Glass for high-performance displays

Abstract

The method of making the glass includes batching ingredients including silica, alumina, boria, magnesia, quicklime, and strontia, one or more of which are derived from "dirty" raw materials containing relatively large amounts of sulfur. The method further includes melting and mixing the batch to produce a blister-free glass having sulfur content suitable for high performance displays.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority under 35 U.S.C. § 120 of U.S. Application No. 18 / 242,623, filed September 6, 2023, which is a division of U.S. Application No. 17 / 991,968, filed November 22, 2022, which claims the benefit of priority to U.S. Provisional Application No. 63 / 424,169, filed November 10, 2022, the contents of each of which are relied upon and incorporated by reference in their entirety. [Technical Field]

[0002] Aspects of the present disclosure relate to glass for use with displays, such as the glass that covers television screens and computer monitors, and the manufacture thereof. [Background technology]

[0003] Glass used in modern displays, such as so-called ultra-high resolution or "8K" displays, is generally of very high quality with respect to optical properties and dimensions. Furthermore, such glass maintains its geometric shape while being subjected to the temperatures associated with manufacturing display devices. Sheets of glass made for these displays may be deemed defective if they contain defects in the glass, such as small air bubbles trapped in the glass, called "blisters." Glass manufacturers have developed the tools and knowledge to create such blister-free glass sheets, but such tools do not come without cost.

[0004] For example, conventional wisdom dictates that the sulfur content of glass batch ingredients, particularly for alkali-free glasses for high-performance displays, needs to be carefully controlled, i.e., minimized or avoided entirely, to prevent blistering. Sulfur and its oxides (e.g., SO2, SO3) can react with ingredients during manufacturing and / or come out of suspension in the glass melt, causing, for example, blistering. To control the sulfur content, applicants have used special raw materials that are processed or otherwise possess very low or zero sulfur content.

[0005] However, processing or otherwise sourcing such specialized raw materials is energy and resource intensive. A need exists for more efficient glass and glass manufacturing that overcomes some or all of these challenges. Summary of the Invention

[0006] Applicants have discovered that a certain subset of "alkali-free" glasses suitable for high-performance displays can be made with relatively large amounts of sulfur without resulting in excessive blistering. Furthermore, sulfur actually aids the melting kinetics of such glasses, reducing the need for fining agents such as nitrates. And, even better, this sulfur is found as an impurity in certain low-grade or "dirty" raw materials, allowing for the use of nearly unprocessed raw materials, thus saving energy and labor when producing such glasses.

[0007] According to one aspect of the present disclosure, a method for making a glass article (e.g., sheet) includes batching ingredients including silica, alumina, boria, magnesia, calcium oxide, and strontia, one or more of which are derived from a "dirty" source containing more than 100 ppm sulfur (e.g., even more than 1000 ppm sulfur). Notably, the glass contains no or little barrier, which may be counter to common sense for those skilled in the art due to the recognized benefits of a barrier on the liquidus of the glass. The method further includes melting and mixing the batch to produce a blister-free glass with a sulfur content suitable for high-performance displays. During the production of glass having the above-described combination of ingredients within the ranges further specified herein, applicant discovered that additional heating of the crown of the glass furnace used to produce the glass further facilitates sulfur outgassing from the molten glass. Thus, this exciting discovery involves a combination of glass composition selection, raw material selection, and process innovation.

[0008] According to aspect A1 of the present disclosure, a method for making a glass sheet includes batching ingredients including 64-69 mol% SiO, 11-13 mol% AlO, 6-8 mol% BO, 2-6 mol% MgO, 3-8 mol% CaO, and 1-6 mol% SrO, where the SrO is derived from a "dirty" SrCO raw material in the batch containing more than 200 ppm, e.g., more than 1000 ppm SO. The method further includes melting and mixing the batch to form the glass in a molten state, and then forming the molten glass into a sheet, such as by fusion draw, float, rolling, forming, or other forming process. According to aspect A2, the method of aspect A1 further includes outgassing a majority of the sulfur from the molten glass. According to aspect A3, the outgassing of the method of aspect A2 further includes heating the crown of a melting furnace in which the batch is melted. According to embodiment A4, the heating of embodiment A3 includes providing greater than 0.5 kJ of heat per kg of molten glass to the crown.

[0009] According to aspect A5 of the present disclosure, aspect A2 further includes forming the molten glass into a sheet and cooling the molten glass, wherein the cooled glass includes sulfur. According to aspect A6, the cooled glass of aspect A5 includes greater than 10 parts per million (ppm) sulfur. According to aspect A7, the cooled glass of aspect A5 includes greater than 25 parts per million (ppm) sulfur. According to aspect A8, the cooled glass of aspect A7 does not include blisters having a cross-sectional dimension greater than 30 μm.

[0010] According to embodiment A9 of the present disclosure, the contaminated SrCO3 feedstock of embodiment A1 contains greater than 1500 ppm sulfur. According to embodiment A10, the batching components of embodiment A9 contain less than 3 mol% nitrates.

[0011] According to embodiment A11 of the present disclosure, the contaminated SrCO feedstock of embodiment A1 includes greater than 3000 ppm sulfur. According to embodiment A10, the batching components of embodiment A9, A10, or A11 include, in combination, less than 0.25 mol % alkali metal oxide and less than 0.5 mol % barrier.

[0012] According to aspect B1 of the present disclosure, a sheet of glass for a high-performance display has a thickness of 200 μm or more and 2 mm or less, a width of 5 cm or more and 5 m or less, and a height of 5 cm or more and 5 m or less. The sheet of glass comprises a composition, analyzed in mole percent on an oxide basis, including 64-69 mol% SiO2, 11-13 mol% Al2O3, 6-8 mol% B2O3, 2-6 mol% MgO, 3-8 mol% CaO, and 1-6 mol% SrO. Furthermore, the analyzed sheet composition includes sulfur. According to aspect B2, the sheet composition of aspect B1 includes greater than 10 ppm sulfur. According to aspect B3, the sheet composition of aspect B1 includes greater than 25 ppm sulfur. According to aspect B4, the composition of aspect B1, B2, or B3, in combination, includes less than 0.25 mol% alkali metal oxides. According to aspect B5, the composition of aspect B4 includes less than 0.5 mol% barrier.

[0013] According to aspect C1 of the present disclosure, the glass comprises, analyzed by mole percent on an oxide basis, 64-69 mol% SiO2, 11-13 mol% Al2O3, 6-8 mol% B2O3, 2-6 mol% MgO, 3-8 mol% CaO, and 1-6 mol% SrO. The glass further comprises sulfur. According to aspect C2, the glass of aspect C1 comprises greater than 25 ppm sulfur. According to C3, the glass of aspect C2 or aspect C1 comprises, in combination, less than 0.25 mol% alkali metal oxides and less than 0.5 mol% barium.

[0014] Additional features and advantages are set forth in the following Detailed Description, and in part will become readily apparent to those skilled in the art from this description or may be learned by the practice of the techniques as set forth in the written description and claims herein and the accompanying drawings. It is to be understood that both the foregoing Summary 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.

[0015] The accompanying figures are included to provide a further understanding, and are incorporated into and constitute a part of this specification. These figures illustrate one or more aspects of the present disclosure, and together with the Detailed Description explain the principles and operation of various aspects. Thus, the present disclosure will be more fully understood when the following Detailed Description is taken in conjunction with the accompanying figures. [Brief explanation of the drawings]

[0016] [Figure 1] 1 is a flowchart of a method of making a glass sheet according to one aspect of the present disclosure. [Figure 2] FIG. 1 is a cross-sectional front view of a glass furnace according to one aspect of the present disclosure. [Figure 3] FIG. 1 is a perspective view of a sheet of glass according to one aspect of the present disclosure. [Figure 4] FIG. 1 is a front view of a display according to one aspect of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0017] Before turning to the following Detailed Description and Figures, which set forth aspects of the present disclosure in detail, it should be understood that the present technology is not limited to the details or methodology described in the Detailed Description or illustrated in the Figures. For example, as will be understood by one of ordinary skill in the art, features and attributes associated with an embodiment shown in one of the Figures or described in the text relating to the embodiment may apply to another embodiment shown in another part of the Figure or described elsewhere in the text.

[0018] 1, a method 110 of making glass (e.g., sheet 310 of FIG. 3) for a display (e.g., display 410 of FIG. 4, OLED, LCD, LED, micro LED, high resolution display, ultra high resolution display, television, monitor) includes step 112 of batching ingredients including silica, alumina, boria, magnesia, quicklime, and strontia, where one or more of these ingredients are from a "dirty" source containing greater than 100 ppm, e.g., greater than 1000 ppm, of sulfur. The glass contains little or no barrier.

[0019] According to one aspect of the present disclosure, the glasses herein include silica, SiO2. SiO2 serves as a basic glass former. The SiO2 concentration can be 64 mole percent or greater to provide the glass with density and chemical durability suitable for flat panel display glass, and a liquidus temperature (liquidus viscosity) that allows the glass to be formed by a downdraw process (e.g., a fusion process). Regarding the upper limit, the SiO2 concentration can generally be about 70 mole percent or less to allow the batch materials to be melted using conventional high-volume melting techniques, such as Joule melting in a refractory melter. As the SiO2 concentration increases, the 200 poise temperature (melting temperature) generally increases.

[0020] According to one embodiment, the silica batched and / or analyzed on a mole percent oxide basis is 64 mol% or more, e.g., 64.9 mol% or more, and / or 70 mol% or less, e.g., 69 mol% or less, e.g., 68.7 mol% or less.

[0021] According to one aspect of the present disclosure, the glasses herein comprise alumina, Al2O3. Al2O3 is another glass former, and applicants have found that Al2O3 concentrations of 11 mole percent or greater provide the glass with a low liquidus temperature and high viscosity, resulting in a high liquidus viscosity. The use of at least 12 mole percent Al2O3 also improves the annealing point and modulus of such glasses. As discussed further herein, the upper limit may allow for balancing the alumina with the alkaline earth oxides combined.

[0022] According to one embodiment, the alumina, batched and / or analyzed on a mole percent oxide basis, is 11 mol% or more, such as 11.5 mol% or more, such as 12 mol% or more, and / or 13.3 mol% or less, such as 13 mol% or less, for example 12.9 mol% or less.

[0023] According to one aspect of the present disclosure, the glasses herein include boria, BO. BO is both a glass former and a flux that aids in melting and lowers the melting temperature. Because the effect of boria on liquidus temperature is at least as great as its effect on viscosity, increasing BO can be used to increase the liquidus viscosity of the glass. To achieve a useful liquidus viscosity of the glasses as disclosed herein for manufacturing (e.g., forming), the compositions have a BO concentration of 6 mole percent or greater. However, because the annealing point decreases as BO increases, as does the Young's modulus, it is desirable to keep the BO content low relative to its typical concentration in amorphous silicon substrates for the durability benefits as disclosed herein.

[0024] According to one embodiment, the boria, batched and / or analyzed on a mole percent oxide basis, is 6 mol% or more, e.g., 6.1 mol% or more, and / or 8 mol% or less, e.g., 7.5 mol% or less, e.g., 7.2 mol% or less.

[0025] In addition to the glass formers, the glasses described herein also include a subset of alkaline earth oxides: MgO, CaO, and SrO. The alkaline earth oxides MgO, CaO, and SrO provide the glass with various properties important for melting, fining, forming, and final application. According to one embodiment of the present disclosure, at least three different alkaline earth oxides are included in the glass composition. However, according to one embodiment, the subset of alkaline earth oxides does not include BaO, as further described herein.

[0026] According to one aspect of the present disclosure, the glasses herein include magnesia, MgO. Applicant has found that the addition and / or superaddition of MgO can act to lower the liquidus temperature of the corresponding glass. At the same time, the viscosity curve typically steepens with the addition of MgO, reducing the melting temperature, but having little or no effect on the low-temperature viscosity. Applicant has further found that the addition of relatively small amounts of MgO is beneficial to melting by reducing the melting temperature, and beneficial to forming by reducing the liquidus temperature and increasing the liquidus viscosity, while maintaining a high anneal point and low compaction.

[0027] In terms of quantitative amounts, according to one embodiment, the magnesia batched and / or analyzed in mole percent on an oxide basis is 2% or more, e.g., 2.5% or more, and / or 7.5% or less, e.g., 6% or less, e.g., 5.6% or less.

[0028] According to one aspect of the present disclosure, the glasses herein include calcium oxide or "quicklime," CaO. Applicants have found that calcium oxide in the glasses of the present disclosure can contribute to lower liquidus temperatures, higher liquidus viscosities, higher anneal points and elastic moduli, and thermal expansion coefficients that are desirable for certain applications, such as flat panel, high-resolution, and ultra-high-resolution displays (see generic display 410 in FIG. 4). Applicants have found that calcium oxide also favorably contributes to the chemical durability of the glasses of the present disclosure. However, at high concentrations, CaO increases the density and thermal expansion coefficient.

[0029] According to one embodiment, the calcium oxide, batched and / or analyzed on a mole percent oxide basis, is 3% or more, e.g., 3.5% or more, e.g., 3.9% or more, and / or 8% or less, e.g., 7.5% or less.

[0030] According to one aspect of the present disclosure, the glasses herein include strontia, SrO. Applicants have found that SrO in the glasses of the present disclosure can contribute to both a low liquidus temperature and a high liquidus viscosity. However, the selection and concentration of these alkaline earth oxides can be balanced with the other components disclosed herein to obtain a suitable combination of physical properties and liquidus viscosity so that the glasses can be formed, for example, by a downdraw process.

[0031] According to one embodiment, the strontia, batched and / or analyzed on a mole percent oxide basis, is 3% or more, e.g., 3.1% or more, and / or 6% or less, e.g., 5.5% or less.

[0032] Applicants have found that the sources and raw materials providing the oxides disclosed herein may carry different relative amounts of sulfur and oxides of sulfur (e.g., SO2, SO3) as impurities. For example, some "dirty" strontia sources may, in some cases, be mostly strontianite SrCO3 raw materials carrying SO2 with sulfur contents greater than 100 ppm, e.g., greater than 200 ppm, e.g., 225 ppm or more, e.g., 250 ppm or more, e.g., 300 ppm or more, e.g., 500 ppm or more, e.g., 1000 ppm or more, e.g., 1500 ppm or more, e.g., 2000 ppm or more, e.g., 2500 ppm or more, e.g., 3000 ppm or more. Other strontium sources, such as celestite, may carry more sulfur. Notably, this parts per million is for the raw material, e.g., SrCO3, and not for the batch. When a feedstock having a SO2 impurity content is added to a batch, the SO2 may comprise more than 200 ppm of the batch, e.g., 225 ppm or more, e.g., 250 ppm or more, or even 300 ppm or more of the batch. Also, by convention, "SO2" in this specification and claims represents oxides of sulfur unless otherwise specified, and the sulfur content may actually be provided as other such sulfur compounds, such as SO3.

[0033] Similarly, some or all of the other alkaline earth oxides and other oxides disclosed herein may carry such amounts of sulfur. When such "dirty" raw material sources are used, the batch may contain very high amounts of sulfur, which was previously thought to result in excessive blistering. However, as further explained herein, the discovery of the compositions disclosed herein combined with the inventive process for glass making can tolerate such amounts of sulfur without excessive blistering.

[0034] According to one aspect of the present disclosure, the glasses include a subset of the alkaline earth oxides described above, but the glasses disclosed herein may be free of, or at least largely free of, the barrier, BaO. While BaO may have benefits in some glasses, such as affecting the liquidus viscosity, applicants have discovered that BaO can exacerbate blistering, particularly in glasses such as those disclosed herein, such as glasses made with raw materials containing significant amounts of sulfur.

[0035] According to one embodiment, the glasses disclosed herein, when batch processed and / or analyzed, may not contain much BaO, such as less than or equal to 1 mol% on an oxide basis, e.g., less than or equal to 0.5 mol%, e.g., less than or equal to 0.25 mol%, e.g., less than or equal to 0.1 mol%, and / or less than or equal to 2000 ppm, e.g., less than or equal to 1000 ppm, e.g., less than or equal to 500 ppm, e.g., less than or equal to 250 ppm, e.g., less than or equal to 200 ppm, e.g., less than or equal to 100 ppm of the analyzed batch or glass.

[0036] Applicants have found that the ratio of the total mole percentage of a subset of alkaline earth metal oxides to the amount of alumina, as disclosed herein, is useful for achieving suitably high values ​​of liquidus viscosity for forming large sheets of thin glass. According to one embodiment, this ratio of (MgO+CaO+SrO) / Al2O3, batched and / or analyzed on an oxide basis mole percent, is 0.95 or greater, e.g., 1 or greater, e.g., 1.05 or greater, e.g., 1.1 or greater, and / or 1.3 or less, e.g., 1.25 or less, e.g., 1.24 or less.

[0037] In addition to the components (or non-components, such as barriers) disclosed above, the glasses described herein may optionally include various other oxides to affect various physical, melting, fining, and forming attributes of the glasses according to one aspect of the present disclosure. Such "optional" oxides include TiO, MnO, FeO, ZnO, NbO, MoO, ZrO, TaO, WO, YO, LaO, and CeO.

[0038] According to one embodiment, the optional oxides (TiO, MnO, FeO, ZnO, NbO, MoO, ZrO, TaO, WO, YO, LaO, or CeO) individually batched and / or analyzed on an oxide basis mole percent may be 2% or less, e.g., 1.5% or less, e.g., 1% or less, e.g., 2000 ppm or less, e.g., 1000 ppm or less, e.g., 500 ppm or less, e.g., 200 ppm or less, e.g., 100 ppm or less, of the analyzed batch or glass, and / or the glass may be free of some and / or all of these oxides (and corresponding non-oxygen elements). According to one embodiment, the optional oxides (TiO, MnO, FeO, ZnO, NbO, MoO, ZrO, TaO, WO, YO, LaO, and CeO) batched and / or analyzed in combination, in mole percent on an oxide basis, may be 5% or less, such as 4% or less, such as 2% or less, e.g., 2000 ppm or less, such as 1000 ppm or less, such as 500 ppm or less, e.g., 200 ppm or less, e.g., 100 ppm or less, of the analyzed batch or glass, and / or the glass may be free of some and / or all of these oxides (and corresponding non-oxygen elements).

[0039] Additionally, the glass compositions may also include various "contaminant" oxides, such as ZrO2 and Fe2O3 (again, by convention, "Fe2O3," but referring to oxides of iron), associated with the batch materials and / or introduced into the glass by the melting, fining, and / or forming equipment used to produce the glass. Similarly, the glasses disclosed herein may also include SnO2, either as a result of Joule melting using tin oxide electrodes and / or through batch processing of tin-containing materials, such as SnO2, SnO, SnCO3, SnCO2, etc.

[0040] According to one embodiment, the contaminant oxides (Fe2O3, ZrO2, or SnO2) individually batched and / or analyzed on an oxide basis mole percent may be 2% or less, e.g., 1.5% or less, e.g., 1% or less, e.g., 2000 ppm or less, e.g., 1000 ppm or less, e.g., 500 ppm or less, e.g., 200 ppm or less, e.g., 100 ppm or less, of the analyzed batch or glass, and / or the glass may be free of some and / or all of these oxides (and corresponding non-oxygen elements). According to one embodiment, the combined batched and / or analyzed contaminant oxides (Fe2O3, ZrO2, and SnO2), on an oxide basis mole percent basis, may be 5% or less, e.g., 4% or less, e.g., 2% or less, e.g., 2000 ppm or less, e.g., 1000 ppm or less, e.g., 500 ppm or less, e.g., 200 ppm or less, e.g., 100 ppm or less, of the analyzed batch or glass, and / or the glass may be free of some and / or all of these oxides (and corresponding non-oxygen elements).

[0041] According to one aspect, the glasses disclosed herein can be largely or completely alkali-free. Applicants find that for high-resolution and ultra-high-resolution display uses, it may be desirable to keep alkali metal oxide levels in the glass below 0.1 mole percent to avoid having a negative impact on thin film transistor (TFT) performance through diffusion of alkali ions from the glass into the silicon of the TFT.

[0042] According to one embodiment, the alkali metal oxides (e.g., NaO, KO, LiO, RbO, or CsO), individually batched and / or analyzed on an oxide basis mole percent, may be 0.5% or less, e.g., 0.25% or less, e.g., 0.1% or less, e.g., 2000 ppm or less, e.g., 1000 ppm or less, e.g., 500 ppm or less, e.g., 200 ppm or less, e.g., 100 ppm or less, of the analyzed batch or glass, and / or the glass may be free of some and / or all of these oxides (and corresponding non-oxygen elements). According to one embodiment, the alkali metal oxides (e.g., NaO, KO, LiO, RbO, and CsO) in combination—on an oxide basis—of the batch processed and / or analyzed may be 1% or less, e.g., 0.5% or less, e.g., 0.25% or less, e.g., 0.1% or less, e.g., 2000 ppm or less, e.g., 1000 ppm or less, e.g., 500 ppm or less, e.g., 200 ppm or less, e.g., 100 ppm or less, of the analyzed batch or glass, and / or the glass may be free of some and / or all of these oxides (and corresponding non-oxygen elements).

[0043] Referring again to Figure 1, method 110 further includes batch melting step 114 and mixing step 116 to produce a glass having a sulfur content suitable for high performance displays, but without blistering (see generic display 410 in Figure 4). Referring now to Figure 2, as disclosed herein, melting of glass 212 may occur in furnace 210. Furnace 210 includes a refractory material (e.g., zirconia) that forms a bottom 214, a sidewall 216, and a crown 218.

[0044] During production, in addition to heating the glass furnace 210 to melt the glass components, Applicant believes that heating the crown 218 of the glass furnace 210, specifically, facilitates sulfur outgassing from the glasses disclosed herein, as shown by bubbles 220 in FIG. 2 . If not outgassed, such bubbles 220 may become trapped within the solidified glass as blisters. However, heating the crown 218 may increase the temperature of the glass 212 and the gases within the furnace 210 that cover the top of the glass 212, which may soften the bubbles 220 and locally affect the viscosity of the top of the glass 212, facilitating the release of the sulfur-bearing gas. Applicant believes that most (i.e., >50%) of the sulfur leaves the glass via outgassing. Advantageously, Applicants have found that sulfur outgassing improves the behavior of the molten glass, allowing it to be produced with less nitrates (e.g., sodium nitrate, or other nitrogen- and oxygen-containing chemicals) or other materials used to facilitate production, such as fining or bleaching; essentially, raw material impurity sulfur replaces agents typically added to achieve high quality, low defect glass. According to one embodiment, the combined batched nitrates, in mole percent on an oxide basis, can be 3% or less, e.g., 1% or less, e.g., 0.5% or less, e.g., 0.25% or less.

[0045] 2 , the crown 218 of the furnace 210 is heated by a notional heat source 222. The heat source 222 may be above and external to the crown 218, as shown, embedded within the crown 218, internal to the furnace, and at least partially directed toward the crown 218, or a combination thereof. The heat source 222 may be a resistive element, a combustible source, directed energy, plasma, microwave, or other heat source. According to one aspect of the present disclosure, the heat source 222 provides greater than 0.5 kJ, e.g., greater than 1 kJ, e.g., greater than 2 kJ, e.g., greater than 10 kJ, of heat to the crown 218 per kg of molten glass 212 in the furnace 210. However, in other cases, the amount of heat provided to and focused on the crown 218 may be less.

[0046] Referring again to FIG. 1 , method 110 further includes step 118 of forming the glass, such as a flat sheet for use with a display (see generic display 410 in FIG. 4 ), and step 120 of cooling the glass, such as below 100° C. to solidify the glass. Applicant has found that fusion forming of the glass sheet, in which molten glass overflows the sides of a trough or “isopipe,” produces a particularly clear surface quality that is useful for superior optical properties, as may be desired for glasses used with displays. The viscosities and corresponding temperatures, and performance of the glasses disclosed herein make fusion forming possible. However, other methods can be used to form the glass, such as so-called “float” forming, in which molten glass is floated on a bath of denser liquid and then polished to achieve sufficient surface quality, as may be required for certain displays.

[0047] Referring now to FIG. 3 , the glass disclosed herein can be formed and cooled as a sheet 310 having a first side 312 (e.g., a front side) and a second side (e.g., a back side) opposite the first side. The side 312 has a height H and a width W. Additionally, the sheet 310 has a thickness T between the first side 312 and the second side, and an edge 314 extending between the sides and defining the periphery of the sheet 310. The thickness T of the glass sheet 310 can be less than the height H and the width W. For example, the thickness T of the glass sheet can be less than 5%, e.g., less than 3%, e.g., less than 1.5%, of the height H and / or width W. For example, the thickness T can be less than 5 mm, e.g., less than 3 mm, within 0.4 mm of such 2 mm, and / or at least 20 μm. The width W and height H can correspond to so-called Gen8, Gen9, Gen10, or Gen10.5 sizes for use in high-resolution or ultra-high-resolution displays. According to one embodiment of the present disclosure, the height H may be greater than the width W. According to one embodiment, the height H and / or width W may be 10 cm or greater, such as 25 cm or greater, such as 50 cm or greater, such as 1 meter or greater. However, while particularly useful for high performance displays, applicants contemplate that the glasses of the present disclosure may be formed into articles of other shapes and used for other purposes.

[0048] While the sheet in FIG. 3 is shown as a rectangular sheet having a constant height H, width W, and thickness T, sheets of other geometric shapes are contemplated. For example, the glass may be formed into a round or circular sheet, the sheet may be bent or curved, such as when attached to a curved display, and portions of the sheet may be thicker than other portions, e.g., the sheet may have a so-called "living hinge" with a narrower thickness that allows the sheet to fold. Some portions of the edges may not be straight, such as having a notch to facilitate the corresponding portion of another component of the display (e.g., frame, logo, console). Applicants also contemplate that the glasses disclosed herein may instead be used for purposes other than display glass, such as windows, glass covering other devices (e.g., solar cells), substrates for devices (e.g., antennas, electronics), etc. [Example]

[0049] In the following tables, Applicant lists the component contents in mole percent on an oxide basis of 90 different glass samples having the properties disclosed herein, as well as the ratio of RO / Al2O3 (typically without any barrier contribution), and an estimate of the SO2 in parts per million for the whole batch, which is provided to the batch as a known impurity in the raw materials, such as from a "dirty" strontia source in combination with sulfur in other component sources. Although listed as SO2 by convention in the tables, SO2 is a representative oxide of sulfur, and the sulfur content may actually be provided as other sulfur compounds, such as SO3.

[0050] Additionally, while the contents in the table are batch processed, the contents represent what was analyzed, except for SO, which was determined to be significantly reduced in the finished glass due to outgassing, as disclosed herein. For example, the analyzed sulfur content for the glasses in the table was measured at about 40 ppm using X-ray fluorescence (XRF). However, this content may vary depending on materials and processing (e.g., use of crown heating techniques, fining, starting content, barrier concentration, etc.). [Table 1] [Table 2] [Table 3] [Table 4] [Table 5] [Table 6] [Table 7] [Table 8] [Table 9]

[0051] According to one aspect of the present disclosure, due at least in part to the use of relatively high sulfur contents in the raw materials, the analyzed sulfur contents of the glasses disclosed herein are non-zero values ​​measurable by XRF that are 5 ppm or more, e.g., 10 ppm or more, e.g., 20 ppm or more, e.g., 25 ppm or more, e.g., 30 ppm or more, e.g., 40 ppm or more, e.g., 50 ppm or more, and / or less than the batched amounts disclosed herein (due to outgassing), e.g., 300 ppm or less, e.g., 200 ppm or less, e.g., 100 ppm or less, e.g., 70 ppm or less.

[0052] Additionally, the present glasses produced using conventional glass manufacturing processes and equipment with the additional process improvements disclosed herein can be formed into large sheets without excessive amounts of blisters, such as may have previously been associated with glasses used in high-performance displays in the past due to a lack of careful control of sulfur content. Such blisters may be defined as gas bubbles or voids trapped within the solidified glass. Blisters may be elongated in shape and may have a longest cross-sectional linear dimension of at least 30 μm measured through their geometric center, such as the major axis of such length. Because such microscopic bubbles may not be a problem for display purposes and / or such bubbles may be substantially imperceptible, even if present, trapped bubbles below such size are excluded from consideration as "blisters" for purposes of this disclosure.

[0053] According to one aspect of the present disclosure, sheets of glass having the dimensions and compositions disclosed herein have no more than 10 total blisters per sheet, e.g., no more than 5 total blisters per sheet, e.g., no more than 2 total blisters per sheet, e.g., no more than 1 total blister per sheet, e.g., no such blisters per sheet.

[0054] According to one aspect of the present disclosure, the glass of the present disclosure may be arranged or formed as an article other than a sheet (e.g., fiber, sphere, rod), and may be formed into a glass having a volume of 15 cm 3 , as defined above. 3 No more than 10 blisters total per 30cm 3 No more than 10 blisters total per 50cm 3 No more than 10 blisters in total per 100cm, e.g. 3 No more than 10 blisters total per 500cm, e.g. 3 According to one aspect of the present disclosure, the glass of the present disclosure may still have few, if any, blisters, such as a total of 10 or fewer blisters per 15 cm 3 No more than 5 blisters total per package, e.g. 15cm 3 No more than two blisters total per container, e.g., 15cm 3 15cm 3 For glass articles as disclosed herein having a glass volume of less than 10, 5, 2, or even 1 blisters or less.

[0055] According to one aspect of the present disclosure, different ranges of components as a batch or on an analyzed oxide basis can be combined as disclosed and shown in the examples. However, certain exemplary combinations of such component ranges can include, for example, 64.9 mol% or more and 68.7 mol% or less silica, 11.5 mol% or more and 13.3 mol% or less alumina, 6.1 mol% or more and 7.2 mol% or less boria, 2.5 mol% or less and 5.6% or less magnesia, 3.9 mol% or more and 7.5% or less calcium oxide, and 3.1 mol% or more and 5.5% or less strontia, where the strontia is derived from a low-grade or "dirty" source material having more than 200 ppm (e.g., more than 1000 ppm, more than 1500 ppm, and / or more than 3000 ppm, e.g., a batch having more than 200 ppm thereof) oxides of sulfur, 0.1 mol% or less baria, and 0.1 mol% or less total alkali metal oxides, optionally including other components such as optional or contaminating oxides disclosed herein in the amounts disclosed herein. Another such combination of component ranges can include: 64 mol% to 69 mol% silica, 12 mol% to 13 mol% alumina, 6 mol% to 7.5 mol% boria, 2% to 6% magnesia, 3.5% to 8% calcium oxide, and 3% to 6% strontia, where the strontia is derived from a low-grade or "dirty" source material having more than 250 ppm (e.g., more than 1000 ppm, more than 1500 ppm, and / or more than 3000 ppm, e.g., a batch having more than 200 ppm thereof) oxides of sulfur, 0.5 mol% or less baria, and 0.5 mol% or less total alkali metal oxides, optionally including other components such as optional or contaminating oxides disclosed herein in the amounts disclosed herein.For such recited glasses, the corresponding analyzed formed glasses may have a detectable sulfur content of at least 10 ppm (e.g., ≥ 15 ppm (≥ including > and / or =), ≥ 20 ppm, ≥ 25 ppm, ≥ 40 ppm, etc.) of the analyzed glass, as disclosed herein, and accordingly may be free of excessive blisters, such as those resulting in part from manufacturing process improvements as disclosed herein, just as disclosed herein above.

[0056] As shown in various aspects, the compositions, structures, assemblies, and structure configurations and arrangements are exemplary only. While only a few examples of these aspects have been described in detail in this disclosure, it will be readily understood that modifications are possible (e.g., variations in the size, dimensions, structure, shape, and proportions of various elements, parameter values, mounting arrangements, material use, color, and orientation) without materially departing from the novel teachings and advantages of the subject matter described herein. For example, one aspect of the present disclosure includes a display device (see, e.g., FIG. 4 and corresponding text) having the glass disclosed herein and / or a sheet as disclosed herein (see, e.g., FIG. 3 and corresponding text). The order or sequence of any process, logical algorithm, or method steps may be modified or reordered according to alternative embodiments. For example, according to one aspect of the present disclosure, the glass as disclosed herein can be made without additional furnace crown heating (see, e.g., FIG. 2 and corresponding text) and, accordingly, may have more blisters and / or sulfur content when analyzed. Other substitutions, modifications, changes, and omissions may be made in the design, operating conditions, and arrangement of the various aspects without departing from the scope of the present technology.

Claims

1. 1. A sheet of glass for a high performance display, comprising: A thickness of 200 μm or more and 2 mm or less; A width of 5 cm or more and 5 m or less; A height of 5 cm or more and 5 m or less; Composition analyzed in mole percent on an oxide basis: 64 to 69 mol% SiO ２ and, 11 to 13 mol% Al ２ O ３ and, 6 to 8 mol% B ２ O ３ and, 2 to 6 mol% MgO; 3 to 8 mol% CaO, 1 to 6 mol% SrO; and a composition, wherein the composition further comprises sulfur.

2. 10. The sheet of claim 1, wherein the composition comprises greater than 10 ppm sulfur.

3. 10. The sheet of claim 1, wherein the composition comprises greater than 25 ppm sulfur.

4. 4. The sheet of claim 1, wherein the composition comprises less than 0.25 mol % of alkali metal oxides in combination.

5. 5. The sheet according to any one of claims 1 to 4, wherein the composition comprises less than 0.5 mol % of a barrier.

6. Glasses analyzed in mole percent on an oxide basis, 64 to 69 mol% SiO ２ and, 11 to 13 mol% Al ２ O ３ and, 6 to 8 mol% B ２ O ３ and, 2 to 6 mol% MgO; 3 to 8 mol% CaO, 1 to 6 mol% SrO; A glass, wherein the glass further comprises sulfur.

7. 7. The glass of claim 6, wherein the glass contains >25 ppm sulfur.

8. 8. The glass of claim 6 or 7, wherein the glass comprises, in combination, less than 0.25 mol % alkali metal oxides and less than 0.5 mol % barrier.

9. 1. A method of making a glass sheet for a high performance display, comprising: 64 to 69 mol% SiO ２ and, 11 to 13 mol% Al ２ O ３ and, 6 to 8 mol% B ２ O ３ and, 2 to 6 mol% MgO; 3 to 8 mol% CaO, 1-6 mol % SrO, The SrO is more than 1000 ppm of SO contained in the batch. ２ SrCO ３ Batch processing, which is derived from raw materials; melting the batch to provide a molten glass; forming the molten glass into the glass sheet.

10. 10. The method of claim 9, further comprising outgassing a majority of the sulfur from the molten glass.

11. The method of claim 10, wherein said outgassing further comprises heating a crown of a melting furnace in which said batch is melted.

12. The method of claim 11 , wherein the heating comprises providing greater than 0.5 kJ of heat per kg of the molten glass to the crown.

13. 13. The method of any one of claims 9 to 12, further comprising cooling the molten glass, wherein the cooled glass comprises sulfur.

14. 14. The method of claim 13, wherein the cooled glass contains >10 ppm sulfur.

15. 14. The method of claim 13, wherein the cooled glass contains >25 ppm sulfur.

16. 16. The method of any one of claims 13 to 15, wherein the cooled glass is free of blisters having a cross-sectional dimension greater than 30 μm.

17. SrCO ３ The feedstock contains more than 1500 ppm SO ２ The method according to any one of claims 9 to 16, comprising:

18. 18. The method of any one of claims 9 to 17, wherein the components of the batching contain less than 3 mol% nitrates.

19. SrCO ３ The feedstock contains more than 3000 ppm of SO ２ The method according to any one of claims 9 to 18, comprising:

20. 20. The method of any one of claims 9 to 19, wherein the components of the batching comprise, in combination, less than 0.25 mol% alkali metal oxide and less than 0.5 mol% barrier.

21. 1. A method of making a glass sheet for a high performance display, comprising: 64 to 69 mol% SiO ２ and, 11 to 13 mol% Al ２ O ３ and, 6 to 8 mol% B ２ O ３ and, 2 to 6 mol% MgO; 3 to 8 mol% CaO, and 1 to 6 mol % SrO in a melting furnace, The SrO is more than 1000 ppm of SO contained in the batch. ２ SrCO ３ melting the raw materials, the melting producing molten glass; outgassing a majority of the sulfur from the molten glass; heating a crown of the melting furnace in which the batch is melting, whereby said heating of the crown facilitates said outgassing.

22. 22. The method of claim 21, wherein the heating comprises providing greater than 0.5 kJ of heat per kg of the molten glass to the crown.

23. 1. A method of making a glass sheet for a high performance display, comprising: 64 to 69 mol% SiO ２ and, 11 to 13 mol% Al ２ O ３ and, 6 to 8 mol% B ２ O ３ and, 2 to 6 mol% MgO; 3 to 8 mol% CaO, and 1 to 6 mol % SrO in a melting furnace, The SrO is more than 1000 ppm of SO contained in the batch. ２ SrCO ３ melting the raw materials, the melting producing molten glass; outgassing a majority of the sulfur from the molten glass; forming the molten glass into the glass sheet; cooling the molten glass to solidify the glass, wherein the cooled glass comprises >10 ppm sulfur.

24. 24. The method of claim 23, wherein the cooled glass contains >25 ppm sulfur.

25. 25. The method of claim 23 or 24, wherein the cooled glass is free of blisters having a cross-sectional dimension greater than 30 μm.

26. SrCO ３ The feedstock contains more than 1500 ppm SO ２ The method of any one of claims 23 to 25, comprising:

27. 27. The method of any one of claims 23 to 26, wherein the components of the batch contain less than 3 mol% nitrates.

28. 28. The method of any one of claims 23 to 27, wherein the components of the batching comprise, in combination, less than 0.25 mol % alkali metal oxide and less than 0.5 mol % barrier.

29. 1. A method of making a glass sheet for a high performance display, comprising: 64 to 69 mol% SiO ２ and, 11 to 13 mol% Al ２ O ３ and, 6 to 8 mol% B ２ O ３ and, 2 to 6 mol% MgO; 3 to 8 mol% CaO, 1-6 mol % SrO, The SrO is more than 3000 ppm of SO contained in the batch. ２ SrCO ３ Batch processing, which is derived from raw materials; melting the batch to provide a molten glass; forming the molten glass into the glass sheet.

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