Glass article and method of making same

Abstract

The glass article includes an interlayer disposed between the second major surface of the first glass substrate and the third major surface of the second glass substrate. The glass article includes a porous interlayer including a plurality of pores and adhered to the second major surface or the third major surface. A polymeric material is disposed in the plurality of pores. In aspects, the first glass transition temperature of the interlayer is about 10 DEG C or higher than the second glass transition temperature of the polymeric material. In aspects, the maximum [Delta] E value is about 2.0 or less. In one embodiment, a method includes filling a plurality of pores of a porous inorganic layer on a first glass substrate with a polymer solution or polymer emulsion, which is then dried to form a polymer material. An interlayer may be used to laminate the first glass substrate to a second glass substrate.

Description

[0001] Cross - reference to related applications

[0002] This application claims priority to U.S. Provisional Application Serial No. 63 / 427,167, filed on November 22, 2022, under 35 U.S.C.§119, the content of which is hereby incorporated herein by reference in its entirety. Technical field

[0003] The present disclosure generally relates to glass articles and methods of making the same, and more particularly to glass articles comprising a porous inorganic layer and methods of forming the same. Background art

[0004] Glaze layers are commonly used as decorative and coloring elements for automotive glass, such as windshields, skylights, and rear windows. As a decoration, the glaze typically takes the form of a dot gradient and a border along the outer periphery of the window glass. For example, the decorative layer can be used both to enhance the appearance and to protect the underlying adhesive from ultraviolet degradation.

[0005] Automotive glass is conventionally formed from heat - tempered soda - lime silica glass. Heat tempering induces surface compressive stress, which strengthens the glass to resist mechanical failure. However, the stresses and inherent risks of the road require conventional automotive glass to be relatively thick and heavy to achieve the desired level of durability. Since, from a durability perspective, such soda - lime silica glass tends to suffer from several drawbacks. Examples of such drawbacks of soda - limesilicates include poor chemical weathering properties, impact properties, and scratch properties.

[0006] Borosilicate glass is being considered for automotive window applications because borosilicate glass has several advantages over soda - lime silica glass, including improved chemical weathering properties, improved scratch resistance, improved impact properties, and a favorable low density. One complication associated with borosilicate glass is that the coefficient of thermal expansion (CTE) of such glass tends to be lower than that associated with soda - lime silica glass or aluminosilicate glass. Such a lower CTE associated with borosilicate glass may be incompatible with commercially available ceramic glazes. The CTE difference between borosilicate glass and commercially available glazes can reduce the mechanical properties of the windshield and prevent the windshield from having the desired appearance.

[0007] It is known that in automotive window applications, a polymer interlayer needs to be provided between glass substrates. The properties of the interlayer aimed at adhering components in automotive window applications may conflict with optical clarity or other properties for more complex automotive control systems.

[0008] Accordingly, there is a need for an improved glaze for use in combination with borosilicate glass or other suitable low CTE materials. Additionally, there is a need for glass articles that can provide both good adhesion and optical clarity. SUMMARY OF THE INVENTION

[0009] Disclosed herein are glass articles comprising a porous inorganic layer, wherein a polymeric material is disposed within pores of the porous inorganic layer. Providing a polymeric material having a low glass transition temperature (e.g., about 85 °C or lower) can enable the polymeric material to be readily disposed within (e.g., fill) the pores of the porous inorganic layer. Providing a polymeric material having a glass transition temperature of about 40 °C or higher can reduce property variations of the polymeric material within the temperature ranges typically encountered during use of the glass article. Providing a polymeric material having a thickness of about 30 μm or less outside of the pores can reduce the visibility of the polymeric material in portions of the glass article that do not have the porous inorganic layer, which can simplify manufacturing because slightly misaligned or overapplied polymeric material precursors may not need to be removed (e.g., cleaned) from the glass substrate. Providing a polymeric thickness of about 1 μm or greater outside of the pores can provide sufficient polymeric material such that the polymeric material can also be disposed within the pores of the porous inorganic layer. Disposing the polymeric material within the pores can provide a substantially uniform appearance having a predetermined color. Additionally, the glass article can exhibit a low maximum ΔE value between portions of the glass article having the polymeric material within the pores of the porous inorganic layer and portions of the glass article not having the polymeric material, thereby providing a substantially uniform color associated with the porous inorganic layer that may not be visually perceptible to an observer.

[0010] When incorporated into a laminate, the porous inorganic layer can act as a decorative layer having a predetermined color appearance. It has been found that the porosity prevents the porous inorganic layer from reducing the mechanical strength of the glass substrate. 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 CTE-induced stress buildup during the manufacture of the decorated glass article, thereby reducing or preventing the formation and propagation of defects. The porosity can also help the porous inorganic layer to have a predetermined color appearance when incorporated into a laminate. For example, a glass substrate having a porous inorganic layer is attached to another glass substrate using an interlayer. As discussed below, the polymeric material can fill the pores of the porous inorganic layer, which can darken the appearance of the portion of the glass article including the porous inorganic layer.

[0011] Providing a porous inorganic layer on the inner surface of a glass article can be used to protect these layers from mechanical degradation and / or oxidation. Additionally, the placement of the porous inorganic layer can also help to hide any additional components (e.g., conductive elements associated with a defogging system) embedded between a first glass substrate 200 and a second glass substrate 220. Further, when the first glass substrate and the second glass substrate are made of glasses having different compositions and / or thicknesses, multiple bands of the porous inorganic layer can provide a predetermined aesthetic appearance. In various aspects, the porous inorganic layer will have a dual function of providing an attractive appearance and acting as a shield against visible light and ultraviolet (UV) light. Additionally, the glass article can include additional functions, e.g., including an infrared reflective coating and / or an anti-reflection coating.

[0012] As described herein, configuring the porous inorganic layer to have a CTE that is substantially equal to the CTE of the first glass substrate can prevent the formation of cracks in the porous inorganic layer during the manufacture of the glass article and also prevent the incorporation 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 comprise a borosilicate glass composition, which can be particularly beneficial as the exterior of an automotive glazing because borosilicate glass can have greater thermal shock resistance and be more resistant to crack formation from impact events caused by road debris (e.g., stones, etc.) than soda-lime silicate glass currently used as the outer glass substrate in automotive glazings. Such glasses have been found to exhibit favorable ring cracking behavior, thereby preventing flaws from radially spreading from the point of impact. Such fusion-formed glasses can also exhibit superior chemical durability, scratch resistance, mechanical strength, and optical properties (e.g., in terms of optical transmission and optical distortion) compared to other borosilicate glasses.

[0013] Providing a polymer material separate from the interlayer can enable the interlayer (or a portion thereof) to have different compositions and / or properties. For example, the concentration of plasticizer in the polymer material can be higher than the concentration of plasticizer in the interlayer (or a portion thereof), and / or even when the polymer in the polymer material is the same as the polymer in the interlayer, the polymer material can have a lower glass transition temperature than the interlayer (or a portion thereof). Providing at least a portion of the interlayer that is free of plasticizer (or has a reduced amount relative to the polymer material) can reduce the incidence of damage (e.g., corrosion) to any wiring or electronic devices that can be disposed therein. Additionally, providing at least a portion of the interlayer that is free of plasticizer (or has a reduced amount relative to the polymer material) can reduce optical distortion and / or haze that can interfere with the operation of an optical device (e.g., a camera) disposed within the interlayer or configured to view an object through a second portion of the glass article (e.g., a camera disposed within an automobile and configured to view the surrounding environment outside the automobile).

[0014] In addition, a polymeric material can be provided by drying a polymer solution or a polymer emulsion. Providing a polymer solution or a polymer emulsion having a low viscosity (e.g., about 8,000 milliPascal - second or lower) can enable the polymer solution or polymer emulsion 1003 to flow into the plurality of pores of the porous inorganic layer. The polymeric material can be formed by drying the polymer solution or polymer emulsion without any reaction (e.g., cross - linking or polymerization). Thus, the polymer in the polymer solution or polymer emulsion can be substantially the same as the polymer in the polymeric material. The limited processing involved in processing the polymeric material can simplify the processing and / or reduce the cost.

[0015] Some example aspects of the present disclosure are described below. It should be understood that any feature of each aspect can be used alone or in combination with each other.

[0016] Aspect 1. A glass article comprising:

[0017] 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 the first major surface;

[0018] 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 the third major surface;

[0019] An interlayer disposed between the second major surface and the third major surface;

[0020] 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

[0021] A polymeric material disposed in the plurality of pores,

[0022] wherein a first glass transition temperature of the interlayer is about 10 °C or higher than a second glass transition temperature of the polymeric material.

[0023] Aspect 2. The glass article according to aspect 1, wherein the first glass transition temperature of the interlayer is about 15 °C to about 30 °C higher than the second glass transition temperature of the polymeric material.

[0024] Aspect 3. The glass article according to any one of Aspects 1 to 2, wherein when irradiated from the first major surface with a D65 illuminant, the maximum ΔE value between a first portion of the glass article and a second portion of the glass article including the porous inorganic layer is about 2.0 or less, in the first portion, the polymeric material is disposed within the plurality of pores of the porous inorganic layer, and in the second portion, the porous inorganic layer is not filled with the polymeric material.

[0025] Aspect 4. A glass article comprising:

[0026] A first glass substrate including a first substrate thickness defined between a first major surface and a second major surface opposite the first major surface;

[0027] A second glass substrate including a second substrate thickness defined between a third major surface and a fourth major surface opposite the third major surface;

[0028] An interlayer disposed between the second major surface and the third major surface;

[0029] A porous inorganic layer including a plurality of pores and adhered to the second major surface or the third major surface; and

[0030] A polymeric material disposed within the plurality of pores,

[0031] wherein when irradiated from the first major surface with a D65 illuminant, the maximum ΔE value between a first portion of the glass article and a second portion of the glass article including the porous inorganic layer is about 2.0 or less, in the first portion, the polymeric material is disposed within the plurality of pores of the porous inorganic layer, and in the second portion, the porous inorganic layer is not filled with the polymeric material.

[0032] Aspect 5. The glass article according to any one of Aspects 3 to 4, wherein the maximum ΔE value is from about 0.1 to about 1.0.

[0033] Aspect 6. The glass article according to any one of Aspects 3 to 5, 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 1 or less.

[0034] Aspect 7. The glass article according to 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.

[0035] Aspect 8. The glass article according to any one of Aspects 3 to 7, wherein the absolute value of the difference between the CIE a* value of the first part and the CIE a* value of the second part is about 0.5 or less.

[0036] Aspect 9. The glass article according to any one of Aspects 3 to 8, wherein the absolute value of the difference between the CIE b* value of the first part and the CIE b* value of the second part is about 0.5 or less.

[0037] Aspect 10. The glass article according to any one of Aspects 1 to 9, wherein the polymer of the polymer material is the same as the polymer of the interlayer.

[0038] Aspect 11. The glass article according to any one of Aspects 1 to 9, wherein the polymer of the polymer material is different from the polymer of the interlayer.

[0039] Aspect 12. The glass article according to Aspect 11, wherein the polymer material is semi-crystalline and the melting temperature of the polymer material is about 100 °C or lower.

[0040] Aspect 13. The glass article according to any one of Aspects 1 to 12, wherein the interlayer comprises poly(vinyl butyral).

[0041] Aspect 14. The glass article according to any one of Aspects 1 to 13, wherein the absolute value of the difference between the refractive index of the polymer material and the refractive index of the first glass substrate or the second glass substrate is about 0.05 or less.

[0042] Aspect 15. The glass article according to any one of Aspects 1 to 14, wherein a part of the glass article comprising the porous inorganic layer surrounds another part of the glass article not having the porous inorganic layer on at least two sides.

[0043] Aspect 16. The glass article according to Aspect 15, wherein at least a part of the other part of the glass article does not contain the polymer material, and at least a part of the part of the glass article comprising the porous inorganic layer comprises the polymer material.

[0044] Aspect 17. The glass article according to any one of Aspects 15 to 16, wherein the interlayer is non-uniform, and at least a part of the interlayer in the other part of the glass article contains a lower concentration of plasticizer than the concentration of plasticizer in the part of the glass article comprising the porous inorganic layer, and the porous inorganic layer comprises the polymer material.

[0045] Aspect 18. The glass article according to any one of Aspects 1 to 16, wherein the concentration of the plasticizer in the polymeric material is greater than the concentration of the plasticizer in the interlayer.

[0046] Aspect 19. The glass article according to any one of Aspects 1 to 16, wherein the polymeric material comprises a plasticizer in an amount of from about 25 wt% to about 50 wt% of the polymeric material.

[0047] Aspect 20. The glass article according to any one of Aspects 1 to 19, wherein in a portion of the glass article comprising the porous inorganic layer, for light having a wavelength from 400 nm to 700 nm perpendicularly incident on the first major surface, the glass article exhibits an integrated visible light transmittance of about 2.0% or less.

[0048] Aspect 21. The glass article according to any one of Aspects 1 to 20, wherein the polymeric material comprises a substantially linear polymer.

[0049] Aspect 22. The glass article according to any one of Aspects 1 to 21, wherein the polymeric thickness of the polymeric material is about 30 microns or less.

[0050] Aspect 23. The glass article according to any one of Aspects 1 to 22, wherein the polymeric material is present at the outer periphery of the glass article, covering the porous inorganic layer.

[0051] Aspect 24. The glass article according to any one of Aspects 1 to 23, wherein the porous inorganic layer comprises a porosity of from about 10 vol% to about 60 vol%.

[0052] Aspect 25. The glass article according to any one of Aspects 1 to 24, wherein the thickness of the porous inorganic layer is from about 10 microns to about 30 microns.

[0053] Aspect 26. The glass article according to any one of Aspects 1 to 25, further comprising a second porous inorganic layer adhered to the third major surface, wherein the porous inorganic layer is adhered to the second major surface, and the polymeric material is disposed within the pores of the first porous inorganic layer and within the pores of the second porous inorganic layer.

[0054] Aspect 27. The glass article according to any one of Aspects 1 to 26, further comprising a wiring or an electronic component disposed between the first glass substrate and the second glass substrate.

[0055] Aspect 28. The glass article according to any one of Aspects 1 to 26, wherein the interlayer comprises a first interlayer and a second interlayer, and the glass article further comprises:

[0056] An additional polymer layer disposed between the first interlayer and the second interlayer; and

[0057] A wiring or an electronic component disposed between the first interlayer and the second interlayer.

[0058] Aspect 29. A method of forming a glass article, comprising:

[0059] Filling a plurality of pores of a porous inorganic layer adhered to a first glass substrate with a polymer solution or a polymer emulsion;

[0060] 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 disposed within the plurality of pores;

[0061] Disposing an interlayer on the porous inorganic layer; and

[0062] Laminating the first glass substrate to a second glass substrate such that the porous inorganic layer and the interlayer are disposed between the first glass substrate and the second glass substrate.

[0063] Aspect 30. The method according to aspect 29, wherein the viscosity of the polymer solution or the polymer emulsion is in the range of about 10 mPa·s to about 8,000 mPa·s.

[0064] Aspect 31. The method according to any one of aspects 29 to 30, wherein filling the plurality of pores comprises disposing a layer of the polymer solution or the polymer emulsion, and the layer of the polymer solution or the polymer emulsion has a thickness of about 30 microns or less.

[0065] Aspect 32. The method according to aspect 31, wherein the polymer solution or the polymer emulsion is disposed by brushing, roll coating or spraying.

[0066] Aspect 33. The method according to any one of aspects 29 to 32, further comprising covering the outer periphery of the porous inorganic layer with the polymer solution or the polymer emulsion before drying the polymer solution or the polymer emulsion.

[0067] Aspect 34. The method according to any one of aspects 29 to 33, wherein a first glass transition temperature of the interlayer is about 10 °C or higher than a second glass transition temperature of the polymer material.

[0068] Aspect 35. The method according to aspect 34, wherein the first glass transition temperature of the interlayer is about 15 °C to about 30 °C higher than the second glass transition temperature of the polymer material.

[0069] Aspect 36. The method according to any one of Aspects 29 to 35, wherein when irradiated from the first major surface with a D65 illuminant, the maximum ΔE value between the first portion and the second portion of the glass article is about 2.0 or less, in the first portion, the polymeric material is disposed within the plurality of pores of the porous inorganic layer, and in the second portion, the porous inorganic layer is not filled with the polymeric material.

[0070] Aspect 37. The method according to Aspect 36, wherein the maximum ΔE value is from about 0.1 to about 1.0.

[0071] Aspect 38. The method according to any one of Aspects 36 to 37, 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 1 or less.

[0072] Aspect 39. The method according to any one of Aspects 36 to 38, wherein the absolute value of the difference between the CIE a* value of the first portion and the CIE a* value of the second portion is about 0.5 or less.

[0073] Aspect 40. The method according to any one of Aspects 36 to 39, wherein the absolute value of the difference between the CIE b* value of the first portion and the CIE b* value of the second portion is about 0.5 or less.

[0074] Aspect 41. The method according to any one of Aspects 29 to 40, wherein the polymer of the polymeric material is the same as the polymer of the interlayer.

[0075] Aspect 42. The method according to any one of Aspects 29 to 41, wherein the polymer of the polymeric material is different from the polymer of the interlayer.

[0076] Aspect 43. The method according to Aspect 42, wherein the polymeric material is semi-crystalline and the melting temperature of the polymeric material is about 100 °C or lower.

[0077] Aspect 44. The method according to any one of Aspects 29 to 43, wherein the interlayer comprises poly(vinyl butyral).

[0078] Aspect 45. The method according to any one of Aspects 29 to 44, wherein the absolute value of the difference between the refractive index of the polymeric material and the refractive index of the first glass substrate or the second glass substrate is about 0.05 or less.

[0079] Aspect 46. The method according to any one of aspects 29 to 45, wherein a part of the glass article including the porous inorganic layer surrounds another part of the glass article without the porous inorganic layer on at least two sides.

[0080] Aspect 47. The method according to aspect 46, wherein at least a part of the other part of the glass article does not contain the polymer material, and at least a part of the part of the glass article including the porous inorganic layer includes the polymer material.

[0081] Aspect 48. The method according to any one of aspects 46 to 47, wherein the interlayer is non-uniform, and at least a part of the interlayer in the other part of the glass article contains a lower concentration of plasticizer than the concentration of plasticizer in the part of the glass article including the porous inorganic layer, and the porous inorganic layer includes the polymer material.

[0082] Aspect 49. The method according to any one of aspects 29 to 47, wherein the concentration of plasticizer in the polymer material is greater than the concentration of plasticizer in the interlayer.

[0083] Aspect 50. The method according to any one of aspects 29 to 47 or 49, wherein the polymer material contains a plasticizer in an amount of about 25 wt% to about 50 wt% of the polymer material.

[0084] Aspect 51. The method according to any one of aspects 29 to 50, wherein in a part of the glass article including the porous inorganic layer, for light of 400 nm to 700 nm, the glass article exhibits an integrated visible light transmittance of about 2.0% or less.

[0085] Aspect 52. The method according to any one of aspects 29 to 51, wherein the polymer material includes a substantially linear polymer.

[0086] Aspect 53. The method according to any one of aspects 29 to 52, wherein the porous inorganic layer has a porosity of about 10 vol% to about 60 vol%.

[0087] Aspect 54. The method according to any one of aspects 29 to 53, wherein the inorganic thickness of the porous inorganic layer is about 10 microns to about 30 microns.

[0088] Aspect 55. The method according to any one of aspects 29 to 54, wherein the interlayer includes a first interlayer and a second interlayer, and the glass article further includes:

[0089] an additional polymer layer disposed between the first interlayer and the second interlayer; and

[0090] A wiring or electronic component disposed between the first interlayer and the second interlayer. BRIEF DESCRIPTION OF THE DRAWINGS

[0091] The above and other features and advantages of various aspects of the present disclosure will be better understood when the following detailed description is read with reference to the accompanying drawings, in which:

[0092] Figure 1 is an illustration of a vehicle including a glass article (e.g., an automotive glazing) according to an aspect of the present disclosure, where a cross-sectional view taken along line 2-2 can be as Figures 2-6 shown;

[0093] Figure 2 depicts a cross-sectional view of a glass article (e.g., an automotive glazing) having a single interlayer taken along line 2-2 according to an aspect of the present disclosure, where the view Figure 1 can be as Figure 7 shown; Figure 7 shown;

[0094] Figure 3 depicts a cross-sectional view of a glass article (e.g., an automotive glazing) taken along line 2-2 according to an aspect of the present disclosure, which shows a curved automotive glazing; Figure 1 of

[0095] Figure 4 depicts a cross-sectional view of a glass article (e.g., an automotive glazing) having an uneven interlayer taken along line 2-2 according to an aspect of the present disclosure; Figure 1 of

[0096] Figure 5 depicts a cross-sectional view of a glass article (e.g., an automotive glazing) taken along line 2-2 according to an aspect of the present disclosure, the glass article having an electronic device in the uneven interlayer; Figure 1 of

[0097] Figure 6 depicts a cross-sectional view of a glass article (e.g., an automotive glazing) taken along line 2-2 according to an aspect of the present disclosure, the glass article having a plurality of layers and an electronic device between glass substrates; Figure 1 of

[0098] Figure 7 depicts Figure 2 an enlarged view Figure 7 which shows a porous inorganic layer and a polymer material;

[0099] Figure 8depicts a glass article having a design corresponding to a porous inorganic layer adapted for an automotive windshield;

[0100] Figure 9 is a flow chart showing an exemplary method of manufacturing a glass article according to aspects of the present disclosure;

[0101] Figure 10 schematically shows a step in a method of manufacturing a glass article, which includes filling a plurality of pores of a porous inorganic layer according to the Figure 9 flow chart;

[0102] Figure 11 schematically shows a step in a method of manufacturing a glass article, which includes drying the material within the pores to form a polymeric material according to the Figure 9 flow chart;

[0103] Figure 12 schematically shows a step in a method of manufacturing a glass article, which includes placing an interlayer between two glass substrates according to the Figure 9 flow chart;

[0104] Figure 13 schematically shows a step in a method of manufacturing a glass article, which includes laminating a first glass substrate to a second glass substrate with the interlayer and the porous inorganic layer disposed between the first glass substrate and the second glass substrate according to the Figure 9 flow chart; and

[0105] Figure 14 depicts a cross-sectional view of a glass article (e.g., an automotive glazing) taken along line 2-2 according to aspects of the present disclosure, the glass article having an electronic device between the glass substrates, wherein the porous inorganic layer occupies the area occupied by the electronic device. Figure 1 Throughout the present disclosure, the drawings are used to emphasize certain aspects. Accordingly, unless otherwise expressly stated, the relative dimensions of the different regions, portions, and substrates shown in the drawings should not be considered to be in proportion to their actual relative dimensions.

[0106] DETAILED DESCRIPTION DETAILED DESCRIPTION

[0107] Aspects will now be described more fully hereinafter with reference to the drawings, in which exemplary aspects are shown. Wherever possible, the same reference numerals are used throughout the drawings to refer to the same or like parts.

[0108] Figure 1Vehicle 100 is shown, which includes a body 110 defining an interior space and at least one opening 120, wherein a glass article 130 (e.g., an automotive glazing) according to an aspect of the present disclosure is disposed in the opening 120. In various aspects, the glass article 130 can be a windshield, but in further aspects, the glass article can also be used for at least one side light, rear window, side window, sunroof, or a combination thereof. Alternatively or additionally, the glass article 130 can be a part of an interior display, engine block cover, headlight cover, taillight cover, door panel cover, pillar cover, or a combination thereof. As used herein, "vehicle" (e.g., vehicle 100) includes automobiles (e.g., see Figure 1 ), rail vehicles, locomotives, boats, ships, airplanes, helicopters, drones, spacecraft, etc. Although the present disclosure is framed in terms of vehicles, it should be understood that the glass articles described herein can be used in other situations, such as architectural glazing or bulletproof glazing applications.

[0109] Figure 2 Schematically depicts a cross-sectional view of a glass article 130 (e.g., an automotive glazing) taken along line 2-2 in Figure 1 . As shown in Figures 2-6 and Figure 14 , the glass articles 130, 300, 400, 500, 600, or 1400 include a first glass substrate 200, a second glass substrate 220, and an interlayer 230, 430, 630, or 1430 disposed between the first glass substrate 200 and the second glass substrate 220. As shown in Figure 2 , 4 -6 and 14, the first glass substrate 200 includes a first major surface 202, a second major surface 204 opposite the first major surface 202, and a first substrate thickness 206, which is defined as the average distance between the first major surface 202 and the second major surface 204. As shown in Figure 2 , 4 -6 and 14, the second glass substrate 220 includes a third major surface 222, a fourth major surface 224 opposite the third major surface 222, and a second substrate thickness 226, which is defined as the average thickness between the third major surface 222 and the fourth major surface 224. The interlayer 230, 430, 630, or 1430 is disposed 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 to the third major surface 222 of the second glass substrate 220, which can be achieved by disposing one or more layers and / or portions of material between the substrates, as discussed below.

[0110] In various 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 various 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 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.

[0111] In various aspects, the second substrate thickness 226 of the second glass substrate 220 is less than the first substrate thickness 206. In various aspects, the second substrate thickness 226 can be about 2.0 mm or less, for example, in the range of 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 various 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 greater.

[0112] As used herein, unless otherwise specified, the coefficient of thermal expansion (CTE) is measured according to ASTM E831 - 19 to calculate the CTE between 25 °C and 300 °C. In various aspects, the CTE of the first glass substrate 200 and / or the second glass substrate 220 can be about 55×10 -7K -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 various aspects, the first glass substrate 200 may comprise, consist of, or consist essentially of a borosilicate glass composition. Accordingly, the CTE of the first glass substrate 200 may be within one or more of the ranges described above in this paragraph. Such a low CTE range may render the first glass substrate 200 incompatible with decoration by existing commercially available glazes. In various aspects, the second glass substrate 220 may be a soda-lime silicate glass or a chemically strengthenable alkali aluminosilicate glass composition (e.g., a borosilicate glass composition) having a CTE greater than the CTE of the first glass substrate 200. In a further aspect, the first glass substrate 200 and the second glass substrate 220 may comprise different compositions. In a further aspect, the CTE of the second glass substrate 220 may 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 various 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 instance is envisioned where 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 instance is envisioned where 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 .

[0113] In all aspects, the first glass substrate 200 comprises a borosilicate glass composition comprising 60 mol% to 90 mol% SiO2, about 1 mol% to about 20 mol% Al2O3, 7 mol% to 16 mol% B2O3, 2 mol% to 20 mol% R2O, wherein R2O comprises a combined amount of Na2O, Li2O, and K2O. An exemplary borosilicate glass composition comprises about 83.60 mol% SiO2, about 1.20 mol% Al2O3, about 11.60 mol% B2O3, about 3.00 mol% Na2O, and about 0.70 mol% K2O, and has a CTE of about 32×10 -7 K -1 . When the first glass substrate 200 is located on the exterior of an automotive glazing (e.g., the glass article 130) such that the first major surface 202 is the outer surface of the automotive glazing, such borosilicate glass can be particularly beneficial because the borosilicate glass can have greater thermal shock resistance than the soda-lime silicate glass currently used as the outer glass substrate in automotive glazings and is more resistant to crack formation from impact events caused by road debris (e.g., stones, etc.). It is known that borosilicate glass exhibits less abnormal cracking behavior and is not prone to forming cracks that radially expand from the point of fragment impact, which is particularly beneficial for the durability of automotive glazings.

[0114] In various aspects, the first glass substrate 200 advantageously comprises one of the fusion-formable borosilicate glass compositions described in the following documents: U.S. Provisional Patent Application No. 63 / 123,863, filed on December 10, 2020, entitled "Fusion Formable Borosilicate Glass Composition and Articles Formed Therefrom"; U.S. Provisional Patent Application No. 63 / 183,271, filed on May 3, 2021, entitled "Fusion Formable Borosilicate Glass Composition and Articles Formed Therefrom"; U.S. Provisional Patent Application No. 63 / 183,292, filed on May 3, 2021, entitled "Glass with Unique Fracture Behavior for Vehicle Windshield"; U.S. Patent Application No. 17 / 363,266, filed on June 30, 2021, entitled "Glass with Unique Fracture 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 respective contents of which are incorporated herein by reference in their entireties. In various aspects, such borosilicate glass compositions comprise SiO2, B2O3, Al2O3, one or more alkali metal oxides, and one or more divalent cation oxides selected from the group consisting of MgO, CaO, SrO, BaO, and ZnO in terms of constituent oxides. In a further aspect, the borosilicate glass composition comprises from about 11 mol% to about 16 mol% B2O3, from about 2 mol% to about 6 mol% Al2O3, and a total of about 7.0 mol% or more of Na2O, K2O, MgO, and CaO. In a further aspect, the first glass substrate 200 comprises a fusion-formable borosilicate glass composition comprising from about 74 mol% to about 80 mol% SiO2, from about 2.5 mol% to about 6 mol% Al2O3, from about 11.5 mol% to about 14.5 mol% B2O3, from about 4.5 mol% to about 8 mol% Na2O, from about 0.5 mol% to about 3 mol% K2O, from about 0.5 mol% to about 2.5 mol% MgO, and from 0 mol% to about 4 mol% CaO (e.g., such that the combined amount of CaO and MgO is less than 5 mol%), and from about 32.5×10 - 7 K -1 to about 56×10 -7 K -1CTE. In a further aspect, the borosilicate glass composition can satisfy the relationships: (R2O + R'O) ≥ Al, (R2O + R'O) ≥ (Al2O3 + 2), and / or 0.80 < (1 - [(2R2O + 2R'O) / (SiO2 + 2Al2O3 + 2B2O3)]) < 0.93, where all concentrations are in mole percentages based on oxides. As used herein, R2O is the sum of the alkali metal oxides (i.e., Li2O, Na2O, K2O, Rb2O, and Cs2O). As used herein, R'O is the sum of the alkaline earth metal oxides including MgO, CaO, SrO, and BaO. Such glasses have been found to exhibit favorable ring cracking behavior, thereby preventing the radial expansion of flaws from the point of impact. Such fusion-formed glasses can also exhibit superior chemical durability, scratch resistance, mechanical strength, and optical properties (e.g., in terms of optical transmission and optical distortion) compared to other borosilicate glasses.

[0115] In aspects, the second glass substrate 220 can comprise, 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 comprises a soda-lime-silicate composition, an aluminosilicate glass composition, an alkaline aluminosilicate glass composition, an alkali-containing borosilicate glass composition, an alkaline aluminophosphate-silicate glass composition, or an alkaline aluminoborosilicate glass composition. Alternatively, in aspects, the second glass substrate 220 comprises one of the borosilicate glass compositions described in U.S. Provisional Patent Application No. 63 / 318221, filed Mar. 9, 2022, entitled “Boroaluminosilicate Glass Composition having High Fusion Flow Rate and Advantaged Pair Shaping Temperature”. In aspects, the second glass substrate 220 is formed from one of the glass compositions described in U.S. Patent Application No. 16 / 002276, filed Jun. 7, 2018, entitled “Automotive Glass Compositions, Articles, and Hybrid Laminates” or U.S. Patent No. 10,125,044, filed Nov. 14, 2014, entitled “Ion Exchangeable High Damage Resistance Glasses”. The entire contents of each of these patent applications are incorporated herein by reference in their entirety.

[0116] Regardless of the specific compositions used to form the first glass substrate 200 and the second glass substrate 220, in various aspects, neither the first glass substrate 200 nor the second glass substrate 220 is 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 alkaline aluminosilicate glass composition), and the first glass substrate 200 is not strengthened (but can optionally be annealed) and exhibits a surface compressive stress of less than about 3 MPa, or about 2.5 MPa or less, 2 MPa or less, 1.5 MPa or less, 1 MPa or less, or about 0.5 MPa or less. These aspects can help reduce the weight of automotive glazing while still providing favorable mechanical strength and meeting various regulatory requirements associated with automotive applications. Alternatively, in various aspects, both the first glass substrate 200 and the second glass substrate 220 can be strengthened.

[0117] In various aspects, the second glass substrate 220 and / or the first glass substrate 200 can be strengthened by one or more compressive stress zones. Chemical strengthening involves an ion exchange process in which ions in the surface layer are replaced or exchanged with larger ions of the same valence or oxidation state. The method of chemical strengthening will be discussed later. The compressive stress zone can extend into a portion of the first part and / or the second part, and the depth reached is called the compressive depth. As used herein, the compressive depth means the depth at which the stress in the chemically strengthened substrate and / or part described herein changes from compressive stress to tensile stress. Depending on the ion exchange treatment and the thickness of the article being measured, the compressive depth is measured using a surface stress meter or a scatter light polariscope (SCALP, where the values reported herein are obtained using the SCALP-5 manufactured by Glasstress Co. of Estonia). 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, a surface stress meter, such as the FSM-6000 (Orihara Industrial Co., Ltd. (Japan)), is used to measure the compressive depth. Unless otherwise specified, the compressive stress (including surface CS) is measured using a commercially available instrument such as the FSM-6000 manufactured by Orihara through a surface stress meter (FSM). Surface stress measurement relies on the accurate measurement of the stress optical coefficient (SOC) related to the birefringence of the glass. Unless otherwise specified, the SOC is measured according to Procedure C (Glass Disc Method) of the standard test method named "Standard Test Method for Measurement of Glass Stress-Optical Coefficient" described in ASTM standard C770-16 (2020), the content of which is incorporated herein by reference in its entirety. In the case where the stress is generated by exchanging sodium ions into the substrate and the thickness of the article being measured is greater than about 400 μm, the compressive depth and the central tension (CT) are measured using SCALP. In the case where the stress in the substrate and / or part is generated by exchanging both potassium ions and sodium ions into the substrate and / or part and the thickness of the article being measured is greater than about 400 μm, the compressive depth and the CT are measured using SCALP. Without wishing to be bound by theory, the exchange depth of sodium ions can indicate the compressive depth, while the exchange depth of potassium ions can indicate the change in the magnitude of the compressive stress (rather than the stress change from compressive to tensile).A graphical representation of the stress distribution can also be obtained using the refracted near-field (RNF; the RNF method is described in U.S. Patent No. 8,854,623, entitled "Systems and methods for measuring a profile characteristic of a glass sample," which is incorporated herein by reference in its entirety). When obtaining a graphical representation of the stress distribution using the RNF method, the maximum central tension value provided by the SCALP is utilized in the RNF method. The graphical representation of the stress distribution obtained by the RNF is force balanced and calibrated based on 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, potassium) have been exchanged into the substrate and / or portion thereof. By this disclosure, when the maximum central tension cannot be directly measured by the SCALP (e.g., when the thickness of the article being measured is less than about 400 μm), the maximum central tension can be approximated by dividing the product of the maximum compressive stress and the compressive depth by the difference between the substrate thickness and twice the compressive depth, where the compressive stress and the compressive depth are measured by the FSM.

[0118] In various aspects, the first compressive stress zone can extend from the third major surface 222 of the second glass substrate 220 to a first compressive depth, and / or the second compressive stress zone can extend from the fourth major surface 224 of the second glass substrate 220 to a second compressive depth. In various aspects, the first compressive depth and / or the second compressive depth, expressed as a percentage of the second substrate thickness, can be about 1% or greater, about 5% or greater, about 10% or greater, about 30% or less, about 25% or less, or about 20% or less. In various aspects, the first compressive depth and / or the second compressive depth, expressed as a percentage of the substrate thickness, can be in the 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 various aspects, the first compressive depth and / or the second compressive depth can be about 1 μm or greater, about 10 μm or greater, about 30 μm or greater, about 50 μm or greater, about 500 μm or less, about 2000 μm or less, about 100 μm or less, or about 60 μm or less. In various aspects, the first compressive depth and / or the second compressive depth can 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 various aspects, the first compressive depth can be substantially equal to the second compressive depth.

[0119] In various aspects, the first compressive stress zone can include the maximum first compressive stress, and / or the second compressive stress zone can include the maximum second compressive stress. In further aspects, the maximum first compressive stress and / or the maximum second compressive stress can 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 the 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 a compressive stress zone having a compressive depth and / or a maximum compressive stress value within one or more of the ranges described above for the first compressive stress zone and / or the second compressive stress zone.

[0120] As Figures 2-6 and Figure 14 shown, the glass articles 130, 300, 400, 500, 600, or 1400 include a first porous inorganic layer 240. In various aspects, the glass articles 130, 300, 400, 500, 600, or 1400 further include a second porous inorganic layer 250. In various aspects in addition to the other aspects described herein, the first porous inorganic layer 240 is not porous but rather another suitable decorative coating (e.g., non-porous enamel, oil-free ink, organic ink, other suitable decorative materials). In various aspects, the first porous inorganic layer 240 can be excluded. In various aspects, the first porous inorganic layer 240 can adhere to the third major surface 222, but in other aspects, the first porous inorganic layer 240 can adhere to the second major surface 204. In further aspects, the second porous inorganic layer 250 can adhere to the second major surface 204, and the first porous inorganic layer 240 can adhere 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 these layers from mechanical degradation and / or oxidation. Additionally, 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 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. As Figure 8As shown, when the first glass substrate 200 and the second glass substrate 220 are made of glasses having different compositions and / or thicknesses, the plurality of bands of the porous inorganic layer can provide a predetermined aesthetic appearance.

[0121] In a further aspect, as Figure 2 shown, the first porous inorganic layer 240 can extend a width in a direction substantially perpendicular to the first substrate thickness 206, the width being different from (e.g., less than) the width of the second porous inorganic layer 250 extending in a direction substantially perpendicular to the first substrate thickness 206. In a further aspect, as Figures 4-6 shown, the first porous inorganic layer 240 and the second porous inorganic layer 250 can extend substantially the same width, the width being substantially perpendicular to the direction of the first substrate thickness 206.

[0122] As Figure 2 、 Figures 4-6 and Figure 14 shown, the glass articles 130, 400, 500, 600 or 1400 include a first portion 294a and a second portion 292, the first portion including the first porous inorganic layer 240 and / or the second porous inorganic layer 250, the second portion being free of the first porous inorganic layer 240 and the second porous inorganic layer 250 (if 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 interlayer 230, 430, 630 or 1430. Further, as Figure 2 、 Figures 4-6 and Figure 14 shown, a cross-sectional view of the glass article 130, 400, 500, 600 or 1400 can be presented as having another first portion 294b, which includes the first porous inorganic layer 240 and / or the second porous inorganic layer 250, the another first portion being separated from the first portion 294a by the second portion 292. Thus, the second portion 292 can be surrounded by the first portions 294a and 294b on at least two sides. By way of example, as Figure 8 shown, the structure 800 includes a glass article 820 surrounded by a boundary 810. The glass article 8320 includes a first portion 894 and a second portion 892, the first portion including a decorative pattern including a porous inorganic layer 840, the second portion including a first glass substrate 830 but being free of the porous inorganic layer 840. As shown, the first portion 894 surrounds the second portion 892 on at least two sides (e.g., as Figure 8As shown, the first part 894 is surrounded by the second part 892 on three sides). In various aspects, 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 part 294a, 294b, and / or 894 or corresponding to a 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 glass article surface.

[0123] When deposited on glass (such as automotive glass), the porous inorganic layers described herein can act as decorative glazes. Decorative glazes can be used for aesthetic purposes, functional purposes, or both. For example, the porous inorganic layer will have the dual function of providing an attractive appearance and acting as a shield against visible light and ultraviolet (UV) light.

[0124] As Figure 7 As shown, the second porous inorganic layer 250 includes an inorganic thickness 746 perpendicular to the second major surface 204. For example, the inorganic thickness 746 can correspond to the distance between a first surface 732 adhered to the second major surface 204 and a second surface 734 opposite 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 a scanning electron microscope (SEM) image. In various aspects, the inorganic thickness of the first porous inorganic layer 240 and / or the second porous inorganic layer 250 can be about 1 micrometer (μm) or greater, about 10 μm or greater, about 15 μm or greater, about 20 μm or greater, about 30 μm or less, about 25 μm or less, or about 20 μm or less. In various aspects, the inorganic thickness of the first porous inorganic layer 240 and / or the second porous inorganic layer 250 can be in the range of about 1 μm to about 30 μm, about 10 μm to about 30 μm, about 15 μm to about 25 μm, or any range or sub-range therebetween. In various aspects, the thickness of the second porous inorganic layer 250 can include a thickness within one or more of the ranges discussed above in this paragraph.

[0125] The first porous inorganic layer 240 and / or the second porous inorganic layer 250 includes a plurality of pores. As Figure 7As shown, 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 the major surface of the material using a scanning electron microscope (SEM), where the SEM image is analyzed using ImageJ with automatic thresholding to determine the fraction of the image corresponding to heights below the threshold. In various aspects, the porosity (vol%) of the first porous inorganic layer 240 and / or the second porous inorganic layer 250 can be about 10% or greater, about 15% or greater, about 20% or greater, about 25% or greater, about 60% or less, about 50% or less, about 40% or less, or about 30% or less. In various aspects, the porosity of the first porous inorganic layer 240 and / or the second porous inorganic layer 250 can be in the range of 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 serve as a decoration with a predetermined color appearance. It has been found that the porosity prevents the porous inorganic layer from reducing the mechanical strength of the glass substrate. 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 during the manufacture of the decorated glass article, thereby reducing or preventing the formation and propagation of defects. When incorporated into a laminate, the porosity can also help the porous inorganic layer to have a predetermined color appearance. For example, a sandwich is used to attach a glass substrate having a porous inorganic layer to another glass substrate. As discussed below, a polymeric material can fill the pores of the porous inorganic layer, which can darken the appearance of the portion of the glass article including the porous inorganic layer.

[0126] The first porous inorganic layer 240 and / or the second porous inorganic layer 250 can include a CTE within 15×10 -7 K -1 of that of the glass substrate such that, despite contact with the glass substrate, the decorative layer does not reduce the mechanical strength of the glass substrate. As discussed above, the porous inorganic layer can be deposited onto the second major surface and / or the third major surface in a pattern suitable for decorative or concealing purposes. Compared to some existing commercially available glazes (e.g., having a CTE of about 80×10 -7 K -1 or higher), the relatively low CTE of the decorative layer described herein 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 glass substrate and the CTE (CTE d ) of the porous inorganic layer (i.e., │CTE g -CTE d │) can be about 15×10 -7 K-1 or less, approximately 10×10 -7 K -1 or less, approximately 9×10 -7 K -1 or less, approximately 8×10 -7 K -1 or less, approximately 7×10 -7 K -1 or less, approximately 6×10 -7 K -1 or less, approximately 5×10 -7 K -1 or less, approximately 4×10 -7 K -1 or less, approximately 3×10 -7 K -1 or less, approximately 2×10 -7 K -1 or less, approximately 1×10 -7 K -1 or less, approximately 0.5×10 -7 K -1 or less, approximately 0.25×10 -7 K -1 or less, approximately 0.2×10 -7 K -1 or less, approximately 0.15×10 -7 K -1 or less, approximately 0.1×10 -7 K -1 or less, approximately 0.05×10 -7 K -1 or less. In all aspects, 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 various aspects, 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 range or sub - range therebetween. As described herein, configuring the porous inorganic layer (e.g., the first porous inorganic layer 240) to have a CTE substantially equal to the CTE of the first glass substrate 200 can prevent cracks from forming in the porous inorganic layer during the manufacture of the glass article and also prevent the incorporation of the porous inorganic layer from reducing the mechanical strength of the first glass substrate and / or the glass article.

[0127] In various aspects, the first porous inorganic layer 240 and / or the second porous inorganic layer 250 can include a low CTE additive component. In a further aspect, the low CTE additive component can be present in an amount of at least 5 wt%, at least 10 wt%, at least 12 wt%, at least 14 wt%, at least 16 wt%, at least 18 wt%, at least 20 wt%, at least 22 wt%, at least 24 wt%, at least 26 wt%, at least 28 wt%, or at least 30 wt% based on the wt% of the corresponding porous inorganic layer. In a further aspect, the low CTE additive component can be present in an amount of about 15 wt% to about 50 wt%, about 15% 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 wt% 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 wt% of the corresponding porous inorganic layer. By way of 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 wt% of the low CTE additive.

[0128] In various aspects, the low CTE additive component can comprise a ceramic or glass-ceramic material having a CTE within any of the above ranges. Exemplary ceramics include the B-eucryptite ceramic having a CTE of about -10×10 K developed by Corning Incorporated or the aluminum titanate ceramic having a CTE less than -10×10 -7 K -1 . The exemplary glass-ceramic material is the -7 K -1 having a CTE of about 0×10 -7 K sold by Eurokera S.N.C. -1 of Plus ceramics. In various aspects, the low CTE additive component includes a negative CTE. Such negative CTE materials can include Bi-Ni-Fe oxides, Zr-W oxides, and other suitable materials. Additionally, the low CTE additive component can be selected such that the resulting porous inorganic layer has a predetermined opacity. For example, the low CTE additive component can be selected to absorb light within the visible spectrum (average) (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). In various aspects, the low CTE additive component is selected such that when irradiated with a D65 illuminant at a 0° illumination angle, the first porous inorganic layer 240 and / or the second porous inorganic layer 250 exhibits 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).

[0129] Before curing, the precursor of the porous inorganic layer can include a mixture of a glaze (e.g., frit) and particles of the low CTE additive component. In various aspects, the low CTE additive component can be present as a filler in the porous inorganic layer. In various aspects, the material of the low CTE additive component can have a melting point or softening temperature higher than the corresponding temperature of the frit component in the glaze. In various aspects, the particles of the low CTE additive component can have 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, e.g., by preventing densification of the glaze (e.g., frit) around the particles during sintering, thereby producing a porous structure. Additionally, it has been found that the porosity can prevent the porous inorganic layer from reducing the strength of the glass substrate and / or the glass article, or even increase the strength of the glass substrate and / or the glass article.

[0130] In various aspects, the low CTE additive component can include 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 -1Or a lower CTE. It has been found that the CTE of the resulting porous inorganic layer after curing is approximately the weighted average of all the constituent components (e.g., between the frit and the low CTE additive component). Thus, the CTE of the low CTE additive can determine the weight percentage required for a given frit to achieve a predetermined CTE. In various aspects, the refractive index of the low CTE additive component can be about 1.5 or less or about 1.6 or less. In various aspects, the refractive index of the low CTE additive component is greater than 1.6. A higher refractive index can be preferred to maintain a higher opacity of the decorative layer. As used herein, the refractive index is measured according to ASTM E1967-19, where the first wavelength includes 589 nm.

[0131] In various aspects, the porous inorganic layer can be formed from a mixture of particles of the low CTE additive component and a commercially available glaze. The addition of the low CTE additive component is used not only to reduce the CTE of the glaze but also to increase the porosity of the resulting porous inorganic layer after curing. In a further aspect, the commercially available glaze comprises a glass or ceramic glaze that includes a frit component, a colorant component, and an optional additive component. The frit component determines various characteristics of the resulting porous inorganic layer, including mechanical strength and the required firing conditions. In a still further aspect, the frit can comprise one or more Bi, B, Zn, or Si oxides. The frit can be characterized by the presence of Bi, B, Zn, or Si oxides as the main component. In a still further aspect, the frit can comprise about 1 wt% or more, about 5 wt% or more, or about 10 wt% or more of Bi, B, Zn, or Si oxides. In a further aspect, the frit can comprise less than 1 mol% Na2O, less than 10 mol% Fe2O3, or less than 25 mol% P2O5. In a further aspect, the frit does not contain Na2O, Fe2O3, or P2O5. In a further aspect, the colorant component is incorporated into the frit and comprises one or more Cu, Co, Fe, Ni, Mn, or Cr oxides. In a still further aspect, the colorant comprises non-Fe oxides or does not contain Fe oxides. Examples of suitable ceramic glazes can be purchased from Ferro Corporation (Mayfield Heights, Ohio), including product number 14 316 (a bismuth-based frit system with a black matte color, a wide firing range from 570 °C to 640 °C for 6 minutes, and a relatively high melting point) and product number 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 the glass substrate, where the medium can comprise an oil or an organic resin suitable for drying by evaporation of the solvent.

[0132] In various aspects, the first porous inorganic layer 240 and / or the second porous inorganic layer 250 can be formed from commercially available ceramic glazes or frits (e.g., particles that do not contain the low CTE additive components discussed above). In various aspects, the first porous inorganic layer 240 and / or the second porous inorganic layer 250 can be formed from frits designed to be ion-exchangeable. For example, the frit can be applied to an ion-exchangeable glass followed by an ion-exchange treatment. Such frits are configured to allow ion exchange between the glass and the treatment bath. In further aspects, the frit can be a Bi-Si-B base system, a Zn-based Bi system, a Bi-Zn system, a Bi system, a Si-Zn-B-Ti system without Bi or with low Bi, a Si-Bi-Zn-B base system, and / or a Si-Bi-Ti-B-Zn base system, etc. Exemplary ion-exchangeable frits including colorants comprise 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% Al2O3, 0.15 mol% P2O5, 0.079 mol% SO3, 0.076 mol% BaO, 0.062 mol% ZrO2, 0.060 mol% Fe2O3, 0.044 mol% MoO3, 0.048 mol% CaO, 0018 mol% Nb2O5, 0.006 mol% Cl, and 0.012 mol% SrO. Other examples of ion-exchangeable frits are disclosed in International Patent Application No. PCT / US2020 / 28176, titled "Filled Pore Decorative Layer for Ion-Exchangeable and Automotive Glass," filed on April 15, 2022, 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.

[0133] In various aspects, the first porous inorganic layer 240 and / or the second porous inorganic layer 250 can include (e.g., in addition to the frit / vitreous-based components described in the foregoing paragraphs) a colorant coating that includes an ink, such as an organic ink. Additionally or alternatively, in various aspects, although not illustrated, the colorant coating can be applied to the third major surface 222 or the fourth major surface 224. Advantageously, when the second glass substrate 220 is in a planar configuration, such a colorant coating can be applied to the second glass substrate 220, and then the second glass substrate 220 can be cold formed into a curved configuration without breaking the colorant coating (e.g., the organic ink coating). In a further aspect, the colorant coating includes at least one pigment, at least one mineral filler, and a binder that includes 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 November 12, 2019) and U.S. Patent No. 9,724,727 (Application No. 14 / 618,398, filed February 10, 2015), both of which are incorporated herein by reference in their entirety. Additionally or alternatively, an infrared reflection (IRR) coating, a frit, an anti-reflection coating, or a pigment coating can be disposed on the first glass substrate and / or the second glass substrate. For example, an IRR coating can be disposed on the second major surface 204 of the first glass substrate 200, or the third major surface 222 of the second glass substrate 220 is coated with an infrared reflection film and optionally coated with one or more layers of transparent dielectric films. In a further aspect, the infrared reflection film can include a conductive metal, such as silver, gold, or copper, which reduces heat transfer through the automotive glazing. In a further aspect, the optional dielectric film can be used to counteract the reflection of the infrared reflection film and control other properties and characteristics of the coating, such as color and durability. In a further aspect, the dielectric film includes one or more oxides of zinc, tin, indium, bismuth, and titanium, among others. In various aspects, the IRR coating includes one or two silver layers, each silver layer being sandwiched between two layers of transparent dielectric films. In an embodiment, the IRR coating is applied using physical vapor deposition, chemical vapor deposition, or via lamination.

[0134] In various aspects, the precursor of the first porous inorganic layer 240 and / or the second porous inorganic layer 250 can include particles of a suitable pigment to provide a predetermined appearance. In a further aspect, the pigment particles can be added in an amount less than or equal to the amount of the low CTE additive component (discussed above). The pigment can also be incorporated into a base frit (such as a ceramic glaze), for example as a colorant component. In a further aspect, the pigment (if included) is added such 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 upon curing (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 pigments, 30C965 (CuCr-based pigment), 20F944 (MgFe-based pigment) from Shepherd (Cincinnati, Ohio), V7709 (CuCr-based pigment) and 240137 (FeCrCoNi-based pigment) from Ferro Corporation (Mayfield Heights, Ohio). Pigments having the following main components can be selected to obtain a predetermined color, for example as follows: black (CuCrFe, CrFe, manganese ferrite spinel, FeCrCoNi), blue (cobalt aluminate, cobalt chromite spinel, CoZnCrAl), green (cobalt titanate green spinel), brown (manganese antimony titanium buff rutile, zinc iron chromite brown spinel, iron titanium brown spinel), orange (rutile tin zinc), purple (cobalt phosphate), yellow (nickel antimony titanium yellow rutile, niobium sulfur tin zinc oxide), and metallic appearance (mica flakes coated with titanate, titanate and tin oxide, or iron oxide). The pigment can be black, blue, green, brown, orange, purple, yellow, or a metallic variant thereof. In a further aspect, the pigment can be the same or a similar color to the frit (e.g., glaze), for example, when irradiated with a D65 illuminant at a 0° illumination angle, the pigment and the glaze can exhibit CIE a* values and CIE b* values that differ from each other by less than 5.

[0135] In various aspects, the first porous inorganic layer 240 and / or the second porous inorganic layer 250 can also include optical properties that are beneficial for decorative automotive applications. For example, in embodiments, the first porous inorganic layer 240 and / or the second porous inorganic layer 250 can exhibit a relatively high blackness at a thickness of about 30 μm or less (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 various aspects, for light with wavelengths from 400 nm to 700 nm incident perpendicularly on the glass article, the first porous inorganic layer 240 and / or the second porous inorganic layer 250 exhibit 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). Such low optical transmittance helps the decorative layer perform various hiding and decorative functions in automotive applications. As used herein, the terms "optical transmission" and "transmittance" are used interchangeably to refer to the percentage of light transmitted through the article within the wavelength range of interest. The "integrated visible light transmittance" of light within a specific wavelength range is determined using the following equation:

[0136]

[0137] where T(λ) represents the transmission spectrum within the wavelength range, and equals the transmission of the light source used to measure the transmission. In various aspects, for light with wavelengths from 400 nm to 700 nm incident perpendicularly on the glass article, a portion (e.g., the first portion 294a or 294b) of the glass articles 130, 300, 400, 500, 600, or 1400 that includes a porous inorganic layer (e.g., the first porous inorganic layer 240 and / or the second porous inorganic layer 250) can have 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).

[0138] In various aspects, the precursor of the porous inorganic layer can be compatible with the temperature requirements for bending and laminating the glass substrate to form the glass article. In a further aspect, the precursor (e.g., uncured modified glaze) can be capable of curing before or during a heating stage associated with bending the glass substrate into a shape suitable for the stained glass application of the glass article. For example, the precursor (e.g., modified glaze) can be cured during the heating cycle of the bending process to enhance process efficiency. Thus, the precursor (e.g., modified glaze) can have a glass softening temperature that is less than or equal to the sagging temperature of the glass substrate. In various aspects, 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 can be about 750 °C or lower (e.g., about 725 °C or lower, about 700 °C or lower, about 675 °C or lower, about 650 °C or lower, about 625 °C or lower, about 600 °C or lower, about 575 °C or lower, about 550 °C or lower) to facilitate such simultaneous bending and curing.

[0139] As Figure 7 shown, the polymeric material 750 can be disposed in a plurality of pores 760 in the second porous inorganic layer 250. In various aspects, as shown, the polymeric material can be disposed in a plurality of pores in the second porous inorganic layer 250 without being disposed in all of the plurality of pores (e.g., see pore 762), but in other aspects, substantially all of the plurality of pores can have the polymeric material disposed therein. For example, as shown, the polymeric material 750 can be disposed in a plurality of pores in the first portion 782 but not in the plurality of pores in the second portion 784. As used herein, a pore “filled” with polymeric material means that the polymeric material is disposed in the pore, and it is not required that 100% of the volume of the pore contains the polymeric material. In various aspects, although not shown, it should be understood that a portion of the material of the interlayer 230, 430, 630, or 1430 can be disposed in one or more of the plurality of pores of the second porous inorganic layer 250.

[0140] Throughout this disclosure, “color shift” or “ΔE” values are measured between two points on the glass article corresponding to subscripts 1 and 2 using CIE 1976 color space L*, a*, and b* values, such that 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 a first portion relative to points in a second portion, where the points in each portion are of the sample at least every 0.1 mm. As used herein, unless otherwise stated, CIE values (and ΔE) are measured using a D65 illuminant incident on the first major surface of the first glass substrate of the glass article and assuming a 2° standard observer. In various aspects, when irradiated with a D65 illuminant from the first major surface 202 (see Figure 2 ), the maximum ΔE value between (1) a first portion 782 of the glass article 130 in which a polymer material 750 is disposed in 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 can 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 various aspects, when irradiated with a D65 illuminant from the first major surface 202 (see Figure 2 ), the maximum ΔE value between (1) a first portion 782 of the glass article 130 in which a polymer material 750 is disposed in 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 can be in the 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 therein. Providing a low maximum ΔE value between these portions of the glass article having a porous inorganic layer can provide a substantially uniform color associated with the porous inorganic layer, which may not be visually perceptible to an observer.

[0141] In various aspects, when irradiated with a D65 illuminant from the first major surface 202 (see Figure 2)Upon irradiation, the absolute value of the difference between the CIE L* value (L*1) of the first portion 782 of the glass article 130 in which the polymer material 750 is disposed in the plurality of pores of the first porous inorganic layer 240 and (2) the CIE L* (L*2) of the 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 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 greater, about 0.1 or greater, about 0.2 or greater, or about 0.3 or greater. In various aspects, when irradiated with a D65 illuminant from the first major surface 202 (see Figure 2 )Upon irradiation, the absolute value of the difference between the CIE L* value (L*1) of the first portion 782 of the glass article 130 in which the polymer material 750 is disposed in the plurality of pores of the first porous inorganic layer 240 and (2) the CIE L* value (L*2) of the 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 the 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 various aspects, the maximum absolute value of the difference between the L*1 value and the L*2 value can be within one or more of the ranges discussed above in this paragraph.

[0142] In various aspects, when irradiated with a D65 illuminant from the first major surface 202 (see Figure 2 )Upon irradiation, the absolute value of the difference between the CIE a* value (a*1) of the first portion 782 of the glass article 130 in which the polymer material 750 is disposed in the plurality of pores of the first porous inorganic layer 240 and (2) the CIE a* (a*2) of the 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 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 various aspects, when irradiated with a D65 illuminant from the first major surface 202 (see Figure 2)Upon irradiation, the absolute value of the difference between the CIE a* value (a*1) of the first portion 782 of the glass article 130 in which the polymer material 750 is disposed in the plurality of pores of the first porous inorganic layer 240 and the CIE a* (a*2) of the 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 the 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 various aspects, the maximum absolute value of the difference between the a*1 value and the a*2 value can be within one or more of the ranges discussed above in this paragraph.

[0143] In various aspects, when irradiated from the first major surface 202 (see Figure 2 ) with a D65 illuminant, the absolute value of the difference between the CIE b* value (b*1) of the first portion 782 of the glass article 130 in which the polymer material 750 is disposed in the plurality of pores of the first porous inorganic layer 240 and the CIE b* (b*2) of the 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 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 various aspects, when irradiated from the first major surface 202 (see Figure 2 ) with a D65 illuminant, the absolute value of the difference between the CIE b* value (b*1) of the first portion 782 of the glass article 130 in which the polymer material 750 is disposed in the plurality of pores of the first porous inorganic layer 240 and the CIE b* (b*2) of the 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 the 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 various aspects, the maximum absolute value of the difference between the b*1 value and the b*2 value can be within one or more of the ranges discussed above in this paragraph.

[0144] In various aspects, the polymer material can be present at the outer periphery of the glass article, with the outer periphery covering the first porous inorganic layer 240 and / or the second porous inorganic layer 250. For example, as Figure 11 shown, the polymer material 750 can be present at the outer periphery of the first glass substrate 200, which outer periphery corresponds to the outer periphery of the resulting glass article. Additionally, as Figure 11As shown, a portion 770 of the polymeric material 750 can cover the second porous inorganic layer 250. As used herein, a polymeric material covers the second porous inorganic layer if there is no path from the exterior of the glass article to the porous inorganic layer without passing through the polymeric material, the interlayer, or the glass substrate. Providing the polymeric material at the outer periphery of the glass article can ensure color uniformity of the glass article (including at the outer periphery of the glass article) by filling pores at the outer periphery. In addition, providing the polymeric material that covers the porous inorganic layer can prevent oxygen and moisture from entering the glass article, which can improve the lifespan of the glass article (including the porous inorganic layer).

[0145] In various aspects, the polymer of the polymeric material 750 can include a substantially linear polymer. As used herein, a substantially linear polymer is substantially free of crosslinks, which are branch points that connect between otherwise distinct polymer chains. As used herein, "thermoplastic" means a polymeric material that can be reformed by heating the material after an initial curing (e.g., polymerization) reaction. Thermoplastic polymers are contrasted with thermosetting polymers, which cannot be reformed after an initial curing reaction. In further aspects, the polymeric material 750 can include any of the polymers discussed above for the interlayer. In further aspects, the polymeric material 750 can 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) can be combined with a plasticizer (discussed below) to form the polymeric material 750. Exemplary aspects of the polymeric material 750 include EVA, plasticized PVB, and plasticized PVC.

[0146] Throughout this disclosure, the glass transition temperature (Tg) of the polymeric material is measured using differential scanning calorimetry (DSC). In various aspects, the second glass transition temperature of the polymeric material 750 (e.g., including any plasticizer, if present) can be about 85 °C or lower, about 80 °C or lower, about 75 °C or lower, or about 70 °C or lower. In various aspects, the second glass transition temperature of the polymeric material 750 can 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 polymeric material having a low glass transition temperature (e.g., about 85 °C or lower) can enable the polymeric material to be easily disposed in (e.g., filled into) the pores of a porous inorganic layer. Providing a polymeric material having a glass transition temperature of about 40 °C or higher can reduce the property changes of the polymeric material within the temperature ranges typically encountered during the use of glass articles. In various aspects, the polymer of the polymeric material 750 can be semi-crystalline and have a melting temperature of about 100 °C or lower, about 90 °C or lower, or about 80 °C.

[0147] In various aspects, the polymeric material 750 can contain a plasticizer in addition to the polymer, but the polymeric material can be substantially free of plasticizer (e.g., consisting essentially of the polymer). As used herein, "plasticizer" refers to a material combined with the polymer that reduces the glass transition temperature of the resulting polymeric material relative to the polymer alone. In a further aspect, the plasticizer can include fish oil, castor oil, tetraethylene glycol di-n-heptanoate, triethylene glycol bis(2-ethylhexanoate), sebacate (e.g., dibutyl sebacate), adipate (e.g., dihexyl adipate, dioctyl adipate, hexyl cyclohexyl adipate), phthalate, trimellitate, organophosphate. Exemplary aspects of the plasticizer include fish oil and castor oil.

[0148] In a further aspect, the polymeric material 750 may comprise a plasticizer in an amount of about 20 wt% or more, about 25 wt% or more, about 30 wt% or more, about 35 wt% or more, about 60 wt% or less, about 55 wt% or less, about 50 wt% or less, about 45 wt% or about 40 wt% or less, by wt% of the polymeric material. In a further aspect, the polymeric material 750 may comprise a plasticizer in an amount of about 20 wt% to about 60 wt%, about 20 wt% to about 55 wt%, about 25 wt% to about 50 wt%, about 30 wt% to about 45 wt%, about 35 wt% to about 40 wt%, or any range or sub-range therebetween, by wt% of the polymeric material. In a further aspect, the plasticizer may reduce the second glass transition temperature of the polymer in the polymeric material 750 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, relative to the glass transition temperature of the polymer alone. In a further aspect, the plasticizer may reduce the second glass transition temperature of the polymer in the polymeric material 750 by 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, relative to the glass transition temperature of the polymer alone. The plasticizer content (e.g., the plasticizer content of the polymeric material 750 or a layer or portion of the laminate) may be determined using spectroscopy (e.g., infrared (IR) spectroscopy). For example, the plasticizer may produce a unique absorption band (e.g., compared to the polymers discussed above), and the absorption intensity may be correlated to the concentration of the plasticizer. In aspects, the absolute value of the difference between the refractive index of the polymeric 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.

[0149] In various aspects, the polymeric material 750 can include an adhesion promoter, an ultraviolet (UV) absorber, an antioxidant, or a combination thereof. In a further aspect, the adhesion promoter, UV absorber, and / or antioxidant can have substantially no effect on the glass transition temperature of the polymeric material 750 (e.g., changing it by about 1 °C or less, 0 °C). In a further aspect, the weight of the adhesion promoter, ultraviolet (UV) absorber, and / or antioxidant can be about 0.01 wt% or greater, about 0.1 wt% or greater, about 0.2 wt% or greater, 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 a further aspect, the weight of the adhesion promoter, ultraviolet (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 polymeric material 750 and the porous inorganic layer 240 or 250, the first glass substrate 200, the second glass substrate 220, and / or the interlayer 230 or 430. Exemplary aspects of the adhesion promoter include silane coupling agents, such as amine-functionalized silanes or epoxy-functionalized silanes. The UV absorber increases the absorption of one or more light wavelengths from about 200 nm to about 380 nm. Exemplary aspects of the UV absorber include the TINUVIN and CHIMASSORB product lines available from BASF Corporation, including benzotriazoles, triazines, and hindered amine light stabilizers. The antioxidant can include phenolic compounds or phosphite compounds.Exemplary aspects of antioxidants containing available phenolic compounds include pentaerythritol tetra(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (e.g., Irganox 1010 (BASF)), thiodiethylene bis[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)), benzenepropanoic acid (e.g., Irganox 1135 (BASF)), 3,3',3',5,5',5'-hexakis(1,1-dimethylethyl)-α,α',α'-(1,3,5-trimethyl-2,4,6-triyl)tris-p-cresol (e.g., Irganox 1330 (BASF)), ((1,1-dimethylethyl)-4-hydroxyphenyl)methyl)ethyl phosphonate (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(octylthio)-1,3,5-triazin-2-ylamino)phenol (e.g., Irganox 565 (BASF)) and 2',3-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoyl]propionohydrazide (e.g., Irganox MD-1024 (BASF)).Exemplary aspects of antioxidants comprising phosphite compounds include 2,2',2"-nitrilo(tris(ethyl-tris[3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl])phosphite) (e.g., Irgafos 12, BASF Corporation), bis[2,4-di-tert-butylphenyl]pentaerythritol diphosphite (e.g., Irgafos 126 (BASF Corporation)), tris[2,4-di-tert-butylphenyl]phosphite (e.g., Irgafos 168 (BASF Corporation)), bis[2,4-di-tert-butyl-6-methylphenyl]ethyl phosphite (e.g., Irgafos 38 (BASF Corporation)), tris(nonylphenyl)phosphite (e.g., Weston 399 (Addivant)), 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane (e.g., Weston 618 (Addivant)), [1,3,2-dioxaphosphorinane, 5-butyl-5-ethyl-2-(2,4,6-tris(1,1-dimethylethyl)phenoxy)-1,3,2-dioxaphosphorinane] (e.g., Ultranox 641 (SI Group)), 2,2'-ethylidene-bis[4,6-di-tert-butylphenyl] fluorophosphite (e.g., Ethenox 398 (SI Group)) and 2,2'-methylidene-bis[4,6-di-tert-butylphenyl]-2-ethylhexyl phosphite (e.g., ADK STAB HP-10 (Adeka)).

[0150] As discussed above, the interlayers 230, 430, 630, or 1430 adhere 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 Figures 2-5 shown, the interlayer 230 or 430 may comprise a single layer of polymeric material having 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 Figure 2 shown, the interlayer 230 may comprise a substantially homogeneous layer of material. Alternatively, in further aspects, as Figures 4-5As shown, the interlayer can be non-uniform (e.g., heterogeneous), where the first part 431a and / or 431b and the second part 433 have different compositions. In a further aspect, the concentration of the plasticizer can be different between these parts. For example, the concentration of the plasticizer in the first part is higher than that in the second part. In a further aspect, the polymer in the first part can be different from the polymer in the second part. In a further aspect, as indicated by reference numerals 448a and 448b, 648a and 648b, and / or 658a and 658b, the boundary between the first part 431a, 431b, 641a, 641b, 651a, and / or 651b and the second part 433, 643, and / or 654 can coincide with the boundary between the first part 294a and / or 294b and the second part 292 of the glass article. However, in other aspects, the first part 431a, 431b, 641a, 641b, 651a, and / or 651b of the interlayer can extend into a portion of the second part 292 of the glass article.

[0151] Alternatively, in a further aspect, as Figure 6 shown, the interlayer 630 can include a first interlayer 640, a second interlayer 650, and an additional polymer layer 660 disposed therebetween. In a further aspect, the first interlayer 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 the first contact surface 642, and a first interlayer thickness 646 is defined between the first contact surface and the second contact surface. In a further aspect, the second interlayer 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 the fourth contact surface 654, and a second interlayer thickness 656 is defined between the fourth contact surface and the third contact surface. As discussed above, the first interlayer 640 and / or the second interlayer 650 can be non-uniform. For example, the boundary between the first part 641a, 641b, 651a, and / or 651b and the second part 643 and / or 653 is indicated by reference numerals 648a, 648b, 658a, and / or 658b. In a further aspect, the additional polymer layer 660 can include a fifth contact surface 662 that contacts the second contact surface 644 of the first interlayer 640 and a sixth contact surface 664 opposite the fifth contact surface 662, where the sixth contact surface can contact the third contact surface 652 of the second interlayer 650. It should be understood that the first porous inorganic layer and / or the second porous inorganic layer can include another part (e.g., see Figure 14 another part 1470 in) that is aligned with and / or covers the occupied area of the electronic device 661 (as described below).

[0152] Alternatively, in a further aspect, as Figure 14 shown, the interlayer 1403 may include a first interlayer 1433 and an additional polymer layer 1460. In a still further aspect, the first interlayer 1433 includes a first contact surface 1432 that may contact the second major surface 204 of the first glass substrate 200 and a second contact surface 1434 opposite the first contact surface 1432, and the first interlayer thickness 236 is defined between the first contact surface and the second contact surface. In a still further aspect, the additional polymer layer 1460 includes a third contact surface 1462 that may contact the second major surface 204 of the first glass substrate 200 and a fourth contact surface 1464 opposite the third contact surface 1462. In a still further aspect, the first contact surface 1432 of the first interlayer 1433 may contact the fourth contact surface 1464 of the additional polymer layer 1460. In a still further aspect, the electronic device 1401 may be disposed on and / or in contact with the second major surface 204 of the first glass substrate 200, and / or the electronic device 1401 may contact the second major surface 204 and be surrounded by the third contact surface 1462 of the additional polymer layer 1460 on other sides. In a still further aspect, the electronic device 1401 may be separated from the first interlayer 1433 by the additional polymer layer 1460. In a still 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. Additionally, the additional portion 1470 may cover the occupied area of the electronic device 1401. As used herein, if the projection of a second portion in the direction of the first substrate thickness onto the plane including the first portion is entirely within the area of the first portion (e.g., the occupied area of the second portion may coincide with the first portion), then the first portion covers the occupied area of the second portion. Providing the additional portion 1470 that covers the electronic device may obscure the electronic device when viewing the glass article from one side while enabling the electronic device to function (e.g., viewing the second side opposite the first side), which may provide an aesthetic benefit to the observer. Thus, the glass article 1400 may include another portion of the first portion 294c that may be surrounded by the second portion 292 on at least two sides, while the second portion 292 may be surrounded by the first portions 294a and 294b on at least two sides. It should be understood that the electronic device may be disposed on the third major surface of the second glass substrate, where another portion of the second porous inorganic layer covers the occupied area of the electronic device. Although Figure 14Depicts a situation where the electronic device 1401 is disposed in contact with the first glass substrate 200, and aspects are also contemplated where the electronic device 1401 is disposed in contact with the second glass substrate 220, where an additional polymer layer 1460 is in contact with the electronic device 1460. 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 (or be in contact with, or include polymer material 750 in its pores and be in contact with the additional polymer layer 1460) with the additional polymer layer 1460. Aspects are contemplated where a plurality of electronic devices are arranged to be 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 arranged to be 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 each electronic device. Additionally, the polymer material 750 described herein may be incorporated into the pores of the second porous inorganic layer 250 in the region overlapping with the additional polymer layer 1460 to facilitate a uniform appearance of the glass article. In aspects, the additional polymer layer 1460 extends the entire distance between the electronic device 1401 and the second porous inorganic layer 250 (and may be in contact with the polymer material 750, e.g., the additional polymer layer 1460 may form part of the sandwich 1430).

[0153] In various aspects, the interlayers 230, 430 (e.g., the first portions 431a or 431b), 630 (e.g., the first interlayer 640, the second interlayer 650), or 1430 (e.g., the first interlayer 1433) can include any of the polymers discussed above for the polymeric material 750. In a further aspect, the polymer of the interlayers 230, 430 (e.g., the first portions 431a or 431b), 630 (e.g., the first interlayer 640, the second interlayer 650), or 1430 (e.g., the first interlayer 1433) can be the same as the polymer of the polymeric material 750, but in a further aspect, the polymer of the interlayer can be different from the polymer of the polymeric material. An exemplary aspect of the polymer for the interlayer is PVB. In other aspects, the interlayers 230, 430 (e.g., the first portions 431a or 431b), 630 (e.g., the first interlayer 640, the second interlayer 650), or 1430 (e.g., the first interlayer 1433) can include a plasticizer, e.g., any of the plasticizers discussed above for the polymeric material 750. However, in other aspects, the concentration of the plasticizer in the polymeric material 750 can be higher than the concentration of the plasticizer in the interlayers 230, 430 (e.g., the first portions 431a or 431b), 630 (e.g., the first interlayer 640, the second interlayer 650, the additional polymeric layer 660), or 1430 (e.g., the first interlayer 1433, the additional polymeric layer 1460). In a still further aspect, as Figures 4-5 shown, the second portion 433 of the interlayer 430 can include a lower concentration of the plasticizer than the first portions 431a and / or 431b of the interlayer 430, and the first portions 431a and / or 431b of the interlayer 430 can include a lower concentration of the plasticizer than the polymeric material 750 (see Figure 7)(e.g., the position in the plurality of pores of the first porous inorganic layer 240 and / or the second porous inorganic layer 250). In a further aspect, the second portion 433 of the interlayer 430, the additional polymer layer 660 of the interlayer 630, and / or the additional polymer layer 1460 of the interlayer 1430 may be substantially free of plasticizer. In a further aspect, the first Tg of the interlayer 230, 430 (e.g., the first portion 431a or 431b), 630 (e.g., the first interlayer 640, the second interlayer 650, the additional polymer layer 660), or 1430 (e.g., the first interlayer 1433, the additional polymer layer 1460) may be about 10 °C or higher, about 15 °C or higher, about 18 °C or higher, about 20 °C or higher, about 40 °C or lower, about 30 °C or lower, about 25 °C or lower, or about 23 °C or lower higher than the second Tg of the polymer material 750. In a further aspect, the first Tg of the interlayer 230, 430 (e.g., the first portion 431a or 431b), 630 (e.g., the first interlayer 640, the second interlayer 650, the additional polymer layer 660), or 1430 (e.g., the first interlayer 1433, the 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 within the sub-ranges therebetween higher than the second Tg of the polymer material 750. It should be understood that a portion of the interlayer may have a first Tg higher than the second Tg of the polymer material. For example, the second portion 433 of the interlayer 430 (see Figures 4-5 ), the additional polymer layer 660 of the interlayer 630 (see Figure 6 ), and / or the additional polymer layer 1460 of the interlayer 1430 (see Figure 14 ) may have a first Tg higher than the second Tg of the polymer material 750 (see Figure 7 ) within one or more of the ranges discussed above in this paragraph, while the remaining portions of the interlayer 430, 630, or 1430 may not necessarily have a Tg higher than the second Tg.

[0154] In various aspects, as shown in Figure 7 , a portion 770 of the polymer material 750 may include a polymer thickness 776 that does not include any portion of the polymer material 750 disposed in the pores of the porous inorganic layer (e.g., the second porous inorganic layer 250). Although the portion 770 of the polymer material is shown in Figure 7is shown disposed on the second porous inorganic layer 250, but it is understood that the portion 770 may alternatively or additionally be disposed on the major surface of the glass substrate (e.g., the second major surface 204 of the first glass substrate 200, the third major surface 222 of the second glass substrate 220). In various aspects, the polymer thickness 776 may 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 greater, about 3 μm or greater, about 5 μm or greater, about 8 μm or greater, or about 10 μm or greater. In various aspects, the polymer thickness 776 may be in the 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 various aspects, as Figure 2 , 4 -6 shows, at least a portion of the second portion 292 of the glass articles 130, 400, 500, 600, or 1400 (e.g., surrounded by the first portions 294a or 294b on at least two sides) may be free of the polymer material 750. In various aspects, 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 a porous inorganic layer. Providing a polymer thickness 776 of about 30 μm or less may reduce the visibility of the polymer material in portions of the glass article that do not have a porous inorganic layer, which may simplify manufacturing because it may not be necessary to remove (e.g., clean) slightly misaligned or overapplied polymer material precursors from the glass substrate. Providing a polymer thickness of about 1 μm or greater may provide sufficient polymer material such that the polymer material may also be disposed in the plurality of pores of the porous inorganic layer.

[0155] In various aspects, the interlayers 230, 430 (e.g., the first part 431a or 431b), 630 (e.g., the first interlayer 640, the second interlayer 650, the additional polymer layer 660) or 1430 (e.g., the first interlayer 1433, the additional polymer layer 1460) comprise a thermoplastic polymer. In a further aspect, the interlayer can comprise any of the polymers discussed above for the polymer material 750. In various aspects, the interlayers 230, 430 (e.g., the first part 431a or 431b), 630 (e.g., the first interlayer 640, the second interlayer 650, the additional polymer layer 660) or 1430 (e.g., the first interlayer 1433, the additional polymer layer 1460) can comprise a polymer such as polyvinyl butyral (PVB) (e.g., acoustic PVB (aPVB)), ionomer, ethylene-vinyl acetate (EVA), and thermoplastic polyurethane (TPU), polyester (PE), polyethylene terephthalate (PET), etc., at least one of which. The interlayer thicknesses 236, 646 or 656 can be about 0.5 mm or greater, about 0.7 mm or greater, 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 a further aspect, as Figures 4-6 and Figure 14 shown, the interlayers 430, 630 or 1430 can comprise a plurality of polymer layers or films providing various functions. For example, as Figures 5-6 and Figure 14 shown, the wiring or electronic device 501, 661 or 1401 can be disposed between the first glass substrate 200 and the second glass substrate 220. In a further aspect, as Figure 6 shown, the additional polymer layer 660 can be disposed between the first interlayer 640 and the second interlayer 650; the wiring or electronic device 661 can be disposed between the first interlayer 640 and the second interlayer 650. For example, the wiring or electronic device 661 can be disposed within the additional polymer layer 660. In a further aspect, as Figure 14As shown, the electronic device 1401 can be disposed on and / or in contact with the second major surface 204 of the first glass substrate 200, and / or the electronic device 1401 can be in contact with the second major surface 404 and surrounded by the third contact surface 1462 of an additional polymer layer 1460 on other sides. For example, the electronic device 1401 can be separated from the first interlayer 1433 by the additional polymer layer 1460. Providing at least a portion of the interlayer without a plasticizer (or with a reduced amount of plasticizer relative to the polymer material 750) (e.g., the second portion 433, the additional polymer layer 660, the additional polymer layer 1460) can reduce the incidence of damage (e.g., corrosion) to the wiring or electronic devices 501, 661, or 1401 that can be disposed therein. Additionally, providing at least a portion of the interlayer in the second portion 292 of the glass article without a plasticizer (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) disposed within the interlayer (e.g., the electronic devices 501, 661, or 1401) or configured to view an object through the second portion 292 of the glass article (e.g., a camera disposed within a vehicle and configured to view the surrounding environment outside the vehicle).

[0156] Alternatively or additionally, the interlayers 230, 430, 630, or 1430 may further incorporate at least one of the following: solar insulation, sound dampening, antennas, anti-glare treatment, or anti-reflection treatment, etc. In various aspects, the interlayers 230, 430 (e.g., the first part 431a or 431b), 630 (e.g., the first interlayer 640, the second interlayer 650), or 1430 (e.g., the first interlayer 1433) are modified to provide ultraviolet (UV) absorption, infrared (IR) absorption, IR reflection, acoustic control / dampening, adhesion promotion, and tint. The interlayers 230, 430 (e.g., the first part 431a or 431b), 630 (e.g., the first interlayer 640, the second interlayer 650), or 1430 (e.g., the first interlayer 1433) may be modified with suitable additives such as dyes, pigments, dopants, etc. to impart predetermined properties. Additionally or alternatively, the interlayers 230, 430 (e.g., the first part 431a or 431b), 630 (e.g., the first interlayer 640, the second interlayer 650), or 1430 (e.g., the first interlayer 1433) may further contain adhesion promoters, UV absorbers, and / or antioxidants. In a further aspect, the additives, adhesion promoters, UV absorbers, and / or antioxidants may have substantially no effect on the glass transition temperature of the interlayers 230, 430 (e.g., the first part 431a or 431b), 630 (e.g., the first interlayer 640, the second interlayer 650), or 1430 (e.g., the first interlayer 1433) (e.g., causing a change of about 1 °C or less, 0 °C).

[0157] Although Figure 2 、 Figures 4-6 and Figure 14 the glass articles 130, 400, 500, 600, or 1400 are shown as flat structures (e.g., where the first glass substrate 200 and the second glass substrate 220 are planar), the glass articles 130, 400, 500, 600, or 1400 may comprise a curved shape. For example, Figure 3 the glass article 300 shown in Figure 3As shown, the second major surface 204 of the first glass substrate 200 has a first depth of curvature 310, which is defined as the maximum depth of the second major surface 204 from a plane (dashed line). In the aspect where 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, which is defined as the maximum depth of the fourth major surface 224 from a plane (dashed line). In various aspects, one or both of the first depth of curvature 310 or the second depth of curvature 320 is about 2 mm or greater. The depth of curvature can be defined as the maximum distance by which 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 can be in the range of about 2 mm to about 30 mm. In various aspects, the first depth of curvature 310 and the second depth of curvature 320 can be substantially equal. In various aspects, the first depth of curvature 310 is within 10% or within 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 can be in the range of about 13.5 mm to about 16.5 mm (within 10% of the second depth of curvature 320).

[0158] Reference will be made Figure 9 to the flowcharts in Figures 10-13 and the exemplary method steps shown therein to discuss aspects of a method of manufacturing a glass article according to aspects of the present disclosure. Reference will now be made Figures 10-13 and Figure 9 to the flowcharts in Figures 1-2 to discuss exemplary aspects of manufacturing the glass article 130 shown therein. It should be understood that the glass article 300 can be curved as in Figure 3 and encompasses changes to the laminate to produce the glass article shown in Figures 4-6

[0159] ​In a first step 901 of the method of the present disclosure, the method can begin with providing a first glass substrate 200 and a second glass substrate 220. In various aspects, the first glass substrate 200 and / or the second glass substrate 220 can be provided by purchasing or otherwise obtaining the substrate or by forming the first glass substrate 200 and / or the second glass substrate 220. In further aspects, the glass substrate can be provided by forming with a variety of ribbon forming processes, such as slot draw, down draw, fusion down draw, up draw, press roll, redraw, or float. In various aspects, the first glass substrate 200 and / or the second glass substrate 220 can be strengthened with one or more compressive stress zones, such as chemical strengthening and / or thermal strengthening, as discussed above. In various aspects, the first substrate thickness 206 and / or the second substrate thickness 226 can be within one or more of the ranges discussed above. In various aspects, one or more of the glass substrates can comprise borosilicate glass. In various aspects, the first glass substrate 200 and / or the second glass substrate 220 can be bent at the end of step 901, but the bending can be performed in a subsequent step or can be omitted entirely. In various aspects, the first glass substrate 200 and / or the second glass substrate 220 can be chemically strengthened at the end of step 901, but chemically strengthening one or more of the glass substrates can be performed in step 903 and / or one or more of the glass substrates can be not chemically strengthened. In various aspects, the first porous inorganic layer 240 can be disposed on one glass substrate (e.g., the second glass substrate 220) and / or the second porous inorganic layer 250 can be disposed on the other glass substrate (e.g., the first glass substrate 200), but one or both of the porous inorganic layers can be disposed in step 903. Although the second porous inorganic layer 250 on the first glass substrate 200 is shown in Figures 10-11 it should be understood that the method encompasses the second porous inorganic layer 250 disposed on the second glass substrate 220.

[0160] In various aspects, as discussed above with reference to Figure 3 a first curvature depth 310 can be induced in the first glass substrate 200 by thermoforming (e.g., the first glass substrate 200 can be bent by gravity sag), and a second curvature depth 320 can be induced in the second glass substrate 220 by cold forming. In various aspects, the first curvature depth 310 and the second curvature depth 320 are induced by thermally bending the first glass substrate 200 and the second glass substrate 220 (e.g., in a co-bending process or in a process where the glass substrates are bent independently of each other).

[0161] In various aspects, curvature is introduced into at least one of the first glass substrate 200 or the second glass substrate 220 through heat treatment. The heat treatment may include a sagging process that, when heated, uses gravity to shape the first glass substrate 200, or both the first glass substrate 200 and the second glass substrate 220. In the sagging 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 allowed to gradually sag under the influence of gravity into the open interior of the mold. In further aspects, the heat treatment may include a pressing process that, when heated or while heating, uses a mold to shape the first glass substrate 200, or both the first glass substrate 200 and the second glass substrate 220.

[0162] In various aspects, two glass substrates (e.g., the first glass substrate 200 and the second glass substrate 220) are shaped together in a "pair-shaping" process. In such a process, one glass substrate is placed on top of the other glass substrate to form a stack (which may also include an intermediate release layer), and the stack is placed on a mold. In further aspects, to facilitate the pair-shaping process, the second glass substrate 220, which in some aspects serves as the inner and / or thinner glass substrate, has a pair-shaping temperature (e.g., at a viscosity of 10 11 poise) that is higher than the pair-shaping temperature of the first glass substrate 200. In various aspects, the mold used during pair sagging may have an open interior for the sagging process. The stack and the mold are both heated by placing them in a furnace, and the stack is gradually heated to the bending or sagging temperature of the glass substrates. During this process, the glass substrates are shaped together into a curved shape. Advantageously, the viscosity curve of at least some of the borosilicate glass compositions included herein at a viscosity of 10 11 poise may be similar to the viscosity curve of the glass used for the second glass substrate 220, allowing the use of existing equipment and techniques. According to an exemplary aspect, the heating time and temperature are selected to obtain the desired curvature and final shape. Subsequently, the glass substrates are removed from the furnace and cooled. For pair-shaped glass substrates, the two glass substrates are separated before reassembly in step 909 (discussed below), reassembled with an interlayer (e.g., the interlayer 230) between the glass substrates, and heated (e.g., the glass substrates and the interlayer are sealed together into a laminate under vacuum), as discussed below with reference to step 911.

[0163] In various aspects, only heat (e.g., by a sag process or a pressing process) is used to bend one glass substrate (e.g., the first glass substrate 200), and a cold forming process is used to bend another glass substrate (e.g., the second glass substrate 220) by pressing the glass substrate at a temperature below the softening temperature of the glass composition (specifically, at a temperature of 200 °C or lower, 100 °C or lower, 50 °C or lower, or at room temperature) to bend it to conform to the already bent glass substrate. The pressure for cold forming one glass substrate against another can be provided by a vacuum, a mechanical press, or one or more clamps. The cold formed glass substrate can be held in conformity with the bent glass substrate via an interlayer and / or mechanically clamped thereto or otherwise coupled.

[0164] After step 901, as Figure 10 shown, the method can proceed to step 903, which includes disposing a porous inorganic layer (e.g., the second porous inorganic layer 250) on one glass substrate (e.g., the first glass substrate 200). In various aspects, the second porous inorganic layer 250 can be disposed by applying a precursor (e.g., a modified glaze) to the second major surface 204 of the first glass substrate 200, the precursor including frit (e.g., glaze) and / or particles of a low CTE additive that can be mixed with a pigment (e.g., ink, colorant, dye). Any suitable technique (e.g., screen printing, spraying, brushing, banding) can be used to dispose the precursor, it being understood that viscosity adjustment (e.g., via addition of water or additional medium) may be required depending on the deposition technique selected. As discussed above, the precursor can be cured by heating at a suitable firing temperature, which can be at least the softening temperature associated with the glaze. Curing the precursor to form the porous inorganic layer can cure the frit into a molten matrix surrounding the low CTE additive component and form a plurality of pores. In various aspects, the glass substrate (e.g., the first glass substrate 200) can be formed as part of step 903, after which the porous inorganic layer is disposed thereon. Alternatively, in various aspects, the glass substrate (e.g., the first glass substrate 200) can be formed and the precursor can be cured to form the porous inorganic layer, both of which can occur simultaneously in step 903. Alternatively, the porous inorganic layer can be disposed on the bent first glass substrate. Similarly, although not shown, the porous inorganic layer can be disposed on the third major surface of the second glass substrate. Additionally, the second glass substrate can be formed either simultaneously with or after the precursor is cured to form the porous inorganic layer. Further, after depositing the porous inorganic layer, one or both of the glass substrates can be chemically strengthened in step 903 (which can also occur after the glass substrates are formed). At the end of step 903, as Figure 10As shown, the second porous inorganic layer 250 includes the inorganic thickness 746 discussed above. In various aspects, the porosity of the second porous inorganic layer 250 can be within one or more of the corresponding ranges discussed above. In various aspects, at the end of step 903, as Figure 10 shown, the second porous inorganic layer 250 adheres to the first glass substrate 200, for example, where a first surface 732 of the second porous inorganic layer 250 contacts a second major surface 204 of the first glass substrate 200.

[0165] After step 901 or step 903, as Figure 10 shown, the method can proceed to step 905, which includes filling a plurality of pores of the second porous inorganic layer 250 with a polymer solution or polymer emulsion 1003. As shown, the polymer solution or polymer emulsion 1003 can be disposed on a second surface 734 of the second porous inorganic layer 250 by brushing with a brush 1001, but roll coating or spraying can also be used. In various aspects, 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 include about 8,000 millipascal-seconds (mPa-s) or less, about 2,000 mPa-s or less, about 1,000 mPa-s or less, about 500 mPa-s or less, about 200 mPa-s or less, about 10 mPa-s or more, about 30 mPa-s or more, about 50 mPa-s or more, about 80 mPa-s or more, or about 100 mPa-s or more, for example, in the range of about 10 mPa-s to about 8,000 mPa-s, about 30 mPa-s to about 2,000 mPa, 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 preceding statement can 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 above in this paragraph can enable the polymer emulsion to form a continuous film on the second porous inorganic layer 250, and the continuous film shown can be disposed in the plurality of pores, for example, after a lamination process (such as step 911 discussed below).

[0166] As used herein, "solution" means a substantially homogeneous mixture of a polymer and a solvent, where the polymer has a non-zero solubility in the solvent. As used herein, "emulsion" is a heterogeneous mixture having at least two distinct phases, e.g., where a droplet phase is dispersed in a second matrix phase. In various aspects, the emulsion can include a solvent in the matrix phase that is immiscible with the polymer in the droplet phase. In various aspects, the solvent for the polymer solution or polymer emulsion can include water, alcohols (e.g., ethanol, methanol, butanol, isopropanol), toluene, ethers (e.g., dipropylene glycol butyl ether), acetates (e.g., ethyl acetate), ketones (e.g., methyl ethyl ketone, acetone, butanone), or combinations thereof. An exemplary aspect of 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).

[0167] The polymer solution or polymer emulsion 1003 includes a polymer within one or more of the materials discussed above for the polymer material 750. The polymer in the polymer emulsion can be a substantially linear polymer. The polymer solution or polymer emulsion 1003 can further include a plasticizer within one or more of the materials discussed above for the plasticizer of the polymer material 750. In various aspects, as Figure 10 shown, the polymer solution of the polymer emulsion 1003 can 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 250. In various aspects, as shown, the thickness 1006 of the polymer solution of the polymer emulsion 1003 can be about 30 μm or less, e.g., within one or more of the ranges discussed above for the polymer thickness 776.

[0168] After step 905, as Figure 11 shown, the method can proceed to step 907, which includes drying the polymer solution of the polymer emulsion 1003 (see Figure 10 ) to form the polymer material 750, including the polymer material 750 disposed within the plurality of pores 760 (see Figure 7)。In various aspects, as shown, the polymer solution of the dried polymer emulsion 1003 can include placing the second porous inorganic layer 250 and the polymer solution of the polymer emulsion 1003 in an oven 1101 maintained at a predetermined temperature for a predetermined period of time. In various aspects, the polymer solution of the polymer emulsion 1003 can be dried at a temperature of about 20 °C or higher, about 30 °C, about 40 °C or higher, about 50 °C or higher, about 80 °C, about 70 °C or lower, about 65 °C or lower, or about 60 °C or lower. In various aspects, the polymer solution of the polymer emulsion 1003 can be dried at a temperature in the range 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 lower can reduce the incidence of air bubbles in the resulting polymer material 750. In various aspects, the polymer solution of the polymer emulsion 1003 can be dried for a period of about 10 minutes or longer, about 20 minutes or longer, about 30 minutes or longer, about 45 minutes or longer, about 1 hour or longer, about 168 hours or shorter, about 24 hours or shorter, about 8 hours or shorter, about 4 hours or shorter, about 2 hours or shorter, or about 1 hour or shorter. In various aspects, no reaction can occur in step 905 such that the polymer material 750 is substantially free of crosslinking points and / or branching points, and the polymer of the polymer material 750 can be substantially the same as the polymer of the polymer solution of the polymer emulsion 1003. In various aspects, the polymer material 750 can include one or more of the plasticizers discussed above, and the plasticizer can be present in an amount within one or more of the corresponding ranges discussed above. In various aspects, the second glass transition temperature of the polymer material 750 can be within one or more of the corresponding ranges discussed above.

[0169] In various aspects, as Figure 11 shown, the polymer material 750 (including portion 770) can be present in (e.g., in a plurality of pores) a first portion 782 but not in (e.g., in a plurality of pores) a second portion 784. As discussed above, in various 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 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.

[0170] After step 907, as Figure 12As shown, the method can proceed to step 909, which includes disposing the interlayer 230 or 430 on the porous inorganic layer (e.g., the first porous inorganic layer 240, the second porous inorganic layer 250). In various aspects, as shown, for example due to the thickness of the porous inorganic layer, a gap 1202 or 1204 can be formed between the interlayer 230 or 430 and the first glass substrate 200 or the second glass substrate 220, respectively. In various aspects, as indicated by reference numerals 448a and 448b, the interlayer 430 can be non-uniform, where the dashed lines marked with reference numerals 448a and 448b indicate the division between different portions of the interlayer 430 having different compositions (e.g., the first portion 431a and / or 431b, the second portion 433 - see Figure 4 ). In a further aspect, the concentration of the plasticizer can be different between these portions (e.g., the concentration of the plasticizer in the second portion 433 is higher than the concentration of the plasticizer in the first portion 431a and / or 431b). In a further aspect, the polymer in the first portion can be different from the polymer in the second portion (e.g., the second portion 433 can include or consist of PVB, while the first portion 431a and / or 431b can include PET or other suitable materials having a relatively high Tg). Alternatively, in a further aspect, the interlayer can include a first interlayer, a second interlayer, and an additional polymer layer disposed therebetween (see Figure 6 ). In a further aspect, wiring or electronic devices can be disposed 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 Figures 5-6 ). In various aspects, the first glass transition temperature of the interlayer can be lower than the second glass transition temperature of the polymer material 750 (see Figure 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 higher than the concentration of the plasticizer in the interlayer. In a further aspect, the polymer of the interlayer can be the same as or different from the polymer of the polymer material.

[0171] After step 909, as Figure 13 shown, the method can proceed to step 911, which includes laminating the first glass substrate 200 to 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 the interlayer 230 or 430 are disposed between the first glass substrate and the second glass substrate.

[0172] In various aspects, as Figure 13As shown, the first surface region 1319 of the first release liner 1317 may be disposed above and / or in contact with the first major surface 202 of the first glass substrate 200. In a further aspect, the third surface 1315 of the first support member 1311 may be disposed above and / or in contact with the first release liner 1317. In aspects, as shown, the first surface region 1329 of the second release liner 1327 may be disposed above and / or in contact with the fourth major surface 224 of the second glass substrate 220. In a further aspect, the third surface 1323 of the second support member 1321 may be disposed above and / or in contact with the second release liner 1327. In aspects, as shown, the method may include placing the assembly in a vacuum container 1303 (e.g., an OBSJ / ABSJ vacuum bag available from Simtech). In aspects, the first support member 1311 and / or the second support member 1321 may include a modulus of elasticity of about 3 GPa or greater, and / or may include a glass-based material and / or a ceramic-based material. Providing one or more release liners may reduce (e.g., prevent) adhesion of the glass article to non-desired materials during the method and may reduce damage to the laminate during processing. Providing one or more support members may reduce deformation (e.g., warping) of the substrate and / or film during processing. Providing a vacuum container may protect the glass article from contamination during processing.

[0173] In aspects, step 911 may further include heating the film and / or reducing the pressure of the chamber 1301 in which the assembly is disposed (e.g., relative to 101.325 kPa). Providing a reduced pressure may remove dissolved gases and / or gases between components of the assembly. In aspects, step 911 includes (e.g., in addition to the aspects previously discussed) heating the assembly to a temperature above the glass transition temperature (and / or melting temperature, if semi-crystalline) of the interlayer 230, which may be done at an elevated pressure (e.g., relative to 101.325 kPa) in the chamber 1301.

[0174] After step 911, the method may proceed to step 913, which includes assembling the glass articles 130, 300, 400, 500, 600, or 1400. It should be understood that the articles may be incorporated into any of the articles or applications discussed above. For example, a glass article may be attached to an automobile by attaching the glass article to the outer periphery of an opening in the automobile using an adhesive.

[0175] After step 911 or step 913, it may be completed at step 915 according to Figure 9The method of manufacturing a glass article of the present disclosure in the flowchart. In various aspects, when irradiated with a D65 illuminant, the glass article may include a first portion 782 in which a polymer material 750 is disposed in a plurality of pores of the first porous inorganic layer 240 and a second portion 784 in which the plurality of pores are not filled with the polymer material 750 (see Figure 7 ), the absolute value of the difference in the maximum ΔE, L* value, the absolute value of the difference in a* value, and / or the absolute value of the difference in b* value therebetween, which may be within one or more of the corresponding ranges discussed above. In various aspects, the integral visible light transmittance of the first portion 294a or 294b of the glass article including the porous inorganic layer may be within one or more of the corresponding ranges discussed above. In various aspects, the method of manufacturing a glass article according to an aspect of the present disclosure may be carried out sequentially along the steps 901, 903, 905, 907, 909, 911, and 913 in the flowchart in Figure 9 , as discussed above. In various aspects, for example, if the porous inorganic layer has adhered to the glass substrate at the end of step 901, arrow 902 may be followed from step 901 to step 905. In various aspects, for example, if the method is completed at the end of step 911, arrow 904 may be followed from step 911 to step 915. Any of the above options may be combined to manufacture a coated article according to an aspect of the present disclosure.

[0176] Examples

[0177] The various aspects will be further illustrated by the following examples. Examples A - C and Comparative Examples AA - BB include borosilicate glass substrates (i.e., a composition of 83.60 mol% SiO2, about 1.20 mol% Al2O3, about 11.60 mol% B2O3, about 3.00 mol% Na2O, and about 0.70 mol% K2O), which have a CTE of 32×10 -7 K -1 and a thickness of 3.8 mm. A porous inorganic layer with 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.

[0178] For Examples A - D, a polymer solution is formed by dissolving plasticized PVB (RF41, available from Saflex) at 14 wt% in ethanol. For Example A, a 100 - μm - thick poly(ethylene terephthalate) (PET) sheet is immersed in the PET polymer solution and then applied to the porous inorganic layer. For Example B, the polymer solution is brush - coated on the porous inorganic layer, and then a 100 - μm - thick PET sheet is applied thereon.

[0179] Comparative example AA involved placing a 100-μm thick PET sheet on a porous inorganic layer without a polymer. Comparative example BB involved placing a pre-formed plasticized PVB (RF41, commercially available from Shoufuxin) film on the porous inorganic layer and then pressing a 100-μm PET sheet into the plasticized PVB film.

[0180] The appearance of Examples A - B and Comparative examples AA - BB was evaluated on 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 boundary at the outer periphery of the PET sheet. It is believed that applying a polymer solution to cover the edges can remove this lighter boundary.

[0181] For Example C, the polymer solution was brushed onto a large area of the porous inorganic layer, and a 100-μm thick PET sheet was applied to the first part of the porous inorganic layer, leaving a second part coated with the polymer solution without PET. A 0.76-mm thick plasticized PVB (RF41, commercially available from Shoufuxin) sheet was placed on the porous inorganic layer, and a second glass substrate containing an aluminosilicate glass composition and having a thickness of 0.7 mm was applied thereon. The assembly was laminated together in an autoclave to produce a glass article. The autoclave treatment involved heating the assembly under vacuum at 110 °C for 45 minutes, followed by heating at 140 °C under an applied pressure of 1.3 MPa (gauge pressure). Comparative example BB was prepared in the same manner as Example C but without using the polymer solution.

[0182] The color of the part of the glass article containing PET (Part 1) appeared to be almost indistinguishable from the part of the glass article comprising the polymer material formed from the polymer solution but without PET (Part 2). Table 1 presents the CIE color space coordinates for these parts of Example C. As shown, the absolute value of the difference in CIE L* values was 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 was 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 was less than about 1, less than about 0.5, and less than about 0.3 (i.e., about 0.12). Thus, ΔE (e.g., maximum ΔE) was about 0.37, which was less than about 2.0, less than about 1.0, and less than about 0.5. This low ΔE value was consistent with the parts of Example C appearing to be almost indistinguishable. In contrast, Comparative example BB appeared light gray (similar to Comparative example A).

[0183] Table 1: CIE color space coordinates of Example C

[0184] Part L* a* b* 1 10.82 -0.91 -1.22 2 10.50 -0.76 -1.34

[0185] The above observations can be combined to provide a glass article that includes a porous inorganic layer, where a polymeric material is disposed within a plurality of pores of the porous inorganic layer. Providing a polymeric material having a low glass transition temperature (e.g., about 85 °C or lower) can enable the polymeric material to be easily disposed within (e.g., fill) the plurality of pores of the porous inorganic layer. Providing a polymeric material having a glass transition temperature of about 40 °C or higher can reduce property variations of the polymeric material within the temperature range typically encountered during use of the glass article. Providing a polymeric material having a thickness of about 30 μm or less outside of the plurality of pores can reduce the visibility of the polymeric material in portions of the glass article that do not have the porous inorganic layer, which can simplify manufacturing because slightly misaligned or overapplied polymeric material precursors may not need to be removed (e.g., cleaned) from the glass substrate. Providing a polymeric thickness of about 1 μm or greater outside of the plurality of pores can provide sufficient polymeric material such that the polymeric material can also be disposed within the plurality of pores of the porous inorganic layer. Disposing the polymeric material within the plurality of pores can provide a substantially uniform appearance having a predetermined color. Additionally, the glass article can exhibit a low maximum ΔE value between portions of the glass article having the polymeric material within the plurality of pores of the porous inorganic layer and portions of the glass article not having the polymeric material, thereby providing a substantially uniform color associated with the porous inorganic layer that may not be visually perceptible to an observer.

[0186] When incorporated into a laminate, the porous inorganic layer can act as a decorative layer having a predetermined color appearance. It has been found that the porosity prevents the porous inorganic layer from reducing the mechanical strength of the glass substrate. 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 that occurs during the manufacture of the decorated glass article, thereby reducing or preventing the formation and propagation of defects. The porosity can also help the porous inorganic layer to have a predetermined color appearance when incorporated into a laminate. For example, a glass substrate having a porous inorganic layer is attached to another glass substrate using an interlayer. As discussed below, the polymeric material can fill the 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.

[0187] Providing a porous inorganic layer on the inner surface of a glass article can be used to protect these layers from mechanical degradation and / or oxidation. Additionally, the placement of the porous inorganic layer can also help to hide any additional components (e.g., conductive elements associated with a defogging system) embedded between a first glass substrate 200 and a second glass substrate 220. Further, when the first and second glass substrates are made of glasses having different compositions and / or thicknesses, multiple bands of the porous inorganic layer can provide a predetermined aesthetic appearance. In various aspects, the porous inorganic layer will have the dual function of providing an attractive appearance and acting as a shield against visible and ultraviolet (UV) light. Additionally, the glass article can include additional functions, e.g., including an infrared reflective coating and / or an anti-reflective coating.

[0188] As described herein, configuring the porous inorganic layer to have a CTE approximately equal to the CTE of the first glass substrate can prevent the formation of cracks in the porous inorganic layer during the manufacture of the glass article and also prevent the incorporation 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 comprise a borosilicate glass composition, which can be particularly beneficial as the exterior of an automotive glazing because borosilicate glass can have greater thermal shock resistance than the soda-lime silicate glass currently used as the outer glass substrate in automotive glazings and is more resistant to crack formation from impact events caused by road debris (e.g., stones, etc.). Such glasses have been found to exhibit favorable ring cracking behavior, thereby preventing the radial propagation of flaws from the point of impact. Such fusion-formed glasses can also exhibit superior chemical durability, scratch resistance, mechanical strength, and optical properties (e.g., in terms of optical transmission and optical distortion) compared to other borosilicate glasses.

[0189] Providing a polymeric material separate from the interlayer can enable the interlayer (or portions thereof) to have different compositions and / or properties. For example, the concentration of plasticizer in the polymeric material can be higher than the concentration of plasticizer in the interlayer (or portions thereof), and / or even when the polymer in the polymeric material is the same as the polymer in the interlayer, the polymeric material can have a lower glass transition temperature than the interlayer (or portions thereof). Providing at least a portion of the interlayer that is free of plasticizer (or has a reduced amount relative to the polymeric material) can reduce the incidence of damage (e.g., corrosion) to any wiring or electronic devices that can be disposed therein. Additionally, providing at least a portion of the interlayer that is free of plasticizer (or has a reduced amount relative to the polymeric material) can reduce optical distortion and / or haze that can interfere with the operation of an optical device (e.g., a camera) disposed within the interlayer or configured to view an object through a second portion of the glass article (e.g., a camera disposed within an automobile and configured to view the surrounding environment outside the automobile).

[0190] In addition, a polymeric material can be provided by drying a polymer solution or a polymer emulsion. Providing a polymer solution or a polymer emulsion having a low viscosity (e.g., about 8,000 millipascal-seconds or lower) can enable the polymer solution or polymer emulsion 1003 to flow into the plurality of pores of the porous inorganic layer. The polymeric material can be formed by drying the polymer solution or the polymer emulsion without any reaction (e.g., crosslinking or polymerization). Thus, the polymer in the polymer solution or polymer emulsion can be substantially the same as the polymer in the polymeric material. The limited processing involved in processing the polymeric material can simplify the processing and / or reduce the cost.

[0191] As used herein, directional terms such as up, down, right, left, front, back, top, bottom are made only with reference to the drawings as drawn and are not intended to imply absolute orientation.

[0192] It should be understood that the various disclosed aspects may involve features, elements, or steps described in connection with the aspects. It should also be understood that although features, elements, or steps are described with respect to one aspect, they may be interchanged or combined with alternative aspects in various unillustrated combinations or arrangements.

[0193] It should also be understood that as used herein, the terms "the", "a", or "an" mean "at least one" and are not to be limited to "only one" unless expressly indicated to the contrary. For example, unless the context clearly indicates otherwise, a reference to "a component" includes aspects having two or more such components. Similarly, "a plurality" is intended to mean "more than one".

[0194] As used herein, the term "about" means that the quantity, size, formulation, parameter, and other quantities and characteristics are not exact and need not be exact, but may be approximate and / or larger or smaller as desired, reflecting tolerances, conversion factors, rounding, measurement errors, and other factors known to those of ordinary skill in the art. In this document, ranges may be expressed as from "about" a particular value and / or to "about" another particular value. When expressing such ranges, the aspects include from one particular value and / or to another particular value. Similarly, when a value is expressed as an approximation by use of the antecedent "about", it should be understood that the particular value forms another aspect. Whether or not the numerical or range endpoint in the specification is recited with "about", the numerical or range endpoint is intended to include two aspects: one modified by "about" and one not modified by "about". It should also be understood that each endpoint of a range is significant relative to the other endpoint and independent of the other endpoint.

[0195] As used herein, the terms "substantially", "essentially" and variations thereof are intended to indicate that the described feature is equal to or approximately equal to a certain value or description. For example, a "substantially flat" surface is intended to mean a flat or approximately flat surface. Further, as defined above, "substantially similar" is intended to mean that two values are equal or approximately equal. In all respects, "substantially similar" may represent values that differ from each other by within about 10%, such as values that differ from each other by within about 5%, or values that differ from each other by within about 2%.

[0196] Unless otherwise expressly stated, no method set forth herein is intended to be construed as requiring that its steps be performed in a particular order. Accordingly, where method claim limitations do not actually recite an order to be followed by its steps or where no particular order is otherwise specifically set forth in the claims or descriptions, no particular order is intended to be inferred.

[0197] The transitional phrase "comprising" can be used to disclose the various features, elements or steps of a particular aspect, but it should be understood that alternative aspects are implied therein, including those aspects that can be described using the transitional phrases "consisting of" or "consisting essentially of". Thus, for example, the implied alternative aspects of an apparatus comprising A + B + C include the aspect where the apparatus consists of A + B + C and the aspect where the apparatus consists essentially of A + B + C. As used herein, unless otherwise specified, the terms "comprising" and "including" and variations thereof shall be construed as synonymous and open-ended.

[0198] The above aspects and features of these aspects are exemplary and may be provided alone or in any combination with any one or more features of other aspects provided herein, without departing from the scope of the present disclosure.

[0199] It will be apparent to those skilled in the art that various modifications and changes can be made to the present disclosure without departing from the spirit and scope of the present disclosure. Accordingly, it is intended that the present disclosure cover modifications and changes to the aspects herein, provided that they are within the scope of the appended claims and their equivalents.

Claims

1. A glass article, 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 the first major surface; A second glass substrate, the second glass substrate including a second substrate thickness defined between a third major surface and a fourth major surface opposite the third major surface; An interlayer disposed between the second major surface and the third major surface; A porous inorganic layer including a plurality of pores and adhered to the second major surface or the third major surface; And A polymer material disposed within the plurality of pores, wherein a first glass transition temperature of the interlayer is about 10 °C or higher than a second glass transition temperature of the polymer material.

2. The glass article according to claim 1, wherein the first glass transition temperature of the interlayer is about 15 °C to about 30 °C higher than the second glass transition temperature of the polymeric material.

3. The glass article according to any one of claims 1 to 2, wherein when irradiated from the first major surface with a D65 illuminant, the maximum ΔE value between a first portion of the glass article and a second portion of the glass article including the porous inorganic layer is about 2.0 or less, in the first portion, the polymeric material is disposed within the plurality of pores of the porous inorganic layer, and in the second portion, the porous inorganic layer is not filled with the polymeric material.

4. A glass article, 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 the first major surface; A second glass substrate, the second glass substrate including a second substrate thickness defined between a third major surface and a fourth major surface opposite the third major surface; An interlayer disposed between the second major surface and the third major surface; A porous inorganic layer including a plurality of pores and adhered to the second major surface or the third major surface; And A polymer material disposed within the plurality of pores, wherein the polymer material is different in composition from the interlayer, wherein when irradiated from the first major surface with a D65 illuminant, a maximum ΔE value between a first portion of the glass article and a second portion of the glass article including the porous inorganic layer is about 2.0 or less, in the first portion, the polymer material is disposed within the plurality of pores of the porous inorganic layer, and in the second portion, the porous inorganic layer is not filled with the polymer material.

5. The glass article according to any one of claims 3 to 4, wherein the maximum ΔE value is about 0.1 to about 1.

0.

6. The glass article according to any one of claims 3 to 5, 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 1 or less.

7. The glass article according to 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.

8. The glass article according to any one of claims 3 to 7, wherein the absolute value of the difference between the CIE a* value of the first part and the CIE a* value of the second part is about 0.5 or less.

9. The glass article according to any one of claims 3 to 8, wherein the absolute value of the difference between the CIE b* value of the first part and the CIE b* value of the second part is about 0.5 or less.

10. The glass article according to any one of claims 1 to 9, wherein the polymer of the polymeric material is the same as the polymer of the interlayer.

11. The glass article according to any one of claims 1 to 9, wherein the polymer of the polymeric material is different from the polymer of the interlayer.

12. The glass article according to claim 11, wherein the polymeric material is semi-crystalline and the melting temperature of the polymeric material is about 100 °C or lower.

13. The glass article according to any one of claims 1 to 12, wherein the interlayer comprises poly(vinyl butyral).

14. The glass article according to any one of claims 1 to 13, wherein the absolute value of the difference between the refractive index of the polymeric material and the refractive index of the first glass substrate or the second glass substrate is about 0.05 or less.

15. The glass article according to any one of claims 1 to 14, wherein a part of the glass article comprising the porous inorganic layer surrounds another part of the glass article not having the porous inorganic layer on at least two sides.

16. The glass article according to claim 15, wherein at least a part of the other part of the glass article does not contain the polymeric material, and at least a part of the part of the glass article comprising the porous inorganic layer comprises the polymeric material.

17. The glass article according to any one of claims 15 to 16, wherein the interlayer is non-uniform, wherein at least a part of the interlayer in the other part of the glass article contains a higher concentration of plasticizer than the concentration of plasticizer in the part of the glass article comprising the porous inorganic layer, and the porous inorganic layer comprises the polymeric material.

18. The glass article according to any one of claims 1 to 16, wherein the concentration of plasticizer in the polymeric material is greater than the concentration of plasticizer in the interlayer.

19. The glass article according to any one of claims 1 to 16, wherein the polymeric material contains a plasticizer in an amount of about 25 wt% to about 50 wt% of the polymeric material.

20. The glass article according to any one of claims 1 to 19, wherein in a part of the glass article including the porous inorganic layer, for light with a wavelength of 400 nm to 700 nm perpendicularly incident on the first main surface, the glass article exhibits an integrated visible light transmittance of about 2.0% or less.

21. The glass article according to any one of claims 1 to 20, wherein the polymer material includes a substantially linear polymer.

22. The glass article according to any one of claims 1 to 21, wherein the polymer thickness of the polymer material is about 30 micrometers or less.

23. The glass article according to any one of claims 1 to 22, wherein the polymer material is present on the outer periphery of the glass article, covering the porous inorganic layer.

24. The glass article according to any one of claims 1 to 23, wherein the porous inorganic layer has a porosity of about 10% to about 60% by volume.

25. The glass article according to any one of claims 1 to 24, wherein the thickness of the porous inorganic layer is about 10 micrometers to about 30 micrometers.

26. The glass article according to any one of claims 1 to 25, further comprising a second porous inorganic layer adhered to the third main surface, wherein the porous inorganic layer is adhered to the second main surface, and the polymer material is disposed within the pores of the porous inorganic layer and within the pores of the second porous inorganic layer.

27. The glass article according to any one of claims 1 to 26, further comprising a wiring or an electronic component disposed between the first glass substrate and the second glass substrate.

28. The glass article according to any one of claims 1 to 26, wherein the interlayer includes a first part and a second part, wherein the first part has a composition different from that of the second part, wherein the first part of the interlayer 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.

29. A method of forming a glass article, comprising: filling a plurality of pores of a porous inorganic layer adhered to a first glass substrate with a polymer solution or a polymer emulsion; 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 disposed within the plurality of pores; disposing an interlayer on the porous inorganic layer; and Laminate the first glass substrate to the second glass substrate such that the porous inorganic layer and the interlayer are disposed between the first glass substrate and the second glass substrate.

30. The method according to claim 29, wherein the viscosity of the polymer solution or the polymer emulsion is in the range of about 10 mPa·s to about 8,000 mPa·s.

31. The method according to any one of claims 29 to 30, wherein filling the plurality of pores comprises disposing a layer of the polymer solution or the polymer emulsion, and the layer of the polymer solution or the polymer emulsion has a thickness of about 30 microns or less.

32. The method according to claim 31, wherein the polymer solution or the polymer emulsion is disposed by brushing, roll coating, or spraying.

33. The method according to any one of claims 29 to 32, further comprising covering the outer periphery of the porous inorganic layer with the polymer solution or the polymer emulsion before drying the polymer solution or the polymer emulsion.

34. The method according to any one of claims 29 to 33, wherein the first glass transition temperature of the interlayer is about 10 °C or higher than the second glass transition temperature of the polymer material.

35. The method according to claim 34, wherein the first glass transition temperature of the interlayer is about 15 °C to about 30 °C higher than the second glass transition temperature of the polymer material.

36. The method according to any one of claims 29 to 35, wherein when irradiated from the first major surface with a D65 illuminant, the maximum ΔE value between a first portion of the glass article and a second portion of the glass article is about 2.0 or less, in the first portion, the polymer material is disposed within the plurality of pores of the porous inorganic layer, and in the second portion, the porous inorganic layer is not filled with the polymer material.

37. The method according to claim 36, wherein the maximum ΔE value is about 0.1 to about 1.

0.

38. The method according to any one of claims 36 to 37, 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 1 or less.

39. The method according to any one of claims 36 to 38, wherein the absolute value of the difference between the CIE a* value of the first portion and the CIE a* value of the second portion is about 0.5 or less.

40. The method according to any one of claims 36 to 39, wherein the absolute value of the difference between the CIE b* value of the first part and the CIE b* value of the second part is about 0.5 or less.

41. The method according to any one of claims 29 to 40, wherein the polymer of the polymer material is the same as the polymer of the interlayer.

42. The method according to any one of claims 29 to 41, wherein the polymer of the polymer material is different from the polymer of the interlayer.

43. The method according to claim 42, wherein the polymer material is semi-crystalline and the melting temperature of the polymer material is about 100 °C or lower.

44. The method according to any one of claims 29 to 43, wherein the interlayer comprises poly(vinyl butyral).

45. The method according to any one of claims 29 to 44, wherein the absolute value of the difference between the refractive index of the polymer material and the refractive index of the first glass substrate or the second glass substrate is about 0.05 or less.

46. The method according to any one of claims 29 to 45, wherein a part of the glass article comprising the porous inorganic layer surrounds another part of the glass article not having the porous inorganic layer on at least two sides.

47. The method according to claim 46, wherein at least a part of the other part of the glass article does not contain the polymer material, and at least a part of the part of the glass article comprising the porous inorganic layer comprises the polymer material.

48. The method according to any one of claims 46 to 47, wherein the interlayer is non-uniform, and at least a part of the interlayer in the other part of the glass article contains a lower concentration of plasticizer than the concentration of plasticizer in the part of the glass article comprising the porous inorganic layer, and the porous inorganic layer comprises the polymer material.

49. The method according to any one of claims 29 to 47, wherein the concentration of plasticizer in the polymer material is greater than the concentration of plasticizer in the interlayer.

50. The method according to any one of claims 29 to 47 or 49, wherein the polymer material contains a plasticizer in an amount of about 25 wt% to about 50 wt% of the polymer material.

51. The method according to any one of claims 29 to 50, wherein in a part of the glass article comprising the porous inorganic layer, for light of 400 nm to 700 nm, the glass article exhibits an integrated visible light transmittance of about 2.0% or lower.

52. The method according to any one of claims 29 to 51, wherein the polymeric material comprises a substantially linear polymer.

53. The method according to any one of claims 29 to 52, wherein the porous inorganic layer has a porosity of from about 10% to about 60% by volume.

54. The method according to any one of claims 29 to 53, wherein the inorganic thickness of the porous inorganic layer is from about 10 microns to about 30 microns.

55. The method according to any one of claims 29 to 54, wherein the interlayer comprises a first interlayer and a second interlayer, and the glass article further comprises: an additional polymer layer disposed between the first interlayer and the second interlayer; and wiring or electronic components disposed between the first interlayer and the second interlayer.

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