties of the more complex control systems that may be used in the automobile.

Therefore, there is a need for an improved glaze for use in combination with borosilicate glass or other suitable low CTE materials. There is also a need for glass products that can provide both good adhesion and optical clarity.

Glass articles comprising a porous inorganic layer are described herein, wherein a polymer material is positioned in a plurality of pores of the porous inorganic layer. Providing a polymer material having a low glass transition temperature (e.g., about 85° C. or less) may allow the polymer material to be easily positioned (e.g., filled) in the plurality of pores of the (one or more) porous inorganic layer. Providing a polymer material having a glass transition temperature of about 40° C. or greater may reduce changes in the properties of the polymer material within a temperature range typically encountered during use of the glass article. Providing a polymer material thickness of about 30 μm or less outside of the plurality of pores may reduce the visibility of the polymer material in portions of the glass article that do not have the (one or more) porous inorganic layer, which may simplify manufacturing because slight misalignment or over-application of a precursor in the polymer material may not require removal (e.g., cleaning) from the (one or more) glass substrates. Providing a polymer thickness of about 1 μm or more outside of the plurality of pores can provide the polymer material sufficient to allow the polymer material to be positioned also in the plurality of pores of the porous inorganic layer. Positioning the polymer material in the plurality of pores can provide a substantially uniform appearance having a predetermined color. In addition, the glass article can exhibit a low maximum ΔE between portions of the glass article having the porous inorganic layer in the plurality of pores and portions of the glass article not having the polymer material, which can provide a substantially uniform color associated with the porous inorganic layer that is visually imperceptible to an observer.

When incorporated into a laminate, the (one or more) porous inorganic layer(s) can be used as a decorative layer having a predetermined color appearance. It has been found that porosity can prevent the (one or more) porous inorganic layer(s) from reducing the mechanical strength of the (one or more) glass substrate(s). Without wishing to be bound by theory, it is believed that the porosity reduces the size of the continuous contact area between the glass substrate and the decorative glaze, which reduces the CTE-induced stress accumulation caused during the manufacture of the decorative glass article, thereby reducing or preventing defect formation and propagation. When incorporated into a laminate, the porosity can also help the porous inorganic layer have a predetermined color appearance. For example, an intermediate layer is used to attach a glass substrate having a porous inorganic layer to another glass substrate. As discussed below, the polymer material may fill the plurality of pores of the porous inorganic layer, which may darken the appearance of the portion of the glass article that includes the porous inorganic layer.

Providing (one or more) porous inorganic layers on the inner surface of the glass article can be used to protect the layer from mechanical degradation and/or oxidation. In addition, the placement of (one or more) porous inorganic layers can also help hide any additional components embedded between the first glass substrate 200 and the second glass substrate 220 (for example, conductive elements associated with the defogging system). In addition, when the first glass substrate and the second glass substrate are constructed of glasses with different compositions and/or thicknesses, multiple bands of (one or more) porous inorganic layers can provide a predetermined aesthetic appearance. In an embodiment, (one or more) porous inorganic layers will have the dual function of providing an attractive appearance and serving as a shield to block visible light and ultraviolet (UV) light. In addition, the glass article may include additional functionality, such as including an infrared reflective coating and/or an anti-reflective coating.

As described herein, constructing the porous inorganic layer(s) to have a CTE approximately equal to the CTE of the first glass substrate can prevent crack formation in the porous inorganic layer during manufacture of the glass article, and also prevent bonding of the porous inorganic layer from reducing the mechanical strength of the first glass substrate and/or the glass article. The first glass substrate can include a borosilicate glass composition, which can be particularly beneficial because borosilicate glass can have greater thermal shock resistance and is more resistant to crack formation due to impact events from road debris (e.g., rocks or the like) than sodium calcium silicate glass currently used as an outer glass substrate in automotive glazing. Such glasses have been found to exhibit favorable annular cracking behavior, thereby preventing defects from radially propagating from an impact point. Such fusion-formed glasses also exhibit superior chemical durability, scratch resistance, mechanical strength, and optical performance (e.g., from the perspective of optical transmittance and optical distortion) compared to other borosilicate glasses.

Providing a polymeric material separate from the interlayer may result in the interlayer (or a portion thereof) having a different composition and/or properties. For example, the concentration of plasticizer in the polymeric material may be greater than the concentration in the interlayer (or a portion thereof), and/or the polymeric material may have a lower glass transition temperature than the interlayer (or a portion thereof), even when the polymer in the polymeric material is the same as the polymer in the interlayer. Providing at least a portion of the interlayer without (or with a reduced amount relative to the polymeric material) plasticizer may reduce the incidence of damage (e.g., corrosion) to any wiring or electronic devices that may be positioned therein. Additionally, providing at least a portion of the interlayer without (or with a reduced amount relative to the polymeric material) plasticizer can reduce optical distortion and/or haze, which may interfere with the operation of an optical device (e.g., a camera) positioned within the interlayer or configured to view an object through a second portion of the glass article (e.g., a camera positioned within a vehicle configured to view the surrounding environment outside the vehicle).

In addition, the polymer material can be provided by drying a polymer solution or polymer emulsion. Providing a polymer solution or polymer emulsion with a low viscosity (e.g., about 8,000 mPa-s or less) may allow the polymer solution or polymer emulsion 1003 to flow into a plurality of pores of the porous inorganic layer. The polymer material can be formed by drying the polymer solution or polymer emulsion without any reaction (e.g., crosslinking or polymerization). Therefore, the polymer in the polymer solution or polymer emulsion can be substantially the same as the polymer in the polymer material. The limited processing involved in providing the polymer material can simplify processing and/or reduce costs.

Some example aspects of the present disclosure are described below, and it should be understood that any of the features of the various aspects may be used alone or in combination with each other.

Aspect 1. A glass product, comprising: a first glass substrate, the first glass substrate comprising a first substrate thickness defined between a first major surface and a second major surface opposite to the first major surface; a second glass substrate, the second glass substrate comprising a second substrate thickness defined between a third major surface and a fourth major surface opposite to the third major surface; an intermediate layer, the intermediate layer positioned between the second major surface and the third major surface; a porous inorganic layer, the porous inorganic layer comprising a plurality of pores and adhered to the second major surface or the third major surface; and a polymer material, the polymer material positioned in the plurality of pores, wherein a first glass transition temperature of the intermediate layer is approximately 10°C or greater than a second glass transition temperature of the polymer material.

Aspect 2. The glass article of Aspect 1, wherein the first glass transition temperature of the intermediate layer is about 15° C. to about 30° C. greater than the second glass transition temperature of the polymer material.

Aspect 3. A glass article as described in any of Aspects 1-2, wherein when illuminated from the first major surface with a D65 illuminant, a maximum ΔE value between a first portion of the glass article in which the polymer 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 in which the porous inorganic layer is not filled with the polymer material is about 2.0 or less.

Aspect 4. A glass product, comprising: a first glass substrate, the first glass substrate comprising a first substrate thickness defined between a first main surface and a second main surface opposite to the first main surface; a second glass substrate, the second glass substrate comprising a second substrate thickness defined between a third main surface and a fourth main surface opposite to the third main surface; an intermediate layer, the intermediate layer positioned between the second main surface and the third main surface; a porous inorganic layer, the porous inorganic layer comprising a plurality of pores and adhered to the second main surface or the third main surface; and a polymer material, the polymer material positioned in the plurality of pores, wherein when illuminated from the first major surface with a D65 illuminant, a maximum ΔE value between a first portion of the glass article in which the polymer 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 in which the porous inorganic layer is not filled with the polymer material is about 2.0 or less.

Aspect 5. The glass article as described in any of Aspects 3-4, wherein the maximum ΔE value is about 0.1 to about 1.0.

Aspect 6. The glass article as described in 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 as described in any one of aspects 1-9, wherein a polymer in the polymer material is the same as a polymer in the intermediate layer.

Aspect 11. The glass article as described in any of aspects 1-9, wherein a polymer in the polymer material is different from a polymer in the intermediate layer.

Aspect 12. The glass article of Aspect 11, wherein the polymer material is semi-crystalline and has a melting temperature of about 100° C. or less.

Aspect 13. The glass article as described in any of Aspects 1-12, wherein the intermediate layer comprises poly(vinyl butyral).

Aspect 14. The glass article as described in any one of aspects 1-13, wherein an absolute value of a difference between a refractive index of the polymer material and a refractive index of the first glass substrate or the second glass substrate is about 0.05 or less.

Aspect 15. The glass article as described in any one of aspects 1 to 14, wherein a portion of the glass article including 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 as described in Aspect 15, wherein at least a portion of the other portion of the glass article does not contain the polymer material, and at least a portion of the portion of the glass article including the porous inorganic layer includes the polymer material.

Aspect 17. A glass article as described in any of Aspects 15-16, wherein the intermediate layer is non-uniform and at least a portion of the intermediate layer in the other portion of the glass article contains a concentration of the plasticizer that is lower than a concentration of the plasticizer in the portion of the glass article that includes the porous inorganic layer comprising the polymer material.

Aspect 18. The glass article as described in any one of aspects 1-16, wherein a concentration of a plasticizer in the polymer material is greater than a concentration of a plasticizer in the intermediate layer.

Aspect 19. The glass article of any one of Aspects 1-16, wherein the polymer material comprises a plasticizer in an amount of about 25 wt % to about 50 wt % of the polymer material.

Aspect 20. The glass article of any of Aspects 1-19, wherein the glass article exhibits an integrated visible light transmittance of about 2.0% or less for light of 400 nm to 700 nm 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 polymer material comprises a substantially linear polymer.

Aspect 22. The glass article of any one of Aspects 1-21, wherein a polymer thickness of the polymer material is about 30 microns or less.

Aspect 23. The glass article as described in any one of Aspects 1-22, wherein the polymer 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 of about 10 volume % to about 60 volume %.

Aspect 25. The glass article of any one of Aspects 1-24, wherein the porous inorganic layer has a thickness of about 10 micrometers to about 30 micrometers.

Aspect 26. The glass article as described in any of aspects 1-25 further comprises: a second porous inorganic layer, the second porous inorganic layer is adhered to the third major surface, wherein the porous inorganic layer is adhered to the second major surface, and the polymer material is positioned in the pores of the first porous inorganic layer and the pores of the second porous inorganic layer.

Aspect 27. The glass product as described in any one of aspects 1 to 26, further comprising: a connection or an electronic component, wherein the connection or the electronic component is positioned between the first glass substrate and the second glass substrate.

Aspect 28. A glass product as described in any of Aspects 1-26, wherein the intermediate layer comprises a first intermediate layer and a second intermediate layer, and the glass product further comprises: an additional polymer layer, the additional polymer layer is positioned between the first intermediate layer and the second intermediate layer; and a wiring or an electronic component, the wiring or the electronic component is positioned between the first intermediate layer and the second intermediate layer.

Aspect 29. A method for forming a glass product, comprising the following steps: Filling a plurality of pores of a porous inorganic layer with a polymer solution or a polymer emulsion, the porous inorganic layer being adhered to a first glass substrate; Drying the polymer solution or the polymer emulsion at a temperature of about 20°C to about 80°C for about 10 minutes or longer to form a polymer material positioned in the plurality of pores; Disposing an intermediate layer on the porous inorganic layer; and Pressing the first glass substrate against a second glass substrate so that the porous inorganic layer and the intermediate layer are positioned between the first glass substrate and the second glass substrate.

Aspect 30. The method of Aspect 29, wherein a viscosity of the polymer solution or the polymer emulsion is in a range of 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 holes comprises providing a layer of the polymer solution or the polymer emulsion comprising a thickness of about 30 microns or less.

Aspect 32. The method according to Aspect 31, wherein the polymer solution or the polymer emulsion is applied by brushing, rolling or spraying.

Aspect 33. The method as described in any one of aspects 29 to 32 further comprises the following step: before drying the polymer solution or the polymer emulsion, covering a periphery of the porous inorganic layer with the polymer solution or the polymer emulsion.

Aspect 34. The method of any one of Aspects 29-33, wherein a first glass transition temperature of the intermediate layer is about 10° C. or greater than a second glass transition temperature of the polymer material.

Aspect 35. The method of Aspect 34, wherein the first glass transition temperature of the intermediate layer is about 15° C. to about 30° C. greater than the second glass transition temperature of the polymer material.

Aspect 36. A method as described in any of Aspects 29-35, wherein when illuminated from the first major surface with a D65 illuminant, a maximum ΔE value between a first portion of the glass article in which the polymer material is positioned within the plurality of pores of the porous inorganic layer and a second portion of the glass article in which the porous inorganic layer is not filled with the polymer material is about 2.0 or less.

Aspect 37. The method of Aspect 36, wherein the maximum ΔE value is 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 in the polymer material is the same as a polymer in the intermediate layer.

Aspect 42. The method of any one of Aspects 29-41, wherein a polymer in the polymer material is different from a polymer in the intermediate layer.

Aspect 43. The method of Aspect 42, wherein the polymer material is semi-crystalline and has a melting temperature of about 100° C. or less.

Aspect 44. The method of any one of Aspects 29-43, wherein the intermediate layer 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 polymer material and a refractive index of 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 including the porous inorganic layer surrounds another portion of the glass article not having the porous inorganic layer on at least two sides.

Aspect 47. The method of Aspect 46, wherein at least a portion of the other portion of the glass article does not contain the polymer material, and at least a portion of the portion of the glass article comprising the porous inorganic layer includes the polymer material.

Aspect 48. A method as described in any of Aspects 46-47, wherein the intermediate layer is non-uniform and at least a portion of the intermediate layer in the other portion of the glass article contains a concentration of the plasticizer that is lower than a concentration of the plasticizer in the portion of the glass article that includes the porous inorganic layer comprising the polymer material.

Aspect 49. The method of any one of Aspects 29-47, wherein a concentration of a plasticizer in the polymer material is greater than a concentration of a plasticizer in the intermediate layer.

Aspect 50. The method of any one of Aspects 29-47 or 49, wherein the polymer material comprises a plasticizer in an amount of about 25 wt % to about 50 wt % of the polymer material.

Aspect 51. The method of any of Aspects 29-50, wherein the glass article exhibits an integrated visible light transmittance of about 2.0% or less for light in the range of 400 nm to 700 nm in a portion of the glass article that includes the porous inorganic layer.

Aspect 52. The method of any one of Aspects 29-51, wherein the polymer material comprises a substantially linear polymer.

Aspect 53. The method of any one of Aspects 29-52, wherein the porous inorganic layer comprises a porosity of about 10 volume % to about 60 volume %.

Aspect 54. The method of any one of Aspects 29-53, wherein the porous inorganic layer has an inorganic thickness of about 10 microns to about 30 microns.

Aspect 55. A method as described in any of Aspects 29-54, wherein the intermediate layer comprises a first intermediate layer and a second intermediate layer, and the glass product further comprises: an additional polymer layer, the additional polymer layer is positioned between the first intermediate layer and the second intermediate layer; and a wiring or an electronic component, the wiring or the electronic component is positioned between the first intermediate layer and the second intermediate layer.

Aspects will now be described more fully hereinafter with reference to the accompanying drawings in which example aspects are shown. Wherever possible, the same reference numerals are used throughout the drawings to refer to the same or similar parts.

FIG . 1 illustrates a vehicle 100 that includes a body 110 that defines an interior and at least one opening 120 and a glass article 130 (e.g., automotive window glass) according to an aspect of the present disclosure positioned in the opening 120. In an aspect, the glass article 130 may be a windshield, but in further aspects, the glass article may also be used in at least one sidelight, a rear window, a side window, a sunroof, or a combination thereof. Alternatively or additionally, the glass article 130 may be part of an interior display, an engine cover, a headlight cover, a taillight cover, a door panel cover, a pillar cover, or a combination thereof. As used herein, a "vehicle" (e.g., vehicle 100 includes an automobile (e.g., see FIG. 1 ) , a rail vehicle, a motorcycle, a boat, a ship, an airplane, a helicopter, a drone, a spacecraft, and the like. Although the present disclosure is framed in a vehicle, it should be understood that the glass articles described herein may be used in other contexts, such as architectural glazing or bulletproof glazing applications.

FIG. 2 schematically depicts a cross-sectional view of a glass product 130 (e.g., automotive window glass) according to an aspect of the present disclosure taken along line 2-2 in FIG . 1. As shown in FIG . 2 to FIG . 6 and FIG . 14 , (one or more) glass products 130 , 300 , 400 , 500 , 600 , or 1400 include a first glass substrate 200 , a second glass substrate 220 , and an intermediate layer 230 , 430 , 630 , or 1430 positioned between the first glass substrate 200 and the second glass substrate 220 . As shown in FIG . 2 , FIG. 4 to FIG. 6 , and FIG. 14 , the first glass substrate 200 includes a first major surface 202 , a second major surface 204 opposite to 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. As shown in FIG . 2 , FIG . 4 to FIG. 6 , and FIG. 14 , the second glass substrate 220 includes a third major surface 222 , a fourth major surface 224 opposite to 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 intermediate layer 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 . The interlayer thickness 236 or 636 is defined as the average distance between the second major surface 204 and the third major surface 222. The interlayer is used 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 achieved with one or more layers and/or material portions positioned therebetween, as discussed below.

In aspects, 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. In aspects, the first substrate thickness 206 is in the range of about 0.1 mm to about 6 mm, about 0.3 mm to about 6 mm, about 0.5 mm to about 6 mm, about 0.8 mm to about 6 mm, about 1 mm to about 6 mm, about 1.2 mm to about 6 mm, about 1.4 mm to about 6 mm, about 1.5 mm to about 6 mm, about 1.6 mm to about 5.8 mm, about 1.6 mm to about 5.6 mm, about 1.6 mm to about 5.5 mm, about 1.6 mm to about 5.4 mm, about 1.6 mm to about 5.2 mm, about 1.6 mm to about 5 mm, about 1.6 mm to about 4.8 mm, about 1.6 mm to about 4.6 mm, about 1.6 mm to about 4.4 mm, about 1.6 mm to about 4.2 mm, about 1.6 mm to about 4 mm, about 1.6 mm to about 3.9 mm, about 1.6 mm to about 3.8 7 mm, about 1.6 mm to about 3.7 mm, about 1.6 mm to about 3.6 mm, about 1.6 mm to about 3.5 mm, about 1.6 mm to about 3.4 mm, about 1.6 mm to about 3.3 mm, about 1.6 mm to about 3.2 mm, about 1.6 mm to about 3.1 mm, about 1.6 mm to about 3 mm, about 1.6 mm to about 2.8 mm, about 1.6 mm to about 2.6 mm, about 1.6 mm to about 2.4 mm, about 1.6 mm to about 2.2 mm, about 1.6 mm to about 2 mm, about 1.6 mm to about 1.8 mm, or any range or sub-range therebetween.

In aspects, the second glass substrate 220 has a second substrate thickness 226 that is less than the first substrate thickness 206. In aspects, the second substrate thickness 226 can be about 2.0 mm or less, such as about 0.1 mm to about 2.0 mm, about 0.1 mm to about 1.8 mm, about 0.1 mm to about 1.6 mm, about 0.5 mm to about 1.5 mm, about 0.7 mm to about 1.4 mm, about 0.7 mm to about 1.2 mm, about 0.7 mm to about 1.1 mm, or any range or sub-range therebetween. In aspects, the 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.

As used herein, unless otherwise indicated, the coefficient of thermal expansion (CTE) is measured according to ASTM E831-19 to calculate the CTE between 25° C. and 300° C. In aspects, the CTE of the first glass substrate 200 and/or the second glass substrate 220 may be about 55×10 ⁻⁷ K ⁻¹ or less, about 50×10 ⁻⁷ K ⁻¹ or less, about 45×10 ⁻⁷ K ⁻¹ or less, about 40×10 ⁻⁷ K ⁻¹ or less, about 35×10 ⁻⁷ K ⁻¹ or less, about 32.5×10 ⁻⁷ K ⁻¹ or less. In aspects, the first glass substrate 200 may include, consist of, or consist essentially of a borosilicate glass composition. As a result, the CTE of the first glass substrate 200 may be within one or more of the ranges mentioned above in this paragraph. Such a low CTE range may make the first glass substrate 200 incompatible with decoration achieved by existing commercial glazes. In an aspect, the second glass substrate 220 can be a sodium calcium silicate glass or a chemically enhanced alkali aluminum silicate glass composition, whose CTE is greater than the CTE of the first glass substrate 200 (e.g., a borosilicate glass composition). In a further aspect, the first glass substrate 200 and the second glass substrate 220 can include different compositions. In further aspects, the CTE of the second glass substrate 220 can be about 60×10 ⁻⁷ K ⁻¹ or greater, e.g., about 60×10 ⁻⁷ K ⁻¹ to about 120×10 ⁻⁷ K ⁻¹ , about 70×10 ⁻⁷ K ⁻¹ to about 120×10 ⁻⁷ K ⁻¹ , about 80×10 ⁻⁷ K ⁻¹ to about 120×10 ⁻⁷ K ⁻¹ , or any range or sub-range therebetween. In aspects, the absolute value of the difference between the CTE of the first glass substrate 200 and the CTE of the second glass substrate 220 may be at least 5× ^10-7 K ^-1 , at least 10× ^10-7 K ^- 1, at least 20× ^10-7 K ^-1 , at least 25× ^10-7 K ^-1 , at least 30× ^10-7 K ^- 1, at least 35× ^10-7 K ^-1 , at least 40× ^10-7 K ^-1 , at least 40× ^10-7 K ^-1 , at least 45× ^10-7 K ^-1 , or at least 50× ^10-7 K ^-1 . For example, an example is contemplated in which the first glass substrate 200 may have a first CTE of approximately 32× ^10-7 K ^-1 , and the second glass substrate 220 may have a second CTE of approximately 90× ^10-7 K ^-1 . Another example is contemplated in which the first glass substrate 200 has a first CTE of approximately 45×10 ⁻⁷ K ⁻¹ and the second glass substrate 220 has a second CTE of approximately 90×10 ⁻⁷ K ⁻¹ .

In one embodiment, the first glass substrate 200 includes a borosilicate glass composition including 60 mol% to 90 mol% _SiO2 , about 1 mol% to about 20 mol% _Al2O3 , 7 mol% to 16 mol% _{B2O3 ,} and 2 mol% to ₂₀ mol% _R2O , wherein _R2O includes a combination of _Na2O , _Li2O , and _K2O . An exemplary borosilicate glass composition includes about 83.60 mol % SiO ₂ , about 1.20 mol % Al ₂ O ₃ , about 11.60 mol % B ₂ O ₃ , about 3.00 mol % Na ₂ O, and about 0.70 mol % K ₂ O, and includes a CTE of about 32×10 ⁻⁷ K ⁻¹ . Such borosilicate glass may be particularly beneficial when the first glass substrate 200 is located on the outside of an automotive glazing (e.g., glass article 130 ) such that the first major surface 202 is the outer surface of the automotive glazing, because the borosilicate glass may have greater thermal shock resistance and is more resistant to crack formation due to impact events from road debris (e.g., rocks or the like) than the sodium calcium silicate glass currently used as the outer glass substrate in automotive glazing. Borosilicate glass is known to exhibit less abnormal cracking behavior and is less susceptible to cracks that propagate radially from the debris impact point, which is particularly beneficial for automotive glazing durability.

In an embodiment, the first glass substrate 200 particularly advantageously includes one of the fusion-formable borosilicate glass compositions described in the following patents: U.S. Provisional Patent Application No. 63/123863, filed on December 10, 2020, entitled “Fusion Formable Borosilicate Glass Composition and Articles Formed Therefrom,” U.S. Provisional Patent Application No. 63/183271, filed on May 3, 2021, entitled “Fusion Formable Borosilicate Glass Composition and Articles Formed Therefrom,” U.S. Provisional Patent Application No. 63/183292, filed on May 3, 2021, entitled “Glass with Unique Fracture Behavior for Vehicle Windshield,” and U.S. Provisional Patent Application No. 63/183293, filed on June 30, 2021, entitled “Glass with Unique Fracture Behavior for Vehicle Windshield.” Behavior for Vehicle Windshield” and International Patent Application No. PCT/US2021/061966, filed on December 6, 2021, entitled “Glass with Unique Fracture Behavior for Vehicle Windshield”, the contents of each of which are hereby incorporated by reference in their entirety. In an embodiment, in terms of constituent oxides, such a borosilicate glass composition includes _SiO2 , _{B2O3 , Al2O3} , one _or more alkali metal oxides, and one or more divalent cationic oxides selected from the group consisting of MgO, CaO, SrO, BaO and ZnO. In a further aspect, the borosilicate glass composition includes about 11 mol % to about 16 mol % B ₂ O ₃ , about 2 mol % to about 6 mol % Al ₂ O ₃ , and about 7.0 mol % or more of the total amount of Na ₂ O, K ₂ O, MgO, and CaO. In a further aspect, the first glass substrate 200 includes a fusion-formable borosilicate glass composition including about 74 mol% to about 80 mol% _SiO2 , about 2.5 mol% to about 6 mol% _Al2O3 , about 11.5 mol _% to about 14.5 mol% _B2O3 , about 4.5 mol% to about 8 mol% _Na2O , about 0.5 mol% to about 3 mol% _K2O , about 0.5 mol% to about 2.5 mol% _MgO , and 0 mol% to about 4 mol% CaO (e.g., such that the combined amount of CaO and MgO is less than 5 mol%), and a CTE of about 32.5× ^10-7 K ^-1 to about 56× ^10-7 K ^-1 . In a further aspect, the borosilicate glass composition can satisfy the following relationships: (R ₂ O + R'O) ≥ Al, (R ₂ O + R'O) ≥ (Al ₂ O ₃ + 2) and/or 0.80 < (1-[(2R ₂ O + 2R'O) / (SiO ₂ + 2Al ₂ O ₃ + 2B ₂ O ₃ )]) < 0.93, wherein all concentrations are molar percentages based on oxides. As used herein, R ₂ O is the sum of alkali metal oxides, i.e., Li ₂ O, Na ₂ O, K ₂ O, Rb ₂ O, and Cs ₂ O. As used herein, R'O is the sum of alkali earth metal oxides including MgO, CaO, SrO, and BaO. Such glasses have been found to exhibit favorable annular cracking behavior, thereby preventing defects from radially propagating from the point of impact. Such fusion-formed glasses also exhibit superior chemical durability, scratch resistance, mechanical strength, and optical performance (e.g., from the perspective of optical transmittance and optical distortion) compared to other borosilicate glasses.

In aspects, the second glass substrate 220 can include, consist of, or consist essentially of a second glass composition that is different from the composition of the glass used to form the first glass substrate 200. In aspects, the second glass substrate includes a sodium calcium silicate composition, an aluminum silicate glass composition, an alkali aluminum silicate glass composition, an alkali borosilicate glass composition, an alkali aluminum phosphosilicate glass composition, or an alkali aluminum borosilicate glass composition. Alternatively, in an aspect, the second glass substrate 220 includes one of the boroaluminosilicate glass compositions described in U.S. Provisional Patent Application No. 63/318221, filed on March 9, 2022, entitled “Boroaluminosilicate Glass Composition having High Fusion Flow Rate and Advantaged Pair Shaping Temperature.” In an aspect, the second glass substrate 220 is formed of one of the glass compositions described in the following patents: U.S. Patent Application No. 16/002276, filed on June 7, 2018, entitled “Automotive Glass Compositions, Articles, and Hybrid Laminates,” or U.S. Patent No. 10,125,044, filed on November 14, 2014, entitled “Ion Exchangeable High Damage Resistance Glasses.” The contents of each of these patent applications are hereby incorporated by reference in their entirety.

Regardless of the specific composition used to form the first glass substrate 200 and the second glass substrate 220 , in aspects, the first glass substrate 200 and the second glass substrate 220 are not strengthened (e.g., chemically strengthened, thermally strengthened, or mechanically strengthened), but in other aspects, at least one of the first glass substrate 200 or the second glass substrate 220 is strengthened (e.g., chemically strengthened, thermally strengthened, or mechanically strengthened). For example, the second glass substrate 220 can be chemically strengthened (e.g., when composed of a suitable alkali aluminum silicate glass composition), while the first glass substrate 200 is not strengthened (but can be annealed as appropriate) 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. Such aspects can help reduce the weight of automotive glazing, while still providing advantageous mechanical strength and meeting various regulatory requirements associated with automotive applications. Alternatively, in an aspect, both the first glass substrate 200 and the second glass substrate 220 can be reinforced.

In an embodiment, the second glass substrate 220 and/or the first glass substrate 200 can be enhanced with one or more compressive stress regions. Chemical enhancement includes an ion exchange process in which ions in the surface layer are replaced by - or exchanged with - larger ions of the same valence or oxidation state. Chemical enhancement methods will be discussed later. The compressive stress region can extend into a portion of the first portion and/or the second portion to a depth referred to as the compression depth. As used herein, the compression depth means the depth at which the stress in the chemically enhanced substrate and/or portion described herein changes from compressive stress to tensile stress. The compression depth is measured by a surface stress gauge or a scattered light polariscope (SCALP, where the values reported herein were obtained using a SCALP-5 manufactured by Glasstress, Estonia), depending on the ion exchange treatment and the thickness of the product being measured. In the case where the stress in the second glass substrate 220 and/or the first glass substrate 200 is generated by exchanging potassium ions into the substrate, the compression depth is measured using a surface stress gauge such as FSM-6000 (Orihara Industries, Ltd. (Japan)). Unless otherwise specified, the compressive stress (including surface CS) is measured by a surface stress meter (FSM) using a commercially available instrument such as FSM-6000 manufactured by Orihara. Surface stress measurements rely on accurate measurements of the stress optical coefficient (SOC), which is related to the birefringence of the glass. Unless otherwise specified, SOC is measured according to Procedure C (Glass Disk Method) as described in ASTM Standard C770-16 (2020), entitled "Standard Test Method for Measurement of Glass Stress-Optical Coefficient," which is incorporated herein by reference in its entirety. SCALP is used to measure compression depth and central tension (CT) when the stress is generated by the exchange of sodium ions into the substrate and the measured article is thicker than about 400 μm. The stress in the substrate and/or portion is generated by the exchange of potassium and sodium ions into the substrate and/or portion and the measured article is thicker than about 400 μm, and the compression depth and CT are measured by SCALP. Without wishing to be bound by theory, the exchange depth of sodium ions can indicate the compression depth, and the exchange depth of potassium ions can indicate a change in the magnitude of the compressive stress (but not a change in stress from compressive stress to tensile stress). Refracted near-field (RNF; RNF methods are 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) methods can also be used to derive a graphical representation of the stress profile. When the RNF method is used to derive a graphical representation of the stress profile, the maximum central tension value provided by SCALP is used in the RNF method. The graphical representation of the stress profile derived by the RNF is force balanced and calibrated to the maximum central tension value provided by the SCALP measurement. As used herein, "depth of layer" (DOL) means the depth to which ions (e.g., sodium ions, potassium ions) have exchanged into the substrate and/or part. In the present disclosure, when the maximum central tension cannot be directly measured by SCALP (such as when the measured product is thinner than about 400 μm), the maximum central tension can be approximated by the product of the maximum compressive stress and the compression depth divided by the difference between the thickness of the substrate and twice the compression depth, where the compressive stress and the compression depth are measured by the FSM.

In an embodiment, the first compressive stress region may extend from the third major surface 222 of the second glass substrate 220 to a first compressive depth, and/or the second compressive stress region may extend from the fourth major surface 224 of the second glass substrate 220 to a second compressive depth. In an embodiment, the first compressive depth and/or the second compressive depth as a percentage of the thickness of the second substrate may 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. In an embodiment, the first compressive depth and/or the second compressive depth as a percentage of the thickness of the substrate may be in a range of about 1% to about 30%, about 5% to about 25%, about 10% to about 20%, or any range or sub-range therebetween. In aspects, the first compression depth and/or the second compression depth may be about 1 μm or more, about 10 μm or more, about 30 μm or more, about 50 μm or more, about 500 μm or less, about 2000 μm or less, about 100 μm or less, or about 60 μm or less. In aspects, the first compression depth and/or the second compression depth may be in the range of about 1 μm to about 500 μm, about 10 μm to about 200 μm, about 30 μm to about 100 μm, about 50 μm to about 60 μm, or any range or sub-range therebetween. In aspects, the first compression depth may be substantially equal to the second compression depth.

In an embodiment, the first compressive stress region may include a maximum first compressive stress, and/or the second compressive stress region may include a maximum second compressive stress. In further embodiments, the maximum first compressive stress and/or the maximum second compressive stress may be about 100 megapascals (MPa) or greater, about 250 MPa or greater, about 500 MPa or greater, about 600 MPa or greater, about 700 MPa or greater, about 1,500 MPa or less, about 1,200 MPa or less, about 1,000 MPa or less, or about 800 MPa or less. In further aspects, the maximum first compressive stress and/or the maximum second compressive stress can be in a range of about 100 MPa to about 1,500 MPa, about 250 MPa to about 1,200 MPa, about 500 MPa to about 1,000 MPa, about 600 MPa to about 1,000 MPa, about 700 MPa to about 800 MPa, or any range or sub-range therebetween. If the first glass substrate 200 is chemically strengthened, it can include compressive stress regions having (one or more) compressive depths 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.

As shown in FIGS . 2 to 6 and 14 , the glass article 130 , 300 , 400 , 500 , 600 or 1400 includes a first porous inorganic layer 240. In an embodiment, the glass article 130 , 300 , 400 , 500 , 600 or 1400 further includes a second porous inorganic layer 250. In an embodiment, in addition to other embodiments described herein, the first porous inorganic layer 240 is not porous, but another suitable decorative coating (e.g., non-porous glaze, inorganic ink, organic ink, other suitable decorative materials). In an embodiment, the first porous inorganic layer 240 may not be included. In embodiments, the first porous inorganic layer 240 may be adhered to the third major surface 222 , but in other embodiments, the first porous inorganic layer 240 may be adhered to the second major surface 204. In further embodiments, the second porous inorganic layer 250 may be adhered to the second major surface 204 , and the first porous inorganic layer 240 may 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 surface of the glass article (e.g., the second major surface 204 , the third major surface 222 ) can be used to protect the layer from mechanical degradation and/or oxidation. In addition, placing the 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 can also help hide 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. As shown in FIG . 8 , when the first glass substrate 200 and the second glass substrate 220 are constructed of glasses having different compositions and/or thicknesses, multiple bands of the porous inorganic layer(s) can provide a predetermined aesthetic appearance.

In a further aspect, as shown in FIG2 , the first porous inorganic layer 240 may extend substantially perpendicularly to the direction of the first substrate thickness 206 to a width that is different from (e.g., smaller than) the width of the second porous inorganic layer 250 extending substantially perpendicularly to the direction of the first substrate thickness 206. In a further aspect, as shown in FIGS . 4 to 6 , the first porous inorganic layer 240 and the second porous inorganic layer 250 may extend substantially the same width with respect to the width in the direction substantially perpendicular to the first substrate thickness 206 .

As shown in FIG . 2 , FIG . 4 to FIG. 6 , and FIG . 14 , the glass article 130 , 400 , 500 , 600 , or 1400 includes a first portion 294a including the first porous inorganic layer 240 and/or the second porous inorganic layer 250 and a second portion 292 that does not contain the first porous inorganic layer 240 and the second porous inorganic layer 250 if the first porous inorganic layer and the second porous inorganic layer are present in the first portion 294a . As used herein, 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 intermediate layer 230 , 430 , 630 , or 1430 . In addition, as shown in FIG . 2 , FIG . 4 to FIG. 6 , and FIG . 14 , a cross-sectional view of the glass article 130 , 400 , 500 , 600 , or 1400 may 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. Therefore, the second portion 292 may be surrounded by the first portions 294a and 294b on at least two sides. For example, as shown in FIG. 8 , the structure 800 includes a glass article 820 surrounded by an edge 810. The glass article 820 includes a first portion 894 including a decorative pattern and a porous inorganic layer 840 , and a second portion 892 including the first glass substrate 830 but not the porous inorganic layer 840 . As shown, the first portion 894 surrounds the second portion 892 on at least two sides (e.g., the first portion 894 is surrounded by the second portion 892 on three sides, as shown in FIG . 8 ). In an embodiment, a portion of the surface of the glass article 130 , 400 , 500 , 600 , 800 , or 1400 (e.g., the first major surface 202 of the first glass substrate 200 ) corresponding to the first portion 294 a , 294 b , and / or 894 or corresponding to the porous inorganic layer (e.g., the first porous inorganic layer 240 , the second porous inorganic layer 250 , the porous inorganic layer 840 ) may 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.

When deposited on glass, such as automotive glass, the porous inorganic layer(s) described herein can function as a decorative glaze. Decorative glazes can be used for aesthetic purposes, functional purposes, or both. For example, the porous inorganic layer(s) would have the dual function of providing an attractive appearance and acting as a shield against visible light and ultraviolet (UV) light.

As shown in FIG . 7 , the second porous inorganic layer 250 includes an inorganic thickness 746 perpendicular to the second major surface 204. For example, the inorganic thickness 746 may correspond to the distance between the first surface 732 adhered to the second major surface 204 and the second surface 734 opposite to the first surface 732. As used herein, the thickness of the first porous inorganic layer 240 and/or the second porous inorganic layer 250 is measured using scanning electron microscope (SEM) images. In an embodiment, the inorganic thickness of the first porous inorganic layer 240 and/or the second porous inorganic layer 250 may be about 1 micrometer (μm) or more, about 10 μm or more, about 15 μm or more, about 20 μm or more, about 30 μm or less, about 25 μm or less, or about 20 μm or less. In an embodiment, the inorganic thickness of the first porous inorganic layer 240 and/or the second porous inorganic layer 250 may range from about 1 μm to about 30 μm, from about 10 μm to about 30 μm, from about 15 μm to about 25 μm, or any range or sub-range therebetween. In an embodiment, the thickness of the second porous inorganic layer 250 may include 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 include a plurality of pores. As shown in FIG. 7 , the second porous inorganic layer 250 includes a plurality of pores 760 . As used herein, the “porosity” of a material is calculated based on an image taken at a major surface of the material using a scanning electron microscope (SEM), wherein the SEM image is analyzed using ImageJ with automatic limiting to determine the portion of the image corresponding to a height below a threshold. In an embodiment, the porosity (volume %) of the first porous inorganic layer 240 and/or the second porous inorganic layer 250 may 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. In embodiments, the porosity of the first porous inorganic layer 240 and/or the second porous inorganic layer 250 can range from about 10% to about 60%, about 15% to about 50%, about 20% to about 40%, about 20% to about 30%, about 25% to about 30%, or any range or sub-range therebetween. When incorporated into a laminate, the porosity can also be used as a decoration having a predetermined color appearance. It has been found that the porosity can prevent the porous inorganic layer(s) from reducing the mechanical strength of the glass substrate(s). Without wishing to be bound by theory, it is believed that porosity reduces the size of the continuous contact area between the glass substrate and the decorative glaze, which reduces CTE-induced stress accumulation caused during the manufacture of the decorative glass article, thereby reducing or preventing defect formation and propagation. Porosity can also help the porous inorganic layer have a predetermined color appearance when incorporated into a laminate. For example, an intermediate layer is used to attach a glass substrate having a porous inorganic layer to another glass substrate. As discussed below, a polymer material can fill a plurality of pores of the porous inorganic layer, which can darken the appearance of the portion of the glass article that includes the porous inorganic layer.

The first porous inorganic layer 240 and/or the second porous inorganic layer 250 may include a CTE within 15× ^10-7 K ^-1 of the CTE of the glass substrate, so that the decorative layer does not reduce the mechanical strength of the glass substrate even if it is in contact with the (one or more) glass substrates. As discussed above, the (one or more) porous inorganic layer can be deposited on the second major surface and/or the third major surface in a pattern suitable for decorative or concealing purposes. The relatively low CTE of the decorative layer described herein, compared to certain existing commercially available glazes (e.g., having a CTE of approximately 80× ^10-7 K ^-1 or greater), enables the use of various borosilicate glasses in automotive glass applications. For example, the absolute value of the difference between the CTE (CTE _g ) of the (one or more) glass substrates and the CTE (CTE _d ) of the porous inorganic layer (i.e., |CTE _g −CTE _d |) may be about 15×10 ⁻⁷ K ⁻¹ or less, about 10×10 ⁻⁷ K ⁻¹ or less, about 9×10 ⁻⁷ K −1 or less, about 8×10 −7 K ⁻¹ or less, about 7×10 ⁻⁷ K ⁻¹ or less, about 6×10 −7 K −1 or less, about 5×10 −7 K −1 or less, about 4×10 −7 K −1 or less, about 3×10 ⁻⁷ K ⁻¹ or less, about 2×10 ⁻⁷ K ⁻¹ or less, about 1×10 −7 K −1 or less, about 0.5×10 ⁻⁷ K ⁻¹ or less, about 0.25×10 ⁻⁷ K −1 or less, about 0.2×10 −7 K ⁻¹ or less, about 0.3×10 ⁻⁷ K ⁻¹ or less, about 0.5×10 −7 K −1 or less, about 0.6×10 ⁻⁷ K −1 or less, about 0.7×10 −7 K ⁻¹ or less, about 0.8×10 ⁻⁷ K ⁻¹ or less, about 0.9×10 ⁻⁷ K ^{−1 or less, about 1.2×10 −7 K −1} or less, about 1.3×10 ⁻⁷ K −1 or less, about 1.4×10 −7 K ⁻¹ or less, about 1.2 ^-7 K ^-1 or less, about 0.15×10 ^-7 K ^-1 or less, about 0.1×10 ^-7 K ^-1 or less, about 0.05×10 ^-7 K ^-1 or less. In an aspect, 20×10 ^-7 K ^-1 ≤ CTE _d ≤ 55×10 ^-7 K ^-1 , 20×10 ^-7 K ^-1 ≤ CTE _d ≤ 50 ×10 ^-7 K ^-1 , 20×10 ^-7 K ^-1 ≤ CTE _d ≤ 45×10 ^-7 K ^-1 , 20×10 ^-7 K ^-1 ≤ CTE _d ≤ 40 ×10 ^-7 K ^-1 , 20×10 ^-7 K ^-1 ≤ CTE _d ≤ 35×10 ^-7 K ^-1 , 20×10 ^-7 K ^-1 ≤ CTE _d ≤ 32.5×10 ^-7 K ^-1 , or any range or sub-range therebetween. In an aspect, 20×10 ⁻⁷ K ⁻¹ ≤ CTE _d ≤ 55×10 ⁻⁷ K ⁻¹ , 35×10 ⁻⁷ K ⁻¹ ≤ CTE _d ≤ 50×10 ⁻⁷ K ⁻¹ , 40×10 ⁻⁷ K ⁻¹ ≤ CTE _d ≤ 50×10 ⁻⁷ K ⁻¹ , and any ranges or sub-ranges therebetween. As described herein, constructing the porous inorganic layer(s) (e.g., the first porous inorganic layer 240 ) to have a CTE approximately equal to the CTE of the first glass substrate 200 can prevent cracks from forming in the porous inorganic layer during manufacture of the glass article, and also prevent bonding of the porous inorganic layer from reducing the mechanical strength of the first glass substrate and/or the glass article.

In an embodiment, the first porous inorganic layer 240 and/or the second porous inorganic layer 250 may include a low CTE additive component. In a further embodiment, the low CTE additive component may 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%, based on the weight of the corresponding porous inorganic layer. In a further embodiment, the low CTE additive component may be present in an amount of about 15 wt% to about 50 wt%, about 15 wt% to about 45 wt%, about 20 wt% to about 45 wt%, about 20 wt% to about 40 wt%, about 25 wt% to 40 wt%, or any range or sub-range therebetween, based on the weight of the corresponding porous inorganic layer. In a further aspect, the low CTE additive component can be present in an amount of about 40 wt % to about 85 wt %, about 50 wt % to about 85 wt %, about 50 wt % to about 80 wt %, about 50 wt % to about 75 wt %, about 50 wt % to about 70 wt %, or any range or sub-range therebetween, based on the weight % of the corresponding porous inorganic layer. For example, the low CTE additive component can be present in an amount of about 40 wt %, 45 wt %, 50 wt %, 55 wt %, 60 wt %, 65 wt %, 70 wt %, 75 wt %, 80 wt %, or 85 wt %, based on the weight % of the low CTE additive.

In an embodiment, the low CTE additive component may include a ceramic or glass ceramic material having a CTE within any range within the above ranges. Exemplary ceramics include B-eucryptite ceramics developed by Corning® Incorporated having a CTE of approximately -10×10 ^-7 K ^-1 , or alumina ceramics having a CTE of less than -10×10 ^-7 K ^-1 . An exemplary glass ceramic material is Kerablack® Plus ceramic sold by Eurokera SNC having a CTE of approximately 0×10 ^-7 K ^-1 . In an embodiment, the low CTE additive component includes a negative CTE. Such negative CTE materials may include Bi-Ni-Fe-oxides, Zr-W-oxides, and other suitable materials. In addition, the low CTE additive component may be selected so that the resulting porous inorganic layer has a predetermined opacity. For example, the low CTE additive component can be selected to absorb light in the visible spectrum (e.g., at least 50% of the light, at least 60% of the light, at least 70% of the light, at least 80% of the light, at least 90% of the light) (on average). In an embodiment, the low CTE additive component is selected so that when illuminated by a D65 illuminant at a 0° illumination angle, the first porous inorganic layer 240 and/or the second porous inorganic layer 250 exhibit a high blackness (e.g., an 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).

Prior to solidification, the precursor of the (one or more) porous inorganic layer may include a mixture of a glaze (e.g., glass frit) and particles of a low CTE additive component. In an embodiment, the low CTE additive component may be present in the (one or more) porous inorganic layer as a filler. In an embodiment, the material of the low CTE additive component may have a melting point or softening temperature higher than the corresponding temperature of the glass frit component in the glaze. In an embodiment, the particles of the low CTE additive component may include an average particle size of about 100 μm or less, about 50 μm or less, about 40 μm or less, about 30 μm or less, or about 20 μm or less. It has been found that the size of the particles of the low CTE additive component affects the porosity of the resulting porous inorganic layer after curing, for example, by preventing the glaze (e.g., glass frit) around the particles from densifying during sintering to produce a porous structure. In addition, it has been found that the porosity prevents the porous inorganic layer from reducing the strength of the glass substrate and/or glass article or even increases the strength of the glass substrate and/or glass article.

In embodiments, the low CTE additive component may comprise a CTE of about 10× ^10-7 K ^-1 or less, about 5× ^10-7 K ^-1 or less, about 0× ^10-7 K ^-1 or less, about -5× ^10-7 K ^-1 or less, about -10× ^10-7 K ^-1 or less, about -50× ^10-7 K ^-1 or less, about -100× ^10-7 K ^-1 or less. It has been found that the CTE of the resulting porous inorganic layer after curing is approximately the weighted average of all constituent components (e.g., between the glass frit and the low CTE additive component). Therefore, the CTE of the low CTE additive may determine the weight percentage required to achieve a predetermined CTE for a given glass frit. In embodiments, the refractive index of the low CTE additive component may be about 1.5 or less or about 1.6 or less. In an embodiment, the refractive index of the low CTE additive component is greater than 1.6. A higher refractive index may be preferred for maintaining a higher opacity of the decorative layer. As used herein, the refractive index is measured according to ASTM E1967-19, wherein the first wavelength includes 589 nm.

In an embodiment, (one or more) porous inorganic layers can be formed by a mixture of particles of a low CTE additive component and a commercially available glaze. The addition of the low CTE additive component is not only used to reduce the CTE of the glaze, but also to increase the porosity of the porous inorganic layer obtained after curing. In a further embodiment, the commercially available glaze comprises a glass or ceramic glaze, which comprises a glass frit component, a dye component and, as the case may be, an additive component. The glass frit component determines various properties of the obtained porous inorganic layer, including mechanical strength and required firing conditions. In a further embodiment, the glass frit may comprise one or more Bi, B, Zn or Si oxides. The glass frit may be characterized by the presence of Bi, B, Zn or Si oxides as the main components. In further aspects, the glass frit may include about 1 wt % or more, about 5 wt % or more, or about 10 wt % or more of Bi, B, Zn, or Si oxides. In further aspects, the glass frit may include less than 1 mol % of Na ₂ O, less than 10 mol % of Fe ₂ O ₃ , or less than 25 mol % of P ₂ O _5. In further aspects, the glass frit does not contain Na ₂ O, Fe ₂ O ₃ , or P ₂ O _5. In further aspects, a dye component is incorporated into the glass frit and includes one or more Cu, Co, Fe, Ni, Mn, or Cr oxides. In further aspects, the dye includes non-Fe oxides, or does not contain Fe oxides. Examples of suitable ceramic glazes are available from Ferro Corporation (Mayfield Heights, Ohio) and include Product No. 14 316 (a bismuth-based frit system with a black, matte color, a wide firing range of 570°C to 640°C in 6 minutes, and a relatively high melting point) and Product No. VPS 4100 (a black glaze that can be fired at 630°C to 650°C). The glaze can be black, white, or any color, such as red, indigo, blue, green, brown, orange, purple, yellow. The commercially available glaze can be dispersed in a suitable medium to form a paste for application to a glass substrate, wherein the medium can include an oil or organic resin suitable for drying by evaporation of a solvent.

In an embodiment, the first porous inorganic layer 240 and/or the second porous inorganic layer 250 may be formed from a commercially available ceramic glaze or glass frit (e.g., without the particles of the low CTE additive component discussed above). In an embodiment, the first porous inorganic layer 240 and/or the second porous inorganic layer 250 may be formed from a glass frit designed to be ion exchangeable. For example, the glass frit may be applied to the ion exchangeable glass before undergoing an ion exchange treatment. Such glass frit is configured to allow ion exchange between the glass and the treatment bath. In a further aspect, the glass frit can be Bi-Si-B alkali system, Bi-Zn based Bi system, Bi system, Si-Zn-B-Ti system without or with low Bi, Si-Bi-Zn-B alkali system and/or Si-Bi-Ti-B-Zn alkali system. An exemplary ion-exchangeable glass frit (including coloring agent) comprises _45.11 mol% _Bi2O3 , 20.61 mol% _SiO2 , 13.56 mol% _Cr2O3 , _5.11 mol% CuO, 3.48 mol% MnO, 3.07 mol% ZnO, 2.35 mol% _B2O3 , 1.68 mol% _TiO2 , _1.60 mol% _Na2O , 1.50 mol% _Li2O , 0.91 mol% _K2O , 0.51 mol% _AbO3 , 0.15 mol% _{P2O5 ,} 0.079 mol% _SO3 , 0.076 mol% BaO, 0.062 mol% _ZrO2 0.060 mol% Fe ₂ O ₃ , 0.044 mol% MoO ₃ , 0.048 mol% CaO, 0.018 mol% Nb ₂ O ₅ , 0.006 mol% Cl and 0.012 mol% SrO. Other examples of ion-exchangeable glass frits are disclosed in International Patent Application No. PCT/US2020/28176, filed on April 15, 2022, entitled “Filled Pore Decorative Layer for Ion Exchangeable and Automotive Glass,” U.S. Patent No. 9,346,708B2 (Application No. 13/464,493, filed on May 4, 2012), and U.S. Publication No. 2016/0002104A1 (Application No. 14/768,832, filed on August 19, 2015), each of which is incorporated herein by reference in its entirety.

In an aspect, the first porous inorganic layer 240 and/or the second porous inorganic layer 250 may include (e.g., in addition to the glaze/frit-based components described in the previous paragraph) a colorant coating composed of an ink such as an organic ink. Additionally or alternatively, in an aspect, although not shown, a colorant coating may be applied to the third major surface 222 or the fourth major surface 224. Advantageously, such a colorant coating may be applied to the second glass substrate 220 when the second glass substrate 220 is in a planar configuration, and then the second glass substrate 220 may be cold formed to a curved configuration without destroying the colorant coating (e.g., organic ink coating). In a further aspect, 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. Examples of such colorant coatings are described in European Patent No. 2617690B1, which is incorporated herein by reference in its entirety. Other suitable colorant coatings and methods of applying colorant coatings are described in U.S. Publication No. 2020/0171800A1 (Application No. 16/613,010, filed on November 12, 2019) and U.S. Patent No. 9,724,727 (Application No. 14/618,398, filed on February 10, 2015), both of which are incorporated herein by reference in their entirety. Additionally or alternatively, an infrared reflective (IRR) coating, a glass frit, an anti-reflective coating, or a pigment coating may be disposed on the first glass substrate and/or the second glass substrate. For example, the IRR coating may 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 coated with one or more layers of an infrared reflective film and an optional transparent dielectric film. In a further embodiment, the infrared reflective film may include a conductive metal, such as silver, gold, or copper, which reduces heat transfer through the automotive window glass. In a further embodiment, the optional dielectric film may be used for anti-reflective infrared reflective film and control other properties and characteristics of the coating, such as color and durability. In a further embodiment, the dielectric film includes one or more oxides of zinc, tin, indium, bismuth, and titanium. In aspects, 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.

In an embodiment, the precursor of the first porous inorganic layer 240 and/or the second porous inorganic layer 250 may include particles of a suitable pigment to provide a predetermined appearance. In a further embodiment, the pigment particles may be added in an amount less than or equal to the amount of the low CTE additive component (as discussed above). The pigment may also be incorporated into the base glass frit (e.g., ceramic glaze), for example as a colorant component. In a further embodiment, the pigment (if included) is added so that the pigment is present in an amount 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., greater than 0 wt % to about 40 wt %, greater than 5 wt % to about 30 wt %, greater than 5 wt % to about 20 wt % or any range or sub-range therebetween). Examples of suitable pigments include B1G pigment, 30C965 (CuCr based pigment), 20F944 (MgFe based pigment) and V7709 (CuCr based pigment) from Shepherd (Cincinnati, Ohio), and 240137 (FeCrCoNi based pigment) from Ferro Corporation (Mayfield Heights, Ohio). The pigments may be selected to have the following main components in order to obtain a predetermined color, such as the following: black (CuCrFe, CrFe, manganese iron spinel, FeCrCoNi), blue (cobalt aluminate, cobalt chromate spinel, CoZnCrAl), green (cobalt titanate green spinel), brown (manganese antimony titanium light yellow rutile, zinc iron chromium brown spinel, iron titanium brown spinel), orange (rutile tin zinc), purple (cobalt phosphate), yellow (nickel antimony titanium yellow rutile, niobium sulfide tin zinc oxide) and metallic aspects (mica flakes covered with titanium oxide, titanium oxide and tin oxide, or iron oxide). The pigment may be black, blue, green, brown, orange, purple, yellow, or metallic variants thereof. In a further aspect, the pigment may have the same or similar color as the frit (e.g., glaze), for example, when illuminated with a D65 illuminant at a 0° illumination angle, the pigment and glaze may exhibit CIE a* and CIE b* values that differ by less than 5 from each other.

In an embodiment, the first porous inorganic layer 240 and/or the second porous inorganic layer 250 may also include optical properties that are advantageous for decorative automotive applications. For example, in an embodiment, at a thickness of about 30 μm or less, 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 of about 20 or less, about 15 or less, about 10 or less, about 5 or less, about 2.5 or less according to the CIE 1976 color space). In an embodiment, the first porous inorganic layer 240 and/or the second porous inorganic layer 250 exhibits an integrated visible light 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 of 400 nm to 700 nm incident normally on the glass article. Such low optical transmittance helps the decorative layer perform various concealing and decorative functions in automotive applications. As used herein, the terms "optical transmittance" and "transmittance" are used interchangeably to refer to the percentage of light transmitted through the article in the wavelength range of interest. The "integrated visible light transmittance" for light in a specific wavelength range is determined using the following equation: Where T(λ) represents the transmission spectrum in the wavelength range, and φ(λ) is equal to the transmittance of the light source used to measure the transmittance. In an embodiment, a portion (e.g., first portion 294a or 294b) of the glass article 130 , 300 , 400 , 500 , 600 , or 1400 that includes a porous inorganic layer (e.g., first porous inorganic layer 240 and /or second porous inorganic layer 250 ) may include an integrated visible light 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 of 400 nm to 700 nm normally incident on the glass article.

In an aspect, the precursor to the porous inorganic layer may be compatible with the temperature requirements for bending and laminating the glass substrate(s) to form the glass article. In a further aspect, the precursor (e.g., an uncured modified glaze) may be 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. For example, the precursor (e.g., modified glaze) may be cured during the heating cycle of the bending process to promote process efficiency. Thus, the precursor (e.g., modified glaze) may include a glass softening temperature that is less than or equal to the sag temperature of the glass substrate(s). In an embodiment, the glass softening temperature of the precursor (e.g., modified glaze), 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 promote such simultaneous bending and curing action.

As shown in FIG . 7 , polymer material 750 may be positioned in a plurality of holes 760 in the second porous inorganic layer 250. In aspects, as shown, the polymer material may be positioned in a plurality of holes in the second porous inorganic layer 250 , without necessarily being positioned in all of the plurality of holes (e.g., see hole 762 ), but in other aspects, substantially all of the plurality of holes may have polymer material positioned therein. For example, as shown, polymer material 750 may be positioned in a plurality of holes in the first portion 782 , but not in a plurality of holes in the second portion 784. As used herein, a hole "filled" with a polymer material means that the polymer material is positioned in the hole, without requiring 100% of the volume of the hole to contain the polymer material. In embodiments, although not shown, it is understood that a portion of the material of the intermediate layer 230 , 430 , 630 , or 1430 may be positioned in one or more of the plurality of pores of the second porous inorganic layer 250 .

Throughout this disclosure, "color shift" or "ΔE" values are measured in CIE 1976 color space between two points corresponding to subscripts 1 and 2 on a glass article using L*, a*, and b* values as ΔE=√((L* ₁ -L* ₂ ) ² +(a* ₁ -a* ₂ ) ² +(b* ₁ -b* ₂ ) ² ). As used herein, the "maximum" color shift or "maximum" ΔE value is the maximum of any ΔE measured between points in the first portion relative to a point in the second portion, where the points in each portion are at least every 0.1 mm of the sample. As used herein, unless otherwise indicated, CIE values (and ΔE) are measured using a D65 illuminant incident on a first major surface of a first glass substrate of a glass article and assuming a 2° standard observer. In one embodiment, when illuminated from the first major surface 202 (see FIG . 2 ) with a D65 illuminant, the maximum ΔE value between (1) a first portion 782 of the glass article 130 in which the polymer material 750 is positioned within a plurality of pores of the first porous inorganic layer 240 and (2) a second portion 784 of the glass article 130 in which the first porous inorganic layer 240 is not filled with the polymer material 750 may be about 2.0 or less, about 1.7 or less, about 1.5 or less, about 1.2 or less, about 1.0 or less, about 0.9 or less, about 0.8 or less, about 0.7 or less, about 0.6 or less, about 0.5 or less, about 0.1 or greater, about 0.2 or greater, about 0.3 or greater, or about 0.4 or greater. In an embodiment, when illuminated from the first major surface 202 (see FIG . 2 ) with a D65 illuminant, the maximum ΔE value between (1) a first portion 782 of the glass article 130 in which the polymer material 750 is positioned within a plurality of pores of the first porous inorganic layer 240 and (2) a second portion 784 of the glass article 130 in which the first porous inorganic layer 240 is not filled with the polymer material 750 may be in a range of about 0.1 to about 2.0, about 0.1 to about 1.7, about 0.1 to about 1.5, about 0.1 to about 1.2, about 0.1 to about 1.0, about 0.2 to about 0.9, about 0.2 to about 0.8, about 0.3 to about 0.7, about 0.3 to about 0.6, about 0.4 to about 0.5, or any range or sub-range therebetween. Providing lower maximum ΔE values between such portions of the glass article having the porous inorganic layer can provide a substantially uniform color associated with the porous inorganic layer that is visually imperceptible to an observer.

In one embodiment, when illuminated from the first major surface 202 (see FIG. 2 ) with a D65 illuminant, the absolute value of the difference between the CIE L* value (L* ₁ ) of a first portion 782 of the glass article 130 in which the polymer material 750 is positioned within a plurality of pores of the first porous inorganic layer 240 and (2) the CIE L* (L* ₂ ) of a second portion 784 of the glass article 130 in which the first porous inorganic layer 240 is not filled with the polymer material 750 may be about 1 or less, about 0.9 or less, about 0.8 or less, about 0.7 or less, about 0.6 or less, about 0.5 or less, about 0.4 or less, about 0.01 or more, about 0.1 or more, about 0.2 or more, or about 0.3 or more. In an embodiment, when illuminated from the first major surface 202 (see FIG. 2 ) with a D65 illuminant, the absolute value of the difference between the CIE L* value (L* ₁ ) of a first portion 782 of the glass article 130 in which the polymer material 750 is positioned within a plurality of pores of the first porous inorganic layer 240 and (2) the CIE L* value (L* ₂ ) of a second portion 784 of the glass article 130 in which the first porous inorganic layer 240 is not filled with the polymer material 750 can be in a range of about 0.01 to about 1, about 0.1 to about 0.9, about 0.1 to about 0.8, about 0.2 to about 0.7, about 0.6 to about 0.2, about 0.3 to about 0.5, about 0.3 to about 0.4, or any range or sub-range therebetween. In one embodiment, the maximum absolute value of the difference between the L* ₁ value and the L* ₂ value can be within the range discussed above in this paragraph or a plurality of ranges therein.

In an embodiment, when illuminated from the first major surface 202 (see FIG . 2 ) with a D65 illuminant, the absolute value of the difference between the CIE a* value (a* ₁ ) of a first portion 782 of the glass article 130 in which the polymer material 750 is positioned within a plurality of pores of the first porous inorganic layer 240 and (2) the CIE a* (a* ₂ ) of a second portion 784 of the glass article 130 in which the first porous inorganic layer 240 is not filled with the polymer material 750 may be about 1 or less, about 0.7 or less, about 0.5 or less, about 0.4 or less, about 0.3 or less, about 0.2 or less, about 0.01 or greater, about 0.05 or greater, about 0.15 or greater, or about 0.2 or greater. In an embodiment, when illuminated from the first major surface 202 (see FIG . 2 ) with a D65 illuminant, the absolute value of the difference between the CIE a* value (a* ₁ ) of a first portion 782 of the glass article 130 in which the polymer material 750 is positioned within a plurality of pores of the first porous inorganic layer 240 and (2) the CIE a* (a* ₂ ) of a second portion 784 of the glass article 130 in which the first porous inorganic layer 240 is not filled with the polymer material 750 can be in a range of about 0.01 to about 1, about 0.05 to about 0.7, about 0.05 to about 0.5, about 0.1 to about 0.4, about 0.15 to about 0.3, about 0.15 to about 0.2, or any range or sub-range therebetween. In one embodiment, the maximum absolute value of the difference between the a* ₁ value and the a* ₂ value can be within the range discussed above in this paragraph or multiple ranges therein.

In an embodiment, when illuminated from the first major surface 202 (see FIG . 2 ) with a D65 illuminant, the absolute value of the difference between the CIE b* value (b* ₁ ) of a first portion 782 of the glass article 130 in which the polymer material 750 is positioned within a plurality of pores of the first porous inorganic layer 240 and (2) the CIE b* (b* ₂ ) of a second portion 784 of the glass article 130 in which the first porous inorganic layer 240 is not filled with the polymer material 750 may be about 1 or less, about 0.7 or less, about 0.5 or less, about 0.4 or less, about 0.3 or less, about 0.2 or less, about 0.01 or more, about 0.05 or more, about 0.15 or more, or about 0.2 or more. In an embodiment, when illuminated from the first major surface 202 (see FIG. 2 ) with a D65 illuminant, the absolute value of the difference between the CIE b* value (b* ₁ ) of a first portion 782 of the glass article 130 in which the polymer material 750 is positioned within a plurality of pores of the first porous inorganic layer 240 and (2) the CIE b* value (b* ₂ ) of a second portion 784 of the glass article 130 in which the first porous inorganic layer 240 is not filled with the polymer material 750 can be in a range of about 0.01 to about 1, about 0.05 to about 0.7, about 0.05 to about 0.5, about 0.1 to about 0.4, about 0.15 to about 0.3, about 0.15 to about 0.2, or any range or sub-range therebetween. In one embodiment, the maximum absolute value of the difference between the b* ₁ value and the b* ₂ value can be within the range discussed above in this paragraph or a plurality of ranges therein.

In an embodiment, the polymer material may be present at the periphery of the glass product and cover the first porous inorganic layer 240 and/or the second porous inorganic layer 250. For example, as shown in FIG. 11 , the polymer material 750 may be present at the periphery of the first glass substrate 200 corresponding to the periphery of the resulting glass product. In addition, as shown in FIG . 11 , a portion 770 of the polymer material 750 may cover the second porous inorganic layer 250. As used herein, if there is no path from the outside of the glass product to the porous inorganic layer without passing through the polymer material, the intermediate layer, or the glass substrate, the polymer material covers the second porous inorganic layer. Providing the polymer material at the periphery of the glass product can ensure color uniformity of the glass product by filling the pores at the periphery, including at the periphery of the glass product. Furthermore, providing a polymer material covering the porous inorganic layer can prevent oxygen and moisture from entering the glass article, which can improve the life of the glass article, including the porous inorganic layer(s).

In an aspect, the polymers in polymer material 750 may include substantially linear polymers. As used herein, substantially linear polymers are substantially free of crosslinks, which are branch points connecting otherwise distinct polymer chains. As used herein, "thermoplastic material" means a polymer material that can be reformed by heating the material after an initial curing (e.g., polymerization) reaction. Thermoplastic polymers are in contrast to thermosetting polymers, which cannot be reformed after an initial curing reaction. In further aspects, polymer material 750 may include any of the polymers discussed above for the intermediate layer. In further aspects, polymer material 750 may include poly(vinyl butyral) (PVB) (e.g., acoustic PVB (aPVB)), poly(vinyl chloride) (PVC), ionomers, poly(ethylene-co-vinyl acetate) (EVA), polyurethanes (e.g., thermoplastic polyurethane (TPU)), or combinations thereof, and any of these polymers (or blends) may be combined with a plasticizer (discussed below) to form polymer material 750. Exemplary aspects of polymer material 750 include EVA, plasticized PVB, and plasticized PVC.

In the present disclosure, the glass transition temperature (Tg) of the polymer material is measured using digital scanning calorimetry (DSC). In an aspect, the second glass transition temperature of the polymer material 750 (e.g., including any plasticizer, if present) may be about 85°C or less, about 80°C or less, about 75°C or less, or about 70°C or less. In an aspect, the second glass transition temperature of the polymer material 750 may be in the range of about -120°C to about 85°C, about 40°C to about 80°C, about 50°C to about 75°C, about 60°C to about 70°C, or any range or sub-range therebetween. Providing a polymer material with a low glass transition temperature (e.g., about 85°C or less) may enable the polymer material to be easily positioned (e.g., filled) in a plurality of pores of the (one or more) porous inorganic layer. Providing a polymer material having a glass transition temperature of about 40°C or greater can reduce changes in the properties of the polymer material over a temperature range typically encountered during use of a glass article. In one embodiment, the polymer in polymer material 750 can be semi-crystalline, having a melting temperature of about 100°C or less, about 90°C or less, or about 80°C.

In an aspect, polymer material 750 may include a plasticizer in addition to the polymer, but the polymer material may be substantially free of plasticizer (e.g., consisting essentially of a polymer). As used herein, "plasticizer" refers to a material combined with a polymer that reduces the glass transition temperature of the resulting polymer material relative to a single polymer. In a further aspect, the plasticizer may include fish oil, castor oil, tetraethylene glycol di-n-heptanoate, triethylene glycol di-(2-ethylhexanoate), sebacate (e.g., dibutyl sebacate), adipate (e.g., dihexyl adipate, dioctyl adipate, hexylcyclohexyl adipate), phthalate, trimellitate, organic phosphate. Exemplary aspects of plasticizers include fish oil and castor oil.

In further aspects, the polymer material 750 may include a plasticizer in an amount of about 20% by weight or more, about 25% by weight or more, about 30% by weight or more, about 35% by weight or more, about 60% by weight or less, about 55% by weight or less, about 50% by weight or less, about 45% by weight, or about 40% by weight or less, based on the weight of the polymer material. In further aspects, the polymer material 750 may include a plasticizer in an amount of about 20% to about 60% by weight, about 20% to about 55% by weight, about 25% to about 50% by weight, about 30% to about 45% by weight, about 35% to about 40% by weight, or any range or sub-range therebetween, based on the weight of the polymer material. In a further aspect, the plasticizer can reduce the second glass transition temperature of the polymer in the polymer material 750 relative to the glass transition temperature of the individual polymer by about 10°C or more, 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. In a further aspect, the plasticizer can reduce the second glass transition temperature of the polymer in the polymer material 750 relative to the glass transition temperature of the individual polymer by a range of about 10°C to about 40°C, about 15°C to about 30°C, about 18°C to about 25°C, about 20°C to about 23°C, or any sub-range therebetween. The plasticizer content (e.g., the plasticizer content of a layer or portion of the polymer material 750 or the intermediate layer) can be determined using spectroscopy (e.g., infrared (IR) spectroscopy). For example, the plasticizer can produce a distinctive absorption band (e.g., compared to the polymer discussed above), and the intensity of the absorption can be related to the concentration of the plasticizer. In an embodiment, the absolute value of the difference between the refractive index of the polymer material 750 and the refractive index of 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.

In an embodiment, the polymer material 750 may include an adhesion promoter, an ultraviolet (UV) absorber, an antioxidant, or a combination thereof. In a further embodiment, the adhesion promoter, UV absorber, and/or antioxidant may have substantially no effect on the glass transition temperature of the polymer material 750 (e.g., about 1° C. or less, 0° C.). In a further embodiment, the weight of the adhesion promoter, ultraviolet (UV) absorber, and/or antioxidant may 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. In further aspects, the weight of the adhesion promoter, UV absorber and/or antioxidant can be in the range of about 0.01 wt % to about 2 wt %, about 0.1 wt % to about 1 wt %, about 0.1 wt % to about 0.5 wt %, about 0.2 wt % to about 0.3 wt %, or any range or sub-range therebetween. The adhesion promoter can increase the adhesion between the polymer material 750 and the (one or more) porous inorganic layer 240 or 250 , the first glass substrate 200 , the second glass substrate 220 and/or the intermediate layer 230 or 430. Exemplary aspects of the adhesion promoter include silane coupling agents, such as amine functionalized silanes or epoxy functionalized silanes. UV absorbers increase absorption of 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, triazine and hindered amine light stabilizers. Antioxidants may include phenolic-based compounds or phosphite-based compounds. Exemplary aspects of useful antioxidants comprising phenolic compounds include pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (e.g., Irganox 1010 (BASF)), thiodiethylenebis[3-(3,5-di-tert-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)), phenylpropionic acid (e.g., Irganox 1135 (BASF)), 3,3',3',5,5',5'-hexa-tert-butyl-a,a',a'-(mesitylene-2,4,6-triyl)tri-p-cresol (e.g., Irganox 1330 (BASF)), and 1,1'-di-(1,1'-di-tert-butyl)tri-p-cresol. (BASF)), (1,1-di-tert-butyl)-4-hydroxyphenyl)methyl)ethylphosphonate (e.g., Irganox 1425 (BASF)), 4,6-bis[octylthiomethyl]-o-cresol (e.g., Irganox 1520 (BASF)), 1,3,5-tris[3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,5(1H,3H,5H)-trione (e.g., Irganox 3114 (BASF)), 2,6-di-tert-butyl-4-(4,6-bis(octanethiol)-1,3,5-triazin-2-ylamino)phenol (e.g., Irganox 565 (BASF)) and 2',3-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]propionylhydrazine (e.g., Irganox MD-1024 (BASF)). Exemplary aspects of antioxidants comprising phosphite-based compounds include 2,2',2''-nitro(triethyl-tris[3,3',5,5'-tert-tert-butyl-1,1'-biphenyl-2,2'-diyl])phosphite (e.g., Irgafos 12 BASF), bis[2,4,-di-tert-butylphenol]pentaerythritol diphosphate (e.g., Irgafos 126 (BASF), tris[2,4-di-tert-butylphenyl]phosphite (e.g., Irgafos 168 (BASF)), bis[2,4-di-tert-butyl-6-methylphenyl]-ethyl-phosphite (e.g., Irgafos 38 (BASF)), trisnonylphenyl phosphite (e.g., Weston 399 (Addivant)), 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiroundecane (e.g., Weston 618 (Addivant)), [1,3,2-dioxaphosphane, 5-butyl-5-ethyl-2-(2,4,6-tris[1,1-dimethylethyl]phenoxy)-1,3,2-dioxaphosphane] (e.g., Ultranox 641 (SI Group)), 2,2'-ethylene-bis[4,6,-di-tert-butylphenyl]fluorophosphate (e.g., Ethenox 398 (SI Group)), and 2,2'-methylene-bis[4,6-di-tert-butylphenyl]-2-ethylhexylphosphite (e.g., ADK STAB HP-10 (Adeka)).

As discussed above, 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. In aspects, as shown in FIGS. 2-5 , the interlayer(s) 230 or 430 may include a single layer of a polymer 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. In further aspects, as shown in FIG . 2 , the interlayer 230 may include a substantially homogeneous layer of material. Alternatively, in further aspects, as shown in FIGS . 4-5 , the intermediate layer may be non-uniform (e.g., heterogeneous), with the first portion 431a and / or 431b and the second portion 433 having different compositions. In further aspects, the concentration of the plasticizer may differ between the portions, for example, where the concentration of the plasticizer in the first portion is greater than the concentration of the plasticizer in the second portion. In further aspects, the polymer in the first portion may be different from the polymer in the second portion. In further embodiments, as indicated by reference numerals 448a and 448b , 648a and 648b , and / or 658a and 658b , the boundary between the first portion 431a , 431b , 641a , 641b , 651a and / or 651b and the second portion 433 , 643 and / or 654 may coincide with the boundary between the first portion 294a and / or 294b and the second portion 292 of the glass article, but in other embodiments, the first portion 431a , 431b , 641a , 641b , 651a and / or 651b of the intermediate layer may extend into a portion of the second portion 292 of the glass article.

Alternatively, in a further aspect, as shown in FIG . 6 , the intermediate layer 630 may include a first intermediate layer 640 , a second intermediate layer 650 , and an additional polymer layer 660 positioned therebetween. In a further aspect, the first intermediate layer 640 includes 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 to the first contact surface 642 , wherein a first intermediate layer thickness 646 is defined between the first contact surface and the second contact surface. In a further aspect, the second intermediate layer 650 includes 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 to the fourth contact surface 654 , wherein the fourth contact surface and the third contact surface define a second intermediate layer thickness 656 therebetween. As discussed above, the first intermediate layer 640 and/or the second intermediate layer 650 can be non-uniform, for example, wherein the boundaries between the first portions 641a , 641b , 651a , and / or 651b and the second portions 643 and / or 653 are indicated by reference numerals 648a , 648b , 658a , and / or 658b . In a further aspect, the additional polymer layer 660 may include a fifth contact surface 662 contacting the second contact surface 644 of the first intermediate layer 640 and a sixth contact surface 664 opposite to the fifth contact surface 662 , wherein the sixth contact surface may contact the third contact surface 652 of the second intermediate layer 650. It should be understood that the first porous inorganic layer and/or the second porous inorganic layer may include another portion (e.g., see another portion 1470 in FIG . 14 ) that is aligned with and/or covers the covering area of the electronic device 661 (as described below).

Alternatively, in a further aspect, as shown in FIG . 14 , the intermediate layer 1403 may include a first intermediate layer 1433 and an additional polymer layer 1460. In a further aspect, the first intermediate layer 1433 includes 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 to the first contact surface 1432 , wherein a first intermediate layer thickness 236 is defined between the first contact surface and the second contact surface. In a further aspect, the additional polymer layer 1460 includes 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 to the third contact surface 1462 . In a further embodiment, the first contact surface 1432 of the first intermediate layer 1433 can contact the fourth contact surface 1464 of the additional polymer layer 1460. In a further embodiment, the electronic device 1401 can be disposed on the second major surface 204 of the first glass substrate 200 and/or contact the second major surface of the first glass substrate, and/or the electronic device 1401 can contact the second major surface 204 and be surrounded on other sides by the third contact surface 1462 of the additional polymer layer 1460. In a further embodiment, the electronic device 1401 can be separated from the first intermediate layer 1433 by the additional polymer layer 1460 . In a further aspect, the first porous inorganic layer 240 may include an additional portion 1470 that may be aligned with the electronic device 1401 in the direction of the first substrate thickness 206. In addition, the additional portion 1470 may cover the coverage area of the electronic device 1401. As used herein, a first portion covers the coverage area of a second portion if the projection of the second portion onto a plane including the first portion in the direction of the first substrate thickness is completely within the area of the first portion (e.g., the coverage area of the second portion may overlap with the first portion). Providing an additional portion 1470 covering the electronic device can shield the electronic device when the glass article is viewed from one side, while enabling the electronic device to function (e.g., viewing a second side opposite the first side), which can provide an aesthetic benefit to the viewer. Thus, the glass article 1400 may include another portion 294c of the first portion, which may be surrounded on at least two sides by the second portion 292 , and the second portion 292 may be surrounded on at least two sides by the first portions 294a and 294b . It should be understood that the electronic device may be disposed on the third major surface of the second glass substrate, wherein another portion of the second porous inorganic layer covers the covering area of the electronic device. Although FIG. 14 depicts a situation in which the electronic device 1401 is positioned to contact the first glass substrate 200 , it is also contemplated that the electronic device 1401 is positioned to contact the second glass substrate 220 and the additional polymer layer 1460 is in contact with the electronic device 1401 . In such aspects, the second porous inorganic layer 250 may include an additional portion covering the electronic device 1401 , and such additional portion may overlap with (or contact, or include the polymer material 750 in the pores of the second porous inorganic layer and contact the additional polymer layer) the additional polymer layer 1460. Aspects are contemplated in which 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 polymer layer 1460 may include a plurality of portions in which such electronic devices are encapsulated. For example, in aspects, a plurality of electronic devices are disposed in contact with the second glass substrate 220 , and the additional polymer layer 1460 may be disposed between such electronic devices and the first glass substrate 200 . In such cases, the second porous inorganic layer 250 may overlap with each electronic device. In addition, the polymer material 750 described herein may be bonded to the pores of the second porous inorganic layer 250 in the area overlapping with the additional polymer layer 1460 to promote a uniform appearance of the glass article. In an embodiment, the additional polymer layer 1460 extends the entire distance between the electronic device 1401 and the second porous inorganic layer 250 (and may contact the polymer material 750 , for example, the additional polymer layer 1460 may constitute a portion of the intermediate layer 1430 ).

In an embodiment, the intermediate layer 230 , 430 (e.g., first portion 431a or 431b ) , 630 (e.g., first intermediate layer 640 , second intermediate layer 650 ) , or 1430 (e.g., first intermediate layer 1433 ) may include any of the polymers discussed above with respect to the polymer material 750. In a further embodiment, the polymer in the intermediate layer 230 , 430 (e.g., first portion 431a or 431b ) , 630 (e.g., first intermediate layer 640 , second intermediate layer 650 ) , or 1430 (e.g., first intermediate layer 1433 ) may be the same as the polymer in the polymer material 750 , but in a further embodiment, the polymer in the intermediate layer may be different from the polymer in the polymer material. An exemplary embodiment of the polymer used for the intermediate layer is PVB. In a further embodiment, the intermediate layer 230 , 430 (e.g., first portion 431a or 431b ) , 630 (e.g., first intermediate layer 640 , second intermediate layer 650 ) , or 1430 (e.g., first intermediate layer 1433 ) may include a plasticizer, such as any of the plasticizers discussed above for polymer material 750 . However, in a further embodiment, the concentration of the plasticizer in the polymer material 750 may be greater than the concentration of the plasticizer in the intermediate layer 230 , 430 (e.g., the first portion 431a or 431b ) , 630 (e.g., the first intermediate layer 640 , the second intermediate layer 650 , the additional polymer layer 660 ) , or 1430 (e.g., the first intermediate layer 1433 , the additional polymer layer 1460 ). In further aspects, as shown in Figures 4 to 5 , the second portion 433 of the intermediate layer 430 may include a lower concentration of plasticizer than the first portion 431a and / or 431b of the intermediate layer 430 , and the first portion 431a and / or 431b of the intermediate layer 430 may include a lower concentration of plasticizer than the polymer material 750 (see Figure 7 ) (e.g., located in a plurality of pores of the first porous inorganic layer 240 and/or the second porous inorganic layer 250 ). In still further aspects, the second portion 433 of the intermediate layer 430 , the additional polymer layer 660 of the intermediate layer 630 , and/or the additional polymer layer 1460 of the intermediate layer 1430 may be substantially free of plasticizer. In a further embodiment, the first Tg of the intermediate layer 230 , 430 (e.g., the first portion 431a or 431b ) , 630 (e.g., the first intermediate layer 640 , the second intermediate layer 650 , the additional polymer layer 660 ) , or 1430 (e.g., the first intermediate layer 1433 , the additional polymer layer 1460 ) may be approximately 10°C or greater, approximately 15°C or greater, approximately 18°C or greater, approximately 20°C or greater, approximately 40°C or less, approximately 30°C or less, approximately 25°C or less, or approximately 23°C or less than the second Tg of the polymer material 750. In further aspects, the first Tg of the intermediate layer 230 , 430 (e.g., first portion 431a or 431b ) , 630 (e.g., first intermediate layer 640 , second intermediate layer 650 , additional polymer layer 660 ) , or 1430 (e.g., first intermediate layer 1433 , additional polymer layer 1460 ) may be about 10°C to about 40 °C, about 15°C to about 30°C, about 18°C to about 25°C, about 20°C to about 23°C, or any range of sub-ranges therebetween, greater than the second Tg of the polymer material 750. It should be understood that a portion of the intermediate layer may include a first Tg greater than the second Tg of the polymer material. For example, the second portion 433 of the intermediate layer 430 (see Figures 4 to 5 ), the additional polymer layer 660 of the intermediate layer 630 (see Figure 6 ), and/or the additional polymer layer 1460 of the intermediate layer 1430 (see Figure 14 ) may include a first Tg that is greater than the second Tg of the polymer material 750 (see Figure 7 ) by one or more of the ranges discussed above in this paragraph, while the remainder of the intermediate layer 430 , 630 or 1430 does not necessarily have a Tg greater than the second Tg.

In an aspect, as shown in FIG7 , portion 770 of polymer material 750 may include a polymer thickness 776 that does not include any portion of polymer material 750 that is positioned in a pore of a porous inorganic layer(s) (e.g., second porous inorganic layer 250 ). Although portion 770 of polymer material is shown in FIG7 as being disposed on second porous inorganic layer 250 , it should be understood that portion 770 may additionally or alternatively be disposed on a major surface of a glass substrate (e.g., second major surface 204 of first glass substrate 200 , third major surface 222 of second glass substrate 220 ). In aspects, the polymer thickness 776 can be about 30 μm or less, about 20 μm or less, about 15 μm or less, about 10 μm or less, about 1 μm or more, about 3 μm or more, about 5 μm or more, about 8 μm or more, or about 10 μm or more. In aspects, the polymer thickness 776 can be in a range of about 1 μm to about 30 μm, about 3 μm to about 20 μm, about 5 μm to about 15 μm, about 8 μm to about 10 μm, or any range or sub-range therebetween. In aspects, as shown in FIG . 2 , FIG . 4-6, or FIG . 14 , at least a portion of the second portion 292 of the glass article 130 , 400 , 500 , 600 , or 1400 (e.g., surrounded on at least two sides by the first portion 294a or 294b ) can be free of the polymer material 750 . In an embodiment, although not shown, a portion of the polymer material may be present in at least a portion of the second portion 292 of the glass article that does not have the porous inorganic layer(s). Providing a polymer thickness 776 of about 30 μm or less can reduce the visibility of the polymer material in the portion of the glass article that does not have the porous inorganic layer(s), which can simplify manufacturing because slight misalignment or over-application of the precursor in the polymer material may not need to be removed (e.g., cleaned) from the glass substrate(s). Providing a polymer thickness of about 1 μm or more can provide sufficient polymer material so that the polymer material can also be positioned in a plurality of pores of the porous inorganic layer.

In an embodiment, the intermediate layer 230 , 430 (e.g., first portion 431a or 431b ) , 630 (e.g., first intermediate layer 640 , second intermediate layer 650 , additional polymer layer 660 ) , or 1430 (e.g., first intermediate layer 1433 , additional polymer layer 1460 ) comprises a thermoplastic polymer. In a further embodiment, the intermediate layer may comprise any of the polymers discussed above with respect to polymer material 750 . In an embodiment, the intermediate layer 230 , 430 (e.g., the first portion 431a or 431b ) , 630 (e.g., the first intermediate layer 640 , the second intermediate layer 650 , the additional polymer layer 660 ) , or 1430 (e.g., the first intermediate layer 1433 , the additional polymer layer 1460 ) may include a polymer such as polyvinyl butyral (PVB) (e.g., acoustic PVB (aPVB)), an ionomer, ethylene vinyl acetate (EVA) and at least one of thermoplastic polyurethane (TPU), polyester (PE), polyethylene terephthalate (PET), or the like. The thickness of the intermediate layer 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 the range of about 0.5 mm to about 2.5 mm, about 0.7 mm to about 1.5 mm. In further aspects, as shown in FIGS . 4 to 6 and 14 , the intermediate layer(s) 430 , 630 or 1430 can include multiple polymer layers or films that provide various functionalities. For example, as shown in FIGS. 5 to 6 and 14 , the wiring or electronic device 501 , 661 or 1401 can be positioned between the first glass substrate 200 and the second glass substrate 220 . In a further aspect, as shown in FIG . 6 , an additional polymer layer 660 may be positioned between the first intermediate layer 640 and the second intermediate layer 650 ; a wiring or electronic device 661 may be positioned between the first intermediate layer 640 and the second intermediate layer 650. For example, the wiring or electronic device 661 may be positioned within the additional polymer layer 660. In a further aspect, as shown in FIG . 14 , an electronic device 1401 may be disposed on and/or contact the second major surface 204 of the first glass substrate 200 , and/or the electronic device 1401 may contact the second major surface 404 and be surrounded on other sides by a third contact surface 1462 of the additional polymer layer 1460 . For example, the electronic device 1401 may be separated from the first intermediate layer 1433 by the additional polymer layer 1460. Providing at least a portion of the intermediate layer (e.g., the second portion 433 , the additional polymer layer 660 , the additional polymer layer 1460 ) without (or with a reduced amount relative to the polymer material 750 ) a plasticizer may reduce the incidence of damage (e.g., corrosion) to the wiring or electronic devices 501 , 661 , or 1401 that may be positioned therein. Additionally, providing at least that portion of the intermediate layer in the second portion 292 of the glass article without (or with a reduced amount of) plasticizer relative to the polymer material 750 can reduce optical distortion and/or haze that may interfere with the operation of an optical device (e.g., a camera) positioned within the intermediate layer (e.g., electronic device 501 , 661 , or 1401 ) or configured to view an object through the second portion 292 of the glass article (e.g., a camera positioned inside a vehicle configured to view the surrounding environment outside the vehicle).

Alternatively or additionally, the (one or more) intermediate layers 230 , 430 , 630 or 1430 may further incorporate at least one of solar insulation, acoustic damping, antenna, anti-glare treatment or anti-reflection treatment, etc. In an embodiment, the intermediate layer 230 , 430 (e.g., first portion 431a or 431b ) , 630 (e.g., first intermediate layer 640 , second intermediate layer 650 ) , or 1430 (e.g., first intermediate layer 1433 ) is modified to provide ultraviolet (UV) absorption, infrared (IR) absorption, IR reflection, acoustic control/damping, adhesion promotion and coloring. The intermediate layer 230 , 430 (e.g., the first portion 431a or 431b ) , 630 (e.g., the first intermediate layer 640 , the second intermediate layer 650 ) , or 1430 (e.g., the first intermediate layer 1433 ) may be modified with suitable additives such as dyes, pigments, dopants, etc. to impart predetermined properties. Additionally or alternatively, the intermediate layer 230 , 430 (e.g., the first portion 431a or 431b ) , 630 (e.g., the first intermediate layer 640 , the second intermediate layer 650 ) , or 1430 (e.g., the first intermediate layer 1433 ) may further include an adhesion promoter, a UV absorber, and/or an antioxidant. In a further aspect, the additive, adhesion promoter, UV absorber and/or antioxidant may have substantially no effect (e.g., about 1°C or less, 0°C) on the glass transition temperature of the intermediate layer 230 , 430 (e.g., first portion 431a or 431b ) , 630 (e.g., first intermediate layer 640 , second intermediate layer 650 ) , or 1430 (e.g., first intermediate layer 1433 ).

Although FIG . 2 , FIG . 4-6 , and FIG . 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 (one or more) 130 , 400 , 500 , 600 , or 1400 may include a curved shape. For example, the glass article 300 shown in FIG. 3 is curved. In an embodiment, the glass article 130 exhibits at least one curvature, and the at least one curvature includes a radius of curvature in the range of 300 mm to about 10 meters along at least a first axis. In an embodiment, the glass article 130 exhibits at least one curvature, the at least one curvature comprising a radius of curvature in a range of 300 mm to about 10 meters along a second axis transverse (e.g., perpendicular) to the first axis. As shown in FIG . 3 , the second major surface 204 of the first glass substrate 200 has a first depth of curvature 310 defined as a maximum depth from a plane (dashed line) of the second major surface 204. In an embodiment in which the second glass substrate 220 is curved, the fourth major surface 224 of the second glass substrate 220 has a second depth of curvature 320 defined as a maximum depth from a plane (dashed line) of the fourth major surface 224. In an embodiment, one or both of the first depth of curvature 310 or the second depth of curvature 320 is about 2 mm or greater. Depth of curvature can be defined as the maximum distance a surface is orthogonally separated from a plane defined by points on the perimeter of the surface. For example, one or both of the first depth of curvature 310 or the second depth of curvature 320 may be in the range of about 2 mm to about 30 mm. In an aspect, the first depth of curvature 310 and the second depth of curvature 320 may be substantially equal. In an aspect, the first depth of curvature 310 is within 10% or 5% of the second depth of curvature 320. For example, when the second depth of curvature 320 is about 15 mm, the first depth of curvature 310 may be in the range of about 13.5 mm to about 16.5 mm (to be within 10% of the second depth of curvature 320 ).

Aspects of methods of making glass articles according to aspects of the present disclosure will be discussed with reference to the flow chart in FIG . 9 and the example method steps illustrated in FIG . 10 to FIG . 13. Example aspects of making glass article 130 illustrated in FIG. 1 to FIG . 2 will now be discussed with reference to FIG. 10 to FIG . 13 and the flow chart in FIG . 9. It should be understood that glass article 300 can be curved as in FIG . 3 , and changes to the intermediate layer are contemplated to produce glass articles as shown in FIG . 4 to FIG . 6 .

In a first step 901 of the method of the present disclosure, the method may begin by providing a first glass substrate 200 and a second glass substrate 220. In an aspect, the first glass substrate 200 and/or the second glass substrate 220 may be provided by purchasing or otherwise obtaining the substrates or by forming the first glass substrate 200 and/or the second glass substrate 220. In a further aspect, the glass substrates may be provided by forming glass substrates using a variety of ribbon forming processes, such as slit drawing, down-drawing, fusion down-drawing, up-drawing, compression rolling, re-drawing, or float. In an aspect, the first glass substrate 200 and/or the second glass substrate 220 may be strengthened with one or more compressive stress regions, such as chemical strengthening and/or thermal strengthening, as discussed above. In an aspect, the first substrate thickness 206 and/or the second substrate thickness 226 may be within one or more of the ranges discussed above. In an aspect, one or more of the glass substrates may include borosilicate glass. In an aspect, the first glass substrate 200 and/or the second glass substrate 220 may be bent at the end of step 901 , but the bending may be performed in a subsequent step or may be omitted entirely. In an aspect, the first glass substrate 200 and/or the second glass substrate 220 may be chemically strengthened at the end of step 901 , but one or more of the chemically strengthened glass substrates may be performed in step 903 and/or one or more of the glass substrates may not be chemically strengthened. In embodiments, the first porous inorganic layer 240 may be disposed on one of the glass substrates (e.g., the second glass substrate 220 ), and/or the second porous inorganic layer 250 may be disposed on the other glass substrate (e.g., the first glass substrate 200 ), but one or two porous inorganic layers may be disposed in step 903. Although the second porous inorganic layer 250 on the first glass substrate 200 is shown in FIGS . 10-11 , it should be understood that the methods contemplate the second porous inorganic layer 250 disposed on the second glass substrate 220 .

In aspects, as discussed above with reference to FIG. 3 , the first depth of curvature 310 may be induced in the first glass substrate 200 by hot forming (e.g., the first glass substrate 200 may be bent due to gravity sag), and the second depth of curvature 320 may be induced in the second glass substrate 220 by cold forming. In aspects, the first depth of curvature 310 and the second depth of curvature 320 are induced by hot bending the first glass substrate 200 and the second glass substrate 220 (e.g., in a common bending process or in a process in which the glass substrates are bent independently of each other).

In an embodiment, the curvature (one or more) is 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 drooping process that uses gravity to shape the first glass substrate 200 or both the first glass substrate 200 and the second glass substrate 220 while being heated. In the drooping step, a glass substrate (e.g., the first glass substrate 200 ) is placed on a mold having an open interior, heated in a furnace (e.g., a box furnace or an annealing furnace), and gradually droops into the open interior of the mold under the influence of gravity. In a further embodiment, the thermal process may include a press 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 while being heated or while being heated.

In an aspect, two glass substrates (e.g., a first glass substrate 200 and a second glass substrate 220 ) are formed together in a "paired forming" process. In such a process, one glass substrate is placed on top of another glass substrate to form a stack (which may also include an intermediate release layer), which is placed on a mold. In a further aspect, to facilitate the paired forming process, the second glass substrate 220 , which in some aspects serves as an inner glass substrate and/or a thinner glass substrate, has a paired forming temperature greater than the first glass substrate 200 (e.g., at a viscosity of 10 ¹¹ poise). In an aspect, the mold used during paired sag may have an open interior for the sag process. Both the stack and the mold are placed in a furnace for heating, and the stack is gradually heated to the bending or sag temperature of the glass substrates. During this process, the glass substrates are formed together into a curved shape. Advantageously, the viscosity curve of at least some of the borosilicate glass compositions included herein can be similar to the viscosity curve of the glass used for the second glass substrate 220 at a viscosity of 10 ¹¹ poise, thereby allowing the use of existing equipment and technology. According to exemplary aspects, the heating time and temperature are selected to obtain the desired curvature and final shape. Subsequently, the glass substrate(s) are removed from the furnace and cooled. For paired formed glass substrates, the two glass substrates are separated and then reassembled at step 909 (discussed below), with an intermediate layer (e.g., intermediate layer 230) reassembled between the glass substrates and heated (e.g., the glass substrates and the intermediate layer are sealed together into a laminate under vacuum), as discussed below with reference to step 911 .

In an embodiment, only one glass substrate (e.g., the first glass substrate 200 ) is bent using heat (e.g., by a sagging process or a pressing process), and the other glass substrate (e.g., the second glass substrate 220 ) is bent using a cold forming process by pressing the glass substrate to be bent to conform to the already bent glass substrate at a temperature less than the softening temperature of the glass composition (particularly at a temperature of 200°C or less, 100°C or less, 50°C or less, or at room temperature). The pressure to cold-form one glass substrate onto 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 in conformity with the bent glass substrate via an intermediate layer and/or mechanically clamped to the bent glass substrate or otherwise coupled.

After step 901 , as shown in FIG. 10 , the method may proceed to step 903 , which includes disposing a porous inorganic layer (e.g., second porous inorganic layer 250 ) on one of the glass substrates (e.g., first glass substrate 200 ). In one embodiment, the second porous inorganic layer 250 may be disposed by applying a precursor (e.g., modified glaze) including a glass frit (e.g., glaze) mixed with particles of a pigment (e.g., ink, colorant, dye) and/or a low CTE additive to the second major surface 204 of the first glass substrate 200 . The precursor may be deposited using any suitable technique (e.g., screen printing, spraying, brushing, tape), but it is understood that viscosity adjustment (e.g., via the addition of water or an additional medium) may be required depending on the deposition technique selected. As discussed above, the precursor may be cured by heating at a suitable firing temperature, which may be at least the softening temperature associated with the glaze. Curing the precursor to form the porous inorganic layer may solidify the glass frit into a fused matrix surrounding the low CTE additive component and forming a plurality of pores. In an embodiment, the glass substrate (e.g., the first glass substrate 200 ) may be formed as part of step 903 after the porous inorganic layer is disposed thereon. Alternatively, in an embodiment, the glass substrate (e.g., the first glass substrate 200 ) may be shaped and the precursor may be cured to form the porous inorganic layer may be performed simultaneously in step 903. Alternatively, the porous inorganic layer may be disposed on the bent first glass substrate. Similarly, although not shown, the porous inorganic layer may be disposed on the third major surface of the second glass substrate. In addition, the second glass substrate may be shaped while or after the precursor is cured to form the porous inorganic layer. In addition, one or both of the glass substrates may be chemically strengthened after the deposition of the porous inorganic layer(s) in step 903 , and the chemical strengthening may also be after the shaping of the glass substrate(s). At the end of step 903 , as shown in FIG. 10 , the second porous inorganic layer 250 includes the inorganic thickness 746 discussed above. In an embodiment, the porosity of the second porous inorganic layer 250 can be within one or more of the corresponding ranges discussed above. In an embodiment, at the end of step 903 , as shown in FIG. 10 , the second porous inorganic layer 250 is adhered to the first glass substrate 200 , for example, wherein the first surface 732 of the second porous inorganic layer 250 contacts the second major surface 204 of the first glass substrate 200 .

After step 901 or step 903 , as shown in FIG. 10 , the method can proceed to step 905 , which includes filling the plurality of pores of the second porous inorganic layer 250 with a polymer solution or polymer emulsion 1003. As shown in the figure, the polymer solution or polymer emulsion 1003 can be disposed on the second surface 734 of the second porous inorganic layer 250 by brushing with a brush 1001 , but a roller or spraying can also be used. In an embodiment, the polymer solution or polymer emulsion 1003 can flow into the plurality of pores of the second porous inorganic layer 250 . For example, the polymer solution or polymer 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, e.g., in a range of about 10 mPa-s to about 8,000 mPa-s, about 30 mPa-s to about 2,000 mPa-s, about 50 mPa-s to about 1,000 mPa-s, about 80 mPa-s to about 500 mPa-s, about 100 mPa-s to about 200 mPa·s, or any range or sub-range therebetween. Providing a viscosity within one of the ranges mentioned in the previous sentence may enable the polymer solution to flow into the plurality of pores of the second porous inorganic layer 250. Similarly, providing a viscosity within one of the ranges mentioned above in this paragraph may enable the polymer emulsion to form a continuous film on the second porous inorganic layer 250 , which continuous film may be positioned in the plurality of pores, for example, after a lamination process (e.g., step 911 discussed below).

As used herein, "solution" means a substantially homogeneous mixture of a polymer and a solvent, wherein the polymer has a non-zero solubility in the solvent. As used herein, an "emulsion" is a heterogeneous mixture having at least two distinct phases, for example, having a droplet phase dispersed in a second matrix phase. In an aspect, the emulsion may include a solvent in a matrix phase that is immiscible with the polymer in the droplet phase. In an aspect, the solvent in the polymer solution or polymer emulsion may include water, an alcohol (e.g., ethanol, methanol, butanol, isopropanol), toluene, an ether (e.g., dipropylene glycol butyl ether), an acetate (e.g., ethyl acetate), a ketone (e.g., methyl ethyl ketone, acetone, butanone), or a combination thereof. An exemplary aspect of the solvent for the polymer emulsion is water. Exemplary aspects of the solvent for the polymer 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).

The polymer solution or polymer emulsion 1003 includes a polymer in one or more of the materials discussed above for the polymer material 750. The polymer in the polymer emulsion may be a substantially linear polymer. The polymer solution or polymer emulsion 1003 may further include a plasticizer in one or more of the materials discussed above for the plasticizer in the polymer material 750. In an embodiment, as shown in FIG . 10 , the polymer solution of the polymer emulsion 1003 may be disposed on the outer periphery of the second porous inorganic layer 250 and/or cover the outer periphery of the second porous inorganic layer. In an embodiment, as shown in the figure , the thickness 1006 of the polymer solution of the polymer emulsion 1003 may be about 30 μm or less, for example, within one or more of the ranges discussed above for the polymer thickness 776 .

After step 905 , as shown in FIG. 11 , the method may proceed to step 907 , which includes drying the polymer solution of polymer emulsion 1003 (see FIG. 10 ) to form polymer material 750 , including polymer material 750 positioned in a plurality of pores 760 (see FIG . 7 ). In an embodiment, as shown in the figure, drying the polymer solution of polymer emulsion 1003 may include placing the second porous inorganic layer 250 and the polymer solution of polymer emulsion 1003 in an oven 1101 maintained at a predetermined temperature for a predetermined time period. In an aspect, the polymer solution of polymer emulsion 1003 can be dried at a temperature of about 20°C or greater, about 30°C, about 40°C or greater, about 50°C or greater, about 80°C, about 70°C or less, about 65°C or less, or about 60°C or less. In an aspect, the polymer solution of polymer emulsion 1003 can be dried at a temperature of about 20°C to about 80°C, about 30°C to about 70°C, about 40°C to about 65°C, about 50°C to about 60°C, or any range or sub-range therebetween. Providing a temperature of about 80°C or less can reduce the incidence of bubbles in the resulting polymer material 750 . In an embodiment, the polymer solution of polymer emulsion 1003 can be dried for a time period 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. In an embodiment, no reaction can be performed in step 905 so that polymer material 750 is substantially free of cross-linking points and/or branching points, and the polymer in polymer material 750 can be substantially the same as the polymer in the polymer solution of polymer emulsion 1003 . In an embodiment, the polymer material 750 may include one or more of the plasticizers discussed above, and the (one or more) plasticizers may be present in an amount within one or more of the corresponding ranges discussed above. In an embodiment, the second glass transition temperature of the polymer material 750 may be within one or more of the corresponding ranges discussed above.

In aspects, as shown in FIG. 11 , the polymer material 750 (including the portion 770 ) may be present in the first portion 782 (e.g., present in the plurality of holes) but not in the second portion 784 (e.g., not present in the plurality of holes). As discussed above, in aspects, the absolute value of the difference between the refractive index of the polymer material 750 and the refractive index of the first glass substrate 200 or the second glass substrate 220 may 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.

After step 907 , as shown in FIG. 12 , the method may proceed to step 909 , which includes disposing an intermediate layer 230 or 430 on a porous inorganic layer (e.g., a first porous inorganic layer 240 , a second porous inorganic layer 250 ). In an embodiment, as shown in the figure, a gap 1202 or 1204 may be formed between the intermediate layer 230 or 430 and the first glass substrate 200 or the second glass substrate 220 , respectively, for example, due to the thickness of the (one or more) porous inorganic layers. In an embodiment, as indicated by reference numerals 448a and 448b , the intermediate layer 430 can be non-uniform, wherein the dashed lines marked with reference numerals 448a and 448b indicate the division between different portions of the intermediate layer 430 having different compositions (e.g., first portion 431a and / or 431b , second portion 433 —see FIG. 4 ) . In a further embodiment, the concentration of the plasticizer can be different between these portions (e.g., wherein the concentration of the plasticizer in the second portion 433 is greater than the concentration of the plasticizer in the first portion 431a and / or 431b ). In further aspects, the polymer in the first portion may be different from the polymer in the second portion (e.g., the second portion 433 may include or consist of PVB, while the first portion 431a and / or 431b may include PET or another suitable material with a relatively high Tg). Alternatively, in further aspects, the interlayer may include a first interlayer, a second interlayer, and an additional polymer layer positioned therebetween (see FIG. 6 ) . In further aspects, wiring or electronic devices may be positioned between the first glass substrate 200 and the second glass substrate 220 (e.g., within the interlayer or the additional polymer layer, if present) (see FIGS . 5-6 ) . In aspects, the first glass transition temperature of the interlayer may be less than the second glass transition temperature of the polymer material 750 (see FIG . 7 ) by an amount within one or more of the corresponding ranges discussed above. In a further aspect, the concentration of the plasticizer in the polymer material can be greater than the concentration of the plasticizer in the intermediate layer. In a further aspect, the polymer in the intermediate layer can be the same as or different from the polymer in the polymer material.

After step 909 , as shown in FIG. 13 , the method may proceed to step 911 , which includes laminating the first glass substrate 200 onto the second glass substrate 220 , such that the porous inorganic layer (e.g., the first porous inorganic layer 240 , the second porous inorganic layer 250 ) and (one or more) intermediate layers 230 or 430 are positioned between the first glass substrate and the second glass substrate.

In an embodiment, as shown in FIG. 13 , a first surface region 1319 of a first release pad 1317 may be disposed on and/or contact the first major surface 202 of a first glass substrate 200. In a further embodiment, a third surface 1315 of a first support member 1311 may be disposed on and/or contact the first release pad 1317. In an embodiment, as shown in the figure, a first surface region 1329 of a second release pad 1327 may be disposed on and/or contact the fourth major surface 224 of a second glass substrate 220 . In a further embodiment, the third surface 1323 of the second support 1321 can be disposed on and/or in contact with the second release pad 1327. In an embodiment, as shown in the figure, the method can include placing the assembly in a vacuum container 1303 (e.g., an OBSJ/ABSJ vacuum bag available from Simtech). In an embodiment, the first support 1311 and/or the second support 1321 can include an elastic modulus of approximately 3 GPa or greater, and/or can include a glass-based material and/or a ceramic-based material. Providing one or more release pads can reduce (e.g., prevent) adhesion of the glass article to undesirable materials during the method, and can reduce damage to the laminate during processing. Providing one or more supports can reduce deformation (e.g., warping) of the substrate and/or film during processing. Providing a vacuum container can protect the glass article from contamination during processing.

In an embodiment, step 911 can further include heating the film and/or reducing the pressure of the chamber 1301 in which the assembly is positioned (e.g., relative to 101.325 kPa). Providing a reduced pressure can remove dissolved gases and/or gases between components of the assembly. In an embodiment, step 911 includes (e.g., in addition to the embodiments discussed previously) heating the assembly to a temperature greater than the glass transition temperature (and/or melting temperature, if semi-crystalline) of the intermediate layer 230 , which can be performed in the chamber 1301 at a high pressure (e.g., relative to 101.325 kPa).

After step 911 , the method may proceed to step 913 , which includes assembling the glass article 130 , 300 , 400 , 500 , 600 , or 1400. It should be understood that the article may be incorporated into any of the articles or applications discussed above. For example, the glass article may be attached to a car by attaching the glass article to the periphery of an opening in the car using an adhesive.

After step 911 or step 913 , the method of making a glass article of the present disclosure according to the flowchart in FIG . 9 may be completed at step 915. In an embodiment, when illuminated with a D65 illuminant, the glass article may include a maximum ΔE, an absolute value of the difference in L * values , an absolute value of the difference in a * values, and/or an absolute value of the difference in b* values between a first portion 782 in which a polymer material 750 ( see FIG. 7 ) is positioned in a plurality of pores of the first porous inorganic layer 240 and a second portion 784 in which a plurality of pores are not filled with the polymer material 750, which values may be within one or more of the corresponding ranges discussed above. In an aspect, the integrated visible light transmittance of the first portion 294a or 294b of the glass article including the porous inorganic layer(s) may be within one or more of the corresponding ranges discussed above. In an aspect, the method for making a glass article according to an aspect of the present disclosure may proceed sequentially along steps 901 , 903 , 905 , 907 , 909 , 911 , and 913 of the flowchart in FIG . 9 , as discussed above. In an aspect, for example, if the porous inorganic layer has been attached to the glass substrate at the end of step 901 , the process may proceed from step 901 to step 905 along arrow 902 . In an aspect , for example, if the method is complete at the end of step 911 , then the method can follow arrow 904 from step 911 to step 915. Any of the above options can be combined to produce a coated article according to an aspect of the present disclosure.

Various aspects will be further illustrated by the following examples. Example AC and Comparative Examples AA-BB include a borosilicate glass substrate having a CTE of 32×10 ⁻⁷ K ⁻¹ and a thickness of 3.8 mm (i.e., a composition of 83.60 mol % SiO ₂ , about 1.20 mol % Al ₂ O ₃ , about 11.60 mol % B ₂ O ₃ , about 3.00 mol % Na ₂ O, and about 0.70 mol % K ₂ O). A porous inorganic layer having a thickness of about 20 μm and a porosity of about 30% is formed on the second major surface of the borosilicate glass substrate by heating a precursor glass frit at about 600° C. for about 8 minutes. The porous inorganic layer has a dark gray appearance.

For Examples A-D, a polymer solution was formed by dissolving 14 wt% plasticized PVB (RF41 available from Saflex) in ethanol. For Example A, a 100 μm thick poly(ethylene terephthalate) (PET) sheet was dipped into the PET polymer solution and then applied to the porous inorganic layer. For Example B, the polymer solution was brushed onto the porous inorganic layer and then a 100 μm thick PET sheet was applied thereon.

Comparative Example AA included placing a 100 μm thick PET sheet on a porous inorganic layer without polymer. Comparative Example BB included placing an already formed plasticized PVB film (RF41 available from Saflex) on the porous inorganic layer and then pressing the 100 μm PET sheet into the plasticized PVB film.

The appearance of Examples A-B and Comparative Examples AA-BB was evaluated the day after application. Comparative Example A had a light gray appearance. Comparative Example B had a gray appearance that was lighter than the underlying porous inorganic layer but darker than Comparative Example A. Examples A and B appeared dark gray or black except for a lighter edge around the outside of the PET sheet. It is believed that applying a polymer solution covering the edge can remove this lighter edge.

For Example C, the polymer solution was brushed onto a larger area of the porous inorganic layer, and a 100 μm thick PET sheet was applied to a first portion of the porous inorganic layer, leaving the second portion coated with the polymer solution without PET. A 0.76 mm thick plasticized PVB sheet (RF41 available from Saflex) was placed on the porous inorganic layer, and a second glass substrate comprising an aluminosilicate glass composition and 0.7 mm thickness was applied thereto. The assembly layers were pressed together in an autoclave to produce a glass article. The autoclave treatment involved heating the assembly at 110° C. for 45 minutes under vacuum, followed by heating at 140° C. and applying a pressure of 1.3 MPa (gauge pressure). Comparative Example BB was prepared identically to Example C, except that no polymer solution was used.

The color of the glass article (portion 1) in which PET appears almost indistinguishable from the portion of the glass article (portion 2) including a polymer material formed from a polymer solution but without PET. Table 1 presents the CIE color space coordinates of these portions of Example C. As shown in the figure, 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). Therefore, ΔE (e.g., maximum ΔE) is about 0.37, which is less than about 2.0, less than about 1.0, and less than about 0.5. This low ΔE value is consistent with these parts of Example C, which look almost indistinguishable. In contrast, Comparative Example BB appears light gray (similar to Comparative Example A). Table 1: CIE color space coordinates of Example C part L* a* b* 1 10.82 -0.91 -1.22 2 10.50 -0.76 -1.34

The above observations can be combined to provide a glass article comprising a porous inorganic layer, wherein a polymer material is positioned in a plurality of pores of the porous inorganic layer. Providing a polymer material having a low glass transition temperature (e.g., about 85° C. or less) may allow the polymer material to be easily positioned (e.g., filled) in the plurality of pores of the (one or more) porous inorganic layer. Providing a polymer material having a glass transition temperature of about 40° C. or greater may reduce changes in the properties of the polymer material within a temperature range typically encountered during use of the glass article. Providing a polymer material thickness of about 30 μm or less outside of the plurality of pores may reduce the visibility of the polymer material in portions of the glass article that do not have the (one or more) porous inorganic layer, which may simplify manufacturing because slight misalignment or over-application of precursors in the polymer material may not require removal (e.g., cleaning) from the (one or more) glass substrates. Providing a polymer thickness of about 1 μm or more outside of the plurality of pores can provide the polymer material sufficient to allow the polymer material to be positioned also in the plurality of pores of the porous inorganic layer. Positioning the polymer material in the plurality of pores can provide a substantially uniform appearance having a predetermined color. In addition, the glass article can exhibit a low maximum ΔE value between portions of the glass article having the porous inorganic layer with the polymer material in the plurality of pores and portions of the glass article without the polymer material, which can provide a substantially uniform color associated with the porous inorganic layer that is visually imperceptible to an observer.

When incorporated into a laminate, the (one or more) porous inorganic layer(s) can be used as a decorative layer having a predetermined color appearance. It has been found that porosity can prevent the (one or more) porous inorganic layer(s) from reducing the mechanical strength of the (one or more) glass substrate(s). Without wishing to be bound by theory, it is believed that the porosity reduces the size of the continuous contact area between the glass substrate and the decorative glaze, which reduces the CTE-induced stress accumulation caused during the manufacture of the decorative glass article, thereby reducing or preventing defect formation and propagation. When incorporated into a laminate, the porosity can also help the porous inorganic layer have a predetermined color appearance. For example, an intermediate layer is used to attach a glass substrate having a porous inorganic layer to another glass substrate. As discussed below, the polymer material may fill the plurality of pores of the porous inorganic layer, which may darken the appearance of the portion of the glass article that includes the porous inorganic layer.

Providing the inner surface of the porous inorganic layer(s) of the glass article can be used to protect the layer from mechanical degradation and/or oxidation. In addition, the placement of the porous inorganic layer(s) can also help to hide 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. In addition, when the first glass substrate and the second glass substrate are constructed of glasses with different compositions and/or thicknesses, multiple bands of the porous inorganic layer(s) can provide a predetermined aesthetic appearance. In an embodiment, the porous inorganic layer(s) will have the dual function of providing an attractive appearance and serving as a shield to block visible light and ultraviolet (UV) light. In addition, the glass article may include additional functionality, such as including an infrared reflective coating and/or an anti-reflective coating.

As described herein, constructing the porous inorganic layer(s) to have a CTE approximately equal to the CTE of the first glass substrate can prevent crack formation in the porous inorganic layer during manufacture of the glass article, and also prevent bonding of the porous inorganic layer from reducing the mechanical strength of the first glass substrate and/or the glass article. The first glass substrate can include a borosilicate glass composition, which can be particularly beneficial as the exterior of automotive glazing because borosilicate glass can have greater thermal shock resistance and is more resistant to crack formation due to impact events from road debris (e.g., rocks or the like) than sodium calcium silicate glass currently used as the exterior glass substrate in automotive glazing. Such glasses have been found to exhibit favorable annular cracking behavior, thereby preventing defects from propagating radially from the impact point. Such fusion-formed glasses also exhibit superior chemical durability, scratch resistance, mechanical strength, and optical performance (e.g., from the perspective of optical transmittance and optical distortion) compared to other borosilicate glasses.

Providing a polymeric material separate from the interlayer may result in the interlayer (or a portion thereof) having a different composition and/or properties. For example, the concentration of plasticizer in the polymeric material may be greater than the concentration in the interlayer (or a portion thereof), and/or the polymeric material may have a lower glass transition temperature than the interlayer (or a portion thereof), even when the polymer in the polymeric material is the same as the polymer in the interlayer. Providing at least a portion of the interlayer without (or with a reduced amount relative to the polymeric material) plasticizer may reduce the incidence of damage (e.g., corrosion) to any wiring or electronic devices that may be positioned therein. Additionally, providing at least a portion of the interlayer without (or with a reduced amount relative to the polymeric material) plasticizer can reduce optical distortion and/or haze, which may interfere with the operation of an optical device (e.g., a camera) positioned within the interlayer or configured to view an object through a second portion of the glass article (e.g., a camera positioned within a vehicle configured to view the surrounding environment outside the vehicle).

In addition, the polymer material can be provided by drying a polymer solution or polymer emulsion. Providing a polymer solution or polymer emulsion with a low viscosity (e.g., about 8,000 mPa-s or less) may allow the polymer solution or polymer emulsion 1003 to flow into a plurality of pores of the porous inorganic layer. The polymer material can be formed by drying the polymer solution or polymer emulsion without any reaction (e.g., crosslinking or polymerization). Therefore, the polymer in the polymer solution or polymer emulsion can be substantially the same as the polymer in the polymer material. The limited processing involved in providing the polymer material can simplify processing and/or reduce costs.

Directional terminology used herein—eg, up, down, right, left, front, back, top, bottom—refers only to the drawings as drawn, and is not intended to imply an absolute orientation.

It should be understood that various disclosed aspects may involve features, components or steps described in conjunction with the aspect. It should also be understood that features, components or steps, although described with respect to one aspect, may be interchanged or combined with alternative aspects in various combinations or arrangements not illustrated.

It should also be understood that, as used herein, unless expressly indicated to the contrary, the terms "the," "a," or "an" mean "at least one" and should not be limited to "only one." For example, reference to a "component" includes aspects of having two or more such components unless the context clearly indicates otherwise. Likewise, "plurality" is intended to mean "more than one."

As used herein, the term "about" means that the amount, size, formula, parameter and other quantities and characteristics are not and need not be exact, but may be approximate and/or larger or smaller as needed, reflecting tolerances, conversion factors, rounding, measurement errors and the like, and other factors known to those skilled in the art. Ranges may be expressed herein as from "about" a particular value and/or to "about" another particular value. When such a range is expressed, aspects include from a particular value and/or to another particular value. Similarly, when a value is expressed as an approximation by using the aforementioned word "about", it should be understood that the particular value forms another aspect. Regardless of whether the numerical value or endpoint of the range in this specification states "about", the numerical value or endpoint of the range is intended to include two aspects: an aspect modified by "about" and an aspect not modified by "about". It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint and independently of the other endpoint.

As used herein, the terms "substantially," "substantially," and variations thereof are intended to indicate that the feature being described is equal to or approximately equal to a value or description. For example, a "substantially planar" surface is intended to mean a planar or approximately planar surface. Additionally, as defined above, "substantially similar" is intended to mean that two values are equal or approximately equal. In aspects, "substantially similar" can mean values that are within about 10% of each other, e.g., within about 5% of each other, or within about 2% of each other.

Unless expressly stated otherwise, it is not intended that any method described herein be construed as requiring that its steps be performed in a specific order. Therefore, in the event that a method claim does not actually state the order in which its steps are to be followed or that the steps are not otherwise specifically stated in the claims or specification to be limited to a specific order, no specific order is intended to be inferred.

Although the transition phrase "comprising" may be used to disclose various features, elements, or steps of a particular aspect, it should be understood that alternative aspects, including those that may be described using the transition phrase "consisting of" or "consisting essentially of," are implied. Thus, for example, an implied alternative aspect of a device comprising A+B+C includes an aspect in which the device consists of A+B+C and an aspect in which the device consists essentially of A+B+C. As used herein, unless otherwise indicated, the terms "comprising" and "including" and variations thereof should be interpreted as synonymous and open ended.

The above-described aspects and features of those aspects are exemplary and may be provided alone or in any combination with any one or more features of the other aspects provided herein without departing from the scope of the present disclosure.

Those skilled in the art will appreciate that various modifications and variations can be made to the disclosure without departing from the spirit and scope of the disclosure. Therefore, the disclosure is intended to cover modifications and variations of the aspects provided herein as long as they are within the scope of the appended claims and their equivalents.

2-2: Line 100: Carrier 110: Body 120: Opening 130: Glass product 7: View/Enlarged view 200: First glass substrate 202: First main surface 204: Second main surface 206: First substrate thickness 220: Second glass substrate 222: Third main surface 224: Fourth main surface 226: Second substrate thickness 230: Intermediate layer 232: First contact surface 234: Second contact surface 236: Intermediate layer thickness/first intermediate layer thickness 240: First porous inorganic layer/porous inorganic layer 250: Second porous inorganic layer/porous inorganic layer 292: Second portion of second porous inorganic layer 294a: first portion of second porous inorganic layer 294b: another first portion of second porous inorganic layer 300: glass product 310: first curvature depth 320: second curvature depth 430: intermediate layer 431a: first portion 431b: first portion 432: first contact surface 433: second portion 434: second contact surface 448a: reference number/dash line 448b: reference number/dash line 500: glass product 501: wiring or electronic device/electronic device 600: glass product 636: intermediate layer thickness 640: first intermediate layer 641a: first portion 641b: first portion 642: first contact surface 643: second part 644: second contact surface 646: first intermediate layer thickness/intermediate layer thickness 648a: reference number/boundary 648b: reference number/boundary 650: second intermediate layer 651a: first part 651b: first part 652: third contact surface 653: second part 654: second part/fourth contact surface 656: second intermediate layer thickness/intermediate layer thickness 658a: reference number/boundary 658b: reference number/boundary 660: additional polymer layer 661: wiring or electronic device/electronic device 662: fifth contact surface 664: sixth contact surface 732: first surface 734: second surface 746: inorganic thickness 760: hole 762: hole 770: part 776: polymer thickness 782: first part 784: second part 810: edge 820: glass article 830: first glass substrate 840: porous inorganic layer 892: second part 894: first part 901,902,903,904,905,907,909,911,913,915: step 1001: brush 1003: polymer solution or polymer emulsion/polymer emulsion 1006: thickness 1101: oven 1202,1204: gap 1301: chamber 1303: vacuum container 1311: first support 1315: third surface 1317: first release pad 1319: first surface area 1321: second support 1323: third surface 1327: second release pad 1329: first surface area 1400: glass article 1401: electronic device/wiring or electronic device 1430: intermediate layer 1432: first contact surface 1433: first intermediate layer 1434: second contact surface 1460: additional polymer layer 1462: third contact surface 1464: fourth contact surface 1470: another part/additional part

The above and other features and advantages of the present disclosure will be better understood when the following detailed description is read with reference to the accompanying drawings, in which:

FIG. 1 is a diagram of a carrier including a glass product (e.g., automotive window glass) according to an aspect of the present disclosure, wherein a cross-sectional view taken along line 2-2 may be presented as shown in FIGS . 2 to 6 ;

FIG. 2 depicts a cross-sectional view of a glass article (e.g., automotive window glass) having a single intermediate layer according to an aspect of the present disclosure, taken along line 2-2 of FIG . 1 , wherein view 7 may be presented as shown in FIG. 7 ;

FIG . 3 depicts a cross-sectional view of a glass product (e.g., automotive window glass) according to an aspect of the present disclosure taken along line 2-2 of FIG. 1 , showing a curved automotive window glass;

FIG . 4 depicts a cross-sectional view of a glass product (e.g., automotive window glass) having a non-uniform intermediate layer according to an aspect of the present disclosure, taken along line 2-2 of FIG . 1 ;

FIG. 5 depicts a cross-sectional view of a glass article (e.g., automotive window glass) having an electronic device in a non-uniform intermediate layer according to an aspect of the present disclosure, taken along line 2-2 of FIG . 1 ;

FIG . 6 depicts a cross-sectional view of a glass product (e.g., automotive window glass) having multiple layers and electronic devices between glass substrates according to an aspect of the present disclosure, taken along line 2-2 of FIG . 1 ;

FIG . 7 depicts an enlarged view of FIG . 2 , showing the porous inorganic layer and the polymer material;

FIG. 8 depicts a glass article having a design corresponding to a porous inorganic layer suitable for an automobile windshield;

FIG. 9 is a flow chart illustrating an example method of manufacturing a glass product according to an aspect of the present disclosure;

FIG. 10 schematically illustrates a step in a method of making a glass article according to the flow chart of FIG . 9 , the step comprising filling a plurality of pores of a porous inorganic layer;

FIG. 11 schematically illustrates a step in a method of making a glass article according to the flow chart of FIG . 9 , the step comprising drying the material in the pores to form a polymer material;

FIG. 12 schematically illustrates a step in a method of making a glass product according to the flow chart of FIG . 9 , the step comprising placing an intermediate layer between two glass substrates;

FIG . 13 schematically illustrates a step in a method of making a glass product according to the flow chart of FIG . 9 , the step comprising laminating a first glass substrate to a second glass substrate such that an intermediate layer and a porous inorganic layer are positioned between the first glass substrate and the second glass substrate; and

FIG. 14 depicts a cross-sectional view of a glass article (e.g., automotive glazing) having an electronic device between glass substrates according to an aspect of the present disclosure, taken along line 2-2 of FIG . 1 , wherein the porous inorganic layer occupies the covering area of the electronic device.

Throughout the disclosure, drawings are used to emphasize certain aspects. Therefore, unless otherwise explicitly indicated, the relative sizes of different regions, parts, and substrates shown in the drawings should not be assumed to be proportional to their actual relative sizes.

Domestic storage information (please note in the order of storage institution, date, and number) None Foreign storage information (please note in the order of storage country, institution, date, and number) None

7: View/Enlarged view

130: Glass products

200: First glass substrate

202: first main surface

204: Second main surface

206: Thickness of the first substrate

220: Second glass substrate

222: Third main surface

224: Fourth main surface

226: Second substrate thickness

230: Middle layer

232: First contact surface

234: Second contact surface

236: Middle layer thickness/first middle layer thickness

240: First porous inorganic layer/porous inorganic layer

250: Second porous inorganic layer/porous inorganic layer

292: The second part of the second porous inorganic layer

294a: The first part of the second porous inorganic layer

294b: Another first part of the second porous inorganic layer

Claims (30)

A glass product, comprising: a first glass substrate, the first glass substrate comprising a first substrate thickness defined between a first major surface and a second major surface opposite to the first major surface; a second glass substrate, the second glass substrate comprising a second substrate thickness defined between a third major surface and a fourth major surface opposite to the third major surface; an intermediate layer, the intermediate layer positioned between the second major surface and the third major surface; a porous inorganic layer, the porous inorganic layer comprising a plurality of pores and adhered to the second major surface or the third major surface; and a polymer material, the polymer material positioned in the plurality of pores, wherein a first glass transition temperature of the intermediate layer is approximately 10°C or greater than a second glass transition temperature of the polymer material. The glass article of claim 1, wherein the first glass transition temperature of the intermediate layer is about 15°C to about 30°C greater than the second glass transition temperature of the polymer material. A glass article as described in claim 1, wherein when illuminated from the first major surface with a D65 illuminant, a maximum ΔE value between a first portion of the glass article in which the polymer material is positioned within the plurality of pores of the porous inorganic layer and a second portion of the glass article in which the porous inorganic layer is not filled with the polymer material and includes the porous inorganic layer is approximately 2.0 or less. A glass product, comprising: a first glass substrate, the first glass substrate comprising a first substrate thickness defined between a first major surface and a second major surface opposite to the first major surface; a second glass substrate, the second glass substrate comprising a second substrate thickness defined between a third major surface and a fourth major surface opposite to the third major surface; an intermediate layer, the intermediate layer positioned between the second major surface and the third major surface; a porous inorganic layer, the porous inorganic layer comprising a plurality of pores and adhered to the second major surface or the third major surface; and a polymer material, the polymer material being positioned in the plurality of pores, wherein the polymer material is different in composition from the intermediate layer, wherein when illuminated from the first major surface with a D65 illuminant, a maximum ΔE value between a first portion of the glass article in which the polymer 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 in which the porous inorganic layer is not filled with the polymer material is about 2.0 or less. The glass article of claim 4, wherein the maximum ΔE value is about 0.1 to about 1.0. The glass article of any one of claims 3-4, 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. The glass article as described in claim 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. The glass article of any one of claims 3-4, 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. The glass article of any one of claims 3-4, 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. A glass article as described in any of claims 3-4, wherein a polymer in the polymer material is the same as a polymer in the intermediate layer. A glass article as described in any of claims 3-4, wherein a polymer in the polymer material is different from a polymer in the intermediate layer. A glass article as described in claim 11, wherein the polymer material is semi-crystalline and has a melting temperature of about 100°C or less. A glass article as described in any one of claims 1-2 or 4-5, wherein the intermediate layer comprises poly(vinyl butyral). The glass article as described in any one of claims 1-2 or 4-5, wherein an absolute value of a difference between a refractive index of the polymer material and a refractive index of the first glass substrate or the second glass substrate is about 0.05 or less. The glass article as described in any one of claims 1-2 or 4-5, wherein a portion of the glass article including the porous inorganic layer surrounds another portion of the glass article without the porous inorganic layer on at least two sides. The glass article as described in claim 15, wherein at least a portion of the other portion of the glass article does not contain the polymer material, and at least a portion of the portion of the glass article comprising the porous inorganic layer includes the polymer material. A glass article as described in claim 15, wherein the intermediate layer is non-uniform and at least a portion of the intermediate layer in the other portion of the glass article contains a concentration of the plasticizer that is higher than a concentration of the plasticizer in the portion of the glass article that includes the porous inorganic layer comprising the polymer material. A glass article as described in any of claims 1-2 or 4-5, wherein a concentration of a plasticizer in the polymer material is greater than a concentration of a plasticizer in the intermediate layer. A glass article as described in any of claims 1-2 or 4-5, wherein the polymer material comprises a plasticizer in an amount of about 25% to about 50% by weight of the polymer material. A glass article as described in any of claims 1-2 or 4-5, wherein the glass article exhibits an integrated visible light transmittance of about 2.0% or less for 400 nm to 700 nm light normally incident on the first major surface in a portion of the glass article containing the porous inorganic layer. A glass article as described in any of claims 1-2 or 4-5, wherein the polymer material comprises a substantially linear polymer. A glass article as described in any of claims 1-2 or 4-5, wherein a polymer thickness of the polymer material is about 30 microns or less. A glass article as described in any one of claims 1-2 or 4-5, wherein the polymer material is present at a periphery of the glass article, covering the porous inorganic layer. The glass article of any one of claims 1-2 or 4-5, wherein the porous inorganic layer comprises a porosity of about 10 volume % to about 60 volume %. The glass article of any one of claims 1-2 or 4-5, wherein the porous inorganic layer has a thickness of about 10 microns to about 30 microns. The glass article as described in any of claims 1-2 or 4-5 further comprises: a second polymer layer, the second polymer layer is adhered to the third major surface, wherein the porous inorganic layer is adhered to the second major surface, and the polymer material is positioned in the pores of the porous inorganic layer and in the pores of the second porous inorganic layer. The glass product as described in any one of claims 1-2 or 4-5 further comprises: a connection or an electronic component, wherein the connection or the electronic component is positioned between the first glass substrate and the second glass substrate. A glass product as described in any of claims 1-2 or 4-5, wherein the intermediate layer comprises a first part and a second part, wherein the first part comprises a composition different from that of the second part, wherein the first part of the intermediate layer is deposited in at least some of the pores of the porous inorganic layer, and wherein the polymer material is disposed in the pores of the porous inorganic layer and between the part and the porous inorganic layer. A method for forming a glass product comprises the following steps: Filling a plurality of pores of a porous inorganic layer with a polymer solution or a polymer emulsion, the porous inorganic layer being adhered to a first glass substrate; Drying the polymer solution or the polymer emulsion at a temperature of about 20°C to about 80°C for about 10 minutes or longer to form a polymer material positioned in the plurality of pores; Disposing an intermediate layer on the porous inorganic layer; and Pressing the first glass substrate against a second glass substrate so that the porous inorganic layer and the intermediate layer are positioned between the first glass substrate and the second glass substrate. The method of claim 29, wherein a viscosity of the polymer solution or the polymer emulsion is in a range of about 10 mPa-s to about 8,000 mPa-s.