Glass with unique fracture behavior for vehicle windshield

Abstract

To provide a borosilicate glass composition with unique fracture behavior capable of being fusion formed at relatively large thicknesses and a glass laminate.SOLUTION: A borosilicate glass composition comprises: at least 75 mol% SiO2; at least 10 mol% B2O3; and Al2O3 in an amount such that sum of SiO2, B2O3, and Al2O3 is at least 90 mol%; wherein the borosilicate glass composition comprises a liquidus viscosity of greater than 500 kP; and wherein the borosilicate glass composition comprises a temperature at which a viscosity of the borosilicate glass composition at 1725°C or less is 200 P. The borosilicate glass composition may further comprise about 2 mol% to about 8 mol% Na2O and about 1 mol% to about 4 mol% K2O.SELECTED DRAWING: Figure 6A

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Patent Application No. 63 / 123,863, filed December 10, 2020, U.S. Provisional Patent Application No. 63 / 183,292, filed May 3, 2021, U.S. Provisional Patent Application No. 63 / 183,271, filed May 3, 2021, and U.S. Patent Application No. 17 / 363,266, filed June 30, 2021, each of which is incorporated herein by reference in its entirety. This application is also a divisional application of Japanese Patent Application No. 2023-535683, filed December 6, 2021. [Technical Field]

[0002] The present disclosure relates to glass compositions and glass articles made therefrom, and more particularly to borosilicate glass compositions that can be melt-formed to relatively large thicknesses and glass articles made therefrom. [Background technology]

[0003] Glass is used in windows due to its optical clarity and durability. Automotive and architectural windows can contain a single ply of glass or a laminate including two plies of glass with an interlayer of polymer material disposed between them. Automotive applications, in particular, tend to use laminates to improve fuel economy and / or impact performance. Certain laminate designs may utilize a thicker outer ply of glass and a thinner inner ply of glass. For example, the thicker ply of glass may be soda-lime glass, which is susceptible to thermal shock and cracking upon impact with, for example, stones or other debris thrown from the road. Summary of the Invention [Problem to be solved by the invention]

[0004] Therefore, there is a need for improved glasses for use as the thicker outer glass plies of laminates. [Means for solving the problem]

[0005] According to one aspect, embodiments of the present disclosure relate to borosilicate glass compositions. Unless otherwise specified, glass compositions disclosed herein are described in mole percent (mol%), analyzed on an oxide basis. In one or more embodiments, the borosilicate glass composition comprises at least 74 mol% SiO, at least 10 mol% B0, and an amount of AlO such that the sum of SiO, B0, and AlO is at least 90 mol%. In one or more embodiments, the borosilicate glass composition has a liquidus viscosity greater than 500 kP. In one or more embodiments, the borosilicate glass composition has a temperature at which the viscosity of the borosilicate glass composition is 200 kP, equal to or less than 1725°C.

[0006] According to another aspect, embodiments of the present disclosure relate to a glass ply having a first major surface and a second major surface opposite the first major surface, the glass ply being made from one or more embodiments of the borosilicate glass composition described herein.

[0007] According to yet another aspect, an embodiment of the present disclosure relates to a laminate. The laminate includes a first glass ply according to one or more embodiments of the glass plies described herein. The laminate also includes a second glass ply and an interlayer bonding the first glass ply to the second glass ply.

[0008] According to yet another aspect, embodiments of the present disclosure relate to automotive glass manufactured from a laminate according to the aforementioned laminate.

[0009] According to a further aspect, an embodiment of the present disclosure relates to a vehicle. The vehicle includes a body defining an interior of the vehicle, at least one opening, and the above-described cover glass disposed in the at least one opening. In the vehicle, the second glass ply is disposed facing the interior of the vehicle, and the first glass ply is disposed facing the exterior of the vehicle. In one or more embodiments, the first glass ply is disposed facing the interior of the vehicle, and the second glass ply is disposed facing the exterior of the vehicle.

[0010] According to a further aspect, embodiments of the present disclosure relate to a method of forming a glass ply, the glass ply having a first major surface and a second major surface. In the method, a trough in an isopipe is flooded with at least two streams of a borosilicate glass composition having a liquidus viscosity greater than 500 kP and a temperature below 1725°C at which the viscosity of the glass composition is 200 kP. In one or more embodiments, the borosilicate glass composition comprises at least 74 mol% SiO2 and at least 10 mol% B2O3. Further, in one or more embodiments, the composition comprises a combined amount of SiO2, B2O3, and Al2O3 of at least 90 mol%. In one or more embodiments of the method, the at least two streams of borosilicate glass composition are fused at the root of the isopipe to form a glass ply having a thickness of at least 2 mm between the first and second major surfaces.

[0011] According to yet another aspect, an embodiment of the present disclosure relates to a glass ply. The glass ply has a first major surface and a second major surface opposite the first major surface. The glass ply is made of a borosilicate glass composition. When the glass ply is subjected to a quasi-static indentation load of 2 kgf (approximately 19.6 N) with a Vickers tip, the glass ply exhibits a ring-shaped crack and multiple radial cracks, each radial crack of the multiple radial cracks being bounded by a ring-shaped crack.

[0012] According to yet another aspect, an embodiment of the present disclosure relates to a glass laminate. The glass laminate includes a first glass ply, a second glass ply, and an interlayer. The first glass ply has a first major surface and a second major surface opposite the first major surface. The first glass ply is made of a borosilicate glass composition. The second glass ply has a third major surface and a fourth major surface opposite the third major surface. The interlayer bonds the second major surface of the first glass ply to the third major surface of the second glass ply. The borosilicate glass composition includes at least 74 mol% SiO, at least 10 mol% B, and Al such that the sum of SiO, B, and Al is at least 90 mol%.

[0013] According to a further embodiment, an embodiment of the present disclosure relates to a system including a sensor and a glass laminate. The glass laminate includes a first glass ply having a first major surface and a second major surface opposite the first major surface. The first glass ply is made of a borosilicate glass composition. The glass laminate includes a second glass ply having a third major surface and a fourth major surface opposite the third major surface. An interlayer bonds the second major surface of the first glass ply to the third major surface of the second glass ply. The borosilicate glass composition includes at least 74 mol% SiO2, at least 10 mol% B2O3, and an amount of Al2O3 such that the sum of SiO2, B2O3, and Al2O3 is at least 90 mol%. The sensor is configured to receive, transmit, or both receive and transmit a signal through the glass laminate, the signal having a peak wavelength in the range of 400 nm to 750 nm, or in the range of 1500 nm or greater.

[0014] According to another aspect, an embodiment of the present disclosure relates to a glass laminate. The glass laminate includes a first glass ply having a first major surface and a second major surface opposite the first major surface. The first glass ply is a melt-formed borosilicate glass composition. The glass laminate also includes a second glass ply having a third major surface and a fourth major surface opposite the third major surface. The glass laminate further includes an interlayer bonding the second major surface of the first glass ply to the third major surface of the second glass ply. The transmittance of ultraviolet light having a wavelength in the range of 300 to 380 nm through the glass laminate is 75% or less. The transmittance of light in the visible spectrum through the glass laminate is 73% or more, and the total solar transmittance through the glass laminate is 61% or less.

[0015] According to another aspect, an embodiment of the present disclosure relates to a glass composition comprising SiO in an amount ranging from about 72 mol% to about 80 mol%, AlO in an amount ranging from about 2.5 mol% to about 5 mol%, and BO in an amount ranging from about 11.5 mol% to about 14.5 mol%, wherein the glass composition has a liquidus viscosity greater than 500 kP, and the glass composition has a temperature of 1725°C or less at which the viscosity of the borosilicate glass composition is 200 P.

[0016] According to another aspect, an embodiment of the present disclosure relates to a glass composition comprising 74 mol% to 80 mol% SiO, 2.5 mol% to 5 mol% AlO, 11.5 mol% to 14.5 mol% BO, 4.5 mol% to 8 mol% NaO, 0.5 mol% to 3 mol% KO, 0.5 mol% to 2.5 mol% MgO, and 0 mol% to 4 mol% CaO.

[0017] Additional features and advantages will be set forth in the following detailed description, and in part will be readily apparent to those skilled in the art from that description, or may be learned by practicing the embodiments described herein, including the following detailed description, claims, and accompanying drawings.

[0018] It is to be understood that both the foregoing general description and the following detailed description are merely exemplary and are intended to provide an overview or framework for understanding the nature and character of the claims.

[0019] The accompanying drawings are included to provide a further understanding, and are incorporated in and constitute a part of this specification. The drawings illustrate one or more embodiments and, together with the description, serve to explain the principles and operation of various embodiments. [Brief explanation of the drawings]

[0020] [Figure 1] FIG. 1 illustrates a vehicle including a glazing article or laminate according to one or more embodiments. [Figure 2] 1 is a side view of a glass article according to one or more embodiments. [Figure 3] FIG. 1 is a side view of a laminate including a glass article according to one or more embodiments. [Figure 4] FIG. 1 is a side view of a laminate including a glass article according to one or more embodiments. [Figure 5A] 1 is a photomicrograph of cracks resulting from indentation testing of the disclosed melt-formed borosilicate glass composition, along with associated graphs. [Figure 5B] 1 is a photomicrograph of cracks resulting from indentation testing of a comparative soda-lime glass composition, along with associated graphs. [Figure 5C] 1 is a photomicrograph of cracks resulting from indentation testing of a comparative float-formed borosilicate glass composition, along with associated graphs. [Figure 6A] Thermal Shock Test Results for Disclosed Melt-Formed Borosilicate Glass Compositions [Figure 6B] Thermal Shock Test Results for Comparative Soda-Lime Glass Compositions [Figure 7] FIG. 1 illustrates a melt-forming apparatus for melt-forming glass plies of a borosilicate glass composition, according to an exemplary embodiment. [Figure 8]Graph of solar transmittance for various borosilicate glass compositions according to example embodiments. [Figure 9] FIG. 1 illustrates a system including a sensor configured to transmit and receive signals through a glass laminate having at least one glass ply made from a borosilicate glass composition, according to an exemplary embodiment. [Figure 10] 1 shows a plot of visible, total solar, and ultraviolet transmittance as a function of iron content in glass, according to an example embodiment; [Figure 11] 1 is a plot of visible, total solar, and ultraviolet transmittance as a function of iron content in glass, according to an example embodiment; [Figure 12] FIG. 1 illustrates a plot of visible light transmittance versus total solar transmittance of a glass composition according to an exemplary embodiment. [Figure 13] FIG. 1 illustrates a plot of visible light transmittance versus total solar transmittance of a glass composition according to an exemplary embodiment. [Figure 14] 1 is a digital image of a cross section of a glass article according to an exemplary embodiment. [Figure 15] 1 is a plot of transmission measurements for two exemplary compositions according to an exemplary embodiment. [Figure 16] 1 is a plot of measured retained strength after indentation before and after thermal shock for samples constructed using exemplary compositions described herein, according to exemplary embodiments. [Figure 17A] 10 is an image of a sample constructed according to an exemplary composition described herein having a scratch from a Knoop scratch test, according to an exemplary embodiment. [Figure 17B] 10 is an image of a sample constructed according to a control composition described herein having scratches from a Knoop's scratch test, according to an exemplary embodiment. [Figure 17C] 10 is an image of a sample constructed according to a control composition described herein having scratches from a Knoop's scratch test, according to an exemplary embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0021] Reference will now be made in detail to various embodiments, examples of which are illustrated in the accompanying drawings. Embodiments of the present disclosure relate to borosilicate glass compositions that can be, or have been, melt-formed into glass plies having a thickness of at least 2 mm, and particularly at least 3 mm, at least 3.3 mm, or at least 3.8 mm. In embodiments, the borosilicate glass composition comprises at least 74 mol% SiO, at least 10 mol% B0, and at least some AlO, and in embodiments, the total amount of SiO, B0, and AlO is at least 90 mol%. The borosilicate glass compositions described herein have a liquidus viscosity of at least 500 kilopoise (kP) and a temperature (T) at or below 1725°C where the viscosity reaches 200 poise (kP). 200P ) is shown.

[0022] Moreover, embodiments of the borosilicate glass compositions disclosed herein are particularly suitable for use in laminates for automotive glass applications. In one or more embodiments, the borosilicate glass compositions are used as the outer plies of such laminates. Compared to conventional automotive glass, including soda-lime glass plies, glass plies made from the borosilicate glass compositions of the present disclosure help prevent the formation (initiation) or propagation (propagation) of radial or central cracks, which tend to densify during deformation and compromise the strength of the glass plies. Furthermore, the borosilicate glass compositions disclosed herein are more resistant to thermal shock than soda-lime glass, which also helps prevent crack initiation and propagation. These performance advantages can be useful when the borosilicate glass compositions are used as the inner or outer glass plies of glass laminates. In some cases, these performance advantages are particularly useful when the borosilicate glass compositions are used as the outer glass plies of laminates. These and other aspects and advantages of the borosilicate glass compositions of the present disclosure and articles formed therefrom are described in further detail below. The embodiments discussed herein are offered by way of example and not limitation.

[0023] Embodiments of borosilicate glass compositions are described herein with reference to a vehicle 100 shown in FIG. 1 . The vehicle 100 includes a body 110 defining an interior and at least one opening 120 communicating with the interior. The vehicle 100 further includes a cover glass 130, i.e., a window, disposed in the opening 120. The cover glass comprises at least one ply of the borosilicate glass composition described herein. The cover glass 130 may form at least one of a side light, a windshield, a rear window, a window, and a sunroof of the vehicle 100. In some embodiments, the cover glass 130 may form an interior partition (not shown) within the interior of the vehicle 100, or may be disposed on the exterior of the vehicle to form an engine block cover, a headlight cover, a taillight cover, a door panel cover, or a pillar cover. As used herein, a vehicle includes automobiles (an example of which is shown in FIG. 1 ), railroad cars, locomotives, boats, ships, and airplanes, helicopters, drones, spacecraft, and the like. Furthermore, although this disclosure is framed in terms of vehicles, the borosilicate glass compositions may also be used in other contexts, such as architectural or bullet-resistant glass applications.

[0024] As shown in Figure 2, in embodiments, cover glass 130 includes at least one glass ply 200 that comprises, consists of, or consists essentially of an embodiment of a borosilicate glass composition described herein. In one or more embodiments, cover glass 130 includes only a single glass ply 200 (i.e., a single glass ply is sometimes referred to in the industry as a monolith). As seen in Figure 2, glass ply 200 has a first major surface 202 and a second major surface 204. First major surface 202 is opposite second major surface 204. A minor surface 206 extends around the periphery of glass ply 200 and connects first major surface 202 and second major surface 204. A first thickness 210 is defined between first major surface 202 and second major surface 204. In embodiments, first thickness 210 is at least 0.5 mm, at least 1 mm, at least 2 mm, at least 3 mm, at least 3.3 mm, or at least 3.8 mm.In one or more embodiments, the first thickness is from about 0.1 mm to about 6 mm, 0.2 mm to about 6 mm, 0.3 mm to about 6 mm, 0.4 mm to about 6 mm, 0.5 mm to about 6 mm, 0.6 mm to about 6 mm, 0.7 mm to about 6 mm, 0.8 mm to about 6 mm, 0.9 mm to about 6 mm, 1 mm to about 6 mm, 1.1 mm to about 6 mm, 1.2 mm to about 6 mm, 1.3 mm to about 6 mm, 1.4 mm to about 6 mm, 1.5 mm to about 6 mm, 1.6 mm to about 6 mm, about 1.8 mm to about 6 mm, about 2 mm to about 6 mm, about 2.2 mm to about 6 mm, about 2.4mm to about 6mm, about 2.6mm to about 6mm, about 2.8mm to about 6mm, about 3mm to about 6mm, about 3.1mm to about 6mm, about 3.2mm to about 6mm, about 3.3mm to about 6mm, about 3.4mm to about 6mm, about 3.5mm to about 6mm, about 3.6mm to about 6mm, about 3.7mm to about 6mm, about 3.8mm to about 6mm, about 3.9mm to about 6mm, about 4mm to about 6mm, about 4.2mm to about 6mm, about 4.4mm to about 6mm, about 4.5mm to about 6mm, about 4.6mm to about 6mm, about 4.8mm to about 6mm, about 5mm to about 6mm about 6mm, about 5.2mm to about 6mm, about 5.4mm to about 6mm, about 5.5mm to about 6mm, about 5.6mm to about 6mm, about 5.8mm to about 6mm, about 1.6mm to about 5.8mm, about 1.6mm to about 5.6mm, about 1.6mm to about 5.5mm, about 1.6mm to about 5.4mm, about 1.6mm to about 5.2mm, about 1.6mm to about 5mm, about 1.6mm to about 4.8mm, about 1.6mm to about 4.6mm, about 1.6mm to about 4.4mm, about 1.6mm to about 4.2mm, about 1.6mm to about 4mm, about 1.6mm to about 3.9mm, about 1 0.6mm to about 3.8mm, about 1.6mm to about 3.7mm, about 1.6mm to about 3.6mm, about 1.6mm to about 3.5mm, about 1.6mm to about 3.4mm, about 1.6mm to about 3.3mm, about 1.6mm to about 3.2mm, about 1.6mm to about 3.1mm, about 1.6mm to about 3mm, about 1.6mm to about 2.8mm, about 1.6mm to about 2.6mm, about 1.6mm to about 2.4mm, about 1.6mm to about 2.2mm, about 1.6mm to about 2mm, about 1.6mm to about 1.8mm, about 3mm to about 5mm, or about 3mm to about 4mm.In other embodiments, the glass plies may be thinner than 2 mm or thicker than 6 mm.

[0025] In some embodiments, the glass ply can have a curvature, such as a rounded or tubular shape, such as when a first major surface is on the exterior of the tube and a second major surface is on the interior surface of the tube. In some embodiments, the perimeter of the glass ply is generally linear, while in other embodiments, the perimeter is complex. The first major surface can have openings, slots, holes, ridges, depressions, or other geometric shapes.

[0026] As discussed in more detail below, in one or more embodiments, the glass ply 200 has a liquidus viscosity of at least 500 kP and a T 200P and a melt-formed borosilicate glass composition having the following properties:

[0027] FIG. 3 illustrates an embodiment of a cover glass 130 in which the cover glass 130 is a laminated structure 300 including the glass ply 200 of FIG. 2 as a first glass ply 310. As referenced above, the glass ply 200 can comprise, consist of, or consist essentially of an embodiment of a borosilicate glass composition described herein. In the embodiment illustrated in FIG. 3, the first glass ply 310 is joined to the second glass ply 320 by an interlayer 330. In particular, the second glass ply 320 has a third major surface 332 and a fourth major surface 334. The third major surface 332 is opposite the fourth major surface 334. A non-major surface 336 extends around the periphery of the second glass ply 320 and connects the third major surface 332 and the fourth major surface 334.

[0028] A second thickness 340 is defined between the third major surface 332 and the fourth major surface 334. In embodiments, the second thickness 340 is less than the first thickness 210 of the first ply of glass 310. In embodiments, the second glass thickness is 2 mm or less. In embodiments, the total glass thickness (i.e., first thickness 210 + second thickness 340) is 8 mm or less, 7 mm or less, 6.5 mm or less, 6 mm or less, 5.5 mm or less, or 5 mm or less. In embodiments, the lower limit of the total glass thickness is about 2 mm.

[0029] In an embodiment, the second ply of glass 320 comprises a glass composition that is different from the borosilicate glass composition of the first ply of glass 310. In an embodiment, the second glass composition comprises a soda-lime silicate composition, an aluminosilicate glass composition, an alkali aluminosilicate glass composition, an alkali-containing borosilicate glass composition, an alkali aluminophosphosilicate glass composition, or an alkali aluminoborosilicate glass composition.

[0030] Furthermore, in embodiments, the first glass ply 310 and / or the second glass ply 320 can be strengthened. For example, the first glass ply 310 and / or the second glass ply 320 can be thermally, chemically, and / or mechanically strengthened. In particular, in embodiments, the first glass ply 310 and / or the second glass ply 320 are chemically strengthened by an ion exchange process. In one or more embodiments, the first glass ply 310 and / or the second glass ply 320 are mechanically strengthened by exploiting a mismatch in thermal expansion coefficients between portions of the plies to create a region of compressive stress and a central region exhibiting tensile stress. In some embodiments, the first glass ply 310 and / or the second glass ply 320 can be thermally strengthened by heating the glass plies to a temperature above their glass transition temperature and then quenching. In some embodiments, the second glass ply 320 can be strengthened using various combinations of chemical, mechanical, and thermal strengthening. In one or more embodiments, the second ply of glass 320 is strengthened while the first ply of glass 310 is not strengthened (but may optionally be annealed) and exhibits a surface compressive stress of less than about 3 MPa, or about 2.5 MPa or less, 2 MPa or less, 1.5 MPa or less, 1 MPa or less, or about 0.5 MPa or less.

[0031] In one or more embodiments, the interlayer 330 bonds the second major surface 204 of the first glass ply 310 to the third major surface 332 of the second glass ply 320. In embodiments, the interlayer 330 includes a polymer, such as polyvinyl butyral (PVB), acoustic PVB (APVB), ionomer, ethylene vinyl acetate (EVA), and at least one of thermoplastic polyurethane (TPU), polyester (PE), polyethylene terephthalate (PET), and the like. The thickness of the interlayer can range from about 0.5 mm to about 2.5 mm, particularly from about 0.7 mm to about 1.5 mm. In other embodiments, the thickness can be less than 0.5 mm or greater than 2.5 mm. Furthermore, in embodiments, the interlayer 330 can include multiple polymer layers or films that provide various functions to the laminate structure 300. For example, interlayer 330 can incorporate at least one of display functionality, solar insulation, sound deadening, antennas, anti-glare treatments, or anti-reflection treatments, among others. In certain embodiments, interlayer 330 is modified to provide ultraviolet (UV) absorption, infrared (IR) absorption, IR reflection, sound control / attenuation, adhesion promotion, and tint. Interlayer 330 can be modified with appropriate additives, such as dyes, pigments, dopants, etc., to impart desired properties.

[0032] In one or more embodiments, the first glass ply 310 or the second glass ply 320 can include a functional or decorative coating in addition to, or instead of, the functional or decorative coating of the interlayer 330. In embodiments, the coating is at least one of an infrared-reflective (IRR) coating, a frit, an anti-reflective coating, or a pigmented coating. In an exemplary IRR embodiment, the second major surface 204 of the first glass ply 310 or the third major surface 332 of the second glass ply 320 is coated with an infrared-reflective film and, optionally, one or more layers of a transparent dielectric film. In embodiments, the infrared-reflective film comprises a conductive metal such as silver, gold, or copper that reduces heat transfer through the coated plies 310, 320. In embodiments, an optional dielectric film can be used to prevent reflection of the infrared-reflective film and to control other properties and characteristics of the coating, such as color and durability. In embodiments, the dielectric film comprises an oxide of one or more of zinc, tin, indium, bismuth, and titanium, among others. In an exemplary embodiment, the IRR coating comprises one or two layers of silver, each sandwiched between two layers of transparent dielectric film. In an embodiment, the IRR coating is applied using, for example, physical vapor deposition or chemical vapor deposition, or by lamination.

[0033] In embodiments, one or both of the first glass ply 310 and the second glass ply 320 include a frit. In embodiments, the frit is applied, for example, to the second major surface 204 of the first glass ply 310, the third major surface 332 of the second glass ply 320, and / or the fourth major surface 334 of the second glass ply 320. In embodiments, the frit provides an enhanced adhesive surface for adhesives, such as the interlayer 330 or adhesives bonding the glass 130 to the bonding surface defining the opening 120 in the vehicle body 110. Additionally, in embodiments, the frit provides a decorative border for the glass 130. Furthermore, in embodiments, the frit can be used in addition to the IRR coating described above. In embodiments, the frit is an enamel frit. In other embodiments, the frit is designed to be ion-exchangeable. That is, the frit can be applied to an ion-exchangeable glass prior to undergoing an ion-exchange treatment. Such a frit is configured to allow ion exchange between the glass and a treatment bath. In embodiments, the frit may be Bi-Si-B-alkali, Zn-based Bi, Bi-Zn, Bi, Bi-free or Bi-poor Si-Zn-B-Ti, Si-Bi-Zn-B-alkali, and / or Si-Bi-Ti-B-Zn-alkali, among others. An example of an ion-exchangeable frit containing a colorant is 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% BO3, 1.68 mol% TiO2, 1.60 mol% Na2O, 1.50 mol% Li2O, 0.91 mol% SiO2. 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, 0.018 mol% Nb2O5, 0.006 mol% Cl, and 0.012 mol% SrO.Other examples of ion-exchangeable frits are disclosed in U.S. Pat. No. 9,346,708 (Application No. 13 / 464,493, filed May 4, 2012) and U.S. Patent Application Publication No. 2016 / 0002104 (Application No. 14 / 768,832, filed August 19, 2015), both of which are incorporated herein by reference in their entireties.

[0034] In an embodiment, the second glass ply 320 can be coated with a colorant coating comprising an ink, such as an organic ink. In an embodiment particularly suited to such a colorant coating, the colorant coating is applied to the third major surface 332 of the second glass ply 320 or the fourth major surface 334 of the second glass ply 320, and the second glass ply 320 is cold-formed relative to the first glass ply 310. Advantageously, such a colorant coating can be applied to the second glass ply 320 while the second glass ply 320 is in a flat configuration, and the second glass ply 320 can then be cold-formed into a curved configuration without destroying the colorant coating, e.g., the organic ink coating. In one embodiment, the colorant coating comprises at least one pigment, at least one inorganic filler, and a binder comprising an alkoxysilane-functionalized isocyanurate or an alkoxysilane-functionalized biuret. Examples of such colorant coatings are described in EP 2617690, which is incorporated herein by reference in its entirety. Other suitable colorant coatings and methods of applying the same are disclosed in U.S. Patent Application Publication No. 2020 / 0171800 (Serial No. 16 / 613,010, filed November 12, 2019) and U.S. Patent No. 9,724,727 (Serial No. 14 / 618,398, filed February 10, 2015), both of which are incorporated herein by reference in their entireties.

[0035] In embodiments, the coating is an antireflective coating. In certain embodiments, the antireflective coating is applied to the fourth major surface 334 of the second ply of glass 320. In embodiments, the antireflective coating includes multiple layers of low and high refractive index materials, or low, medium, and high refractive index materials. For example, in embodiments, the antireflective coating includes 2 to 12 layers of alternating low and high refractive index materials, such as silica (low refractive index) and niobia (high refractive index). In another exemplary embodiment, the antireflective coating includes 3 to 12 layers of alternating low, medium, and high refractive index materials, such as silica (low refractive index), alumina (medium refractive index), and niobia (high refractive index). In yet other embodiments, the low refractive index material in the stack can be an ultra-low refractive index material, such as magnesium fluoride or porous silica. Generally, an antireflective coating with more layers in the stack will perform better at higher angles of incidence than an antireflective coating with fewer layers in the stack. For example, at angles of incidence greater than, say, 60°, an antireflective coating stack having four layers will perform better (be less reflective) than an antireflective coating stack having two layers. Furthermore, in embodiments, an antireflective coating stack having an ultra-low refractive index material will perform better (be less reflective) than an antireflective coating stack having a low refractive index material. Other antireflective coatings known in the art may also be suitable for application to stack 300.

[0036] In embodiments, the glass ply 200 or laminate 300 exhibits at least one curvature, including a radius of curvature along at least a first axis ranging from 300 mm to about 10 m. In embodiments, the glass ply 200 or laminate 300 exhibits at least one curvature, including a radius of curvature along a second axis transverse to the first axis, particularly perpendicular to the first axis, ranging from 300 mm to about 10 m. In other embodiments, the glass ply exhibits curvature, but the curvature has a radius of curvature less than 300 μm or greater than 10 m. In some embodiments, the curvature is complex and varies.

[0037] In embodiments, curvature(s) are introduced into glass ply 200 or each glass ply 310, 320 of glass laminate 300 through a thermal process. The thermal process may include a bending process, which uses gravity to shape glass ply 200 or glass plies 310, 320 as it is heated. In the bending process, a glass ply, such as glass ply 200, is placed on a mold having an open interior and heated in a furnace (e.g., a box furnace or annealing furnace), allowing it to gradually bend into the open interior of the mold under the influence of gravity. In one or more embodiments, the thermal process may include a pressing process, which uses a mold to shape glass ply 200 or glass plies 310, 320 as or while it is heated. In some embodiments, two glass plies, such as glass plies 310, 320, are formed together in a "pair-forming" process. In such a process, one glass ply is placed on top of another to form a stack (which may also include an intervening release layer) that is then placed on a mold. In embodiments, to facilitate the pair-forming process, the glass plies 310, 320 used as the inner and / or thinner glass plies can be subjected to a higher pair-forming temperature (10°C) than the outer and / or thicker glass plies 310, 320. 11 Poise temperature).

[0038] In one or more embodiments, the mold may have an open interior for use in the bending process. Both the stack and mold are heated by placing them in a furnace, and the stack is gradually heated to the bending or bending temperature of the glass plies. During this process, the plies are formed together into a curved shape. Advantageously, 10 11 At least some of the viscosity curves of the borosilicate glass compositions of the present disclosure, in poise viscosities, are similar to conventional float-formed borosilicate glass compositions, allowing existing equipment and techniques to be utilized to form the glass ply 200 or plies 310, 320.

[0039] According to an exemplary embodiment, the heating time and temperature are selected to achieve the desired degree of curvature and final shape. The glass ply or plies are then removed from the furnace and allowed to cool. For pair-formed glass plies, the two glass plies are separated and reassembled with an interlayer, such as interlayer 330, between the glass plies and heated, for example under vacuum, to seal the glass plies and interlayer together into a laminate.

[0040] In one or more embodiments, only one glass ply is curved using heat (e.g., by a bending or pressing process), while the other glass ply is curved using a cold-forming process by pressing the glass ply to be curved against the already curved glass ply at a temperature below the softening temperature of the glass composition (particularly, a temperature of 200°C or less, 100°C or less, 50°C or less, or room temperature). The pressure to cold-form the glass ply against the other glass ply can be provided, for example, by vacuum, a mechanical press, or one or more clamps. The cold-formed glass ply can be held to conform to the curved glass ply via an interlayer and / or mechanically clamped or otherwise bonded to the interlayer.

[0041] Figure 4 shows an exemplary embodiment of a curved glass laminate 400. As can be seen in Figure 4, the second major surface 204 of the first glass ply 310 has a first depth of curvature 410, defined as the maximum depth from the plane (dashed line) of the second major surface 204. In embodiments in which the second glass ply 320 is curved, the fourth major surface 334 of the second glass ply 320 has a second depth of curvature 420, defined as the maximum depth from the plane (dashed line) of the fourth major surface 334.

[0042] In embodiments, one or both of the first depth of curvature 410 and the second depth of curvature 420 are approximately 2 mm or greater. The depth of curvature can be defined as the maximum distance a surface is perpendicularly spaced from a plane defined by points on the periphery of the surface. For example, one or both of the first depth of curvature 410 and the second depth of curvature 420 can range from approximately 2 mm to approximately 30 mm. In embodiments, the first depth of curvature 410 and the second depth of curvature 420 are substantially equal to one another. In one or more embodiments, the first depth of curvature 410 is within 10% of the second depth of curvature 420, particularly within 5% of the second depth of curvature 420. For illustrative purposes, the second depth of curvature 420 is approximately 15 mm, and the first depth of curvature 410 is in the range of approximately 13.5 mm to approximately 16.5 mm (or within 10% of the second depth of curvature 420).

[0043] In one or more embodiments, the first curved glass ply 310 and the second curved glass ply 330 include a shape deviation between the first curved glass ply 310 and the second curved glass ply 320 of ±5 mm or less, as measured by an optical three-dimensional scanner, such as an ATOS Triple Scan from GOM GmbH of Braunschweig, Germany. In one or more embodiments, the shape deviation is measured between the second major surface 204 and the third major surface 332, or between the first major surface 202 and the fourth major surface 334. In one or more embodiments, the shape deviation between the first glass ply 310 and the second glass ply 320 is about ±4 mm or less, about ±3 mm or less, about ±2 mm or less, about ±1 mm or less, about ±0.8 mm or less, about ±0.6 mm or less, about ±0.5 mm or less, about ±0.4 mm or less, about ±0.3 mm or less, about ±0.2 mm or less, or about ±0.1 mm or less. As used herein, shape deviation applies to stacked glass plies (i.e., without interlayers) and refers to the maximum deviation from the desired curvature between aligned positions on the second major surface 204 and the third major surface 332 or the first major surface 202 and the fourth major surface 334, respectively.

[0044] In one or more embodiments, one or both of first major surface 202 and fourth major surface 334 exhibit minimal optical distortion. For example, one or both of first major surface 202 and fourth major surface 334 exhibit less than about 400 millidiopters, less than about 300 millidiopters, less than about 250 millidiopters, or less than about 200 millidiopters, as measured with an optical strain detector using transmission optics in accordance with ASTM 1561. A suitable optical strain detector is available from ISRA VISIION AG, Darmstadt, Germany, under the trade name SCREENSCAN-Faultfinder. In one or more embodiments, one or both of first major surface 202 and fourth major surface 334 exhibits about 190 millidiopters or less, about 180 millidiopters or less, about 170 millidiopters or less, about 160 millidiopters or less, about 150 millidiopters or less, about 140 millidiopters or less, about 130 millidiopters or less, about 120 millidiopters or less, about 110 millidiopters or less, about 100 millidiopters or less, about 90 millidiopters or less, about 80 millidiopters or less, about 70 millidiopters or less, about 60 millidiopters or less, or about 50 millidiopters or less. As used herein, optical distortion refers to the maximum optical distortion measured at the respective surface.

[0045] The reduction in optical distortion of the glass ply 200 or plies 310, 320 is believed to be related to both the borosilicate glass compositions disclosed herein and the melt-forming process enabled by the borosilicate glass compositions of the present disclosure. Regarding the forming process, conventional float glass techniques for forming borosilicate glass compositions involve floating molten glass on liquid tin, which inevitably results in glass thicknesses of 6 mm or greater when floated on the tin. To produce thinner thicknesses, the glass is stretched or drawn while floating, which creates thickness variations known as draw lines across the surface of the glass and creates internal stresses. Both draw lines and internal stresses can contribute to optical distortion. By melt-forming the borosilicate glass compositions of the present disclosure, such draw lines and internal stresses are substantially avoided. Furthermore, the outer surfaces of the glass ply 200 or plies 310, 320 do not come into contact with any structure during melt-forming, which also reduces optical distortion. In terms of composition, the borosilicate glasses disclosed herein have a liquidus viscosity of at least 500 kP and a T 200P , thereby enabling the melt forming of glass ply 200 or plies 310, 320. Furthermore, borosilicate glass compositions according to the present disclosure are also believed to reduce refractive index variation across the surface of glass ply 200 or plies 310, 320 compared to conventionally used soda-lime silicate glass compositions. Refractive index variation is also known to cause optical distortion, and therefore, reduced refractive index variation is expected to reduce optical distortion.

[0046] In one or more embodiments, the first or second major surface of the first curved glass ply exhibits low membrane tensile stress. Membrane tensile stress can arise during cooling of the curved plies and laminate. As the glass cools, the major surfaces and edge surfaces (orthogonal to the major surfaces) can develop surface compression that is offset by a central region that exhibits tensile stress. Such stress can become problematic in certain circumstances, at the periphery where edge cooling effects induce stress and bending tools create stress-generating thermal gradients. The low CTE associated with embodiments of the borosilicate glass compositions of the present disclosure minimizes deleterious residual stresses that can develop during the annealing process of hot forming. Such stresses are proportional to the CTE; therefore, lowering the CTE of a borosilicate glass composition also reduces residual stress.

[0047] Bending or forming can introduce additional surface tension near the edges, bringing the central tension region closer to the glass surface. Thus, the membrane tensile stress is the tensile stress measured near the edge (e.g., about 10-25 mm from the edge surface). In one or more embodiments, the membrane tensile stress at the first or second major surface of the first curved glass ply is less than about 7 megapascals (MPa), as measured with an edge stress meter according to ASTM C1279. Examples of such surface stress meters are an edge stress meter or a VRP (both commercially available from Strainoptic Technologies). In one or more embodiments, the membrane tensile stress at the first or second major surface of the first curved glass ply is less than about 6 MPa, less than about 5 MPa, less than about 4 MPa, or less than about 3 MPa. In one or more embodiments, the lower limit of the membrane tensile stress is about 0.01 MPa or about 0.1 MPa. In other embodiments, the membrane tensile stress may be negligibly small (e.g., about 0). As described herein, stress is designated as either compressive or tensile, and the magnitude of such stress is provided as an absolute value.

[0048] In one or more embodiments, the laminate 300, 400 can have a thickness of 10 mm or less, 9 mm or less, 8 mm or less, 7 mm or less, or 6 mm or less, which thickness includes the combined thickness of the first glass ply 310, the second glass ply 320, and the interlayer 330. In various embodiments, the laminate 300, 400 has a thickness in the range of about 1.8 mm to about 10 mm, or in the range of about 1.8 mm to about 9 mm, or in the range of about 1.8 mm to about 8 mm, or in the range of about 1.8 mm to about 7 mm, or in the range of about 1.8 mm to about 6 mm, or in the range of about 1.8 mm to about 5 mm, or in the range of about 2.1 mm to about 10 mm, or in the range of about 2.1 mm to about 9 mm, or in the range of about 2.1 mm to about 8 mm, or in the range of about 2.1 mm to about 7 mm, or in the range of about 2.1 mm to about 6 mm, or in the range of about 2.1 mm to about 5 mm. The laminate may have a thickness in the range of about 2.4 mm to about 10 mm, or about 2.4 mm to about 9 mm, or about 2.4 mm to about 8 mm, or about 2.4 mm to about 7 mm, or about 2.4 mm to about 6 mm, or about 2.4 mm to about 5 mm, or about 3.4 mm to about 10 mm, or about 3.4 mm to about 9 mm, or about 3.4 mm to about 8 mm, or about 3.4 mm to about 7 mm, or about 3.4 mm to about 6 mm, or about 3.4 mm to about 5 mm. In other embodiments, the thickness of the laminate may be less than 1.8 mm or greater than 10 mm.

[0049] In one or more embodiments, the second curved glass ply (or the second glass ply used to form the second curved glass ply) is relatively thin compared to the first curved glass ply (or the first glass ply used to form the first curved glass ply). In other words, the first curved glass ply (or the first glass ply used to form the first curved glass ply) has a thickness that is greater than the second curved glass ply (or the second glass ply used to form the second curved glass ply). In one or more embodiments, the first thickness (or the thickness of the first glass ply used to form the first curved glass ply) is more than twice the second thickness. In one or more embodiments, the first thickness (or the thickness of the first glass ply used to form the first curved glass ply) is in a range of about 1.5 to about 10 times the second thickness (e.g., about 1.75 to about 10 times, about 2 to about 10 times, about 2.25 to about 10 times, about 2.5 to about 10 times, about 2.75 to about 10 times, about 3 to about 10 times, about 3.25 to about 10 times, about 3.5 to about 10 times, about (3.75x to about 10x, about 4x to about 10x, about 1.5x to about 9x, about 1.5x to about 8x, about 1.5x to about 7.5x, about 1.5x to about 7x, about 1.5x to about 6.5x, about 1.5x to about 6x, about 1.5x to about 5.5x, about 1.5x to about 5x, about 1.5x to about 4.5x, about 1.5x to about 4x, about 1.5x to about 3.5x, about 2x to about 7x, about 2.5x to about 6x, about 3x to about 6x). In other embodiments, the plies can be sized differently, with the second ply being thicker or the same thickness as the first ply.

[0050] In one or more embodiments, the second thickness (or the thickness of the second ply of glass used to form the second curved ply of glass) is less than 2.0 mm (e.g., 1.95 mm or less, 1.9 mm or less, 1.85 mm or less, 1.8 mm or less, 1.75 mm or less, 1.7 mm or less, 1.65 mm or less, 1.6 mm or less, 1.55 mm or less, 1.5 mm or less, 1.45 mm or less, 1.4 mm or less, 1.35 mm or less, 1.3 mm or less, 1.25 mm or less). (The thickness may be less than or equal to 1.2 mm, less than or equal to 1.15 mm, less than or equal to 1.1 mm, less than or equal to 1.05 mm, less than or equal to 1 mm, less than or equal to 0.95 mm, less than or equal to 0.9 mm, less than or equal to 0.85 mm, less than or equal to 0.8 mm, less than or equal to 0.75 mm, less than or equal to 0.7 mm, less than or equal to 0.65 mm, less than or equal to 0.6 mm, less than or equal to 0.55 mm, less than or equal to 0.5 mm, less than or equal to 0.45 mm, less than or equal to 0.4 mm, less than or equal to 0.35 mm, less than or equal to 0.3 mm, less than or equal to 0.25 mm, less than or equal to 0.2 mm, less than or equal to 0.15 mm, or less than or equal to about 0.1 mm.) The lower limit of the thickness may be 0.1 mm, 0.2 mm, or 0.3 mm. In some embodiments, the second thickness (or the thickness of the second glass ply used to form the second curved glass ply) is from about 0.1 mm to less than about 2.0 mm, from about 0.1 mm to about 1.9 mm, from about 0.1 mm to about 1.8 mm, from about 0.1 mm to about 1.7 mm, from about 0.1 mm to about 1.6 mm, from about 0.1 mm to about 1.5 mm, from about 0.1 mm to about 1.4 mm, from about 0.1 mm to about 1.3 mm, from about 0.1 mm to about 1.2 mm, from about 0.1 mm to about 1.1 mm, or from about 0.1 mm to about 1.2 mm. mm to about 1 mm, about 0.1 mm to about 0.9 mm, about 0.1 mm to about 0.8 mm, about 0.1 mm to about 0.7 mm, about 0.2 mm to less than about 2.0 mm, about 0.3 mm to less than about 2.0 mm, about 0.4 mm to less than about 2.0 mm, about 0.5 mm to less than about 2.0 mm, about 0.6 mm to less than about 2.0 mm, about 0.7 mm to less than about 2.0 mm, about 0.8 mm to less than about 2.0 mm, about 0.9 mm to less than about 2.0 mm, or about 1.0 mm to about 2.0 mm. In other embodiments, the second ply may be thicker than 2.0 mm or thinner than 0.1 mm, for example, less than 700 μm, less than 500 μm, less than 300 μm, less than 200 μm, less than 100 μm, less than 80 μm, less than 40 μm, and / or at least less than 10 μm.

[0051] In some embodiments, the first thickness (or the thickness of the first ply of glass used to form the first curved ply of glass) is about 2.0 mm or greater. In such embodiments, the first thickness (or the thickness of the first ply of glass used to form the first curved ply of glass) and the second thickness (or the thickness of the second ply of glass used to form the second curved ply of glass) are different from one another. For example, the first thickness (or the thickness of the first glass ply used to form the first curved glass ply) is about 2.0 mm or more, about 2.1 mm or more, about 2.2 mm or more, about 2.3 mm or more, about 2.4 mm or more, about 2.5 mm or more, about 2.6 mm or more, about 2.7 mm or more, about 2.8 mm or more, about 2.9 mm or more, about 3.0 mm or more, about 3.1 mm or more, about 3.2 mm or more, about 3.3 mm or more, 3.4 mm or more, 3.5 mm or more, 3.6 mm or more, 3.7 mm or more, 3.8 mm or more, 3.9 mm or more, 4 mm or more, 4.2 mm or more, 4.4 mm or more, 4.6 mm or more, 4.8 mm or more, 5 mm or more, 5.2 mm or more, 5.4 mm or more, 5.6 mm or more, 5.8 mm or more, or 6 mm or more. In some embodiments, the first thickness (or the thickness of the first glass ply used to form the first curved glass ply) is from about 2.0 mm to about 6 mm, from about 2.1 mm to about 6 mm, from about 2.2 mm to about 6 mm, from about 2.3 mm to about 6 mm, from about 2.4 mm to about 6 mm, from about 2.5 mm to about 6 mm, from about 2.6 mm to about 6 mm, from about 2.8 mm to about 6 mm, from about 3 mm to about 6 mm, from about 3.2 mm to about 6 mm, from about 3.4 mm to about 6 mm, from about 3.6 mm to about 6 mm, from about 3.8 mm to about 6 mm, from about 4 mm to about 6 mm, or from about 2.0 mm to about 6 mm. 2.0 mm to about 4.8 mm, about 2.0 mm to about 4.6 mm, about 2.0 mm to about 4.4 mm, about 2.0 mm to about 4.2 mm, about 2.0 mm to about 4 mm, about 2.0 mm to about 3.8 mm, about 2.0 mm to about 3.6 mm, about 2.0 mm to about 3.4 mm, about 2.0 mm to about 3.2 mm, or about 2.0 mm to about 3 mm.In other embodiments, the first ply may be thicker than 10.0 mm or thinner than 2.0 mm, such as less than 1.5 mm, less than 1.0 mm, less than 700 μm, less than 500 μm, less than 300 μm, less than 200 μm, less than 100 μm, less than 80 μm, less than 40 μm, and / or at least less than 10 μm.

[0052] In one or more specific examples, the first thickness (or the thickness of the first ply of glass used to form the first curved ply of glass) is from about 2.0 mm to about 3.5 mm, and the second thickness (or the thickness of the second ply of glass used to form the second curved ply of glass) is in the range of from about 0.1 mm to less than about 2.0 mm. In embodiments, the ratio of the first thickness to the total thickness of the glass is at least 0.7, or at least 0.75, or at least 0.8, or at least 0.85, or at least 0.9.

[0053] In one or more embodiments, the laminate 300, 400 is substantially free of visual distortion as measured by ASTM C1652 / C1652M. In certain embodiments, the first curved glass ply and / or the second curved glass ply of the laminate are substantially free of wrinkles or distortions visually detectable with the naked eye in accordance with ASTM C1652 / C1652M.

[0054] In one or more embodiments, first major surface 202 or second major surface 204 comprises a surface compressive stress of less than 3 MPa as measured with a surface stress meter, such as a surface stress meter ("FSM") commercially available under the trade name FSM-6000 from Orihara Seisakusho Co., Ltd. (Japan). In some embodiments, the first curved glass ply is not strengthened as described herein (but may optionally be annealed) and exhibits a surface compressive stress of less than about 3 MPa, or about 2.5 MPa or less, 2 MPa or less, 1.5 MPa or less, 1 MPa or less, or about 0.5 MPa or less. In some embodiments, such surface compressive stress ranges are present on both the first major surface and the second major surface.

[0055] In one or more embodiments, the first and second glass plies used to form the first and second curved glass plies are substantially planar before being pair-formed to form the first and second curved glass plies. In some cases, one or both of the first and second glass plies used to form the first and second curved glass plies may have a 3D or 2.5D shape that does not exhibit the desired depth of curvature ultimately formed during the pair-forming process and present in the resulting laminate. Additionally or alternatively, the thickness of one or both of the first curved glass ply (or the first glass ply used to form the first curved glass ply) and the second curved glass ply (or the second glass ply used to form the second curved glass ply) may be constant along one or more dimensions or may vary along one or more dimensions for aesthetic and / or functional reasons. For example, the edges of one or both of the first curved glass ply (or the first glass ply used to form the first curved glass ply) and the second curved glass ply (or the second glass ply used to form the second curved glass ply) may be thicker compared to more central regions of the glass plies.

[0056] The dimensions of the length (e.g., the longest centerline of a surface (e.g., the first major surface)), width (e.g., the longest dimension of the surface perpendicular to the length), and thickness (e.g., the dimensions of the ply perpendicular to the length and width) of the first curved glass ply (or the first glass ply used to form the first curved glass ply) and the second curved glass ply (or the second glass ply used to form the second curved glass ply) can also vary depending on the application or use of the article. In one or more embodiments, the first curved glass ply (or the first glass ply used to form the first curved glass ply) comprises a first length and a first width (the first thickness is perpendicular to both the first length and the first width), and the second curved glass ply (or the second glass ply used to form the second curved glass ply) comprises a second length and a second width perpendicular to the second length (the second thickness is perpendicular to both the second length and the second width). In one or more embodiments, either or both of the first length and the first width is about 0.25 meters (m) or greater. For example, the first length and / or the second length can be in the range of about 1 m to about 3 m, about 1.2 m to about 3 m, about 1.4 m to about 3 m, about 1.5 m to about 3 m, about 1.6 m to about 3 m, about 1.8 m to about 3 m, about 2 m to about 3 m, about 1 m to about 2.8 m, about 1 m to about 2.8 m, about 1 m to about 2.8 m, about 1 m to about 2.8 m, about 1 m to about 2.6 m, about 1 m to about 2.5 m, about 1 m to about 2.4 m, about 1 m to about 2.2 m, about 1 m to about 2 m, about 1 m to about 1.8 m, about 1 m to about 1.6 m, about 1 m to about 1.5 m, about 1.2 m to about 1.8 m, or about 1.4 m to about 1.6 m. In some embodiments, the surface dimension from perimeter to perimeter through the center of gravity of each surface (e.g., first surface, second surface, monolith major surface, ply surface) is at least 1 mm, at least 1 cm, at least 10 cm, at least 1 m, and / or no more than 10 m, such that contained spalling will not cause failure of the respective ply. In other embodiments, the plies may be of other sizes.

[0057] For example, the first width and / or the second width can be in the range of about 0.5 m to about 2 m, about 0.6 m to about 2 m, about 0.8 m to about 2 m, about 1 m to about 2 m, about 1.2 m to about 2 m, about 1.4 m to about 2 m, about 1.5 m to about 2 m, about 0.5 m to about 1.8 m, about 0.5 m to about 1.6 m, about 0.5 m to about 1.5 m, about 0.5 m to about 1.4 m, about 0.5 m to about 1.2 m, about 0.5 m to about 1 m, about 0.5 m to about 0.8 m, about 0.75 m to about 1.5 m, about 0.75 m to about 1.25 m, or about 0.8 m to about 1.2 m. In other embodiments, the plies may be of other sizes.

[0058] In one or more embodiments, the second length is within 5% of the first length (e.g., about 5% or less, about 4% or less, about 3% or less, or about 2% or less). For example, if the first length is 1.5 m, the second length can be in the range of about 1.425 m to about 1.575 m and still be within 5% of the first length. In one or more embodiments, the second width is within 5% of the first width (e.g., about 5% or less, about 4% or less, about 3% or less, or about 2% or less). For example, if the first width is 1 m, the second width can be in the range of about 1.05 m to about 0.95 m and still be within 5% of the first width.

[0059] Having described the glass plies, their laminated structures, and their uses, the borosilicate glass composition will now be described in more detail. In embodiments, the borosilicate glass composition comprises at least 74 mol% SiO, at least 10 mol% B0, and at least some AlO. In particular embodiments, the borosilicate glass composition comprises at least 0.03 mol% iron oxide (e.g., Fe0 or FeO). In more particular embodiments, the SiO, Al0, and B0 comprise at least 90 mol% of the borosilicate glass composition. Furthermore, the borosilicate glass composition has a liquidus viscosity of at least 500 kilopoise (kP) and a temperature (T) at or below 1725°C where the viscosity reaches 200 poise (kP). 200P ) and

[0060] In embodiments, the borosilicate glass composition comprises SiO in an amount ranging from at least about 72 mol%, more specifically from about 72 mol% to about 80 mol%, and particularly from 74 mol% to 80 mol%. For example, the borosilicate glass composition may contain SiO in an amount ranging from about 72 mol% to about 85 mol%, from about 73 mol% to about 85 mol%, from about 74 mol% to about 85 mol%, from about 75 mol% to about 85 mol%, from about 76 mol% to about 85 mol%, from about 77 mol% to about 85 mol%, from about 78 mol% to about 85 mol%, from about 79 mol% to about 85 mol%, from about 80 mol% to about 85 mol%, from about 81 mol% to about 85 mol%, from about 82 mol% to about 85 mol%, or from about 83 mol% to about 85 mol%. mol%, from about 84 mol% to about 85 mol%, from about 74 mol% to about 84 mol%, from about 74 mol% to about 84 mol%, from about 74 mol% to about 83 mol%, from about 74 mol% to about 82 mol%, from about 74 mol% to about 81 mol%, from about 74 mol% to about 80 mol%, from about 74 mol% to about 79 mol%, from about 74 mol% to about 78 mol%, from about 74 mol% to about 77 mol%, from about 74 mol% to about 76 mol%, and all ranges and subranges therebetween. In other embodiments, the glass may have less than 74 mol% SiO.

[0061] In embodiments, the borosilicate glass composition includes B2O3 in an amount ranging from about 10 mol% to about 16 mol%, particularly from about 11.5 mol% to about 14.5 mol%. In various embodiments, the borosilicate glass composition includes B2O3 in an amount ranging from about 10 mol% to about 16 mol%, from about 11 mol% to about 16 mol%, from about 12 mol% to about 16 mol%, from about 13 mol% to about 16 mol%, from about 14 mol% to about 16 mol%, from about 15 mol% to about 16 mol%, from about 11 mol% to about 15 mol%, from about 11 mol% to about 14 mol%, from about 11 mol% to about 13 mol%, from about 11 mol% to about 12 mol%, from about 12 mol% to about 13 mol%, from about 12 mol% to about 14 mol%, from about 14 mol% to about 15 mol%, or any ranges and subranges therebetween. In other embodiments, the glass may have less than 10 mol % B2O3 or more than 16 mol % B2O3.

[0062] In embodiments, the borosilicate glass composition includes Al2O3 in an amount ranging from about 2 mol% to about 6 mol%, particularly from about 2.5 mol% to about 5 mol%. In various embodiments, the borosilicate glass composition includes Al2O3 in an amount ranging from about 2 mol% to about 6 mol%, from about 3 mol% to about 6 mol%, from about 4 mol% to about 6 mol%, from about 5 mol% to about 6 mol%, from about 3 mol% to about 5 mol%, from about 3 mol% to about 4 mol%, from about 4 mol% to about 5 mol%, or any range and subrange therebetween. Advantageously, Al2O3 present in these amounts helps prevent phase separation of the borosilicate glass composition. In other embodiments, the glass can have less than 2 mol% Al2O3 or more than 6 mol% Al2O3.

[0063] In embodiments, the borosilicate glass composition includes NaO in an amount ranging from about 3 mol% to about 8 mol%, particularly from about 4.5 mol% to about 8 mol%. In various embodiments, the borosilicate glass composition includes NaO in an amount ranging from about 3 mol% to about 8 mol%, from about 4 mol% to about 8 mol%, from about 5 mol% to about 8 mol%, from about 6 mol% to about 8 mol%, from about 7 mol% to about 8 mol%, from about 3 mol% to about 7 mol%, from about 4 mol% to about 7 mol%, from about 5 mol% to about 7 mol%, from about 6 mol% to about 7 mol%, from about 4 mol% to about 6 mol%, from about 5 mol% to about 6 mol%, or any range and subrange therebetween. In other embodiments, the glass can have less than 3 mol% NaO or more than 8 mol% NaO.

[0064] In embodiments, the borosilicate glass composition includes KO in an amount ranging from about 0.5 mol% to about 5 mol%, particularly from about 0.5 mol% to about 3 mol%. In various embodiments, the borosilicate glass composition includes KO in an amount ranging from about 0.5 mol% to about 5 mol%, from about 0.6 mol% to about 5 mol%, from about 0.7 mol% to about 5 mol%, from about 0.8 mol% to about 5 mol%, from about 0.9 mol% to about 5 mol%, from about 1 mol% to about 5 mol%, from about 2 mol% to about 5 mol%, from about 3 mol% to about 5 mol%, from about 4 mol% to about 5 mol%, from about 2 mol% to about 4 mol%, from 3 mol% to 4 mol%, or any range and subrange therebetween. In other embodiments, the glass may have less than 0.8 mol% KO or more than 5 mol% KO.

[0065] The presence of Na2O and K2O affects the liquidus viscosity. Thus, in embodiments, at least one of Na2O or K2O is present in an amount of at least 4 mol%. In embodiments, the combined amount of Na2O and K2O is present in an amount of at least 5.5 mol% when other alkaline earth oxides (e.g., CaO or MgO) are present in an amount of at least 1.5 mol%. In other embodiments, the combined amount of Na2O and K2O is present in an amount of at least 8 mol%, regardless of the alkaline earth oxide. In certain cases, K2O and Na2O tend to lower the liquidus temperature, thereby increasing the viscosity of the liquid. Furthermore, the combination of B2O3 with Al2O3, K2O, and Na2O tends to increase the liquidus viscosity.

[0066] In embodiments, the ratio of K2O to Na2O is from about 0.1 to about 0.75. In embodiments, the ratio of K2O to Na2O is from about 0.15 to about 0.75, from about 0.20 to about 0.75, from about 0.25 to about 0.75, from about 0.30 to about 0.75, from about 0.35 to about 0.75, from about 0.40 to about 0.75, from about 0.45 to about 0.75, from about 0.50 to about 0.75, from about 0.55 to about 0.75, from about 0.60 to about 0.75, from about 0.65 to about 0.7 0.5, about 0.70 to about 0.75, about 0.1 to about 0.70, about 0.1 to about 0.65, about 0.1 to about 0.60, about 0.1 to about 0.55, about 0.1 to about 0.50, about 0.1 to about 0.45, about 0.1 to about 0.40, about 0.1 to about 0.35, about 0.1 to about 0.30, about 0.1 to about 0.25, about 0.1 to about 0.20, or about 0.1 to about 0.15.

[0067] In embodiments, the borosilicate glass composition includes P2O5 in an amount ranging from 0 mol% to about 4 mol%, from about 1 mol% to about 4 mol%, from about 2 mol% to about 4 mol%, from about 3 mol% to about 4 mol%, from about 1 mol% to about 3 mol%, from about 2 mol% to about 3 mol%, from about 1 mol% to about 2 mol%, or any range or subrange therebetween. P2O5 tends to decrease the density of the borosilicate glass composition, which can result in increased densification during deformation, as described below. Furthermore, it is believed that P2O5 may increase the liquidus viscosity.

[0068] In embodiments, the borosilicate glass composition includes CaO in an amount ranging from 0 mol% to about 5 mol%, 0 mol% to about 4 mol%, 0 mol% to about 3 mol%, 0 mol% to about 2 mol%, 0 mol% to about 1 mol%, about 1 mol% to about 5 mol%, about 2 mol% to about 5 mol%, about 3 mol% to about 5 mol%, about 4 mol% to about 5 mol%, about 2 mol% to about 4 mol%, about 2 mol% to about 3 mol%, about 3 mol% to about 4 mol%, and all ranges and subranges therebetween.

[0069] In embodiments, the borosilicate glass composition includes MgO in an amount ranging from 0 mol% to about 5 mol%, particularly from 0.5 mol% to 2.5 mol%. In various embodiments, the borosilicate glass composition includes MgO in an amount ranging from 0 mol% to about 5 mol%, 0 mol% to about 4 mol%, 0 mol% to about 3 mol%, 0 mol% to about 2 mol%, 0 mol% to about 1 mol%, about 1 mol% to about 5 mol%, about 2 mol% to about 5 mol%, about 3 mol% to about 5 mol%, about 4 mol% to about 5 mol%, about 2 mol% to about 4 mol%, about 2 mol% to about 3 mol%, about 3 mol% to about 4 mol%, and all ranges and subranges therebetween.

[0070] In an embodiment, the total amount of CaO and MgO is at most 5 mol %. In an embodiment, the total amount of CaO and MgO is at least 1.5 mol %, where the total amount of KO and NaO is less than 7 mol %. Alkaline earth oxides such as CaO and MgO tend to lower the liquidus temperature and increase the liquidus viscosity.

[0071] In embodiments, the borosilicate glass composition includes SnO in an amount up to about 0.25 mol%, in an amount ranging from 0 mol% to about 0.25 mol%, from about 0.05 mol% to about 0.25 mol%, from about 0.10 mol% to about 0.25 mol%, from about 0.15 mol% to about 0.25 mol%, from about 0.20 mol% to about 0.25 mol%, from about 0.05 mol% to about 0.20 mol%, from about 0.05 mol% to about 0.15 mol%, from about 0.05 mol% to about 0.10 mol%, from about 0.10 mol% to about 0.15 mol%, from about 0.10 mol% to about 0.20 mol%, from about 0.15 mol% to about 0.20 mol%, or all ranges and subranges therebetween. In some embodiments, SnO2 may be replaced with another fining agent, such as a polyvalent or other oxygen absorber, including antimony, arsenic, iron, cerium, and the like.

[0072] In embodiments, the borosilicate glass composition includes one or more iron compounds, for example, in the form of iron(III) oxide (FeO) or iron(II) oxide (FeO; e.g., provided from an iron oxalate (CFeO) source), particularly to absorb infrared radiation from sunlight. In embodiments, the borosilicate glass composition includes the iron compound in an amount up to about 0.50 mol %, particularly in the range of about 0.20 to about 0.40 mol %. In embodiments, the borosilicate glass composition includes an iron compound in an amount ranging from about 0.03 mol% to about 0.50 mol%, from about 0.10 mol% to about 0.50 mol%, from about 0.15 mol% to about 0.50 mol%, from about 0.20 mol% to about 0.50 mol%, from about 0.25 mol% to about 0.50 mol%, from about 0.30 mol% to about 0.50 mol%, from about 0.35 mol% to about 0.50 mol%, from about 0.40 mol% to about 0.50 mol%, from about 0.45 mol% to about 0.50 mol%, or any range or subrange therebetween. In other embodiments, other modifiers, such as TiO, can be used in addition to or in place of the iron compound to reduce the transmission of ultraviolet radiation. In embodiments, TiO can be provided in an amount of from about 0.04 mol% to about 0.12 mol%.

[0073] In embodiments, the glass composition (or glass article formed therefrom) exhibits a liquidus viscosity of at least 500 kilopoise (kP) and up to 50,000 kP. Advantageously, glass compositions having a liquidus viscosity greater than 1000 kP are less susceptible to sagging warpage during the fusion draw. As used herein, the term "liquidus viscosity" refers to the viscosity of molten glass at its liquidus temperature, where the term "liquidus temperature" refers to the temperature at which crystals first appear as the molten glass cools from its melting point (or the temperature at which the last crystals melt as the temperature increases from room temperature).

[0074] Borosilicate glass compositions described herein having a liquidus viscosity of at least 500 kP can be melt-formed to thicknesses of at least 2 mm, at least 3 mm, at least 3.3 mm, or at least 3.8 mm. In some embodiments, the melt-formed glass plies are substantially free of the draw lines present in typical float-formed glass articles. Liquidus viscosity is determined by the following method. First, the first liquidus temperature of the glass is measured in accordance with ASTM C829-81(2015) entitled "Standard Practice for Measurement of Liquidus Temperature of Glass by the Gradient Furnace Method." Next, the viscosity of the glass at the liquidus temperature is measured in accordance with ASTM C965-96(2012) entitled "Standard Practice for Measuring Viscosity of Glass Above the Softening Point."

[0075] In embodiments, the borosilicate glass composition exhibits a strain point temperature in the range of about 480°C to about 560°C, about 490°C to about 560°C, about 500°C to about 560°C, about 510°C to about 560°C, about 520°C to about 560°C, about 530°C to about 560°C, about 540°C to about 560°C, about 550°C to about 560°C, about 480°C to about 550°C, about 480°C to about 540°C, about 480°C to about 530°C, about 480°C to about 520°C, about 480°C to about 510°C, about 480°C to about 500°C, or any range or subrange therebetween. In embodiments, the strain point temperature is determined using the beam bending viscosity method of ASTM C598-93(2013). In embodiments, the strain point is determined when the viscosity is 10 14.68 It is defined as the temperature at which the viscosity becomes poise.

[0076] In embodiments, the borosilicate glass composition exhibits an annealing point temperature in the range of about 520°C to about 590°C, about 530°C to about 590°C, about 540°C to about 590°C, about 550°C to about 590°C, about 560°C to about 590°C, about 570°C to about 590°C, about 580°C to about 590°C, about 520°C to about 580°C, about 520°C to about 570°C, about 520°C to about 560°C, about 520°C to about 550°C, about 520°C to about 540°C, about 520°C to about 530°C, or any range or subrange therebetween. The annealing point is determined using the beam bending viscosity method of ASTM C598-93(2013). In embodiments, the annealing point is determined when the viscosity is 10 13.18 It is defined as the temperature at which the viscosity becomes poise.

[0077] In embodiments, the glass composition has a viscosity at temperature (T) of about 200 poise, measured by a Fulcher fit to high temperature viscosity (HTV) data (i.e., all temperature measurements from 100 kP to 100 poise), up to 1725°C. 200P For example, the glass composition may have a melting point of about 1500°C to about 1725°C, about 1525°C to about 1725°C, about 1550°C to about 1725°C, about 1575°C to about 1725°C, about 1600°C to about 1725°C, about 1625°C to about 1725°C, about 1650°C to about 1725°C, about 1675°C to about 1725°C, about 1700°C to about 1725°C , about 1500°C to about 1700°C, about 1500°C to about 1675°C, about 1500°C to about 1650°C, about 1500°C to about 1625°C, about 1500°C to about 1600°C, about 1500°C to about 1575°C, about 1500°C to about 1550°C, about 1500°C to about 1525°C, or any range or subrange therebetween. 200P It can be shown that:

[0078] In one or more embodiments, the glass composition or glass article formed therefrom has a viscosity of 2.4 g / cm 3 In an embodiment, the density at 20°C is less than 2.39 g / cm 3 Below, 2.38g / cm 3 Below, 2.37g / cm 3Below, 2.36g / cm 3 Below 2.35g / cm 3 Below, 2.34g / cm 3 Below, 2.33g / cm 3 Below, 2.32g / cm 3 Below, 2.31g / cm 3 Below 2.30g / cm 3 Below, 2.29g / cm 3 Below, 2.28g / cm 3 Below, 2.27g / cm 3 Below, 2.26g / cm 3 Below 2.25g / cm 3 Below, 2.24g / cm 3 Below, 2.23g / cm 3 Below, 2.22g / cm 3 Below, 2.21g / cm 3 or less, or 2.20 g / cm 3 In an embodiment, the density is determined by the buoyancy method of ASTM C693-93(2013). Advantageously, it is 2.4 g / cm 3 The density is less than that of soda lime glass conventionally used in automotive glass laminates.

[0079] As mentioned, borosilicate glass compositions according to the present disclosure can be melt-formed. The resulting glass plies can be described as melt-formed. FIG. 7 shows an exemplary embodiment of an apparatus 700 for melt-forming glass plies from borosilicate glass compositions. The melt-forming apparatus 700 includes an isopipe 702 defined by a trough 704, a first forming surface 706, and a second forming surface 708. The first forming surface 706 and the second forming surface 708 slope inwardly below the trough 704 and meet at a root 710 of the isopipe 702. A borosilicate glass composition 712 of the present disclosure is fed into the trough 704 in a molten state, and the borosilicate glass composition 712 overflows the trough 704, forming two streams that flow down the forming surfaces 706, 708. The molten glass streams meet at the root 710 to form a glass ply 714, which is cooled and severed from the flowing stream.

[0080] In an embodiment, fusion-forming apparatus 700 includes a second isopipe 716 having a second trough 718, a third shaping surface 720, and a fourth shaping surface 722. A glass composition 724, having the same or a different composition as borosilicate glass composition 712, is provided in a molten state to second trough 718 and overflows second trough 718. The molten glass composition 724 flows down third and fourth shaping surfaces 720, 722, where it flows outwardly around borosilicate glass composition 712. In this manner, glass composition 724 flows down first and second shaping surfaces 706, 708 outside the flow of borosilicate glass composition 712. At root 710 of isopipe 702, the combination of the flow of borosilicate glass composition 7122 and the flow of glass composition 7242 produces glass ply 714 having cladding layers 726a, 726b. Such cladding layers can mechanically strengthen the glass based on residual stresses generated due to different thermal expansion coefficients between the compositions 712, 724, or the cladding layers can be chemically strengthened, such as by ion exchange treatment. The cladding layers 726a, 726b can also provide other characteristics, such as specific optical properties, to the glass ply 714 formed in this manner.

[0081] The melt-forming process offers the advantage that, because the two glass streams flowing up the channel are fused together, neither outer surface of the resulting glass article comes into contact with any part of the equipment. Thus, the surface properties of the melt-drawn glass article are not affected by such contact. In embodiments, the melt-formed borosilicate glass compositions of the present disclosure exhibit optical distortion of 75 millidiopters or less, as measured with an optical distortion detector using transmission optics according to ASTM 1561. Liquidus viscosities of less than 500 kP and T values ​​greater than 1725°C are also advantageous. 200P Conventional borosilicate glass compositions having temperatures above 2 mm cannot be melt-formed to thicknesses of 2 mm or greater using the fusion draw process; instead, conventional borosilicate glass compositions of such thickness have typically been formed using the float process. [Example]

[0082] Various embodiments of melt-formable borosilicate glass compositions are shown in the table below.

[0083] [Table 1]

[0084] Examples 1-6 are exemplary glass compositions according to one or more embodiments of the present disclosure. As can be seen from Table 1, the liquidus viscosities of these glass compositions are well above the 500 kP required for melt forming of the glass compositions. Furthermore, the T 200P is well below 1725°C. Also advantageously, these glasses have a melting point of 2.4 g / cm 3 Conventional laminates have a density of less than 2.4 g / cm 3 Thus, in addition to the enhanced mechanical properties discussed below, the melt-formable borosilicate glass compositions of the present disclosure utilize a thick outer glass ply of soda-lime glass exceeding 2.4 g / cm 3 Less than 2.35 g / cm 3 The resulting glass plies also have improved thermal properties, such as a low temperature coefficient of thermal expansion (LTCTE), determined by measuring the expansion of the glass at temperatures between 0°C and 300°C. In embodiments, the LTCTE is 5.6 ppm / °C or less, specifically 5.3 ppm / °C or less, and more specifically 5.1 ppm / °C or less. In addition to the properties described herein, Table 1 also includes information regarding strain point temperature, annealing point temperature, high temperature CTE (HTCTE), Young's modulus, and Poisson's ratio.

[0085] Table 2 below provides additional exemplary compositions according to the present disclosure.

[0086] [Table 2]

[0087] Again, Table 2 shows that Examples 7-9 of the melt-formable borosilicate glass compositions of the present disclosure exhibit the properties necessary for melt-forming to thicknesses greater than 2 mm. Furthermore, the properties of the borosilicate glass compositions, such as density and LTCTE, are superior to those of soda-lime glass. However, as can be seen from Comparative Examples 10 and 11, compositions other than those disclosed herein with respect to melt-formability do not possess the properties necessary for melt-forming to relatively large thicknesses. Comparative Example 10 has a low B2O3 content of 8.47 mol% such that the total amount of SiO2, B2O3, and Al2O3 is less than 90 mol%, and Comparative Example 11 does not contain K2O or MgO, and contains little CaO, which, as discussed above, tend to increase the liquidus viscosity. However, as discussed below, some embodiments may be useful as windshields or other articles due to their fracture behavior, etc., regardless of whether the respective compositions are melt-formable.

[0088] Table 3 below provides further exemplary compositions of borosilicate glass compositions according to the present disclosure.

[0089] [Table 3]

[0090] Examples 12 to 14 and 18 of the borosilicate glass compositions in Table 3 have the liquid viscosity and T required for melt forming. 200P The borosilicate glass compositions of the present disclosure have advantageous properties of density and LTCTE for use as the outer ply of an automotive glass laminate. Furthermore, as can be seen, these examples demonstrate that increasing the amount of B2O3 has the effect of decreasing density. Examples 12-17 each have a density of 2.3 g / cm 3 One particular example has a density of less than 2.250 g / cm 3 Comparative Examples 15 to 17 have a T exceeding 1725°C. 200PThe temperatures shown are for comparison. Compared to Examples 12-14 and 18, Comparative Examples 15-17 have too little alkali oxide and too little alkali and alkaline earth oxide (also referred to as alkaline earth metal oxide) for some of the melt-formability properties disclosed herein, but may have sufficient alkali and alkaline earth metal oxide for other embodiments, such as windshields and other articles having loop cracks, including transverse and radial cracks from a Vickers indenter, as discussed below. In particular, Examples 12-14 and 15 each contain at least 5.5 mol% Na2O+K2O and a total of at least 7.0 mol% Na2O+K2O+MgO+CaO. From the examples in Tables 1-3, it can be seen that embodiments of the present disclosure achieve the T required for melt forming when the total amount of Na2O+K2O+MgO+CaO is at least 7.0 mol%, particularly when at least 5.5 mol% Na2O+K2O and at least 1.5 mol% MgO+CaO are present. 200P Furthermore, embodiments of the present disclosure are believed to exhibit a T required for melt formation when Na2O+K2O is at least 8 mol%, regardless of the amount of MgO and CaO. 200P and liquidus viscosity.

[0091] Table 4 provides additional exemplary compositions of borosilicate glass compositions of the present disclosure further incorporating an iron compound (e.g., as iron(II) oxide or iron(III) oxide) to absorb sunlight, particularly infrared (IR) radiation that can cause vehicle interior temperature increases. Thus, by providing IR absorption, automotive glass comprising a laminate with an outer ply of a borosilicate glass composition of the present disclosure can provide increased fuel efficiency and comfort by reducing heat buildup within the vehicle and strain on the air-cooling system. Table 4 also provides examples of borosilicate glass compositions of Table 4, with the amount of iron (FeO) increasing from 0 mol% to 0.44 mol%, as well as one composition (Example 25) containing primarily iron(II) oxide (FeO) as the primary iron compound. In Example 25, the iron(II) oxide is provided by using iron oxalate (CFeO) as a batch material source. The carbon from the iron oxalate remains as carbon dioxide (CO), leaving primarily iron(II) oxide and some iron(III) oxide in the glass.

[0092] [Table 4]

[0093] Tables 5 and 6 below provide transmittance data for the borosilicate glass compositions of Table 4 for glass plies having thicknesses of 3.3 mm and 2.1 mm, respectively. In embodiments, for a given borosilicate glass composition, the addition of iron compounds serves to reduce visible light (i.e., from about 400 nm to about 750 nm), total solar transmittance, and UV transmittance. All transmittance values ​​were measured at normal incidence. Example 3 had a visible light transmittance (T) of 92.4%, measured in accordance with ISO 13837A (A / 2°). VIS ) and 92.0% total solar transmittance (TTS). By adding an increment of Fe2O3, T VIS As shown in Table 4, the addition of 0.07 mol% (or 0.19 wt%) of Fe2O3 resulted in a stepwise decrease in T VIS The addition of 0.37 mol% (or 0.92 mass%) of Fe2O3 reduces TVIS According to ISO 13837, T VIS The minimum requirement for TTS is 73% for road vehicle glazing. Figure 8 provides a graph of the transmittance for Examples 3, 19-24. As can be seen, the addition of Fe2O3 reduces the overall measured transmittance, with a significant reduction in the transmittance measured between about 750 nm and 1500 nm, which corresponds to the near-infrared spectrum. In embodiments, automotive glazing with a laminate 300, 400 comprising at least one glass ply of the melt-formable borosilicate glass composition of the present disclosure exhibits a TTS of 61% or less and / or a TTS of at least 73%, as measured in accordance with ISO 13837A(A / 2°). VIS In such embodiments, the inventors have determined from previous experience preparing such glasses and laminates that the interlayer and other glass plies have T VIS It is believed that the effect on TTS will be minimal (e.g., a maximum decrease of about 0.5%) and will further decrease TTS by, for example, 3-5%. This is especially true when the melt-formable borosilicate glass plies of the present disclosure are used as the thicker outer plies of laminate glass.

[0094] [Table 5]

[0095] As can be seen from Table 5, increasing the iron content VIS In addition to the decrease in TTS, the UV cutoff wavelength (i.e., the wavelength at which UV transmittance is less than 10%) increases, and the total UV transmittance in the range of 300 to 380 nm decreases. In Example 3, the glass composition contains no iron. The UV cutoff wavelength is less than 300 nm, and the UV transmittance is 85.7%. As the iron content increases from 0 wt % (or 0 mol %) to 0.92 wt % (or 0.37 mol %), the UV cutoff wavelength increases to 365 nm, and the T UV decreases to 6.1%. VISIn addition to the TTS requirements, in laminate 300, 400 embodiments that include at least one glass ply, the melt-formable borosilicate glass compositions of the present disclosure have a T UV Advantageously, reducing the UV transmittance of the laminate can help reduce yellowing of the polymer interlayer. Figure 10 shows the T of Examples 3, 19-23, and 25 as a function of iron content of the single glass ply, based on the data contained in Table 5. VIS , T UV , and TTS plots are shown.

[0096] Table 6 shows the transmittance data for glass plies of the same composition included in Table 5 (with the exception of Example 24, which was not included). However, the thickness of the glass plies was reduced from 3.3 mm to 2.1 mm. As can be seen from Table 6, the UV cutoff wavelength decreased slightly as the ply thickness decreased, resulting in a T UV , T VIS , and TTS, respectively, are increased over the thicker 3.3 mm ply in Table 5. However, Table 6 still shows that T UV , T VIS , and TTS gradually decreases with increasing iron content. Figure 11 shows the TTS as a function of iron content for a single gas ply based on the data contained in Table 6. VIS , T UV Tables 5 and 6 also show plots of the iron(II) oxide derived from the iron oxalate fed to the batches, when considered on a weight percent basis, resulting in UV and solar radiation absorption levels that are equal to or greater than those of iron(III) oxide.

[0097] [Table 6]

[0098] 12 and 13 show the T VIS12 and 13 show graphs plotting TTS against T. As can be seen from Figures 12 and 13, the iron content increases as the plotted points move from the top right to the bottom left, defining a quadratic relationship. VIS The relationship between TTS and TTS is expressed as TTS = 0.0097(T VIS ) 2 -0.6609(T VIS ) + 68.688. In Figure 13, T VIS The relationship between TTS and TTS is expressed as TTS = 0.014(T VIS ) 2 -1.4278(T VIS ) + 103.47. Using iron oxalate as the source of the iron compound in borosilicate glass shifts the curve to the right, resulting in a T of 0.01 for the same level of TTS. VIS is expected to increase.

[0099] In embodiments, the laminates 300, 400 described herein can be used in a system 800 that also includes a sensor 810, as shown in FIG. 9. In particular, the preceding discussion demonstrates that the laminates 300, 400 are transparent to electromagnetic radiation in the visible spectrum, and as shown in FIG. 8, the laminates are also substantially transparent to electromagnetic radiation with wavelengths greater than 1500 nm (e.g., short-wave infrared). Signals carried in electromagnetic radiation in these ranges can be transmitted through the laminates 300, 400. FIG. 9 illustrates a sensor 810 receiving an input signal 820 and transmitting an output signal 830 through the laminates 300, 400. For example, in one or more embodiments, the laminates 300, 400 are included as glass 130 within a vehicle 100, as shown in FIG. 1. In such an embodiment, the sensor 810 is located inside the vehicle 100. In this manner, signals 820, 830 can be transmitted to and from the vehicle 100. In one or more embodiments, the signals 820, 830 have peak wavelengths in the visible light (about 400 nm to about 750 nm) or short-wave infrared spectrum (1500 nm or greater). In embodiments, such signals facilitate automated or semi-automated vehicle operation, public road toll collection, telecommunications, traffic monitoring and control, and vehicle-to-vehicle communications, among other possibilities. One example of a sensor 810 that can be utilized in the system 800 is a LIDAR, which utilizes either or both visible light or short-wave infrared radiation. In embodiments of the laminate 300, 400 that include an IRR coating, the IRR coating can be peeled from a ply applied to an area configured to transmit and receive signals through the laminate 300, 400.

[0100] As noted above, the borosilicate glass compositions of the present disclosure have surprisingly improved deformation characteristics compared to conventional soda-lime glass compositions, and even compared to conventional borosilicate glass compositions. In particular, the inventors have discovered that glass plies formed from the borosilicate glass compositions disclosed herein surprisingly and unexpectedly densify upon deformation, thereby limiting the propagation of radial cracks caused by, for example, rocks and other flying road debris.

[0101] 5A-5C show the formation of cracks produced by quasi-static indentation using a 2 kilogram force (kgf) with a Vickers indentation tip in glass plies made from a borosilicate glass composition of the present disclosure ( FIG. 5A ), a conventional soda-lime silicate glass composition ( FIG. 5B ), and a conventional borosilicate glass composition ( FIG. 5C ). Quasi-static indentation testing using a Vickers tip is believed to provide a good indication of how a windshield will perform when impacted with a projectile such as a stone on its exterior surface.

[0102] In this test, a more conventional borosilicate glass composition for formability contained 83.60 mol% SiO, 1.20 mol% AlO, 11.60 mol% BO, 3.00 mol% NaO, and 0.70 mol% KO. This conventional borosilicate glass composition had a mass of 2.23 g / cm. 3 The glass had a density of 1000 kJ / cm2, a strain point of 518°C, an annealing point of 560°C, an LTCTE of 3.25 ppm / °C, a Young's modulus of 64 GPa, and a Poisson's ratio of 0.2. Thus, compared to embodiments of the borosilicate glass compositions of the present disclosure, conventional borosilicate glass compositions contain less Al2O3, less total alkali content, particularly K2O, and less total alkaline earth content. Such conventional borosilicate glass compositions can be used in situations where a low coefficient of thermal expansion (e.g., 3.3 ppm / °C or less) is desirable. Alkali and alkaline earth oxides tend to increase the coefficient of thermal expansion. Herein, a slight increase in the coefficient of thermal expansion to about 5-6 ppm / °C increases the liquidus viscosity and reduces the T 200P This balances the ability to melt and form the borosilicate glass compositions of the present disclosure at reduced temperatures. Moreover, as described below, the borosilicate glass compositions of the present disclosure have surprising and unexpected effects on the fracture properties of glass plies made from the borosilicate glass compositions.

[0103] As seen in Figures 5A-5C, each glass composition exhibits a radial crack 510 extending outward from the point where the Vickers indenter tip pressed into the respective ply. However, as shown in Figure 5A, glass plies of the borosilicate glass composition of the present disclosure exhibit the formation of a ring crack 520 that bounds the radial crack 510 and prevents its further growth. Notably, because the radial crack 510 is likely (e.g., greater than 50% probability, statistically likely, at least 51% probability, e.g., at least 60% probability, at least 80% probability, out of a sample size of 100) not to intersect (e.g., be interrupted by) the ring crack 520, the radial crack 510 will not continue to propagate radially. Advantageously, limiting the propagation of the radial crack 510 reduces its impact on (strength-reducing) the overall strength of the glass ply.

[0104] The graphs in Figures 5B and 5C show the topography of the crack line segment shown in the micrographs of Figures 5B and 5C. As can be seen in Figure 5B, the radial crack 510 has a valley 530 (deepest subsurface depth) in the center of the graph. In the soda-lime silicate glass of Figure 5B, the structure of the glass results in a relatively small free volume, and the broken glass network shears under sharp contact, causing the surface to pile up to a peak 540. Therefore, the surface around the radial crack 510 is raised, as shown in the micrograph of Figure 5B.

[0105] The conventional borosilicate glass composition of Figure 5C has a relatively larger free volume and a highly connected network within the glass structure than soda-lime silicate glass, which causes it to preferentially densify under sharp contacts. The radial crack 510 still contains a central valley 530 at the center of the graph, but due to volume conservation caused by the densification of the structure (indicated by arrow 550), there is no substantial peak at the edge of the radial crack 510, resulting in high ring stresses and the cluster of ring cracks shown in the micrograph of Figure 5C.

[0106] Returning to FIG. 5A , a contrast can be seen between the conventional borosilicate glass composition in FIG. 5C and the borosilicate glass composition of the present disclosure. The graph in FIG. 5A shows ring crack stress as a function of distance from the indenter's contact circle. In the conventional borosilicate glass composition (represented by curve 560), the ring stress decreases with increasing distance from the contact circle, with the maximum ring crack stress occurring around the contact circle. However, in the borosilicate glass composition of the present disclosure, stress field analysis of the crack in FIGS. 5A and 5C shows that the maximum ring crack stress (represented by asterisk 570) is surprisingly and unexpectedly located away from the periphery of the contact circle. By forming a ring at a distance away from the crack boundary, the borosilicate glass composition of the present disclosure contains the strength-limiting central and radial cracks 510 within the ring crack 520.

[0107] While the Vickers indentation test considers quasi-static loading (i.e., the load is applied slowly enough that the inertial effects of the load are negligible), using the Vickers dart drop test, melt-formed borosilicate glass compositions were found to perform similarly to conventional float-formed borosilicate glass and superior to soda-lime silicate glass when subjected to dynamic loading. In the Vickers dart drop test, a dart with a Vickers indenter tip (136°) and a weight of 8.6 g was dropped from increasing heights (50 mm increments) until a visible crack (i.e., a crack having a length of at least 10 mm) formed in the glass ply. The soda-lime silicate glass exhibited an average height of visible crack formation of less than 600 mm. The borosilicate glasses of the present disclosure exhibited an average height before visible crack formation of greater than 600 mm, particularly greater than 650 mm, which is approximately the height expected from conventional borosilicate glass compositions. The dart drop test is believed to provide an indication of the contact speed and force required to form a radial crack that exceeds the ability of the glass to densify to form a ring crack in the borosilicate glass compositions of the present disclosure.

[0108] As also noted above, glass plies formed from the disclosed borosilicate glass composition are more resistant to thermal shock than soda-lime silicate glass. The effect of thermal shock loading is shown in Figures 6A and 6B. Specifically, test specimens of the disclosed melt-formed glass composition (Figure 6A) and soda-lime glass (Figure 6B) were indented with a Vickers indenter at 2 kgf (approximately 19.6 N), as described above in connection with Figures 5A and 5B. The test specimens were then heated up to 150°C, and a water droplet (25°C ± 5°C) was applied to the indentation site while the specimens were still hot. As seen in Figure 6B, the crack in the soda-lime silicate glass readily propagates during this thermal shock event. In comparison, the crack in the melt-formed borosilicate glass composition remains confined within the ring crack boundary, as shown in Figure 6A. One reason for the resistance to thermal shock is the ring crack boundary, which prevents radial crack propagation. Another reason for the resistance to thermal shock is that the LTCTE of melt-formed borosilicate glass compositions is much lower than that of soda-lime silicate (~5.6 ppm / °C for melt-formable borosilicate glass compositions, compared to 8.0 ppm / °C for soda-lime silicate).

[0109] Unless otherwise expressly stated, it is in no way intended that any method described herein be construed as requiring that its steps be performed in a particular order. Thus, unless a method claim actually recites the order in which its steps should be followed, or the claim or specification specifically states that the steps are to be limited to a particular order, no particular order is intended to be inferred. Additionally, as used herein, the article "a" is intended to include one or more components or elements, and is not intended to be construed to mean only one.

[0110] It will be apparent to those skilled in the art that various modifications and variations can be made without departing from the spirit or scope of the disclosed embodiments. Since modifications, combinations, subcombinations, and variations of the disclosed embodiments that incorporate the spirit and essence of the embodiments may occur to those skilled in the art, the embodiments of the present disclosure should be construed as including everything within the scope of the appended claims and their equivalents.

[0111] According to exemplary embodiments, in furtherance of the information disclosed above, a vehicle windshield or other article may include a first ply (e.g., an outer ply, a glass sheet; see, e.g., first glass ply 310 in FIG. 3 ) including a first major surface (e.g., exterior, front-facing surface) and a second major surface opposite the first major surface, a second ply (e.g., an outer ply, a glass sheet; see, e.g., second glass ply 320) including a third major surface and a fourth major surface opposite the third major surface, and an interlayer (see, e.g., interlayer 330) bonding the second major surface of the first ply to the third major surface of the second ply. In contemplated embodiments, any of the first, second, third, and / or fourth surfaces may be coated with a functional layer, such as, for example, an ultraviolet-reflecting layer, a hydrophobic layer, an adhesion-promoting layer, etc., as disclosed above.

[0112] In some embodiments, the second ply is tempered soda-lime glass. In other embodiments, the second ply is ion-exchanged aluminoborosilicate glass. In yet other embodiments, the second ply is a glass-ceramic. In some embodiments, the interlayer comprises a polymer such as polyvinyl butyral.

[0113] With reference to Tables 1-3, the low temperature thermal expansion coefficient of the compositions disclosed herein can range from greater than 4.4 ppm / °C to less than 6.09 ppm / °C, such as from 4.5 ppm / °C to 6 ppm / °C, 5.8 ppm / °C, and / or 5.6 ppm / °C. As indicated, the LTCTE is obtained by measuring the expansion of the glass at temperatures from 0°C to 300°C, such as by thermomechanical analysis as described in ASTM Test Method E831 (Ref 4). In other contemplated embodiments, glasses having the unique fracture behavior disclosed herein may not have viscosities for melt forming, and the glasses may have lower or higher LTCTEs. In some embodiments, the LTCTE of the compositions disclosed herein is less than 8.7 ppm / °C, which may be associated with soda-lime glass, and / or greater than 3.25 ppm / °C, which may be associated with lower CTE borosilicates. Therefore, the glasses disclosed herein may have lower thermal shock resistance than some low-CTE borosilicates, which may seem counterintuitive. However, applicants have discovered that higher CTEs (e.g., greater than 3.25 ppm / °C) result in higher surface compression after thermal modification. The drawbacks associated with lower thermal shock resistance can be offset by the unique fracture mechanisms of the glasses disclosed herein, discussed further below. As a result, the glasses disclosed herein may have LTCTEs lower than 8.7 ppm / °C, making them more heat resistant than soda lime and potentially offering improved blunt impact performance compared to other borosilicates.

[0114] In some embodiments, the first ply has a thickness of at least 200 μm and no more than 1 cm, and / or a thickness as disclosed above, such as from 0.1 mm to about 6 mm. In other contemplated embodiments, a first ply, single ply, monolith sheet, substrate, or other article of borosilicate glass disclosed herein can have a thickness as disclosed above, or other thicknesses, such as less than 200 μm and / or at least 20 μm, or at least 1 cm and / or less than 1 m, where the thickness may be constant or nearly constant throughout the article (e.g., glass sheet, ply), such as within 100 μm of the average thickness of the respective article, e.g., within 10 μm of the average thickness, or the thickness may vary throughout the article, such as a glass container with a thicker edge or bottom.

[0115] According to exemplary embodiments, the interlayer cushions the first ply against the second ply, thereby mitigating crack propagation therebetween. In contemplated embodiments, the interlayer has a modulus of rigidity that is less than the modulus of rigidity of the glass of the first ply and / or second ply, e.g., less than 0.7, e.g., less than 0.5.

[0116] According to exemplary embodiments, the intermediate layer adheres to the first ply, thereby reducing debris loss due to failure of the first ply. In some embodiments, the intermediate layer directly contacts the first ply. As discussed above, in some embodiments, the intermediate layer adheres to the first ply, the second ply, and / or both, bonding the first and second plies together. According to exemplary embodiments, the second ply strengthens the first ply and stiffens it against bending forces applied thereto. However, in other contemplated embodiments, the first ply may be independent of the second ply or the intermediate layer and may instead be, for example, a monolith.

[0117] According to an exemplary embodiment, the first ply has a curvature such that the second major surface is concavely curved and the second ply has a curvature such that the third major surface is convexly curved to mate with the second major surface, such that the first major surface of the first ply is configured as an exterior-facing surface of a glass, e.g., laminated glass such as a windshield, and is configured to be exterior when installed in a vehicle, as disclosed above.

[0118] According to an exemplary embodiment, the first ply includes a borosilicate glass composition, such as those disclosed herein. With respect to constituent oxides, the borosilicate glass composition of the first glass ply includes (i) SiO, BO, and / or AI2O; and (ii) one or more alkali metal oxides (also referred to as alkali oxides; e.g., LiO, NaO, KO, RbO, CsO) and / or one or more divalent cation oxides (zinc oxide and / or alkaline earth metal oxides, also referred to as alkaline earth oxides, such as MgO, CaO, SrO, BaO).

[0119] According to some embodiments that exhibit the self-terminating crack loop behavior disclosed herein, the mole percent concentrations, on an oxide basis, of SiO, BO, one or more alkali metal oxides, and, if present in the composition, AI2O3 and one or more divalent cation oxides satisfy some (e.g., a combination of one or more) or all of the following relationships: (relationship 1) SiO≥72 mol%, e.g., SiO≥72.0, e.g., SiO≥73.0, e.g., SiO≥74.0, and / or SiO≤92, e.g., SiO≤90; (relationship 2) BO≥10 mol%, e.g., BO≥10.0, e.g., BO≥10.5, and / or BO≤20, e.g., BO≤18; (relationship 3) (RO+RO)≥AI2O, e.g., (RO+RO)≥(AI2O) 3+ 1), for example, (RO+RO)≧(AlO 3+2), and / or (Relationship 4) 0.80≦(1−[(2R2O+2R'O) / (SiO2+2Al2O3+2B2O3)])≦0.93, where R2O is the sum of the concentrations of one or more alkali metal oxides and, if present in a borosilicate glass composition, R'O is the sum of the concentrations of one or more divalent cation oxides. R2O can be, for example, the sum of Li2O, Na2O, KO, Rb2O, and Cs2O, and R'O can be, for example, the sum of MgO, CaO, SrO, BaO, and ZnO.

[0120] The inventive glasses disclosed herein can include additional components. In some embodiments, borosilicate glass compositions can further include P2O5. In particular, when P2O5 is added to a glass, it must be treated as a non-rotatable network former (u or v) considering relationship (4), such as R2O or R'O, where relationships (3) and (4) can be modified such that (R2O + R'O + P2O5) ≥ Al2O3 and 0.80 ≤ (1 - [(2R2O + 2R'O + 2P2O5) / (SiO2 + 2Al2O3 + 2B2O3)]) ≤ 0.93. Other minor chemical components of fining agents, such as SnO2, Sb2O3, and NaCl, can generally be ignored with respect to rotatability and fracture behavior. Other minor chemical components, such as colorants, can be ignored, for example, if their concentration is less than 0.5 mol%.

[0121] Applicants believe that relationships (3) and (4) are relevant to the fracture behavior of the borosilicate glass compositions disclosed herein and can each characterize the "rotatability" aspect of the composition. For compositions of the form SiO2·yAl2O3·zB2O3·uR2O·vR0, x, y, z, u, and v can represent the mole percent or mole fraction of each type of oxide. When (u + v) ≥ y, Applicants believe that the fracture behavior is related to the rotatability parameter (1 - [(2R2O + 2R'O) / (SiO2 + 2Al2O3 + 2B2O3)]). Applicants have found that when the rotatability parameter is between 0.80 and 0.93, Vickers indentation testing produces radial and transverse cracks contained within small (less than 1 mm diameter) crack loops. As a result, glass sheets within this range will not break due to cracks during a Vickers indentation test, and only small, rounded cracks will form that contain other cracks, preventing the cracks from propagating.

[0122] Similarly, applicants believe that density may be related to the fracture behavior of the borosilicate glass compositions disclosed herein. According to an exemplary embodiment, the density of the glass is 2.230 g / cm 3 greater than or equal to 2.397 g / cm 3 less than this range and this cracking behavior has been observed in this range.

[0123] Vickers indentation testing can be used to characterize the fracture behavior of glass, as discussed in Gross et al., Crack-resistant glass with high shear band density, Journal of Non-Crystalline Solids, 494 (2018) 13-20; and Gross, Deformation and cracking behavior of glasses indented with diamond tips of various sharpness, Journal of Non-Crystalline Solids, 358 (2012) 3445-3452, both of which are incorporated herein by reference. In some embodiments, the glass having the borosilicate glass composition of the first glass ply is at least 2 x 2 cm 2At least 10 polished, flat samples (e.g., 2 cm × 2 cm squares) 1 mm thick with a major surface area of ​​1 mm were tested at 25°C and 50% relative humidity using a Vickers indenter with a 136° square pyramid shape with a square base oriented perpendicular to the center of the major surface. When the indenter was quasi-statically displaced at a rate of 60 μm / s up to a maximum load of 3 kgf (approximately 29.4 N) and the indentation load was held for 10 seconds (unless specimen failure by fracture occurred first), in many cases (at least 51 out of 100 tests; at least 6 out of 10 tests), all of the cracks extending radially and / or laterally from the indenter tip through the specimen (i.e., the location where the indenter tip contacted the glass) were intercepted by a self-terminating crack loop (e.g., a ring-shaped crack), thereby limiting specimen failure by the Vickers indenter to the cracks within the loop. Essentially, the indenter crushes the glass beneath it, causing a crack. However, a crack loop forms, halting crack propagation due to indenter contact beyond the crack loop. In contrast, in other glasses, transverse or radial cracks may form prior to and / or pass through such crack loops (e.g., abnormal cracks), or crack loops may not form (e.g., normal cracks), in either case the transverse or radial crack is not contained within the crack loop and may propagate throughout the glass article, causing fracture and failure of the entire article.

[0124] The following Table 100 summarizes the values ​​of the rotatability parameter (1-[(2R2O+2R'O) / (SiO2+2Al2O3+2B2O3)]), density, and Vickers indentation fracture behavior for the various borosilicate glass compositions tested.

[0125] [Table 7]

[0126] In Table 100, for some compositions, the fracture behavior is identified as "contained" rather than "abnormal" or "normal" fracture behavior. Radial and transverse cracks contained within the crack loop (e.g., circular ring cracks) did not propagate beyond the crack loop, even after several hours (e.g., 12, 24, and 72 hours) following indentation testing. Thus, the crack-containing specimens only cracked locally within the crack loop and did not fail beyond the crack loop. As summarized in Table 100, Applicant observed polished flat specimens, ranging from 1 mm to 3.3 mm thick, tested using a square-based, 136° pyramidal Vickers indenter, quasi-statically displaced at a rate of 60 μm / s until failure or until a maximum indentation load of 3 kgf (approximately 29.4 N) was applied for 10 seconds. Furthermore, when the corresponding specimens were rapidly cooled in cold water, evidence of the presence of radial and transverse cracks was found to be that the cracks did not propagate beyond the crack loop, and the specimens observed did not fail outside the crack loop. When the specimens were rapidly cooled, the radial and transverse cracks contained within the crack loop did not propagate beyond the crack loop even after several hours (e.g., 2 hours, 12 hours, 24 hours, and 72 hours) of the indentation test.

[0127] For the composition labeled DUE in Table 100, the crack loops were observed to be in the form of circular rings or ring-shaped cracks (see generally Figures 5A and 6A). When a load of 2 kgf (approximately 19.6 N) was applied, the ring radii ranged from 101 to 136 micrometers. When a load of 3 kgf (approximately 29.4 N) was applied, the ring radii ranged from 119 to 229 micrometers.

[0128] Additionally, for the composition labeled DUE in Table 100, 19 different indentation tests were performed on 1 mm thick samples, with 19 of the 19 tests resulting in a circular ring crack that included radial and lateral cracks from the indenter. Applicants expect similar results in more tests, e.g., at least 90, e.g., at least 95, or at least 98, of the 100 samples.

[0129] Applicants observed that cracking may be delayed in some samples, appearing within approximately two hours after indentation testing. However, the radial and transverse cracks in the DUE samples were contained within the crack loop and did not extend beyond the crack loop even after several hours (e.g., 2, 12, 24, and 72 hours) of indentation testing.

[0130] For compositions labeled DQS in Table 100, 10 different indentation tests were performed on 1 mm thick samples, resulting in 10 of the 10 samples producing a crack loop in the shape of a circular ring crack that included radial and lateral cracks from the indenter. The radial and lateral cracks did not extend beyond the crack loop even after several hours (e.g., 2 hours, 12 hours, 24 hours, 72 hours) of the indentation test. Applicants expect similar results in more tests, e.g., at least 90 out of 100 samples, e.g., at least 95, at least 98.

[0131] When the same DQS composition was tested on 3.3 mm thick specimens, 16 of 20 different tests produced circular ring cracks, including cracks radial and transverse to the indenter. Applicants expect similar results in more tests, e.g., at least 50 out of 100 specimens, e.g., at least 60, or at least 75. Without being bound by any theory, Applicants believe that the reduced incidence in the 3.3 mm specimens may be due to sample inhomogeneity rather than thickness.

[0132] For the samples of the DSX composition in Table 100, 21 different indentation tests were performed on 1 mm thick samples, with 19 producing a circular ring crack that included radial and lateral cracks from the indenter. Applicants expect similar results in more tests, e.g., at least 70 out of 100 samples, e.g., at least 80, or at least 90. These radial and lateral cracks did not propagate beyond the crack loop even after several hours (e.g., 2 hours, 12 hours, 24 hours, 72 hours) of indentation testing.

[0133] As shown in Figure 14, Applicants were able to view a cross section of a borosilicate glass sample as disclosed herein and observe cracking in the sample by fractography. The image shows a regular conical crack below the indentation location, which then appears to change direction and return to the same surface, presumably forming a crack loop. Furthermore, the crack cone continues through the sample to the opposite surface. Applicants believe this is a newly discovered fracture behavior for the glasses and structures of the present disclosure.

[0134] In contemplated embodiments, a glass article (e.g., sheet, ply, film, cover, tube, container) of borosilicate glass disclosed herein includes one or more crack loops having a substantially rounded perimeter, e.g., a circular perimeter, as disclosed above. The crack loops can be particularly small, such as having a cross-sectional dimension along the surface of the glass article of less than 10 mm, e.g., less than 2 mm, e.g., less than 1 mm, e.g., less than 0.7 mm (e.g., as shown in FIG. 6A ), and / or at least 10 μm, e.g., at least 50 μm, e.g., at least 100 μm, e.g., at least 200 μm.

[0135] The thickness of the article, the dimensional uniformity of the article, the loading rate, the composition and microstructure of the borosilicate glass, the support underlying the article, the geometry of the indenter, or other parameters may affect the fracture behavior. For example, applicants have demonstrated different sized crack loops with DUE compositions resulting from different loads, as discussed above.

[0136] As shown in Figure 14, if the cone extends to the opposing surface and the crack loop intersects with the cone, the ring-shaped crack combined with the cone can form a cracked portion of the article that penetrates completely through the article. At least a portion of the cracked portion can have a rounded periphery, such as on the surface of the article. The cracked portion can generally have a conical, hourglass, or other shape. Due to the unique fracture behavior of borosilicate glass disclosed herein, intentional mechanical fracture of the glass article can be used to create holes or other precise shapes, such as surface depressions, where the cone does not penetrate completely through the article. The article can be further processed using etchants, lasers, plasma, heat, etc. to arrest the crack, blunt sharp edges associated with the crack, etc.

[0137] In contemplated embodiments, the article can have at least one crack loop and / or associated structure (e.g., hole), as disclosed above. Alternatively, the article may have multiple crack loops, e.g., at least 10, at least 100, or at least 1000, which can couple with a cone to pass completely through such an article and form a hole when the (broken) glass interior leading up to the crack loop is removed mechanically or by a chemical etchant, etc. Such articles can be useful, for example, as sieves, meshes, panels, substrates, or components of batteries or electronic devices. A line of continuous small crack loops (e.g., a line of perforations) can aid in the controlled separation of sheets or shapes through induced fracture between the loops. Holes formed in the article can allow the article to breathe and / or allow liquids, adhesives, polymers in a fluid state, conductive metals, etc. to pass through the article. The loop cracks can be arranged in one or more patterns on the article. In some contemplated embodiments, for example, with an article (e.g., a sheet) having more than one crack loop, the crack loops may vary in size, for example, with one crack loop having a diameter that is at least 20% larger than another crack loop in the same article.

[0138] Controlled cracking of articles, such as sheets of borosilicate glass, as disclosed herein, may differ from using a laser to crack a glass sheet to form a via or other hole or feature because the crack loops disclosed herein may be a single, continuous crack ring, as opposed to multiple smaller cracks extending in various directions. As demonstrated by the tests disclosed herein, crack loops will be less likely to propagate beyond the loop. In some embodiments, articles containing one or more crack loops or related structures may not require, or may require less, etchants or other means to blunt edges or microcracks.

[0139] That said, some inventive glasses disclosed herein may have conventional fracture behavior, such as, for example, glasses that are borosilicate glasses that can be melt formed but have normal or abnormal cracks in a Vickers indentation test as disclosed herein. Conversely, some inventive glasses disclosed herein may have unique crack loop fracture behavior, such as glasses that are borosilicate glasses but are more difficult to melt form. Still other embodiments have unique fracture behavior and melt formability, which may provide glasses that are particularly advantageous for the outer plies of laminated windshields or other articles disclosed herein.

[0140] U.S. Provisional Patent Application No. 63 / 023518, filed May 12, 2020, U.S. Provisional Patent Application No. 17 / 327870, filed May 24, 2021, U.S. Provisional Patent Application No. 63 / 088525, filed October 7, 2020, U.S. Provisional Patent Application No. 17 / 068272, filed October 12, 2020, U.S. Provisional Patent Application No. 63 / 136381, filed January 12, 2021, U.S. Provisional Patent Application No. 63 / 151210, filed February 19, 2021, U.S. Provisional Patent Application No. 63 / 177536, filed April 21, 2021, and U.S. Provisional Patent Application No. 63 / 209489, filed May 11, 2021, are each incorporated herein by reference in their entirety. U.S. Provisional Patent Application No. 63 / 059105, filed July 30, 2020, is hereby incorporated by reference in its entirety. U.S. Provisional Patent Application No. 63 / 050181, filed July 10, 2020, is hereby incorporated by reference in its entirety.

[0141] In accordance with exemplary embodiments, further examples are provided herein to further facilitate the information disclosed above. Further examples are summarized in Table 200 below.

[0142] [Table 8]

[0143] As shown in Table 200, the composition of Example 26 includes 12 mol% or more of B2O3, Al2O3 in an amount equal to or greater than 3 mol% and equal to or less than 5 mol%, and Na2O in an amount equal to or greater than 4 mol% and equal to or less than 6 mol%, and satisfies relationships (1), (2), (3), and (4) described herein. Thus, the glass constructed according to Example 26 exhibits the favorable fracture behavior described herein and can also be melt-formed to produce glass articles suitable for the applications described herein.

[0144] In embodiments, the glass compositions described herein include Al2O3 and Na2O in amounts that satisfy the following relationship: Na2O > Al2O3 + 1 (e.g., Na2O > Al2O3 + 1.25, Na2O > Al2O3 + 1.5, Na2O > Al2O3 + 1.75, Na2O > Al2O3 + 2.0). In embodiments, the Al2O3 content of the glass compositions described herein is 2.0 mol% or more and 5.0 mol% or less (e.g., 2.5 mol% or more and 5.0 mol% or less, 3.0 mol% or more, or 5 mol% or less). When combined with compositions having 12.0 mol% or more B2O3 (e.g., 13.0 mol% or more B2O3, 14.0 mol% or more B2O3, 15.0 mol% or more B2O3, and 16 mol% or less B2O3), such an Al2O3 content is sufficient to prevent phase separation of the borosilicate glass, yet low enough so that SiO2 and B2O3 become the primary network formers within the glass. At such levels of Al2O3 content, the Na2O content in excess of Al2O3 aids in the dissolution of silica during melting of the glass. In embodiments, the Na2O content in the glass compositions described herein is 6.25 mol% or less (e.g., 6.20 mol% or less, 6.15 mol% or less, 6.10 mol% or less, 6.05 mol% or less, 6.0 mol% or less), as Na2O above this amount may result in an undesirably high CTE of the glass. In such embodiments, the Na2O content is at least 4.0 mol%. In embodiments, when the NaO content meets these criteria, KO, if included, is included in an amount less than NaO, e.g., an amount equal to or greater than 0.8 mol % and equal to or less than 5 mol %, because KO tends to increase the CTE per compositional unit more than NaO. For example, in embodiments, the glass compositions described herein include a ratio of KO to NaO of about 0.1 to about 0.75. Glass compositions meeting the foregoing constraints are suitable for melt forming and can exhibit the characteristic fracture behavior described herein while having a desirably low CTE.

[0145] In embodiments, the glass compositions of the present disclosure comprise 12.0 mol% or more B2O3, 2.0 mol% or more and 5.0 mol% or less Al2O3, or 3.0 mol% or more and 5.0 mol% or less Al2O3, 4.0 mol% or more and 6.25 mol% or less Na2O, and 0.8 mol% or more and 5.0 mol% or less K2O, where Na2O is 1.0 or more Al2O3 and the ratio of the K2O content to the Na2O content is 0.1 or more and 0.75 or less. This set of composition ranges facilitates the production of the glasses described herein that have liquidus viscosities of 500 kP or more and meet the CTE requirements described herein (e.g., LTCTE of 5.1 ppm / °C or less).

[0146] Samples having the composition of Example 26 provided in Table 300 were tested for various properties. In the first set of tests, the samples were subjected to various chemical treatments to determine their chemical durability. As a basis for comparison, two glass samples (2 inches (approximately 5.08 cm) x 2 inches (approximately 5.08 cm)) with different compositions were subjected to the same chemical treatments. Comparative Example 26A was a borosilicate glass containing 83.60 mol% SiO2, 1.20 mol% Al2O3, 11.60 mol% BO3, 3.00 mol% Na2O, and 0.70 mol% KO. Comparative Example 26B was an untinted soda-lime glass. Each sample was immersed in a 5% w / w HCl solution at an elevated temperature of 95°C for 24 hours. A sample of the same composition was immersed in a 5% w / w NaOH solution at an elevated temperature of 95°C for 6 hours. After immersion, the samples were washed and then dried. The light transmittance at 450 nm of each sample was measured. Haze was also measured. The results are shown in Table 300 below.

[0147] As used herein, the terms "transmission haze" and "haze" refer to the percentage of transmitted light that is scattered outside an angular cone of approximately ±2.5°, in accordance with ASTM procedure D1003, entitled "Standard Test Method for Haze and Luminous Transmittance of Transparent Plastics," the entire contents of which are incorporated herein by reference. Unless otherwise noted, all haze measurements reported in this disclosure were obtained with a Hazegard Transmittance Meter (Paul N. Gardner Company). Optically smooth surfaces generally have a transmission haze close to zero.

[0148] [Table 9]

[0149] As shown in Table 300, the sample according to Example 26 described herein showed a denaturation of about 0.010 mg / cm as a result of the acidic chemical treatment in HCl solution. 2 The samples from Example 26 and Comparative Example 26A had relatively low weight loss (of which % was 0.01%) and exhibited favorable optical quality with superior transmittance compared to both Comparative Examples. Basic chemical treatment in NaOH solution resulted in relatively large weight loss in both the samples from Example 26 and Comparative Example 26A. The sample from Comparative Example 26B (soda-lime glass) experienced lower weight loss in the basic solution, but such treatment resulted in increased haze and exhibited poor optical appearance. These results indicate that the compositions described herein may have the chemical durability for use in applications such as various liquid glass containers (e.g., pharmaceutical containers such as vials, syringes, ampoules, and cartridges).

[0150] As shown in Table 200, Example 26 contained 0.1% by weight Fe2O3. The transmission spectrum of a 3.3 mm thick sample was measured for comparison with the results contained in Table 5 herein. FIG. 15 shows a graph of the transmittance measured in accordance with ISO 13837 for a sample from Example 26 as well as another example using 0 mole % Fe2O3 (Example 3 in Table 1 above). As can be seen, the addition of Fe2O3 reduces the overall measured transmittance, particularly in the infrared spectrum (750 nm and above). The UV cutoff wavelength is also greater than 300 nm (approximately 320 nm), suggesting greater UV absorption than the iron-free embodiment, with transmittance greater than 90% across the entire visible spectrum. These results demonstrate that the glasses described herein are suitable for use in windshields, providing protection from solar heat and UV rays while offering favorable transmittance in the visible spectrum. The composition according to Example 26 has relatively high transmittance across the visible spectrum, providing advantageous transparency for use in windshields while blocking both the UV and IR portions of sunlight.

[0151] A 3.3 mm thick sample having the composition according to Example 26 and a 2.1 mm thick sample having the composition according to Example 29 were prepared for optical testing. For each sample, the visible light transmittance (T VIS The transmittance of the film was measured for the total solar transmittance (TTS). The results are shown in Table 400 below.

[0152] [Table 10]

[0153] As shown in Table 400, the samples containing 0.1 wt. % Fe2O3 had visible transmittance values ​​above 90% despite having a greater thickness, while the samples with higher Fe2O3 contents did not. Depending on the visible transmittance requirements, the glass compositions described herein may contain an appropriate amount of iron oxide.

[0154] Referring to FIG. 16, 2 mm thick specimens and the compositions of Example 26 and Control Examples 26a and 26b were subjected to flexural strength tests after indentation with a Vickers indenter before and after inducing thermal shock. The flexural strength tests were performed using a ring-on-ring test in accordance with the ASTM C-1499-03 standard test method for Monotonic Equibiaxial Flexural Strength of Advanced Ceramics at Ambient Temperatures. Specifically, specimens according to Example 26 and Control Examples 26a and 26b described herein were indented with a Vickers indenter at 3 kgf (approximately 29.4 N), as described above in connection with FIGS. 5A and 5B. Ring-on-ring tests were then performed on some specimens immediately after indentation. After indentation, thermal shock was induced on some specimens by heating them on a hot plate at 125°C for 10 minutes. After heating, while the specimens were still hot, a drop of water (25°C ± 5°C) was placed on the indentation site. The cooled specimens were then subjected to ring-on-ring tests to determine the effect of thermal shock on flexural strength.

[0155] As shown in Figure 16, the sample according to Example 26 exhibited a level of strength retention equivalent to that of the sample according to Control Example 26a after being subjected to thermal shock. Similar results would be expected from the ring-on-ring testing procedure. During testing, the ring was centered on the indentation and contacted the glass on the surface opposite the indentation. Due to the alignment of the ring and indentation, the internal fracture behavior (ring cracks with radially extending cracks) exhibited by the glass according to Example 26 is believed to have had minimal impact on the measured retained strength. Given the higher CTE of certain glasses of the present disclosure than conventional borofloat glasses, it is not surprising that thermal shock results in a reduction in flexural strength compared to samples that were not subjected to thermal shock. However, despite the higher LTCTE, the sample according to Example 26 had a level of retained strength equivalent to that of the sample constructed according to Control Example 26a. The sample according to Example 26 had a higher level of retained strength than the sample constructed according to Control Example 26b, indicating that the glasses described herein provide more favorable retained strength and thermal performance than certain existing glass compositions used in existing glass laminates.

[0156] Referring to Figures 17A-17C, samples having compositions according to Example 26 and Control Examples 26a and 26b were subjected to a Knoop scratch test transverse to their surfaces to determine their scratch resistance. A mechanical tester equipped with a Knoop diamond was used to scratch the surfaces of the samples at approximately 23°C and a relative humidity of approximately 50%. The samples were scratched at a rate of 24 mm / min, and the scratch length for each sample was 5.0 mm. Figure 17A shows images of samples having the composition according to Example 26 scratched with loads of 5N and 7N. Figure 17B shows images of samples having the composition according to Control Example 26a scratched with loads of 5N and 7N. Figure 17C shows images of samples having the composition according to Control Example 26b scratched with loads of 5N and 7N. As shown, the samples constructed according to Example 26 exhibited better scratch performance than the controls. When the samples were scratched using a load of 5 N, the scratch lateral crack widths of these samples had a maximum value of 67.7 μm. The samples constructed according to Control Examples 26a and 26b had maximum lateral crack widths of 337.44 μm and 485 μm, respectively. These results demonstrate that the glass compositions described herein can provide beneficial scratch resistance superior to certain glasses currently used in various applications (e.g., automotive glass). In embodiments, glass articles including glass compositions according to the present disclosure can exhibit a maximum lateral crack width of 80 μm or less (e.g., 75 μm or less, 70 μm or less) when scratched with a Knoop diamond at a scratching speed of 24 mm / min.

[0157] As described herein with respect to Figures 3-4, the glass compositions described herein can be used in curved glass articles, such as curved glass laminates. For example, a glass according to the present disclosure can be used as the first glass ply 310 shown in Figures 3-4, while a glass having a different composition (e.g., annealed soda-lime glass, ion-exchanged aluminoborosilicate glass, etc.) can be used as the second glass ply 310. During the manufacture of the curved glass laminate 400 (see Figure 4), for example, the glass plies 310, 320 can be subjected to a co-bending process, in which the glass plies 310, 320 are initially in a flat state but can be heated to an appropriate bending temperature to bend them to the appropriate curvature depth. As used herein, "bending temperature" refers to the temperature at which the viscosity of the glass substrate reaches a temperature above about 10°C. 11 Deflection temperature refers to the temperature at which the viscosity is in poise. Deflection temperature is determined by fitting the Vogel-Fulcher-Tamman (VFT) equation: Log h=A+B / (TC), where T is temperature, A, B, and C are fitting constants, and h is the dynamic viscosity, relative to annealing point data measured using bending beam viscosity (BBV) measurements and softening point data measured by fiber elongation. In embodiments, the glass compositions used in glass plies 310, 320 comprise deflection temperatures that differ from one another by 5°C or more, by about 10°C or more, by about 15°C or more, by about 20°C or more, by about 25°C or more, by about 30°C or more, or by about 35°C or more.

[0158] In embodiments, the glasses described herein (such as those according to the examples described herein) can be melt-hardened at temperatures of 590°C or more and 630°C or less, with a melt-hardening rate of 10 11 The glass has a viscosity in poise. Such viscosity is comparable to certain soda-lime compositions used in glass laminates at the same temperature. As a result, glasses according to the present disclosure are suitable for co-flexing using existing methods and processes to form laminates with the favorable optical distortion and shape conformal performance described herein.

[0159] After heating to an appropriate deflection temperature and deflecting into a desired curved shape, the glass plies 310, 320 may be cooled at an appropriate cooling rate. As a result of the cooling, the surface of the glass ply 310 (which may be formed from a glass composition according to examples described herein) may cool at a faster rate than the central region of the glass ply 310, resulting in compressive stresses extending inward from the surface of the glass ply 310 to a compression depth and tensile stresses in the central region extending inward from the compression depth. Such tensile and compressive stresses are "annealing stresses." In an embodiment, the compression depth into the glass ply 310 due to post-deflection cooling compressive stresses is equal to 0.21 times the thickness 210 of the glass ply 310 (see FIG. 2). The magnitude of the tensile stress induced by post-deflection cooling in such an embodiment can be approximated as:

[0160]

number

[0161] where E is the Young's modulus of the glass ply 310, α is the coefficient of thermal expansion of the glass over the cooling temperature range, t is the thickness of the glass ply 310, R is the cooling rate, K is the thermal diffusivity of the glass, and ν is the Poisson's ratio of the glass. The compressive stress integrated from the compression depth to the surface of the glass ply 26 is -2*σ CT The membrane stress was calculated for glasses constructed according to Example 26 and Controls 26a and 26b described herein. The results are included in Table 500 below.

[0162] [Table 11]

[0163] As shown, the magnitude of the annealed center tension (denoted "CT" in Table 500) and compressive stress (denoted "CS" in Table 500) of Example 26 is between the values ​​of Control Example 26b (soda-lime glass) and Control Example 26a (existing borosilicate glass). The values ​​of CS and CT were calculated at thicknesses of 2.1 mm and 3.8 mm. 2.1 mm is a thickness typically used for the outer ply of automotive glass. As shown, at a thickness of 2.1 mm, the sample constructed according to Example 26 contains an annealed tensile stress of 0.19 MPa, which is greater than the 0.13 MPa achieved with the existing borosilicate glass and less than the 0.52 MPa achieved with the soda-lime glass. At a thickness of 3.8 mm, the sample constructed according to Example 26 contains an annealed tensile stress of 0.62 MPa, which is greater than the 0.42 MPa achieved with the existing borosilicate glass and less than the 1.69 MPa achieved with the soda-lime glass. The annealing stress can be measured using a SCALP device.

[0164] In accordance with exemplary embodiments, and to further the information disclosed above, additional aspects of the exemplary glass compositions described herein will now be described.

[0165] In the following paragraphs, the term "tramp," when used to describe a specific component in a glass composition, refers to a component that is not intentionally added to the glass composition and is present in an amount less than 0.10 mole %. A tramp component may be unintentionally added to a glass composition as an impurity in another component and / or through migration of the tramp component into the composition during processing of the glass composition.

[0166] In the following paragraphs, the terms "free" and "substantially free" are used interchangeably herein and refer to the amount and / or absence of a particular component in a glass composition that is not intentionally added to the glass composition. It is understood that a glass composition may contain trace amounts of a particular component as a contaminant or tramp in an amount less than 0.10 mole %.

[0167] In the following paragraphs, the term "glass former" is used herein to refer to a component that is present alone in a glass composition (i.e., without other components except for tramp) and that is capable of forming a glass when the melt is cooled at a rate of about 300°C / min or less.

[0168] In the following paragraphs, the term "modifier" refers to an oxide of a monovalent or divalent metal, i.e., R2O or R2O, where "R" represents a cation. Modifiers can be added to glass compositions to change the atomic structure of the melt and the resulting glass. In some embodiments, modifiers can change the coordination number of cations present in the glass former (e.g., boron in B2O3), which can lead to the formation of a more polymerized atomic network and, consequently, provide better glass formation.

[0169] In the following paragraphs, the term "rare earth metal" refers to the metals listed in the lanthanide series of the IUPAC periodic table, plus yttrium and scandium. As used herein, the term "rare earth metal oxide" refers to oxides of rare earth metals in various redox states, such as, for example, lanthanum "+3" in La2O3, cerium "+4" in CeO2, and europium "+2" in EuO. In general, the redox state of rare earth metals in oxide glasses can change; specifically, the redox state can change during melting based on the batch composition and / or redox conditions in the furnace in which the glass is melted and / or heat-treated (e.g., annealed). Unless otherwise specified, rare earth metal oxides herein refer to normalized formulas in which the rare earth metal has a redox state of "+3." Therefore, when a rare earth metal with a redox state other than "+3" is added to a glass composition batch, the glass composition is recalculated by adding or removing oxygen to maintain stoichiometry. For example, if CeO2 (cerium in the "+4" redox state) is used as a batch component, the resulting batch composition is recalculated assuming that 2 moles of CeO2 equals 1 mole of Ce2O3, and the resulting batch composition is expressed as Ce2O3. As used herein, "RE" refers to a mixture of CeO2 and CeO3. m O n The term "RE2O3" is used to refer to the total content of rare earth metal oxides in all redox states present, and the term "RE2O3" is used to refer to the total content of rare earth metal oxides in the "+3" redox state, also designated "trivalent equivalent."

[0170] In the formulas used in the following paragraphs, the term "min(A,B)" means the minimum of the values ​​A and B, the term "max(A,B)" means the maximum of the quantities A and B, where "A" and "B" can be any quantities (concentration of a component, property value, etc.), and the term "abs(X)" means the absolute value (unsigned) of the quantity X.

[0171] In the glass compositions described herein, SiO2 may serve as a primary glass former. Without being bound by theory, it is believed that tetrahedra [SiO4] are connected as part of the structural network of the glass, particularly with other structural units that may be rotatable, such as tetrahedra [AlO4] and triangles [BO3]. Such connections between tetrahedra and triangles can cause the anomalous fracture behavior described herein. In addition, SiO2 has been found to increase the viscosity of the glass-forming melt, increase the liquidus viscosity, decrease the thermal expansion coefficient, and increase the Young's modulus, thus improving mechanical properties. Second, a high silica content can increase the chemical durability of the glass. However, if the SiO2 content in the glass composition becomes too high, the high-temperature viscosity may become unacceptably large, which may cause some melting difficulties, such as corrosion of refractories in the glass-melting tank. Also, if the SiO2 content is too high, the structural network of the glass may contain an insufficient amount of rotatable units, and the anomalous fracture behavior may be lost. Thus, in embodiments, the glass compositions described herein can include SiO in an amount of at least 60.0 mol% and at most 96.0 mol%, at least 60.0 mol% and at most 80.0 mol%, at least 60.0 mol% and at most 77.5 mol%, at least 72.0 mol% and at most 78.0 mol%, at least 73.0 mol% and at most 77.0 mol%, at least 73.4 mol% and at most 76.8 mol%, at least 73.8 mol% and at most 76.4 mol%, at least 74.62 mol% and at most 75.88 mol%, at least 65.0 mol% and at most 75.9 mol%, at least 72.0 mol% and at most 75.9 mol%, at least 73.0 mol% and at most 96.0 mol%, and at least 74.6 mol% and at most 75.9 mol%, in addition to other ranges of SiO content described herein.

[0172] In the glass compositions described herein, B2O3 may act as a network former along with SiO2 and Al2O3. As part of the structural network of the glass, boron oxide can form either tetrahedrons [BO4] or triangles [BO3], depending on the content of other components. While not wishing to be bound by theory, it is believed that the amount of tetrahedrons [BO4] increases when the content of modifiers (monovalent metal oxides R2O and divalent metal oxides R2O) in a particular glass composition exceeds the amount of alumina. In embodiments, both triangles [BO3] and tetrahedrons [BO4] can play important roles in the glass compositions described herein. Tetrahedrons [BO4] can increase the connectivity of the structural network, increase the stiffness of the network, particularly at low temperatures, increase viscosity, and prevent undesirable precipitation of refractory minerals from the melt. Triangles [BO3] may be rotatable structural units, which may result in the unusual fracture behavior described herein. Therefore, the glass compositions of the present disclosure include boron oxide. However, too high a B2O3 content can decrease the liquidus viscosity, potentially resulting in the precipitation of refractory minerals within the glass. Also, a high boron oxide content may result in the glass composition not being sufficiently resistant to alkalis and acids, or the glass-forming melt may be prone to liquid-liquid phase separation, causing the glass to become opaque. In embodiments, the glass compositions described herein can include B2O3 in an amount of 1.0 mol% to 25.0 mol%, 5.0 mol% to 20.0 mol%, 5.0 mol% to 17.0 mol%, 10.5 mol% to 19.0 mol%, 11.75 mol% to 17.75 mol%, or 12.07 mol% to 13.8 mol%, in addition to the other B2O3 content ranges described herein.

[0173] In investigations, it has been empirically determined that the addition of even small amounts of rare earth metal oxides to the glass compositions described herein can cause an increase in the liquidus temperature and the precipitation of refractory minerals. It has also been empirically determined that the addition of rare earth oxides can reduce the chemical durability of the resulting glass, particularly its resistance to acids. For this reason, in some embodiments of the present disclosure, the content of rare earth metal oxides in the glass composition may be limited, or the glass composition may preferably be free (or substantially free) of rare earth metal oxides.

[0174] The glass compositions of the present disclosure may also contain lithium oxide (LiO). Lithium oxide, like other alkali metal oxides, can act as a modifier. However, it has been empirically found that adding LiO to the glass compositions of the present disclosure can increase the liquidus temperature and decrease the liquidus viscosity. Glasses containing LiO may also have lower chemical durability compared to glasses containing the same amount of other alkali metal oxides. LiO has also been found to potentially cause a decrease in the anomalous fracture behavior described herein. Without being bound by theory, it is believed that the addition of LiO increases the cation packing density, which may increase density and reduce the anomalous fracture behavior. Therefore, in embodiments, the content of LiO in the glass compositions described herein may be limited, or it may be preferable that the glass compositions be free (or substantially free) of LiO.

[0175] The glass compositions of the present disclosure may also include magnesia (MgO). In embodiments, magnesia may be added to a glass composition to increase the Young's modulus and / or improve other mechanical properties of the resulting glass. Magnesia advantageously does not increase the density of the glass to the same extent as other glass modifiers, nor may it increase the coefficient of thermal expansion. It has also been found that adding small amounts of magnesia to glass compositions of the present disclosure can improve anomalous fracture behavior. However, too much MgO in the glass composition can cause the glass-forming melt to precipitate refractory minerals, which can increase the liquidus temperature and / or cause crystalline defects in the glass article. Thus, in embodiments, the glass compositions of the present disclosure may include magnesia (MgO) in an amount from greater than or equal to 0.0 mol% to less than or equal to 5.0 mol%, including all ranges and subranges therebetween. In embodiments, the glass composition can include MgO in an amount of 5.0 mol% or less, 2.5 mol% or less, 2.0 mol% or less, 1.8 mol% or less, or 1.75 mol% or less. In embodiments, the glass composition can include MgO in an amount of 0.0 mol% to 5.0 mol%, 0.0 mol% to 2.0 mol%, 0.0 mol% to 1.8 mol%, 0.35 mol% to 1.75 mol%, 0.68 mol% to 1.75 mol%, or 0.0 mol% to 1.75 mol%.

[0176] The glass compositions of the present disclosure may also include calcium oxide (CaO). Adding calcium oxide to a glass composition improves chemical durability, increases Young's modulus, and therefore improves mechanical properties. Furthermore, alkaline earth oxides such as CaO and MgO tend to lower the liquidus temperature and increase the liquidus viscosity. It has been empirically found that adding small amounts of CaO can improve abnormal fracture behavior. However, high CaO contents can cause precipitation of refractory minerals, which can result in crystalline defects in the glass article. Furthermore, adding large amounts of CaO to glass compositions with high B2O3 contents can cause liquid-liquid phase separation in the melt, resulting in reduced light transmittance. Therefore, in embodiments, the glass composition may include calcium oxide (CaO) in an amount from 0.0 mol% to 5.0 mol% inclusive, including all ranges and subranges therebetween. In some other embodiments, the glass composition can include CaO in an amount of 5.0 mol% or less, 2.5 mol% or less, 2.0 mol% or less, 1.9 mol% or less, 1.7 mol% or less, 1.5 mol% or less, or 1.0 mol% or less. In some further embodiments, the glass composition can include CaO in an amount of 0.0 mol% to 2.0 mol%, 0.0 mol% to 1.9 mol%, 0.0 mol% to 1.7 mol%, 0.0 mol% to 1.5 mol%, 0.02 mol% to 1.02 mol%, 0.0 mol% to 5.0 mol%, or 0.0 mol% to 1.0 mol%.

[0177] In embodiments, the glass compositions of the present disclosure may have a combined amount of CaO and MgO (CaO+MgO) of 5.0 mol% or less, or 2.5 mol% or less, or 0.0 mol% or more and 5.0 mol% or less, or 0.0 mol% or more and 2.5 mol% or less.

[0178] The glass compositions of the present disclosure may also include zirconia (ZrO). Zirconia can be added to the glass compositions of the present disclosure to improve mechanical properties and / or increase the viscosity of the glass-forming melt. However, in some embodiments of the present disclosure, it has been empirically determined that the addition of zirconia to a glass composition, even in very small amounts, can increase the liquidus temperature and / or cause refractory minerals to precipitate from the glass-forming melt, particularly when the total alkali metal oxide content (in mole percent) does not exceed, or only slightly exceeds, the alumina content (in mole percent). Therefore, in some embodiments of the present disclosure, the content of zirconia in the glass composition may be limited, or the glass composition may be substantially free of ZrO. In embodiments, the glass composition may include zirconia (ZrO) in an amount from 0.0 mole percent to 5.0 mole percent, inclusive, and all ranges and subranges therebetween. In some other embodiments, the glass composition can include ZrO in an amount of 5.0 mol% or less, 2.5 mol% or less, 1.5 mol% or less, 1.35 mol% or less, 1.2 mol% or less, or 1.0 mol% or less. In some further embodiments, the glass composition can include ZrO in an amount of 0.0 mol% to 1.5 mol%, 0.0 mol% to 1.35 mol%, 0.0 mol% to 1.2 mol%, 0.01 mol% to 1.01 mol%, 0.0 mol% to 5.0 mol%, or 0.0 mol% to 1.0 mol%.

[0179] The glass compositions of the present disclosure may contain barium oxide (BaO). Barium oxide may be unintentionally added to the glass composition as an impurity in other raw materials, or it may be intentionally added to prioritize lower melting temperatures or greater chemical durability. Empirical evidence has shown that adding BaO to the glass compositions of the present disclosure can increase the liquidus temperature and potentially cause crystallization of the glass-forming melt during cooling and forming. Additionally, barium, as a large cation, may mitigate abnormal fracture behavior. Therefore, the content of BaO in the glass compositions of the present disclosure is limited, and the glass composition may preferably be free of BaO. In embodiments, the glass compositions may contain barium oxide (BaO) in an amount from 0.0 mol% to 0.2 mol% and all ranges and subranges therebetween. In some other embodiments, the glass compositions may contain BaO in an amount of 0.2 mol% or less, or 0.1 mol% or less. In some further embodiments, the glass composition may include BaO in an amount of 0.0 mol % or more and 0.2 mol % or less, or 0.0 mol % or more and 0.1 mol % or less.

[0180] The glass compositions of the present disclosure may contain potassium oxide (KO). Potassium oxide may be unintentionally added to the glass composition as an impurity in other raw materials, or it may be intentionally added, for example, to protect the glass-forming melt from liquid-liquid phase separation. The addition of KO may improve the chemical durability of the glass and / or lower the liquidus temperature. Without being bound by theory, it is believed that KO converts the structural units generated by boron oxide from triangular [BO3] to tetrahedral [BO4], thereby improving the balance between these structural units in the glass composition and, consequently, improving the anomalous fracture behavior. However, the addition of KO to the glass compositions of the present disclosure may decrease the Young's modulus of the glass, which may reduce the mechanical properties of the glass article. Additionally, the addition of large amounts of KO may unacceptably increase the thermal expansion coefficient of the glass. Therefore, in some embodiments of the present disclosure, the content of KO in the glass composition may be limited, or the glass composition may be substantially free of KO. In embodiments, the glass composition may include potassium oxide (KO) in an amount from 0.0 mol% to 10.0 mol%, inclusive, and all ranges and subranges therebetween. In embodiments, the glass composition may include KO in an amount of 0.0 mol% to 3.0 mol%, 0.3 mol% to 2.8 mol%, 0.6 mol% to 2.5 mol%, 0.92 mol% to 2.18 mol%, 0.0 mol% to 10.0 mol%, 0.3 mol% to 2.2 mol%, 0.6 mol% to 10.0 mol%, 0.6 mol% to 2.2 mol%, 0.8 mol% to 2.2 mol%, 0.9 mol% to 2.2 mol%, and 5.0 mol% to 7.0 mol%.

[0181] The glass compositions of the present disclosure may also contain alumina (Al2O3). In the glass compositions of the present disclosure, alumina acts as a network former along with B2O3 and SiO2. As a network former, alumina increases the viscosity of the glass-forming melt, increasing the liquidus viscosity and providing better protection against crystallization. The addition of alumina, even in small amounts, can prevent phase separation in the melt. As a result, alumina can improve the chemical durability of the glass. Therefore, the glass compositions of the present disclosure contain a certain amount of alumina. However, adding a large amount of alumina can cause precipitation of refractory minerals from the melt, which can result in crystalline defects in the glass article. Furthermore, a high alumina content can result in excessively high viscosity, which can lead to corrosion of refractories in the glass melting tank. Therefore, in some embodiments of the present disclosure, the alumina content is limited. In an embodiment, the glass composition can contain alumina (Al2O3) in an amount of 0.3 mol% or more to 5.3 mol% or less, and all ranges and subranges therebetween. In some embodiments, the glass composition can include Al2O3 in an amount of 0.3 mol% or more, 2.0 mol% or more, 2.2 mol% or more, 2.4 mol% or more, 2.5 mol% or more, 3.45 mol% or more, 3.8 mol% or more, 4.3 mol% or more, 4.8 mol% or more, or 5.0 mol% or more. In some other embodiments, the glass composition can include Al2O3 in an amount of 5.3 mol% or less, 5.0 mol% or less, 4.8 mol% or less, 4.3 mol% or less, 4.0 mol% or less, 3.9 mol% or less, 3.8 mol% or less, 3.65 mol% or less, 3.53 mol% or less, or 2.5 mol% or less.In some further embodiments, the glass composition may include Al2O3 in an amount of from 0.3 mol% to 5.3 mol%, from 2.0 mol% to 4.0 mol%, from 2.2 mol% to 3.9 mol%, from 2.4 mol% to 3.65 mol%, from 3.45 mol% to 3.53 mol%, from 0.3 mol% to 2.5 mol%, from 2.0 mol% to 5.3 mol%, from 2.0 mol% to 2.5 mol%, from 2.2 mol% to 2.5 mol%, from 2.4 mol% to 2.5 mol%, from 2.5 mol% to 5.3 mol%, or from 3.8 mol% to 3.9 mol%.

[0182] The glass compositions of the present disclosure may also include sodium oxide (NaO). Sodium oxide acts as a modifier, converting the structural units formed by aluminum and boron cations into tetrahedral types ([AlO] and [BO]), potentially resulting in a better balance between assumed rotatable and non-rotatable structural units and improving the glass's unusual fracture behavior. The addition of NaO may also improve the glass's chemical durability, lower its liquidus temperature, and increase its liquidus viscosity, thereby better protecting the glass-forming melt from crystallization. However, adding large amounts of NaO can unacceptably decrease the Young's modulus and thus degrade the mechanical properties of the glass article. The inclusion of large amounts of NaO in a glass composition may also unacceptably increase the thermal expansion coefficient and, in some cases, reduce the glass's chemical durability. Therefore, in some embodiments of the present disclosure, the sodium oxide content in the glass composition may be limited, or the glass composition may be substantially free of NaO. In embodiments, the glass composition can include sodium oxide (NaO) in an amount from 0.0 mol% or more to 10.0 mol% or less, and all ranges and subranges therebetween. In some embodiments, the glass composition can include NaO in an amount of 0.0 mol% or more, 2.0 mol% or more, 2.5 mol% or more, 2.9 mol% or more, 3.4 mol% or more, 4.55 mol% or more, 5.0 mol% or more, 7.0 mol% or more, 8.0 mol% or more, or 9.0 mol% or more. In some other embodiments, the glass composition can include NaO in an amount of 10.0 mol% or less, 9.7 mol% or less, 9.0 mol% or less, 8.0 mol% or less, 7.0 mol% or less, 6.0 mol% or less, 5.5 mol% or less, 5.45 mol% or less, 5.3 mol% or less, 5.2 mol% or less, or 5.0 mol% or less.In some further embodiments, the glass composition may include NaO in an amount of from 0.0 mol% to 5.2 mol%, from 2.0 mol% to 8.0 mol%, from 2.0 mol% to 6.0 mol%, from 2.5 mol% to 5.3 mol%, from 2.9 mol% to 5.5 mol%, from 3.4 mol% to 6.0 mol%, from 4.55 mol% to 5.45 mol%, from 0.0 mol% to 10.0 mol%, from 2.0 mol% to 5.0 mol%, from 2.5 mol% to 5.0 mol%, from 3.4 mol% to 5.0 mol%, or from 4.55 mol% to 5.0 mol%.

[0183] The glass compositions of the present disclosure may contain fluorine (F). Fluorine can be added in small amounts to the glass compositions of the present disclosure as a fining agent or as a component to lower the liquidus temperature. However, adding fluorine to a glass composition can pose environmental concerns. As such, in some embodiments of the present disclosure, the fluorine content is limited, and preferably, the glass composition may be fluorine-free.

[0184] In embodiments, glass compositions of the present disclosure may include a total amount of iron, chromium, molybdenum, vanadium, copper, and cobalt (Fe+Cr+Mo+V+Cu+Co) that is 1.0 mol% or less, or 0.5 mol% or less. In embodiments, Fe+Cr+Mo+V+Cu+Co is 0.0 mol% or more and 1.0 mol% or less, or 0.0 mol% or more and 0.5 mol% or less.

[0185] In embodiments, the glass compositions of the present disclosure may include a combined amount of iron(II) oxide and iron(III) oxide (FeO + Fe2O3) that is 0.5 mol% or less, or 0.25 mol% or less. In embodiments, FeO + Fe2O3 is 0.0 mol% or more and 0.5 mol% or less, or 0.0 mol% or more and 0.25 mol% or less.

[0186] In embodiments, the glass compositions of the present disclosure may have a combined amount of lanthanum oxide and yttrium(III) oxide, La2O3 + Y2O3, of 1.0 mol% or less, or 0.5 mol% or less. In embodiments, La2O3 + Y2O3 is 0.0 mol% or more and 1.0 mol% or less, or 0.0 mol% or more and 0.5 mol% or less.

[0187] In embodiments, glass compositions of the present disclosure may have a combined amount of sodium oxide and potassium oxide (Na2O + KO) of at least 0.0 mol%, at least 5.0 mol%, or at least 6.11 mol%. In embodiments, Na2O + KO is at most 6.84 mol%, or at most 5.0 mol%. In embodiments, Na2O + KO is at least 0.0 mol% and at most 6.84 mol%, or at most 0.0 mol% and at most 5.0 mol%.

[0188] In embodiments, glass compositions of the present disclosure may have a combined amount of sodium oxide and alumina (Na2O + Al2O3) of 0.0 mol% or more, 5.0 mol% or more, or 7.7 mol% or more. In embodiments, Na2O + Al2O3 is 9.7 mol% or less, 8.9 mol% or less, or 5.0 mol% or less. In embodiments, Na2O + Al2O3 is 0.0 mol% or more and 9.7 mol% or less, 0.0 mol% or more and 8.9 mol% or less, 0.0 mol% or more and 5.0 mol% or less, 5.0 mol% or more and 9.7 mol% or less, 5.0 mol% or more and 8.9 mol% or less, or 7.7 mol% or more and 9.7 mol% or less.

[0189] In embodiments, the glass compositions of the present disclosure may have a total amount of sodium oxide, potassium oxide, magnesium oxide, calcium oxide, zinc oxide, alumina, boron oxide, and silica (NaO+KO+MgO+CaO+ZnO+AlO+BO+SiO) that is greater than or equal to 95.0 mol%.

[0190] In embodiments, the glass compositions of the present disclosure may have a value for the ratio (NaO + KO + MgO + CaO + SrO + BaO + ZnO) / (RO + RO) that is 0.000 or greater, or 0.95 or greater. Sodium and potassium oxides, as well as alkaline earth metal oxides and zinc oxide, are the most common choices for modifiers (RO and RO) because they do not reduce the light transmittance of the resulting glass article and are highly soluble in the glass melts of the present disclosure. Other monovalent and divalent metal oxides, such as MnO, NiO, CuO, AgO, and PbO, may have low solubility, or may result in undesirable coloration, raise environmental concerns, or be more expensive.

[0191] In embodiments, glass compositions of the present disclosure may have a Na2O / Al2O3 ratio. When Na2O is added to a glass composition, it may be desirable to bond it with structural units formed by a different network former. When this occurs, the mobility of sodium ions decreases, potentially slightly improving the chemical durability of the glass. Without being bound by theory, it is believed that such bonding may occur when the content of Na2O in the glass composition is equal to or greater than the content of Al2O3. Thus, in some embodiments of the present disclosure, it may be desirable for the Na2O / Al2O3 ratio (in mole percent) to be about 1.0 or greater. On the other hand, if the Na2O / Al2O3 ratio becomes too high, the anomalous fracture behavior described herein may be suppressed. Thus, in embodiments, Na2O / Al2O3 is 1.0 mol% or greater, 1.01 mol% or greater, 1.1 mol% or greater, or 1.5 mol% or greater. In embodiments, Na2O / Al2O3 is 1.67 mol% or less, 1.6 mol% or less, 1.5 mol% or less, or 1.35 mol% or less. In embodiments, Na2O / Al2O3 is 1.0 mol% to 1.35 mol%, 1.01 mol% to 1.67 mol%, 1.0 mol% to 1.67 mol%, 1.0 mol% to 1.67 mol%, 1.0 mol% to 1.6 mol%, 1.0 mol% to 1.5 mol%, 1.01 mol% to 1.6 mol%, 1.01 mol% to 1.5 mol%, or 1.01 mol% to 1.35 mol%, 1.1 mol% to 1.67 mol%, 1.1 mol% to 1.6 mol%, 1.1 mol% to 1.5 mol%, or 1.1 mol% to 1.35 mol%.

[0192] In embodiments, glass compositions of the present disclosure may include the parameter B2O3 + 3.5*Al2O3 within certain numerical ranges. It has been empirically determined that the anomalous fracture behavior described herein is preferably observed when the sum of (B2O3 + 3.5*Al2O3) is about 25 mol%. Thus, in embodiments, B2O3 + 3.5*Al2O3 is 20.3 mol% or greater, 24.2 mol% or greater, or 25 mol% or greater. In embodiments, B2O3 + 3.5*Al2O3 is 27.5 mol% or less, 25.9 mol% or less, or 25 mol% or less. In embodiments, B2O3+3.5*Al2O3 is equal to or greater than 20.3 mol% and equal to or less than 27.5 mol%, equal to or greater than 20.3 mol% and equal to or less than 25.9 mol%, or equal to or greater than 20.3 mol% and equal to or less than 25 mol%, 24.2 mol% and equal to or less than 27.5 mol%, 24.2 mol% and equal to or less than 25.9 mol%, or 24.2 mol% and equal to or less than 25 mol%, 25 mol% and equal to or less than 27.5 mol%, or 25 mol% and equal to or less than 25.9 mol%.

[0193] In some embodiments, the glass compositions described herein have a liquidus viscosity (Log(eta)) of 5.5 or more and 8.0 or less. liq In an embodiment, the decimal logarithm of Log(eta P) may be used. liq P) is 5.5 or greater, 5.9 or greater, 6.0 or greater, 6.5 or greater, 7.4 or greater, 7.5 or greater, 7.6 or greater, or 7.8 or greater. liq P) is 8.0 or less, 7.8 or less, 7.7 or less, 7.6 or less, 7.5 or less, 7.4 or less, 6.5 or less, or 6.0 or less. liq P) is 5.5 or more and 8.0 or less, 5.9 or more and 7.7 or less, 5.5 or more and 6.0 or less, 5.9 or more and 6.0 or less, 6.0 or more and 8.0 or less, 6.0 or more and 6.5 or less, 7.4 or more and 8.0 or less, 7.4 or more and 7.5 or less.

[0194] In embodiments, glass compositions according to the present disclosure have a modifier excess parameter M calculated according to the following relationship: exc can be shown: M exc =max(0, (Alk2O+RO)-(Al2O3+B2O3)), (Equation 2) Here, Alk2O is the sum of alkali metal oxides, RO is the sum of divalent metal oxides, and the chemical formulas indicate the amounts of the corresponding components in the glass composition. exc represents the excess of modifiers R2O and RO relative to the network formers Al2O3 and B2O3. The modifier excess parameter is defined as equal to zero when the total content of Al2O3 + B2O3 exceeds the total content of R2O + RO. Without being bound by theory, M exc The value of is believed to correlate with the amount of non-bridging oxygen atoms in the structural network of the glass.

[0195] In embodiments, glass compositions according to the present disclosure have a total polyhedron parameter P calculated according to the following relationship: total can be shown: P total =SiO2+2*Al2O3+2*B2O3, (Equation 3) Here, the chemical formula indicates the amount of the corresponding component in the glass composition. total is the network forming cation Si4 in gram atoms per 100 moles of the total oxides present in the glass composition. + , Al3 + and B3 + The total number of

[0196] In embodiments, glass compositions according to the present disclosure have a boron excess parameter B calculated according to the following relationship: exc can be shown: B exc =max(0,B2O3-max(0,R2O+RO-Al2O3)), (Eq. 4) Here, R2O is the sum of monovalent metal oxides, R0 is the sum of divalent metal oxides, and the chemical formulas indicate the amounts of the corresponding components in the glass composition. excis the excess boron oxide in mole % relative to the content (in mole %) of the modifiers RO and RO after subtracting the content (in mole %) of alumina in the glass composition. If the content of alumina is equal to or greater than the combined content of RO and RO, the boron excess parameter is assumed to be equal to the content of boron oxide in the glass composition.

[0197] In embodiments, the glass compositions according to the present disclosure have a silica excess parameter S calculated according to the following relationship: exc can be shown: Si exc =SiO2-6*min(Alk2O,Al2O3)-2*min(Alk2O+RO-Al2O3,B2O3), (Equation 5) Here, Alk2O is the sum of alkali metal oxides, RO is the sum of divalent metal oxides, and the chemical formulas indicate the amounts of the corresponding components in the glass composition. exc approximates the silica content, which is assumed not to be associated with the structural polyhedra formed by aluminum and boron cations.

[0198] In embodiments, the parameter P of the glass compositions described herein total , M exc , B exc , and S exc can satisfy the following relationship: (abs(2*M exc +2*min(B2O3,R2O+RO-Al2O3)+0.65*P total -80))-- 0.5*(abs(Si exc -max(24+2*B exc ,44))))≦0.000 In embodiments, the parameter P of the glass compositions described herein total , M exc , B exc , and S exc can satisfy the following relationship: (abs(2*M exc +2*min(B2O3,R2O+RO-Al2O3)+0.65*P total-80))-(2.8-0.5*(abs(Si exc -max(24+2*B exc ,44))))≦0.000.

[0199] In some embodiments, glasses comprising the compositions described herein have a 1-2*(AlkO+RO) / P total may have an amount of

[0200] Glasses comprising the compositions described herein also have a non-rotatable polyhedron parameter P, calculated as follows: nr May include: P nr =2*max(0,(Alk2O+RO)-(Al2O3+B2O3))+2*min(B2O3,R2O+RO-Al2O3), (Equation 6) where Alk2O is the sum of alkali metal oxides, RO is the sum of divalent metal oxides, and RO is the sum of monovalent metal oxides, and the chemical formulas refer to the amounts of the corresponding components in the glass composition. nr is the number of gram atoms of non-rotatable network-forming cations per 100 moles of total oxides present in the glass composition, and is the number of gram atoms of non-rotatable network-forming cations Si4 + , Al3 + and B3 + It is thought to represent an approximate number.

[0201] Glasses comprising the compositions described herein also have a network rotatability ratio, R, calculated by the following formula: nr May include: R nr =1-2*(Alk2O+RO) / (SiO2+2*Al2O3+2*B2O3), (Equation 7) where AlkO is the sum of alkali metal oxides, R0 is the sum of divalent metal oxides, and the chemical formulas refer to the amounts of the corresponding components in the glass composition. nris related to the fracture behavior of the borosilicate glass compositions disclosed herein and can characterize the "rotatability" aspect of each composition. For compositions of the form xSiO2·yAl2O3·zB2O3·uRO2O·vRO, x, y, z, u, and v can represent the mole percent or mole fraction of each type of oxide. When (u+v)≧y, Applicants believe that fracture behavior is related to the network rotatability ratio R, as determined by Equation 7: nr I think it's related to R nr Applicant has discovered that when the σ is between about 0.80 and about 0.93, the Vickers indentation test produces radial and transverse cracks contained within small (less than 1 mm diameter) crack loops. As a result, glass sheets within this range do not crack and break during the Vickers indentation test; instead, small, round cracks are formed that contain other cracks, preventing crack propagation.

[0202] In embodiments, glass compositions according to the present disclosure may be characterized by a network balance criterion C, calculated as follows: nb May include: C nb =abs(SiO2-6*min(Alk2O,Al2O3)-2*min(Alk2O+RO-Al2O3,B2O3)-max(24+2*max(0,B2O3-max(0,R2O+RO-Al2O3)),44)), Equation (8) Here, Alk2O is the sum of alkali metal oxides, RO is the sum of divalent metal oxides, and RO is the sum of monovalent metal oxides, and the chemical formulas indicate the amounts of the corresponding components in the glass composition. nb is the parameter Si exc and B exc For the exemplary compositions described herein, Si exc Set the parameter value to B exc When plotted as a function of the parameter, the examples are grouped around the lines y=24-x and y=44-3*x, where y is the parameter Si exc corresponds to, and x is the parameter B excThe examples described herein fall near the highest values ​​calculated by these formulas, which can be expressed as: Si exc =max(24-B exc , 44-4*B exc ), (Equation 9) Without being bound by theory, Si exc and the formula max(24-B exc , 44-4*B exc ) can characterize the balance of silicon and boron bonding in the structural network. The absolute value of this difference is Si exc and B exc Substituting this into the formula, we finally get C nb In other words, the network balance criterion is Si exc and B exc can be expressed as follows: C nb =abs(Si exc -max(24-B exc , 44-4*B exc ))(Equation 10) Exemplary compositions described herein that exhibit abnormal and intermediate fracture behavior have relatively small values ​​of C, such as, for example, 5.0 or less, or 4.5 or less, or 4.0 or less, or 3.5 or less, or 3.0 or less, or 2.5 or less, or even 2.0 or less. nb It is characterized by:

[0203] The term "fracture category" refers to the type of fracture behavior observed during Vickers indentation testing and is described using three categories: "normal," "abnormal," and "intermediate." The Vickers indentation test can be used to characterize the fracture behavior of glass, as discussed in Gross et al., Crack-resistant glass with high shear band density, Journal of Non-Crystalline Solids, 494 (2018) 13-20; and Gross, Deformation and cracking behavior of glasses indented with diamond tips of various sharpness, Journal of Non-Crystalline Solids, 358 (2012) 3445-3452, both of which are incorporated herein by reference. In some embodiments, the glass having the borosilicate glass composition of the first glass ply is at least 2 x 2 cm. 2At least 10 polished, flat specimens (e.g., 100 specimens) with a major surface area of ​​1 mm (e.g., 2 cm × 2 cm square) are fabricated and tested at 25°C and 50% relative humidity using a Vickers indenter with a 136° square-based pyramidal shape oriented perpendicular to the center of the major surface. When the indenter is quasi-statically displaced at a rate of 60 μm / s with a maximum load of 3 kgf (approximately 29.4 N), and the indentation load is held for 10 seconds (unless specimen fracture occurs first), in many cases (at least 51 out of 100 tests; at least 6 out of 10 tests), all of the cracks extending radially and / or laterally from the indenter tip through the specimen (i.e., the point where the indenter tip contacts the glass) are intercepted by self-terminating crack loops (e.g., ring-shaped cracks), thereby limiting specimen fracture by the Vickers indenter to the cracks within the loop. In these cases, the fracture category is identified as "intermediate." Essentially, the indenter crushes the glass beneath it, causing a crack. However, a crack loop forms, preventing the crack from propagating beyond the crack loop, resulting from the indenter's contact. In contrast, in other glasses, transverse or radial cracks may form prior to and / or pass through such a crack loop (e.g., an abnormal crack), or no crack loop may form (e.g., a normal crack); in either case, the transverse or radial crack may not be contained within the crack loop and may propagate throughout the glass article, causing the entire article to fracture and fail. This type of fracture behavior is recognized as "normal."

[0204] In embodiments, glass compositions according to the present disclosure may be provided with a rotational balance criterion C in an amount calculated as follows: rb May include: C rb =abs(2*max(0,(Alk2O+RO)-(Al2O3+B2O3))+2*min(B2O3,R2O+RO-Al2O3)+0.65*(SiO2+2*Al2O3+2*B2O3)-80), (Equation 11) Here, Alk2O is the sum of alkali metal oxides, RO is the sum of divalent metal oxides, and RO is the sum of monovalent metal oxides, and the chemical formulas indicate the amounts of the corresponding components in the glass composition. rb is the quantity P described herein total and P nr For the examples described herein, P nr Set the parameter value to P total When plotted as a function of the parameter value, the P nr The values ​​are located near the line y=80-0.65*x, where y is the parameter P nr corresponds to, and x is the parameter P total which can be expressed mathematically as: P nr =80-0.65*P total , (Equation 12) where P total and P nr refers to the total polyhedron parameters and non-rotatable polyhedron parameters described herein. Without being bound by theory, P nr and the equation defined on the right side of Equation 12, 80-0.65*P total The difference between the two can be considered to characterize the balance between the rotatable and non-rotatable structural polyhedrons. The absolute value of the difference is defined as P nr and P total Substituting this into the formula, we finally get C rb In other words, the network balance criterion is Si exc and B exc can be expressed as follows: C rb =abs(P nr -(80-0.65*P total ). (Formula 13) The density at room temperature (referred to herein as "d RT") is a property of glass that can be predicted from the glass composition. Linear regression analysis of the examples of the present disclosure as well as certain existing compositions was performed to generate an equation that can be used to predict the compositional dependence of density for various glass compositions.

[0205] To select from among existing glass compositions, the SciGlass Information System was searched using the criteria set forth in Table 600 below.

[0206] [Table 12]

[0207] Approximately 100 glass compositions were randomly selected from the search results and exemplary glasses derived from the embodiments presented herein. A linear regression analysis on the dataset specified above was used to determine the formula, eliminating insignificant variables and outliers. The resulting formula is shown in Table 700 below.

[0208] [Table 13]

[0209] Another set of compositions meeting the criteria of Table 600 was used as a validation set to evaluate the ability of Equation 14 herein to interpolate within predefined compositional limits corresponding to the standard deviations specified in Table 700. An external data set of prior art glass compositions, also randomly selected from the SciGlass Information System database, was used to evaluate the ability to predict properties outside the specified compositional limits with reasonable accuracy. This process was repeated multiple times to determine the best-fitting random variables for each property corresponding to the above regression equations specified in Table 700.

[0210] The compositional data used in the linear regression modeling, including the training data set, validation data set, and external data set, were obtained from the publicly available SciGlass Information System database. The following equation (14) was obtained from the linear regression analysis and used to predict the density of the glass: P d =2.487-0.0068998*B2O3+0.041371*BaO+0.13897*Bi2O3+0.011637*CaO+0.055366*Cs2O+0.025420*Fe2O 3+0.10294*Gd2O3+0.0051134*K2O+0.079903*La2O3+0.0041594*Li2O+0.0084582*MgO+0.019720*MnO+0.0 064419*Na2O+0.018282*NiO+0.065781*PbO-0.002953*SiO2+0.027682*SrO+0.0055367*TiO2+0.0068497 *V2O5+0.048699*Y2O3+0.021527*ZnO+0.026527*ZrO2+0.011033*(min(B2O3,max(0,Alk2O+RO-Al2O3))). (Formula 14) In Equation 14, the density parameter P d is the density [g / cm 3 ] at room temperature calculated from the components of the glass composition expressed in mole percent. 3] is a parameter that predicts the density of the glass composition. In Equation 14, each component of the glass composition is listed by a chemical formula, where the chemical formula refers to the concentration of the component expressed in mole percent. For example, for purposes of Equation 14, B2O3 refers to the concentration of B2O3 in the glass composition expressed in mole percent. It should be understood that not all components listed in Equation 14 are necessarily present in a particular glass composition, and Equation 14 is equally valid for glass compositions that contain fewer than all of the components listed in the formula. It should also be understood that Equation 14 is valid for glass compositions within the scope and claims of this disclosure that include components in addition to those listed in the formula. If a component listed in Equation 14 is not present in a particular glass composition, the concentration of that component in the glass composition is 0 mole percent, and the component's contribution to the value calculated from the formula will be zero. Equation 14 was used to generate predicted values ​​for the density of glasses found in the examples described herein as well as in the prior art. The predicted values ​​were calculated based on the room temperature d RT Equation 14 plots the actual measured density to within ±0.024 g / cm 3 It was found that the prediction was accurate within an error of

[0211] For certain glass compositions according to the examples contained herein, applicants have determined a density parameter P that represents the predicted density of each composition from its constituent components. d as a function of the Na2O / Al2O3 ratio. The first set of examples described herein were selected as meeting the following criteria, listed in Table 800 below: In Table 800, "No restrictions" refers to restrictions that were not considered when selecting the compositions.

[0212] [Table 14]

[0213] In a first set of examples, the density parameter P d The values ​​were plotted as a function of the Na2O / Al2O3 values ​​for each composition. The first set of examples was found to satisfy the following relationship: P d -(2.58-0.2*Na2O / Al2O3)<0.0 (Equation 15).

[0214] A subset of the first set of examples was found to satisfy the following relationship: P d -(2.54-0.2*Na2O / Al2O3)<0.0 (Equation 16).

[0215] Certain existing glass compositions do not satisfy the relationship defined by Equation 15 (and therefore do not satisfy the relationship defined by Equation 16). That is, glass compositions according to the examples described herein have lower density parameter values ​​(and lower measured d) than certain existing glass compositions having comparable NaO / AlO ratios. RT As described herein, such low densities may facilitate glasses according to the present disclosure exhibiting the unique fracture behavior described herein.

[0216] The second set of examples described herein were selected as meeting the following criteria, listed in Table 900 below:

[0217] [Table 15]

[0218] In an embodiment, the second set of examples may also satisfy each of the following conditions: 1.01≦Na2O / Al2O3 [mol %]≦1.67, B2O3+3.5*Al2O3 [mol %]≦27.5, C rb -(3.4-0.5*C nb )<0.000, where C rb is the rotational balance criterion defined herein, and C nb is a network balance criterion as defined herein, or C rb -(2.8-0.5*C nb )<0.000, and 1-2*(Alk2O+RO) / P total>0.83, where P total is the total polyhedron parameter. It has been found that certain existing compositions do not satisfy the above conditions.

[0219] The third set of examples described herein were selected as meeting the following criteria, listed in Table 1000 below.

[0220] [Table 16]

[0221] The third set of examples was found to satisfy the following conditions: 20.3≦B2O3+3.5*Al2O3 [mol %]≦27.5, d RT -(2.58-0.2*(Na2O / Al2O3))<0.00, d RT is the density at room temperature, or in some cases, d RT -(2.54-0.2*(Na2O / Al2O3))<0.000. It has been found that certain existing compositions do not meet the above criteria.

[0222] The fourth set of examples described herein were selected as meeting the following criteria, listed in Table 1100 below:

[0223] [Table 17]

[0224] For each example in the fourth set, C rb Calculate the parameters, C nb The C for each example in the fourth set was plotted as a function of the parameter rb Parameters and C nb The parameters were found to satisfy the following relationship: C rb -(3.4-0.5*C nb )<0.00. (Formula 17) Glasses according to the present disclosure have been found to be distinguishable from certain existing compositions in that Equation 17 is satisfied.

[0225] In a subset of the fourth set of examples, C rb and C nb It was found that the parameter values ​​also satisfy the following relationship: C rb -(2.8-0.5*C nb )<0.00. (Formula 16) Such glasses have been found to be further distinguishable from certain existing compositions in that Equation 16 is satisfied.

[0226] Embodiments of the present disclosure can be further understood in view of the following aspects.

[0227] A first aspect of the present disclosure includes a borosilicate glass composition comprising at least 74 mol% SiO; at least 10 mol% B2O3; and Al2O3 in an amount such that the sum of SiO2, B2O3, and Al2O3 is at least 90 mol%, wherein the borosilicate glass composition comprises a liquidus viscosity greater than 500 kP; and the borosilicate glass composition comprises a temperature equal to or less than 1725°C at which the viscosity of the borosilicate glass composition is 200 P.

[0228] A second aspect of the present disclosure comprises the borosilicate glass of the first aspect, further comprising about 2 mol % to about 8 mol % Na2O.

[0229] A third aspect of the present disclosure comprises the borosilicate glass of any of the first to second aspects, further comprising about 0.8 mol% to about 4 mol% KO.

[0230] A fourth aspect of the present disclosure comprises the borosilicate glass of any of the first to third aspects, wherein the total amount of Na2O and K2O is at least 4 mol%.

[0231] A fifth aspect of the present disclosure comprises the borosilicate glass of any of the first to fourth aspects, wherein the total amount of MgO and CaO is up to 5 mol %.

[0232] A sixth aspect of the present disclosure comprises the borosilicate glass of any of the first through fifth aspects, further comprising P2O5, wherein P2O5 is present in an amount up to 4 mol %.

[0233] A seventh aspect of the present disclosure comprises the borosilicate glass of any of the first through sixth aspects, further comprising about 0.05 mol % to about 0.25 mol % SnO2.

[0234] An eighth aspect of the present disclosure comprises the borosilicate glass of any of the first to seventh aspects, further comprising 0.05 mol % to 0.50 mol % of an iron compound.

[0235] A ninth aspect of the present disclosure comprises the borosilicate glass according to any one of the first to eighth aspects, having a total solar transmittance of 90% or less as measured in accordance with ISO 13837A.

[0236] A tenth aspect of the present disclosure comprises the borosilicate glass of any of the first to ninth aspects, having a visible transmittance of at least 73% measured according to ISO 13837A.

[0237] An eleventh aspect of the present disclosure comprises the borosilicate glass of any of the first to tenth aspects, comprising a thermal expansion coefficient of 5.6 ppm / °C or less measured over a temperature range of 0°C to 300°C.

[0238] A twelfth aspect of the present disclosure is a method for producing a cellulose acylate having a viscosity of 2.4 g 3 The borosilicate glass of any of the first to eleventh aspects comprises a density of less than

[0239] A thirteenth aspect of the present disclosure comprises the borosilicate glass of any of the first through twelfth aspects, comprising a strain point of about 480°C to about 560°C.

[0240] A fourteenth aspect of the present disclosure comprises the borosilicate glass of any of the first to thirteenth aspects, comprising an annealing point of about 520°C to about 590°C.

[0241] A fifteenth aspect of the present disclosure comprises the borosilicate glass of any of the first to fourteenth aspects, wherein the glass ply comprises the borosilicate glass composition of any of the first to fourteenth aspects.

[0242] A sixteenth aspect of the present disclosure comprises the borosilicate glass of any of the first to fifteenth aspects, wherein when subjected to a quasi-static Vickers tip indentation load of 2 kgf (approximately 19.6 N), the glass ply exhibits a ring-shaped crack and a plurality of radial cracks, each radial crack of the plurality of radial cracks being bounded by a ring-shaped crack.

[0243] A seventeenth aspect of the present disclosure comprises the borosilicate glass of any of the first to sixteenth aspects, wherein the glass ply is formed by fusion draw and has a thickness between the first and second major surfaces greater than 2 mm.

[0244] An eighteenth aspect of the present disclosure comprises the borosilicate glass of any of the first to seventeenth aspects, having a thickness of at least 3 mm.

[0245] A nineteenth aspect of the present disclosure includes a laminate including a first glass ply of any of the first through eighteenth aspects, a second glass ply, and an interlayer bonding the first glass ply to the second glass ply.

[0246] A twentieth aspect of the present disclosure includes the laminate of the nineteenth aspect, wherein the first ply of glass is thicker than the second ply of glass.

[0247] A twenty-first aspect of the present disclosure comprises the laminate of any of the nineteenth to twentieth aspects, wherein the second ply of glass is reinforced.

[0248] A twenty-second aspect of the present disclosure comprises the laminate of any of the nineteenth to twenty-first aspects, wherein the first and second glass plies are mated, the first glass ply comprising a first depth of curvature of at least 2 mm, and the second glass ply comprising a second depth of curvature of at least 2 mm, the first depth of curvature being within 10% of the second depth of curvature.

[0249] A twenty-third aspect of the present disclosure comprises the laminate of any of the nineteenth to twenty-second aspects, wherein the first ply of glass is deflected and comprises a curvature depth of at least 2 mm, and the second ply of glass is cold-formed to conform to the first ply of glass.

[0250] A 24th aspect of the present disclosure includes a cover glass comprising the laminate according to any one of the 19th to 24th aspects.

[0251] A twenty-fifth aspect of the present disclosure includes a vehicle having a body and at least one opening defining an interior of the vehicle; and a cover glass according to the twenty-fourth aspect disposed in the at least one opening, wherein the second glass ply is disposed facing the interior of the vehicle and the first glass ply faces the exterior of the vehicle.

[0252] A twenty-sixth aspect of the present disclosure includes the vehicle of the twenty-fifth aspect, wherein the automotive glass is at least one of a side light, a windshield, a rear window, a window, or a sunroof.

[0253] A twenty-seventh aspect of the present disclosure includes a method of forming a glass ply, the glass ply including a first major surface and a second major surface, the method including the steps of flooding a trough in an isopipe with at least two streams of a borosilicate glass composition having a liquidus viscosity greater than 500 kP and a temperature of 1725°C or less at which the viscosity of the borosilicate glass composition is 200 P, wherein the borosilicate glass composition comprises at least 74 mol% SiO and at least 10 mol% B2O3, and wherein the total amount of SiO2, B2O3, and Al2O3 is at least 90 mol%; and fusing the at least two streams of borosilicate glass composition at the root of the isopipe to form a glass ply having a thickness of at least 2 mm between the first major surface and the second major surface.

[0254] A twenty-eighth aspect of the present disclosure comprises the method of the twenty-seventh aspect, wherein the glass ply comprises a coefficient of thermal expansion of 5.6 ppm / °C or less, measured over a temperature range of 0°C to 300°C.

[0255] A 29th aspect of the present disclosure is a glass ply having a glass density of 2.4 g / cm 3 Aspects 27 to 28 include a method according to any of aspects 27 to 28, wherein the density is less than

[0256] A thirtieth aspect of the present disclosure comprises the method of any of the twenty-seventh to twenty-ninth aspects, wherein the borosilicate glass composition further comprises about 2 mol% to about 8 mol% NaO.

[0257] A thirty-first aspect of the present disclosure comprises the method of any of the twenty-seventh to thirtieth aspects, wherein the borosilicate glass composition further comprises about 0.8 mol% to about 4 mol% KO.

[0258] A thirty-second aspect of the present disclosure comprises the method of any of the twenty-seventh to thirtieth aspects, wherein the total amount of Na2O and K2O is at least 4 mol%.

[0259] A thirty-third aspect of the present disclosure comprises the method of any of the twenty-seventh to thirty-second aspects, wherein the borosilicate glass composition further comprises at least one of MgO or CaO, the total amount of MgO and CaO being up to 5 mol%.

[0260] A thirty-fourth aspect of the present disclosure comprises the method of any of the twenty-seventh to thirty-third aspects, wherein the borosilicate glass composition further comprises about 0.05 mol % to about 0.25 mol % SnO 2 .

[0261] A thirty-fifth aspect of the present disclosure comprises the method of any of the twenty-seventh to thirty-fourth aspects, wherein the borosilicate glass composition further comprises 0.05 mol % to 0.50 mol % of an iron compound.

[0262] A thirty-sixth aspect of the present disclosure comprises the method of any of the twenty-seventh to thirty-fifth aspects, further comprising P2O5, wherein the P2O5 is present in an amount up to 4 mol %.

[0263] A thirty-seventh aspect of the present disclosure includes a glass ply including a first major surface and a second major surface opposite the first major surface, the glass ply comprising a borosilicate glass composition; and when subjected to a quasi-static 2 kgf (approximately 19.6 N) indentation load with a Vickers tip, the glass ply exhibits a ring-shaped crack and a plurality of radial cracks, wherein each radial crack of the plurality of radial cracks is bounded by a ring-shaped crack.

[0264] A thirty-eighth aspect of the present disclosure comprises the glass ply of the thirty-seventh aspect, wherein the borosilicate glass composition comprises at least 74 mol% SiO; at least 10 mol% B2O3; and Al2O3 in an amount such that the sum of SiO2, B2O3, and Al2O3 is at least 90 mol%.

[0265] A thirty-ninth aspect of the present disclosure comprises the glass ply of the thirty-eighth aspect, wherein the borosilicate glass composition comprises a liquidus viscosity greater than 500 kP.

[0266] A fortieth aspect of the present disclosure comprises the glass ply of any of the thirty-eighth to thirty-ninth aspects, wherein the borosilicate glass composition comprises a temperature of 1725°C or less at which the viscosity of the borosilicate glass composition is 200P.

[0267] A forty-first aspect of the present disclosure comprises the glass ply of any of the thirty-eighth to fortieth aspects, wherein the borosilicate glass composition comprises about 2 mol% to about 8 mol% NaO.

[0268] A forty-second aspect of the present disclosure includes the glass ply of any of the thirty-eighth to fortieth aspects, wherein the borosilicate glass composition comprises about 0.8 mol% to about 4 mol% KO.

[0269] A forty-third aspect of the present disclosure comprises the glass ply of any of the thirty-eighth to forty-second aspects, wherein the borosilicate composition comprises a total amount of NaO and KO of at least 4 mol%.

[0270] A forty-fourth aspect of the present disclosure comprises the glass ply of any of the thirty-eighth to forty-third aspects, wherein the borosilicate glass composition comprises at least one of MgO or CaO, and the total amount of MgO and CaO is up to 5 mol%.

[0271] A forty-fifth aspect of the present disclosure comprises the glass ply of any of the thirty-eighth to forty-fourth aspects, wherein the borosilicate glass composition comprises P2O5 in an amount up to 4 mol%.

[0272] A forty-sixth aspect of the present disclosure includes the glass ply of any of the thirty-eighth to forty-fifth aspects, wherein the borosilicate glass composition includes about 0.05 mol % to about 0.25 mol % SnO2.

[0273] A forty-seventh aspect of the present disclosure comprises the glass ply of any of the thirty-eighth to forty-sixth aspects, wherein the borosilicate glass composition comprises 0.05 mol % to 0.50 mol % of an iron compound.

[0274] A forty-eighth aspect of the present disclosure comprises the glass ply of any of the thirty-eighth to forty-seventh aspects, wherein the total solar transmittance through the glass ply is 90% or less, measured according to ISO 13837A.

[0275] A forty-ninth aspect of the present disclosure comprises the glass ply of any of the thirty-eighth to forty-eighth aspects, wherein the visible transmission through the glass ply is at least 73% measured according to ISO 13837A.

[0276] A 50th aspect of the present disclosure comprises the glass ply of any of the 38th to 49th aspects, wherein the first major surface exhibits an optical distortion of at most 200 millidiopters as measured with an optical distortion detector using transmission optics in accordance with ASTM 1561.

[0277] A fifty-first aspect of the present disclosure includes a glass laminate comprising: a first glass ply including a first major surface and a second major surface opposite the first major surface, the first glass ply comprising a borosilicate glass composition; a second glass ply including a third major surface and a fourth major surface opposite the third major surface; and an interlayer bonding the second major surface of the first glass ply to the third major surface of the second glass ply; wherein the borosilicate glass composition comprises at least 74 mol% SiO; at least 10 mol% B2O3; and Al2O3 in an amount such that the sum of SiO2, B2O3, and Al2O3 is at least 90 mol%.

[0278] A fifty-second aspect of the present disclosure comprises the glass laminate of the fifty-second aspect, wherein the first ply of glass is thicker than the second ply of glass.

[0279] A fifty-third aspect of the present disclosure comprises the glass laminate of the fifty-first or fifty-second aspect, wherein the second ply of glass is toughened.

[0280] A fifty-fourth aspect of the present disclosure comprises the glass laminate of any of the fifty-first to fifty-third aspects, wherein the second ply of glass is chemically strengthened by an ion exchange treatment.

[0281] A 55th aspect of the present disclosure includes the glass laminate of any of the 51st to 54th aspects, wherein the glass laminate is configured for use in a vehicle having a body and an opening defining an interior, the glass laminate being configured to be positioned within the opening, with the first glass ply positioned facing the exterior of the vehicle and the second glass ply positioned facing the interior of the vehicle.

[0282] A 56th aspect of the present disclosure comprises the glass laminate of any of the 51st to 55th aspects, wherein the first glass ply has a first thickness between the first and second major surfaces of at least 2 mm, and the second glass ply has a second thickness between the third and fourth major surfaces of less than 2 mm.

[0283] A 57th aspect of the present disclosure comprises the glass laminate of any of the 51st to 56th aspects, wherein the glass laminate comprises a total glass thickness equal to the sum of the first thickness and the second thickness, and wherein the ratio of the first glass thickness to the total glass thickness is at least 0.7.

[0284] A fifty-eighth aspect of the present disclosure comprises the glass laminate of any of the fifty-first to fifty-seventh aspects, wherein the first glass thickness is at least 3 mm and the second glass thickness is 1.1 mm or less.

[0285] A fifty-ninth aspect of the present disclosure comprises the glass laminate of any of the fifty-first to fifty-eighth aspects, wherein the first glass thickness is at least 3.3 mm and the second glass thickness is 0.7 mm or less.

[0286] A sixtieth aspect of the present disclosure comprises the glass laminate of any of the fifty-first to fifty-ninth aspects, wherein the second glass ply comprises a second glass composition.

[0287] A sixty-first aspect of the present disclosure comprises the glass laminate of any of the fifty-first to sixtieth aspects, wherein the second glass composition is different from the borosilicate glass composition.

[0288] A sixty-second aspect of the present disclosure comprises the glass laminate of any of the fifty-first to sixty-first aspects, wherein the second glass composition is selected from the group consisting of a soda-lime silicate glass composition, an aluminosilicate glass composition, an alkali aluminosilicate glass composition, an alkali-containing borosilicate glass composition, an alkali aluminophosphosilicate glass composition, an alkali aluminoborosilicate glass composition, and combinations thereof.

[0289] A sixty-third aspect of the present disclosure comprises the glass laminate of any of the fifty-first to sixty-second aspects, wherein the visible transmission through the glass laminate is at least 73% measured according to ISO 13837A.

[0290] A 64th aspect of the present disclosure comprises the glass laminate of any of the 51st to 62nd aspects, wherein the total solar transmittance through the glass laminate is 90% or less, measured according to ISO 13837A.

[0291] A sixty-fifth aspect of the present disclosure comprises the glass laminate of any of the fifty-first to sixty-fourth aspects, wherein the first major surface, the fourth major surface, or both the first and fourth major surfaces exhibit an optical distortion of at most 200 millidiopters as measured with an optical distortion detector using transmission optics according to ASTM 1561.

[0292] A sixty-sixth aspect of the present disclosure comprises the glass laminate of any of the fifty-first to sixty-fifth aspects, wherein the interlayer is selected from the group consisting of polyvinyl butyral (PVB), acoustic PVB (APVB), ionomer, ethylene vinyl acetate (EVA), thermoplastic polyurethane (TPU), polyester (Pe), polyethylene terephthalate (PET), and combinations thereof.

[0293] A sixty-seventh embodiment of the present disclosure comprises the glass laminate of any of the fifty-first to sixty-second embodiments, wherein the interlayer comprises a thickness in the range of about 0.5 mm to about 2.5 mm.

[0294] A sixty-eighth aspect of the present disclosure comprises the glass laminate of any of the fifty-first to sixty-seventh aspects, wherein the interlayer comprises at least one functional layer or film.

[0295] A sixty-ninth aspect of the present disclosure comprises the glass laminate of any of the fifty-first to sixty-eighth aspects, wherein the functional layer or film provides a function selected from the group consisting of ultraviolet absorption, infrared absorption, infrared reflection, acoustic attenuation, tinting, antenna, adhesion promotion, anti-glare treatment, anti-reflection treatment, and combinations thereof.

[0296] A seventieth aspect of the present disclosure comprises the glass laminate of any of the fifty-first to sixty-ninth aspects, wherein the first and second glass plies are mated, the first glass ply comprising a first depth of curvature of at least 2 mm, and the second glass ply comprising a second depth of curvature of at least 2 mm, the first depth of curvature being within 10% of the second depth of curvature.

[0297] A seventy-first aspect of the present disclosure comprises the glass laminate of any of the fifty-first to seventieth aspects, wherein the first glass ply is deflected and comprises a curvature depth of at least 2 mm, and the second glass ply is cold-formed to conform to the first glass ply.

[0298] A seventy-second aspect of the present disclosure includes a system including a sensor and a glass laminate including: a first glass ply including a first major surface and a second major surface opposite the first major surface, the first glass ply comprising a borosilicate glass composition; a second glass ply including a third major surface and a fourth major surface opposite the third major surface; and an interlayer bonding the second major surface of the first glass ply to the third major surface of the second glass ply; wherein the borosilicate glass composition comprises at least 74 mol% SiO, at least 10 mol% B2O3, and Al2O3 in an amount such that the sum of SiO2, B2O3, and Al2O3 is at least 90 mol%; the sensor is configured to receive, transmit, or both receive and transmit a signal through the glass laminate; and the signal comprises a peak wavelength in the range of 400 nm to 750 nm, or in the range of 1500 nm or greater.

[0299] A seventy-third aspect of the present disclosure includes the system described in the seventy-second aspect, wherein the sensor is a LIDAR.

[0300] A seventy-fourth aspect of the present disclosure includes the system of any of the seventy-second to seventy-third aspects, wherein the glass laminate is a glass for a vehicle.

[0301] A 75th aspect of the present disclosure comprises the system of any of the 72nd to 74th aspects, wherein the visible transmission through the glass laminate is at least 73% as measured according to ISO 13837A.

[0302] A 76th aspect of the present disclosure comprises the system of any of the 72nd to 75th aspects, wherein the total solar transmittance through the glass laminate is 90% or less, as measured in accordance with ISO 13837A.

[0303] A 77th aspect of the present disclosure includes the system of any of the 72nd to 76th aspects, wherein the first major surface, the fourth major surface, or both the first and fourth major surfaces exhibit an optical distortion of up to 200 millidiopters as measured with an optical distortion detector using transmission optics in accordance with ASTM 1561.

[0304] A 78th aspect of the present disclosure includes the system of any of the 72nd to 77th aspects, wherein the first ply of glass is thicker than the second ply of glass.

[0305] A seventy-ninth aspect of the present disclosure includes the system of any of the seventy-second to seventy-eighth aspects, wherein the second ply of glass is reinforced.

[0306] An eightieth aspect of the present disclosure includes the system of any of the seventy-second to seventy-ninth aspects, wherein the second ply of glass is chemically strengthened by an ion exchange process.

[0307] An eighty-first aspect of the present disclosure includes a glass laminate comprising: a first glass ply including a first major surface and a second major surface opposite the first major surface, the first glass ply comprising a melt-formed borosilicate glass composition; a second glass ply including a third major surface and a fourth major surface opposite the third major surface; and an interlayer bonding the second major surface of the first glass ply to the third major surface of the second glass ply; wherein the transmittance of ultraviolet light having a wavelength in the range of 300 to 380 nm through the glass laminate is 75% or less; the transmittance of light in the visible spectrum through the glass laminate is 73% or more; and the total solar transmittance through the glass laminate is 61% or less.

[0308] An 82nd aspect of the present disclosure comprises the glass laminate of the 81st aspect, wherein the borosilicate glass composition comprises at least 74 mol% SiO, at least 10 mol% B0, and AlO in an amount such that the sum of SiO, B0, and AlO is at least 90 mol%.

[0309] An eighty-third aspect of the present disclosure comprises the glass laminate of the eighty-first or eighty-second aspect, wherein the first ply of glass is thicker than the second ply of glass.

[0310] An eighty-fourth aspect of the present disclosure comprises the glass laminate of any of the eighty-first to eighty-third aspects, wherein the second ply of glass is toughened.

[0311] An eighty-fifth aspect of the present disclosure comprises the glass laminate of any of the eighty-first to eighty-fourth aspects, wherein the second ply of glass is chemically strengthened by an ion exchange treatment.

[0312] An 86th aspect of the present disclosure comprises the glass laminate of any of the 81st to 85th aspects, wherein the second glass ply comprises an ion-exchangeable frit applied to the third major surface, the fourth major surface, or both the third and fourth major surfaces.

[0313] An 87th aspect of the present disclosure comprises the glass laminate of any of the 81st to 86th aspects, wherein the first glass ply has a first thickness between the first and second major surfaces of at least 2 mm, and the second glass ply has a second thickness between the third and fourth major surfaces of less than 2 mm.

[0314] An 88th aspect of the present disclosure comprises the glass laminate of any of the 81st to 87th aspects, wherein the glass laminate comprises a total glass thickness equal to the sum of the first thickness and the second thickness, and wherein the ratio of the first glass thickness to the total glass thickness is at least 0.7.

[0315] An 89th aspect of the present disclosure comprises the glass laminate of any of the 81st to 88th aspects, wherein the first glass thickness is at least 3 mm and the second glass thickness is 1.1 mm or less.

[0316] A 90th aspect of the present disclosure comprises the glass laminate of any of the 81st to 89th aspects, wherein the first glass thickness is at least 3.3 mm and the second glass thickness is 0.7 mm or less.

[0317] A ninety-first aspect of the present disclosure comprises the glass laminate of any of the eighty-first to ninety aspects, wherein the second glass ply comprises a second glass composition.

[0318] A 92nd aspect of the present disclosure comprises the glass laminate of any of the 81st to 91st aspects, wherein the second glass composition is different from the borosilicate glass composition.

[0319] A 93rd aspect of the present disclosure comprises the glass laminate of any of the 81st to 92nd aspects, wherein the second glass composition is selected from the group consisting of an aluminosilicate glass composition, an alkali aluminosilicate glass composition, an alkali-containing borosilicate glass composition, an alkali aluminophosphosilicate glass composition, an alkali aluminoborosilicate glass composition, and combinations thereof.

[0320] A 94th aspect of the present disclosure comprises the glass laminate of any of the 81 to 93rd aspects, wherein the interlayer is selected from the group consisting of polyvinyl butyral (PVB), acoustic PVB (APVB), ionomer, ethylene vinyl acetate (EVA), thermoplastic polyurethane (TPU), polyester (Pe), polyethylene terephthalate (PET), and combinations thereof.

[0321] A 95th embodiment of the present disclosure comprises the glass laminate of any of the 81st to 93rd embodiments, wherein the interlayer comprises a thickness in the range of about 0.5 mm to about 2.5 mm.

[0322] A 96th aspect of the present disclosure comprises the glass laminate of any of the 81st to 95th aspects, wherein the interlayer comprises at least one functional layer or film.

[0323] A 97th aspect of the present disclosure comprises the glass laminate of any of the 81 to 96th aspects, wherein the functional layer or film provides a function selected from the group consisting of ultraviolet absorption, infrared absorption, infrared reflection, acoustic attenuation, tinting, antenna, adhesion promotion, anti-glare treatment, anti-reflection treatment, and combinations thereof.

[0324] A 98th aspect of the present disclosure comprises the glass laminate of any of the 81 to 97 aspects, wherein the first and second glass plies are mated, the first glass ply comprising a first depth of curvature of at least 2 mm, and the second glass ply comprising a second depth of curvature of at least 2 mm, the first depth of curvature being within 10% of the second depth of curvature.

[0325] A ninety-ninth aspect of the present disclosure is a glass fiber reinforced plastic (WFP) comprising: a first glass ply having a viscosity of 10 11 a first temperature at which the viscosity of the second glass ply is 10 poise; 11 Aspect 98 includes a second temperature at which the glass laminate becomes poise, and the first temperature is different from the second temperature.

[0326] A hundredth aspect of the present disclosure comprises the glass laminate of any of the eighty-first to ninety-ninth aspects, wherein the first ply of glass is thicker than the second ply of glass and the second temperature is greater than the first temperature.

[0327] A 101st aspect of the present disclosure comprises the glass laminate of any of the 81st to 100th aspects, wherein the first glass ply is deflected and comprises a curvature depth of at least 2 mm, and the second glass ply is cold formed to conform to the first glass ply.

[0328] A hundred-second aspect of the present disclosure comprises the glass laminate of any of the eighty-first to hundred-first aspects, wherein the second ply of glass comprises a pigment coating on the third major surface.

[0329] A hundred and third aspect of the present disclosure comprises the glass laminate of any of the eighty-first to hundred and second aspects, wherein the first ply of glass or the second ply of glass comprises a coating.

[0330] A 104th aspect of the present disclosure comprises the glass laminate of any of the 81st to 103rd aspects, wherein the coating comprises an infrared reflective coating having at least one metal layer and, optionally, at least a dielectric layer.

[0331] A one hundred and fifth aspect of the present disclosure includes a glass composition comprising SiO in an amount ranging from about 72 mol% to about 80 mol%; AlO in an amount ranging from about 2.5 mol% to about 5 mol%; and BO in an amount ranging from about 11.5 mol% to about 14.5 mol%; wherein the glass composition comprises a liquidus viscosity greater than 500 kP; and wherein the glass composition comprises a temperature of 1725°C or less at which the viscosity of the borosilicate glass composition is 200 P.

[0332] A hundred and sixth aspect of the present disclosure comprises the glass composition according to the hundred and fifth aspect, further comprising Na2O in an amount ranging from about 4 mol% to about 8 mol%.

[0333] A 107th embodiment of the present disclosure comprises the glass composition of any of the 105th to 106th embodiments, wherein the amount of Na2O ranges from about 4.5 mol% to about 8 mol%.

[0334] A 108th embodiment of the present disclosure comprises the glass composition of any of the 105th to 107th embodiments, further comprising KO in an amount ranging from about 0.5 mol% to about 3 mol%.

[0335] A 109th embodiment of the present disclosure comprises the glass composition according to any of the 105th to 108th embodiments, further comprising MgO in an amount ranging from about 0.5 to about 2.5 mol %.

[0336] A 110th aspect of the present disclosure comprises the glass composition of any of the 105th to 109th aspects, further comprising up to about 4 mol% CaO.

[0337] A 111th embodiment of the present disclosure comprises the glass composition according to any of the 105th to 110th embodiments, wherein the amount of SiO2 is at least 74 mol %.

[0338] A 112th aspect of the present disclosure includes a glass composition comprising: 74 mol% to 80 mol% SiO; 2.5 mol% to 5 mol% AlO; 11.5 mol% to 14.5 mol% BO; 4.5 mol% to 8 mol% NaO; 0.5 mol% to 3 mol% KO; 0.5 mol% to 2.5 mol% MgO; and 0 mol% to 4 mol% CaO.

[0339] A 113th embodiment of the present disclosure comprises the glass composition according to the 112th embodiment, wherein the combined amount of Na2O and K2O is at least 5.5 mol %.

[0340] A 114th embodiment of the present disclosure comprises the glass composition according to any of the 112th to 113th embodiments, wherein the combined amount of MaO and CaO is at least 1.5 mol %.

[0341] A 115th embodiment of the present disclosure comprises the glass composition according to any of the 112th to 114th embodiments, wherein the combined amount of Na2O, KO, MaO, and CaO is at least 7 mol%.

[0342] A 116th embodiment of the present disclosure comprises the glass composition according to any of the 112th to 114th embodiments, wherein the combined amount of Na2O and K2O is at least 8 mol%.

[0343] A 117th embodiment of the present disclosure comprises the glass composition of any of the 112th to 116th embodiments, comprising a total amount of Fe2O3 and FeO of 0.03 mol% to 0.5 mol%.

[0344] A 118th aspect of the present disclosure includes an article comprising: a first glass ply including a first major surface and a second major surface opposite the first major surface, the first glass ply comprising a borosilicate glass composition; a second glass ply including a third major surface and a fourth major surface opposite the third major surface; and an interlayer bonding the second major surface of the first glass ply to the third major surface of the second glass ply; wherein: (A) the borosilicate glass composition of the first glass ply comprises (i) SiO, B, and optionally Al, O and / or P, and; and (ii) one or more alkali metal oxides, and optionally one or more alkaline earth metal oxides and / or ZnO; wherein the SiO, B, one or more alkali metal oxides, and, if present in the composition, Al, O, P, and one or more alkaline earth metal oxides and / or ZnO. The mole percent concentrations of nO, on an oxide basis, satisfy the following relationships: SiO ≥ 72; B O ≥ 10; (R O + R' O + P O ) ≥ Al O ; and 0.80 ≤ (1 - [(2R O + 2R' O + 2P O ) / (SiO + 2Al O + 2B O )]) ≤ 0.93; where R O is the sum of the concentrations of one or more alkali metal oxides, and R' O is the sum of the concentrations of one or more alkaline earth metals, if present in a borosilicate glass composition. (B) when glass having the borosilicate glass composition of the first glass ply is subjected to a quasi-static Vickers indentation test using a 2 kgf (approximately 19.6 N) indentation load and a 136° Vickers indenter, the glass exhibits multiple radial cracks and a ring crack that limits the propagation of the radial cracks; and (C) when the article is installed in a vehicle, the first glass ply is on the outside of the second glass ply.

[0345] A 119th aspect of the present disclosure includes the article of the 118th aspect, wherein the first ply of glass is thicker than the second ply of glass, and the second ply of glass is chemically strengthened by an ion exchange process.

[0346] A 20th aspect of the present disclosure includes the article of any of the 118th to 119th aspects, wherein the first glass ply has a first thickness between the first and second major surfaces of at least 2 mm, and the second glass ply has a second thickness between the third and fourth major surfaces of less than 2 mm.

[0347] A 121st aspect of the present disclosure comprises the article of any of the 118th to 120th aspects, wherein the ratio of the first thickness to the sum of the first thickness and the second thickness is at least 0.7.

[0348] A 122nd embodiment of the present disclosure comprises the article of any of the 118th to 121st embodiments, wherein the first thickness is at least 3.3 mm and the second thickness is no greater than 0.7 mm.

[0349] A 123rd aspect of the present disclosure comprises the article of any of the 118th to 122nd aspects, wherein the second glass ply comprises a second glass composition different from the borosilicate glass composition of the first glass ply, the second glass composition being selected from the group consisting of soda-lime silicate glass compositions, aluminosilicate glass compositions, alkali aluminosilicate glass compositions, alkali-containing borosilicate glass compositions, alkali aluminophosphosilicate glass compositions, and alkali aluminoborosilicate glass compositions.

[0350] A 124th aspect of the present disclosure comprises the article of any of the 118th to 123rd aspects, wherein the article has a visible transmittance, measured in accordance with ISO 13837A, of at least 73%, and a total solar transmittance, measured in accordance with ISO 13837A, of 90% or less.

[0351] A 125th aspect of the present disclosure includes the article of any of the 118th to 124th aspects, wherein the first major surface, the fourth major surface, or both the first and fourth major surfaces exhibit an optical distortion of up to 200 millidiopters as measured with an optical distortion detector using transmission optics according to ASTM 1561.

[0352] A 126th embodiment of the present disclosure comprises the article of any of the 118 to 125th embodiments, wherein the intermediate layer is selected from the group consisting of polyvinyl butyral (PVB), acoustic PVB (APVB), ionomer, ethylene vinyl acetate (EVA), thermoplastic polyurethane (TPU), polyester (Pe), polyethylene terephthalate (PET), and combinations thereof; the intermediate layer has a thickness ranging from 0.5 mm to 2.5 mm; and the intermediate layer comprises at least one functional layer or film, and the functional layer or film provides a function selected from the group consisting of ultraviolet absorption, infrared absorption, infrared reflection, sound attenuation, coloration, antenna, adhesion promotion, anti-glare treatment, anti-reflection treatment, and combinations thereof.

[0353] A 127th embodiment of the present disclosure includes the article of any of embodiments 118 to 126, wherein the first and second glass plies are mated, the first glass ply including a first depth of curvature of at least 2 mm, and the second glass ply including a second depth of curvature of at least 2 mm, and the first depth of curvature is within 10% of the second depth of curvature.

[0354] A 128th embodiment of the present disclosure includes the article of any of the 118th to 127th embodiments, wherein the first ply of glass is deflected and includes a curvature depth of at least 2 mm, and the second ply of glass is cold-formed to conform to the first ply of glass.

[0355] A 129th embodiment of the present disclosure includes the article of any of the 118 to 128th embodiments, wherein the first glass ply is made by a downdraw process, the downdraw process being a fusion downdraw process, and the glass having a borosilicate glass composition of the first glass ply has a liquidus viscosity of 500 kpoise or greater, and the glass having a borosilicate glass composition of the first glass ply has a 200 poise temperature of 1725° C. or less.

[0356] A 130th aspect of the present disclosure is an article, comprising an outer ply comprising borosilicate glass and having a thickness of at least 200 μm and no more than 1 cm, wherein, in terms of constituent oxides, the composition of the borosilicate glass comprises SiO, BO, AlO, one or more alkali metal oxides, and one or more divalent cation oxides from the group consisting of MgO, CaO, SrO, BaO, and ZnO, wherein the mole percent concentrations, on an oxide basis, of SiO, BO, one or more alkali metal oxides, AlO, and one or more alkaline earth metal oxides satisfy the following relationship: (RO + RO) ≧ AlO 3、 0.80<(1-[(2R2O+2R'O) / (SiO2+2Al2O3+2B2O3)])<0.93, where R2O is the sum of the concentrations of one or more alkali metal oxides and R'O is the sum of the concentrations of one or more alkaline earth metal oxides, an outer ply; an inner ply comprising a second glass different from the borosilicate glass composition of the outer ply, the inner ply strengthening and stiffening the outer ply against applied bending forces, and the composition of the second glass being selected from the group consisting of soda-lime silicate glass compositions, aluminosilicate glass compositions, alkali aluminosilicate glass compositions, alkali-containing borosilicate glass compositions, alkali aluminophosphosilicate glass compositions, and alkali aluminoborosilicate glass compositions; and an interlayer bonding the inner and outer plies, the interlayer being polymeric and attenuating crack propagation from the outer ply to the inner ply.

[0357] A 131st aspect of the present disclosure is a glass having an outer ply borosilicate glass composition of 2×2 cm 2and when the specimen is formed as 100 polished flat specimens of 1 mm thickness and having a major surface of an area of ​​1 mm, and tested at 25°C and 50% relative humidity using a Vickers indenter in the shape of a 136° pyramid with a square base oriented perpendicular to the center of the major surface, the indenter is quasi-statically displaced at a rate of 60 μm / sec up to a maximum load of 3 kgf (about 29.4 N), and the indentation load is held for 10 seconds, most of the cracks extending radially and / or laterally from the indenter through the specimen are contained within crack loops.

[0358] A 132nd aspect of the present disclosure includes the article of any of the 130th to 131st aspects, wherein when the sample is rapidly cooled from 25°C to 1°C by immersion in cold water, in most cases, cracks extending radially and / or laterally through the sample do not propagate beyond the crack loop.

[0359] A 133rd embodiment of the present disclosure comprises the article of any of the 130th to 132nd embodiments, wherein the majority of the crack loops of the specimen are circular and have a radius of less than 1 mm.

[0360] A 134th aspect of the present disclosure is an article, comprising a first ply of glass including a first major surface and a second major surface opposite the first major surface, the first ply of glass comprising borosilicate glass, wherein, in terms of constituent oxides, the composition of the borosilicate glass comprises SiO, BO, AlO, one or more alkali metal oxides, and one or more divalent cation oxides from the group consisting of MgO, CaO, SrO, BaO, and ZnO, wherein the mole percent concentrations, on an oxide basis, of SiO, BO, one or more alkali metal oxides, AlO, and one or more divalent cation oxides satisfy the following relationships: (RO + R'O) ≥ AlO, 0.80 < (1 - [(2RO and an interlayer bonding the second major surface of the first ply of glass to the third major surface of the second ply of glass; wherein the transmittance of ultraviolet light having a wavelength in the range of 300 to 380 nm through the article is 75% or less; the transmittance of light in the visible spectrum through the article is 73% or more; and the total solar transmittance through the article is 61% or less.

[0361] A 135th aspect of the present disclosure includes the article of the 134th aspect, wherein the borosilicate glass composition comprises at least 74 mol% SiO, at least 10 mol% B0, and AlO in an amount such that the sum of SiO, B0, and AlO is at least 90 mol%.

[0362] A 136th aspect of the present disclosure is an article, comprising a borosilicate glass, wherein, in terms of constituent oxides, the composition of the borosilicate glass comprises SiO2, BO3, AI2O3, one or more alkali metal oxides, and one or more divalent cation oxides from the group consisting of MgO, CaO, SrO, BaO, and ZnO, wherein the mole percent concentrations, on an oxide basis, of SiO2, BO3, one or more alkali metal oxides, AI2O3, and one or more divalent cation oxides satisfy the following relationship: (R2O+R'O)≧Al2O3, 0.80<(1-[(2R2O+2R'O) / (SiO2+2Al2O3+2B2O3)])<0.93, where R2O is the sum of the concentrations of one or more alkali metal oxides and R'O is the sum of the concentrations of one or more divalent cation oxides; an article comprising a borosilicate glass and a crack loop formed in the borosilicate glass, the article comprising: a borosilicate glass; and a crack loop formed in the borosilicate glass, the article comprising: a borosilicate glass; and a crack loop formed in the borosilicate glass, the article comprising: a borosilicate glass; and a crack loop formed in the borosilicate glass, the article comprising: a borosilicate glass; and a crack loop formed in the borosilicate glass; ... a borosilicate glass; and a crack loop formed in the borosilicate glass; the article comprising: a borosilicate glass; a borosilicate glass; and a crack loop formed in the borosilicate glass; the article comprising: a borosilicate glass; a borosilicate glass; and a crack loop formed in the borosilicate glass; the article comprising: a borosilicate glass; a borosilicate glass; and a crack loop formed in the borosilicate glass; the article comprising: a borosilicate glass; a borosilicate glass; and a crack loop formed in the bo

[0363] A 137th embodiment of the present disclosure includes the article of the 136th embodiment, wherein the crack loop has a circular circumference.

[0364] A 138th embodiment of the present disclosure includes the article of any of the 136th to 137th embodiments, wherein the circular perimeter has a diameter of less than 1 mm.

[0365] A 139th embodiment of the present disclosure comprises the article of any of the 136th to 138th embodiments, wherein the borosilicate glass has a thickness of at least 200 μm and no more than 1 cm.

[0366] A 140th embodiment of the present disclosure comprises the article of any of the 136th to 139th embodiments, wherein the borosilicate glass has a low temperature coefficient of thermal expansion greater than 3.25 ppm / °C and less than 8.7 ppm / °C.

[0367] A 141st aspect of the present disclosure comprises the article of any of the 136th to 140th aspects, wherein the thickness is 2.0 mm or greater.

[0368] A 142nd embodiment of the present disclosure includes the article of any of the 136th to 141st embodiments, wherein the borosilicate glass composition includes greater than or equal to 4 mol% and less than or equal to 6 mol% NaO.

[0369] A 143rd embodiment of the present disclosure includes the article of any of the 136th to 142nd embodiments, wherein the borosilicate glass composition includes: greater than or equal to 3 mol% and less than or equal to 5 mol% AlO; and greater than or equal to 12 mol% and less than or equal to 16 mol% BO.

[0370] A 144th embodiment of the present disclosure includes the article of any of the 136th to 143rd embodiments, wherein the borosilicate glass has at least one of a composition of 0.03 mol % or more and 0.5 mol % or less Fe2O3, a thickness of 3.3 mm or less, or the outer ply has a transmittance of 90% or more and 92.5% or less across the visible spectrum.

[0371] A 145th aspect of the present disclosure includes the article of any of the 136th to 144th aspects, wherein the outer glass ply comprises borosilicate glass.

[0372] A 146th aspect of the present disclosure includes a borosilicate glass composition comprising 60 mol% or more and 96.0 mol% or less of SiO2; 1.0 mol% or more and 25.0 mol% or less of B2O3, 0.3 mol% or more of Al2O3; 0.0 mol% or more and 0.3 mol% or less of Li2O; a non-zero amount of Na2O; and one or more divalent metal oxides RO, wherein the compositional amount in mol% of each component, represented by the molecular formula of each component, satisfies the relationship B2O3 + 3.5 * Al2O3 ≦ 27.5 mol%, and at least one of the following applies: (A) the compositional amount of each component satisfies both of the following conditions: (i) C rb -(3.4-0.5*C nb )<0.000; and (ii) 1-2*(Alk2O+RO) / P total >0.83, where (a)C rb is the value of the rotatability balance parameter calculated from the composition expressed in mole % of the components according to the following formula: C rb=abs(2*max(0,(Alk2O+RO)-(Al2O3+B2O3))+2*min(B2O3,R2O+RO-Al2O3)+0.65*(SiO2+2*Al2O3+2*B2O3)-80), (b)C nb is the value of the network balance parameter calculated from the composition expressed in mole % of the components according to the following formula: C nb =abs(SiO2-6*min(Alk2O,Al2O3)-2*min(Alk2O+RO-Al2O3,B2O3)-max(24+2*max(0,B2O3-max(0,R2O+RO-Al2O3)),44)), (c) Alk2O represents one or more alkali metal oxides, if present in the composition, and (d) P total is the value of the total polyhedral parameter, calculated from the glass composition in mole percent of the components according to the following formula: P total =SiO2+2*Al2O3+2*B2O3, and (B) the composition amount of each component satisfies the following conditions:P d -(2.58-0.2*(Na2O / Al2O3))<0.000, where P d is the value of the density parameter, calculated from the glass composition in mole percent of the components according to the following formula: d =2.487-0.0068998*B2O3+0.041371*BaO+0.13897*Bi2O3+0.011637*CaO+0.055366*Cs2O+0.025420*Fe2O 3+0.10294*Gd2O3+0.0051134*K2O+0.079903*La2O3+0.0041594*Li2O+0.0084582*MgO+0.019720*MnO+0.0 064419*Na2O+0.018282*NiO+0.065781*PbO-0.002953*SiO2+0.027682*SrO+0.0055367*TiO2+0.0068497 *V2O5+0.048699*Y2O3+0.021527*ZnO+0.026527*ZrO2+0.011033*(min(B2O3,max(0,Alk2O+RO-Al2O3))).

[0373] A 147th aspect of the present disclosure includes the borosilicate glass composition according to the 146th aspect, wherein the compositional amounts of each component satisfy both of the following conditions: (i) C rb -(3.4-0.5*C nb )<0.000; and (ii) 1-2*(Alk2O+RO) / P total >0.83, the composition comprising a combined amount of Na2O and Al2O3 of 9.7 mol% or less, and the composition being substantially free of BaO, fluorine, and rare earth oxides.

[0374] A 148th aspect of the present disclosure comprises the borosilicate glass composition of any of the 146th to 147th aspects, wherein the composition comprises 60.0 mol% or more and 78 mol% or less of SiO, 5.0 mol% or more and 17.0 mol% or less of B2O3, 2.5 mol% or more and 5.3 mol% or less of Na2O, 0.3 mol% or more and 5.3 mol% or less of Al2O3, 0.0 mol% or more and 3.0 mol% or less of K2O, 0.0 mol% or more and 1.5 mol% or less of CaO, 0.0 mol% or more and 0.2 mol% or less of Li2O, and 5.0 mol% or more of Na2O + K2O, wherein the compositional amounts of each component satisfy the following condition: 20.3≦B2O3 + 3.5 * Al2O3 ≦ 27.5.

[0375] A 149th aspect of the present disclosure is a composition comprising: 0.0 mol% or more and 5.0 mol% or less MgO; 0.0 mol% or more and 4.0 mol% or less P2O5; 0 mol% or more and 0.25 mol% or less SnO2; a total amount of (Na2O+K2O+MgO+CaO+ZnO+Al2O3+BO3+SiO2) equal to or greater than 95.0 mol%; a total amount of (CaO+MgO) equal to or greater than 0.0 mol% and 5.0 mol% or less; The borosilicate glass composition according to any one of aspects 146 to 148, comprising a total amount of (FeO + Fe2O3) of 0.0 mol% or more and 0.5 mol% or less, wherein the compositional amounts of each component of the composition satisfy both of the following conditions: (C) (Na2O + KO + MgO + CaO + SrO + BaO + ZnO) / (RO + RO) ≦ 0.95, and (D) 1.01 ≦ Na2O / Al2O3 ≦ 1.35.

[0376] A 150th aspect of the present disclosure comprises the borosilicate glass composition of any of the 146th to 149th aspects, wherein the composition comprises: 72.0 to 78.0 mol% SiO, 5.0 to 20.0 mol% BO, 2.0 to 8.0 mol% NaO, 2.0 to 4.0 mol% AlO, 0.0 to 3.0 mol% KO, 0.0 to 2.0 mol% CaO, 0.0 to 2.0 mol% MgO, and 0.0 to 0.2 mol% SnO.

[0377] A 151st aspect of the present disclosure comprises the borosilicate glass composition of any of the 146th to 150th aspects, wherein the composition comprises: 0.0 to 0.5 mol% MnO, 0.0 to 0.5 mol% MnO, 0.0 to 0.5 mol% TiO, and 0.0 to 1.0 mol% total of (Fe+Cr+Mo+V+Cu+Co), wherein the composition is substantially free of LiO and substantially free of PbO.

[0378] A 152nd aspect of the present disclosure comprises the borosilicate glass composition of any of the 146th to 151st aspects, wherein the compositional amounts of each component of the composition satisfy the following condition: (E) 0.0≦2*M exc +2*min(B2O3,R2O+RO-Al2O3)+0.65*P total -80≦3.0, where M exc is the value of the modifier excess parameter, calculated from the glass composition in mole percent of the components according to the following formula: M exc =max(0,(Alk2O+RO)-(Al2O3+B2O3)), and (F)0.0≦abs(Si exc -3*((B2O3+Al2O3)-(Alk2O+RO))-max(24-B exc ,44-3*B exc ))≦3.0, where: (i) Si exc is the value of the silica excess parameter, calculated from the glass composition in mole percent of the components according to the following formula: Si exc=SiO2-6*min(Alk2O,Al2O3O3)-2*min(Alk2O+RO-Al2O3O3,B2O3), and (ii)B exc is the value of the boron excess parameter, calculated from the glass composition in mole percent of the components according to the following formula: exc =max(0,B2O3-max(0,R2O+RO-Al2O3)).

[0379] A 153rd aspect of the present disclosure is a composition in which the composition amount of each component satisfies the following conditions: P d -(2.58-0.2*(Na2O / Al2O3O3))<0.000.

[0380] A 154th aspect of the present disclosure comprises the borosilicate glass composition of any of the 146th to 153rd aspects, wherein the composition comprises: 60.0 to 77.5 mol% SiO, 5.0 to 17.0 mol% BO, 2.5 to 5.3 mol% NaO, 0.3 to 5.3 mol% AlO, 0.0 to 3.0 mol% KO, 0.0 to 0.2 mol% LiO, 0.0 to 0.2 mol% BaO, and a total amount of (NaO + KO) equal to or greater than 5.0 mol%.

[0381] A 155th aspect of the present disclosure comprises the borosilicate glass composition of any of the 146th to 154th aspects, wherein the composition comprises: greater than or equal to 5.0 mol% and less than or equal to 5.2 mol% NaO, greater than or equal to 0.3 mol% MgO, and greater than or equal to 0.0 mol% and less than or equal to 0.3 mol% TiO; and the composition is substantially free of fluorine.

[0382] A 156th aspect of the present disclosure is a method for producing a cellulose acetate composition comprising: total 156. The borosilicate glass composition of any one of aspects 146 to 155, wherein the borosilicate glass composition satisfies the following:

[0383] A 157th aspect of the present disclosure is a method for manufacturing a cellulose ester resin composition comprising: exc +2*min(B2O3,R2O+RO-Al2O3))+0.65*P total ≦82, where M exc is the value of the modifier excess parameter, calculated from the glass composition in mole percent of the components according to the following formula: M exc =max(0,(Alk2O+RO)-(Al2O3+B2O3)), and (H)0.84≦1-2*(Alk2O+RO) / P total ≦0.90.

[0384] A 158th aspect of the present disclosure comprises the borosilicate glass composition of any of the 146th to 157th aspects, wherein the composition comprises 0.0 mol% or more and 4.0 mol% or less of P2O5, 0 mol% or more and 0.25 mol% or less of SnO2, a total amount of (Na2O+K2O+MgO+CaO+ZnO+Al2O3+BO3+SiO2) of 95.0 mol% or more, a total amount of (CaO+MgO) of 0.0 mol% or more and 5.0 mol% or less, and a total amount of (FeO+Fe2O3) of 0.0 mol% or more and 0.5 mol% or less, and the compositional amounts of each component of the composition satisfy both of the following conditions: (I) (Na2O+K2O+MgO+CaO+SrO+BaO+ZnO) / (RO+RO)≦0.95, and (J) 1.01≦Na2O / Al2O3≦1.35.

[0385] A 159th aspect of the present disclosure comprises the borosilicate glass composition of any of the 146 to 158th aspects, wherein the composition comprises: greater than or equal to 72.0 mol% and less than or equal to 77.5 mol% SiO, greater than or equal to 2.0 mol% and less than or equal to 4.0 mol% AlO, greater than or equal to 0.0 mol% and less than or equal to 2.0 mol% CaO, greater than or equal to 0.0 mol% and less than or equal to 2.0 mol% MgO, and greater than or equal to 0.0 mol% and less than or equal to 0.2 mol% SnO.

[0386] A 160th aspect of the present disclosure comprises the borosilicate glass composition of any of the 146th to 159th aspects, wherein the composition comprises: 0.0 to 0.5 mol% MnO2; 0.0 to 0.5 mol% MnO; 0.0 to 0.5 mol% TiO2; 0.0 to 1.0 mol% combined total of (Fe+Cr+Mo+V+Cu+Co); and 0.0 to 1.0 mol% combined total of (La2O3+YO3).

[0387] A 161st aspect of the present disclosure comprises the borosilicate glass composition of any of the 146th to 160th aspects, wherein the composition is substantially free of fluorine, BaO, LiO2, and PbO.

[0388] A 162nd aspect of the present disclosure comprises the borosilicate glass composition of any of the 146th to 161st aspects, wherein the amount of each component of the composition satisfies the following condition: (K)0.0≦2*M exc +2*min(B2O3,R2O+RO-Al2O3)+0.65*P total -80≦3.0, where M exc is the value of the modifier excess parameter, calculated from the glass composition in mole percent of the components according to the following formula: M exc =max(0,(Alk2O+RO)-(Al2O3+B2O3)), and (L)0.0≦abs(Si exc -3*((B2O3+Al2O3)-(Alk2O+RO))-max(24-B exc ,44-3*B exc ))≦3.0, where: (i) Si exc is the value of the silica excess parameter, calculated from the glass composition in mole percent of the components according to the following formula: Si exc =SiO2-6*min(Alk2O,Al2O3O3)-2*min(Alk2O+RO-Al2O3O3,B2O3), and (ii)B exc is the value of the boron excess parameter, calculated from the glass composition in mole percent of the components according to the following formula: exc =max(0,B2O3-max(0,R2O+RO-Al2O3)).

[0389] A 163rd aspect of the present disclosure comprises the borosilicate glass composition of any of the 146th to 162nd aspects, wherein the composition comprises: ≧11 mol% and ≦16 mol% BO, ≧2 mol% and ≦6 mol% AI, and ≧7.0 mol% total of NaO, KO, MgO, and CaO.

[0390] A 164th aspect of the present disclosure comprises the borosilicate glass composition of any of the 146th to 163rd aspects, wherein the composition comprises greater than or equal to 4 mol% and less than or equal to 6 mol% Na2O.

[0391] A 165th aspect of the present disclosure comprises the borosilicate glass composition of any of the 146th to 164th aspects, wherein the borosilicate glass composition comprises: greater than or equal to 3 mol% and less than or equal to 5 mol% Al2O3; and greater than or equal to 12 mol% and less than or equal to 16 mol% B2O3.

[0392] A 166th aspect of the present disclosure includes a glass article comprising the borosilicate glass composition according to any of the 146th to 165th aspects.

[0393] A 167th aspect of the present disclosure is a glass article having a glass fiber strength of 2.5 g / cm 3 166. The glass article of claim 166, wherein the glass article has a density measured at 20°C of less than 166.

[0394] A 168th embodiment of the present disclosure has a density of 2.3 g / cm 3 measured at 20°C. 3 The glass article of embodiment 167, wherein the glass article has a thickness of less than 1 / 2 mm.

[0395] A 169th aspect of the present disclosure is a glass having a borosilicate composition, the glass having a size of 2×2 cm 2169. The glass article of aspect 167 or 168, wherein when formed as 100 polished flat samples of 1 mm thickness and having a major surface of an area of ​​1 mm, and tested at 25°C and 50% relative humidity using a Vickers indenter in the shape of a 136° square pyramid with a square base oriented perpendicular to the center of the major surface, the indenter is quasi-statically displaced at a rate of 60 μm / s up to a maximum load of 3 kgf (about 29.4 N), and the indentation load is held for 10 seconds, most of the cracks extending radially and / or laterally from the indenter through the sample are contained within crack loops.

[0396] A 170th embodiment of the present disclosure comprises the glass article of the 169th embodiment, wherein the majority of the crack loops of the specimen are circular and have a radius of less than 1 mm.

[0397] The construction and arrangement of the compositions, assemblies, and structures shown in the various exemplary embodiments are merely illustrative. While only a few embodiments are described in detail in this disclosure, many modifications (e.g., variations in the size, dimensions, structure, shape, and proportions of various elements, parameter values, mounting arrangements, material use, color, orientation) are possible without substantially departing from the novel techniques and advantages of the subject matter described herein. Materials such as glazing disclosed herein can be used for glazing in architectural applications (e.g., windows, partitions) or for other applications, such as packaging (e.g., containers). The order or sequence of any process, logic algorithm, or method steps can be modified or re-sequenced according to alternative embodiments. Other substitutions, modifications, changes, and omissions can also be made in the design, operating conditions, and arrangement of the various exemplary embodiments without departing from the scope of the inventive technology.

[0398] Preferred embodiments of the present invention will be described below in detail.

[0399] Embodiment 1 1. A borosilicate glass composition comprising: at least 75 mol% SiO2; at least 10 mol% B2O3; and Al2O3 in an amount such that the sum of SiO2, B2O3, and Al2O3 is at least 90 mole % where: the borosilicate glass composition has a liquidus viscosity greater than 500 kP; and The borosilicate glass composition has a temperature of 1725°C or less, at which the viscosity of the borosilicate glass composition is 200P. Borosilicate glass compositions.

[0400] Embodiment 2 10. The borosilicate glass composition of claim 1, further comprising about 2 mol% to about 8 mol% NaO.

[0401] Embodiment 3 3. The borosilicate glass composition of claim 1 or 2, further comprising about 1 mol% to about 4 mol% KO.

[0402] Embodiment 4 4. The borosilicate glass composition of any one of claims 1 to 3, wherein the total amount of Na2O and K2O is at least 4 mol%.

[0403] Embodiment 5 5. The borosilicate glass composition of embodiment 4, further comprising at least one of MgO or CaO, wherein the total amount of MgO and CaO is up to 5 mol %.

[0404] Embodiment 6 6. The borosilicate glass composition of embodiment 5, wherein the total amount of Na2O, KO, MgO, and CaO is at least 7 mol%.

[0405] Embodiment 7 7. The borosilicate glass composition of any one of claims 1 to 6, further comprising P2O5, wherein P2O5 is present in an amount up to 4 mol%.

[0406] Embodiment 8 8. The borosilicate glass composition of any one of claims 1 to 7, further comprising about 0.05 mol% to about 0.25 mol% SnO2.

[0407] Embodiment 9 9. The borosilicate glass composition of any of the preceding claims, further comprising 0.05 to 0.50 mol% Fe2O3.

[0408] Embodiment 10 2.4g / cm 3 10. The borosilicate glass composition of any of claims 1 to 9, comprising a density of less than

[0409] Embodiment 11 11. The borosilicate glass composition of any one of claims 1 to 10, comprising a strain point of about 500°C to about 560°C.

[0410] Embodiment 12 12. The borosilicate glass composition of any of claims 1 to 11, comprising an annealing point of about 550°C to about 590°C.

[0411] Embodiment 13 In goods, An outer ply comprising borosilicate glass and having a thickness of at least 200 μm and no greater than 1 cm, wherein, in terms of constituent oxides, the composition of the borosilicate glass comprises SiO2, B2O3, Al2O3, one or more alkali metal oxides, one or more divalent cation oxides from the group consisting of MgO, CaO, SrO, BaO, and ZnO, wherein the mole percent concentrations of SiO2 and B2O3 on an oxide basis are: 11 mol% or more and 16 mol% or less of B2O3, 2 mol% or more and 6 mol% or less of Al2O3, and A total amount of Na2O, K2O, MgO, and CaO of 7.0 mol% or more where: The one or more alkali metal oxides, Al2O3, and the one or more alkaline earth metal oxides satisfy the following relationship: (R2O+R'O)≧Al2O3 0.80<(1-[(2R2O+2R'O) / (SiO2+2Al2O3+2B2O3)])<0.93, wherein R2O is the sum of the concentrations of the one or more alkali metal oxides and R'O is the sum of the concentrations of the one or more alkaline earth metal oxides. outer ply, an inner ply comprising a second glass different in composition from the borosilicate glass of the outer ply, the inner ply strengthening the outer ply and strengthening the outer ply against applied bending forces, the composition of the second glass being selected from the group consisting of soda-lime silicate glass compositions, aluminosilicate glass compositions, alkali aluminosilicate glass compositions, alkali-containing borosilicate glass compositions, alkali aluminophosphosilicate glass compositions, and alkali aluminoborosilicate glass compositions; an interlayer joining the inner and outer plies, the interlayer being polymeric and attenuating crack propagation from the outer ply to the inner ply; Including, goods.

[0412] Embodiment 14 The outer ply of glass having the borosilicate glass composition has an area of ​​2×2 cm 2 14. The article of claim 13, wherein when formed as 100 polished flat samples 1 mm thick having a major surface of 136° angle θ and tested at 25° C. and 50% relative humidity using a Vickers indenter in the shape of a 136° square pyramid with a square base oriented perpendicular to the center of the major surface, the indenter is displaced quasi-statically at a rate of 60 μm / sec up to a maximum load of 3 kgf (about 29.4 N), and the indentation load is held for 10 seconds, generally all of the cracks extending radially and / or laterally from the indenter through the sample are contained within crack loops.

[0413] Embodiment 15 15. The article of claim 14, wherein when the sample is rapidly cooled from 25°C to 1°C by placing it in cold water, in most cases, cracks extending radially and / or laterally through the sample do not propagate beyond the crack loop.

[0414] Embodiment 16 15. The article of claim 14, wherein the majority of the crack loops in the sample are circular and have a radius of less than 1 mm.

[0415] Embodiment 17 17. The article of any one of claims 13 to 16, wherein the borosilicate glass of the outer ply comprises at least 74 mol% SiO2 and at least 10 mol% B2O3; and the borosilicate glass of the outer ply comprises at least 90 mol% of the sum of SiO2, B2O3, and Al2O3.

[0416] Embodiment 18 18. The article of any one of claims 13 to 17, wherein the outer ply is thicker than the inner ply, and the second glass of the inner ply is chemically strengthened by an ion exchange process.

[0417] Embodiment 19 19. The article of any one of claims 13 to 18, wherein the outer ply has a first thickness, the first thickness being at least 2 mm, and the inner ply has a second thickness less than 2 mm.

[0418] Embodiment 20 20. The article of any one of claims 13 to 19, wherein a ratio of the first thickness to the sum of the first thickness and the second thickness is at least 0.7.

[0419] Embodiment 21 21. The article of any one of claims 13 to 20, wherein the first thickness is at least 3.3 mm and the second thickness is no greater than 0.7 mm.

[0420] Embodiment 22 22. The article of any one of claims 13 to 21, wherein the article has a visible transmittance, measured in accordance with ISO 13837A, of at least 73%; and a total solar transmittance, measured in accordance with ISO 13837A, of 90% or less.

[0421] Embodiment 23 23. The article of any one of claims 13 to 22, wherein a major surface of the outer ply farthest from the inner ply and a major surface of the inner ply farthest from the outer ply both exhibit an optical distortion of up to 200 millidiopters as measured with an optical distortion detector using transmission optics in accordance with ASTM 1561.

[0422] Embodiment 24 24. The article of any one of claims 13 to 23, wherein the intermediate layer is selected from the group consisting of polyvinyl butyral (PVB), acoustic PVB (APVB), ionomer, ethylene vinyl acetate (EVA), thermoplastic polyurethane (TPU), polyester (Pe), polyethylene terephthalate (PET), and combinations thereof; and the intermediate layer has a thickness ranging from 0.5 mm to 2.5 mm.

[0423] Embodiment 25 25. The article of any one of claims 13 to 24, wherein the outer ply and the inner ply are mated, the outer ply comprising a first depth of curvature of at least 2 mm, and the inner ply comprising a second depth of curvature of at least 2 mm, the first depth of curvature being within 10% of the second depth of curvature.

[0424] Embodiment 26 26. The article of any one of claims 13 to 25, wherein the outer ply includes a curvature depth of at least 2 mm, and the inner ply is stressed by being cold formed to conform to the outer ply.

[0425] Embodiment 27 27. The article of any one of claims 13 to 26, wherein the glass having the borosilicate glass composition of the outer ply has a liquidus viscosity of 500 kpoise or more and the glass having the borosilicate glass composition of the outer ply has a 200 poise temperature of 1725°C or less.

[0426] Embodiment 28 28. The article of any one of claims 13 to 27, wherein the outer ply is configured to be outside the inner ply when the article is installed in a vehicle.

[0427] Embodiment 29 29. The article of any one of claims 13 to 28, wherein the transmittance of ultraviolet light having a wavelength in the range of 300 to 380 nm through the article is 75% or less; the transmittance of light in the visible spectrum through the article is 73% or more; and the total solar transmittance through the article is 61% or less.

[0428] Embodiment 30 30. The article of any one of claims 13 to 29, wherein the borosilicate glass has a low temperature coefficient of thermal expansion greater than 3.25 ppm / °C and less than 8.7 ppm / °C.

[0429] Embodiment 31 14. The article of claim 13, wherein the thickness is 2.0 mm or greater.

[0430] Embodiment 32 14. The article of claim 13, wherein the composition of the borosilicate glass comprises greater than or equal to 4 mol% and less than or equal to 6 mol% Na2O.

[0431] Embodiment 33 The composition of the borosilicate glass is 3 mol% or more and 5 mol% or less Al2O3; and 12 mol% or more and 16 mol% or less B2O3 33. The article of embodiment 32, comprising:

[0432] Embodiment 34 the composition of the borosilicate glass comprises greater than or equal to 0.03 mol % and less than or equal to 0.5 mol % Fe2O3; and the thickness is 3.3 mm or less, and the outer ply has a transmittance of 90% or more and 92.5% or less across the visible spectrum; 14. The article of embodiment 13, wherein at least one of:

[0433] Embodiment 35 14. The article of claim 13, wherein the outer glass ply comprises the borosilicate glass.

[0434] Embodiment 36 The glass laminate is a first ply of glass including a first major surface and a second major surface opposite the first major surface, the first ply of glass including a borosilicate glass composition; a second ply of glass including a third major surface and a fourth major surface opposite the third major surface; and an interlayer joining the second major surface of the first ply of glass to the third major surface of the second ply of glass; Including, The borosilicate glass composition is at least 74 mol% SiO2; at least 10 mol% B2O3; and Al2O3 in an amount such that the sum of SiO2, B2O3, and Al2O3 is at least 90 mole % A glass laminate comprising:

[0435] Embodiment 37 37. The glass laminate of claim 36, wherein the first ply of glass is thicker than the second ply of glass.

[0436] Embodiment 38 38. The glass laminate of claim 36 or 37, wherein the second ply of glass is tempered.

[0437] Embodiment 39 39. The glass laminate of claim 38, wherein the second ply of glass is chemically strengthened by an ion exchange process.

[0438] Embodiment 40 40. The glazing laminate of any one of claims 36 to 39, wherein the glazing laminate is configured for use in a vehicle having a body and an opening defining an interior, the glazing laminate being configured to be positioned within the opening, with the first glass ply positioned facing the exterior of the vehicle and the second glass ply positioned facing the interior of the vehicle.

[0439] Embodiment 41 41. The glass laminate of any of claims 36 to 40, wherein the first glass ply has a first thickness between the first major surface and the second major surface of at least 2 mm, and the second glass ply has a second thickness between the third major surface and the fourth major surface of less than 2 mm.

[0440] Embodiment 42 42. The glass laminate of claim 41, wherein the glass laminate comprises a total glass thickness equal to the sum of the first thickness and the second thickness, and wherein the ratio of the first glass thickness to the total glass thickness is at least 0.7.

[0441] Embodiment 43 43. The glass laminate of claim 41 or 42, wherein the first glass thickness is at least 3 mm and the second glass thickness is no greater than 1.1 mm.

[0442] Embodiment 44 44. The glass laminate of any one of claims 41 to 43, wherein the first glass thickness is at least 3.3 mm and the second glass thickness is no greater than 0.7 mm.

[0443] Embodiment 45 45. The glass laminate of any of claims 36 to 44, wherein the second glass ply comprises a second glass composition.

[0444] Embodiment 46 46. ​​The glass laminate of claim 45, wherein the second glass composition is different from the borosilicate glass composition.

[0445] Embodiment 47 47. The glass laminate of claim 45 or 46, wherein the second glass composition is selected from the group consisting of a soda-lime silicate glass composition, an aluminosilicate glass composition, an alkali aluminosilicate glass composition, an alkali-containing borosilicate glass composition, an alkali aluminophosphosilicate glass composition, an alkali aluminoborosilicate glass composition, and combinations thereof.

[0446] Embodiment 48 48. The glass laminate of any one of claims 36 to 47, wherein the visible transmission through the glass laminate is at least 73%, measured according to ISO 13837A.

[0447] Embodiment 49 49. The glass laminate of any one of claims 36 to 48, wherein the total solar transmittance through the glass laminate is 90% or less, measured according to ISO 13837A.

[0448] Embodiment 50 50. The glass laminate of any one of claims 36 to 49, wherein the first major surface, the fourth major surface, or both the first and fourth major surfaces exhibit an optical distortion of up to 200 millidiopters as measured with an optical strain detector using transmission optics according to ASTM 1561.

[0449] Embodiment 51 51. The glass laminate of any of claims 36 to 50, wherein the interlayer is selected from the group consisting of polyvinyl butyral (PVB), acoustic PVB (APVB), ionomer, ethylene vinyl acetate (EVA), thermoplastic polyurethane (TPU), polyester (Pe), polyethylene terephthalate (PET), and combinations thereof.

[0450] Embodiment 52 42. The glass laminate of any one of claims 36 to 41, wherein the interlayer comprises a thickness in the range of about 0.5 mm to about 2.5 mm.

[0451] Embodiment 53 53. The glass laminate of any of claims 36 to 52, wherein the interlayer comprises at least one functional layer or film.

[0452] EMBODIMENT 54 54. The glass laminate of claim 53, wherein the functional layer or film provides a function selected from the group consisting of ultraviolet absorption, infrared absorption, infrared reflection, acoustic attenuation, tinting, antenna, adhesion promotion, anti-glare treatment, anti-reflective treatment, and combinations thereof.

[0453] Embodiment 55 55. The glass laminate of any one of claims 36 to 54, wherein the first and second glass plies are mated, the first glass ply comprising a first depth of curvature of at least 2 mm, and the second glass ply comprising a second depth of curvature of at least 2 mm, the first depth of curvature being within 10% of the second depth of curvature.

[0454] Embodiment 56 37. The glass laminate of claim 36, wherein the first ply of glass is deflected and includes a depth of curvature of at least 2 mm, and the second ply of glass is cold-formed to conform to the first ply of glass.

[0455] Embodiment 57 1. A borosilicate glass composition comprising: at least 75 mol% SiO2; at least 10 mol% B2O3; and Al2O3 in an amount such that the sum of SiO2, B2O3, and Al2O3 is at least 90 mole % where: the borosilicate glass composition has a liquidus viscosity greater than 500 kP; and The borosilicate glass composition has a temperature of 1725°C or less, at which the viscosity of the borosilicate glass composition is 200P. Borosilicate glass compositions.

[0456] Embodiment 58 58. The borosilicate glass composition of embodiment 57, further comprising about 2 mol% to about 8 mol% NaO.

[0457] Embodiment 59 59. The borosilicate glass composition of embodiment 57 or 58, further comprising about 1 mol% to about 4 mol% KO.

[0458] Embodiment 60 59. The borosilicate glass composition of embodiment 57 or 58, wherein the total amount of Na2O and K2O is at least 4 mol%.

[0459] Embodiment 61 61. The borosilicate glass composition of embodiment 60, further comprising at least one of MgO or CaO, wherein the total amount of MgO and CaO is up to 5 mol%.

[0460] Embodiment 62 62. The borosilicate glass composition of embodiment 61, wherein the total amount of Na2O, KO, MgO, and CaO is at least 7 mol%.

[0461] Embodiment 63 59. The borosilicate glass composition of embodiment 57 or 58, further comprising 0.03 mol % to 0.50 mol % Fe2O3.

[0462] EMBODIMENT 64 2.4g / cm 3 59. The borosilicate glass composition of claim 57 or 58, comprising a density of less than

[0463] Embodiment 65 a strain point of about 500°C to about 560°C; and Annealing point of approximately 550°C to approximately 590°C 59. The borosilicate glass composition of claim 57 or 58, comprising:

[0464] Embodiment 66 A glass laminate comprising: 66. A first glass ply comprising the borosilicate glass composition of any one of claims 57 to 65, a first major surface, and a second major surface opposite the first major surface; a second ply of glass including a third major surface and a fourth major surface opposite the third major surface; and an interlayer bonding the second major surface of the first ply of glass to the third major surface of the second ply of glass, the second ply of glass comprising a second glass composition different from the borosilicate glass composition, the second glass composition being selected from the group consisting of a soda-lime silicate glass composition, an aluminosilicate glass composition, an alkali aluminosilicate glass composition, an alkali-containing borosilicate glass composition, an alkali aluminophosphosilicate glass composition, an alkali aluminoborosilicate glass composition, and combinations thereof; A glass laminate comprising: [Explanation of symbols]

[0465] 100 vehicles 110 Vehicle body 120 opening 130 Automotive Glass 200 glass ply 202 First main surface 204 Second main surface 206 Non-major surface 210 First Thickness 300 laminate / laminate structure 310 First glass ply 320 Second glass ply 330 Middle Class 332 Third Principal Surface 334 Fourth Principal Surface 336 Non-major surface 340 Second Thickness 400 curved glass laminate 410 First Curvature Depth 420 Second Curvature Depth 510 Radial Cracks 520 Ring-shaped crack 700 Melt Forming Equipment 702 Isopipe 704 Trough 706 First molding surface 708 Second molding surface 710 Routes 712 Borosilicate glass composition 714 Glass ply 716 Second Isopipe 718 Second Trough 720 Third molding surface 722 Fourth molding surface 724 Molten Glass Composition 726a, 726b Cladding layer 800 System 810 Sensors 820 input signal 830 Output Signal

Claims

[Claim 1] 1. A borosilicate glass composition comprising: At least 75 mol % SiO ２ ; At least 10 mol % B ２ O ３ and SiO ２ , B ２ O ３ , and Al ２ O ３ and Al in an amount such that the sum of ２ O ３ where: the borosilicate glass composition having a liquidus viscosity greater than 500 kP; and The borosilicate glass composition has a temperature of 1725°C or less at which the viscosity of the borosilicate glass composition is 200P. Borosilicate glass compositions.

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