Ion exchangeable glass with low Al2O3 content for display devices

Abstract

The present disclosure relates to glasses having a low Al2O3 content and glass articles made from the glasses. The glass articles include flat glass suitable for use in display devices, particularly foldable display devices, such as electronic devices including smartphones, smartwatch and tablet computers. In addition, a method of manufacturing a glass article is described.

Description

Technical Field

[0001] This disclosure relates to glass with a low Al2O3 content and glass articles made from said glass. The glass articles include flat glass suitable for display devices, particularly foldable display devices (e.g., electronic devices including smartphones, smartwatches, and tablets). Furthermore, a method for manufacturing the glass articles is also described. Background Technology

[0002] Display devices, especially foldable displays (such as smartphones and tablets), are becoming increasingly popular. Foldable devices offer the advantage of a large screen when unfolded and portability when folded. For the glass to be used in such foldable displays, it must be extremely thin. Extremely thin glass is fragile. However, this glass must also possess sufficient strength to withstand repeated folding and unfolding operations.

[0003] Aluminosilicate glass is typically used in portable electronic devices. It possesses certain properties that make it well-suited for use as display glass, particularly in display cover glasses where flexibility or foldability is required and the thickness is less than 100µm. However, the compressive stress of aluminosilicate glass decreases with decreasing thickness. Furthermore, further improving the impact resistance of alkali metal aluminosilicate glass often leads to a higher tendency for devitrification during production, thus reducing yield. Therefore, a solution must be found that can both increase the compressive stress of thin glass and maintain devitrification stability. Additionally, better acid resistance in this new type of glass would be advantageous, as the glass surface of touchscreens may be exposed to the acidic environment of user skin.

[0004] There is an urgent need for a type of glass that can overcome the shortcomings of existing technologies. Summary of the Invention

[0005] In a first aspect, this disclosure relates to a glass comprising the following components: i.SiO2, ii. Al2O3 in a content of 0.0 to 6.0% by weight, ii. A content of at least 8.0% by weight of ZrO2, iii. A content of at least 12.0% by weight of Na₂O, iv. 0.0 to 5.0% by weight of B2O3, v. 0.0 to 5.0 wt% Li₂O, vi. 0.0 to 10.0% by weight of K₂O; and vii. Optionally, one or more components selected from P2O5 and TiO2.

[0006] In a second aspect, this disclosure relates to a glass comprising the following components by weight percentage: In addition, optionally, it contains dyes or colorants, such as Fe2O3, CoO and / or Cr2O3.

[0007] The inventors have discovered that the glass according to the first and second aspects provides a novel combination of desired properties. It has been found that, even after chemical strengthening, existing glasses suffer from insufficient devitrification stability and impact resistance. Therefore, the glass of this disclosure was developed to improve impact resistance while maintaining devitrification stability.

[0008] In this invention, a higher packing density is achieved by significantly reducing the Al2O3 content and significantly increasing the ZrO2 content. Zirconium exhibits octahedral coordination in the glass network, thus resulting in a higher packing density than commonly used alkali metal aluminosilicate glasses. High yield (high devitrification stability) production is achieved when the Al2O3 content is limited to below 5 wt%. Furthermore, alkali metal zirconium silicates have a lower operating point (at least at a viscosity equal to or less than 10) compared to commonly used aluminosilicates. 4 At temperatures below dPa*s, such glass can be produced at lower temperatures, thus protecting the environment and reducing energy costs.

[0009] Despite its relatively low Al2O3 content, the glass exhibits a surprisingly high sensitivity to chemical strengthening. This means that when chemically toughened by immersion in a salt bath, the glass will develop high compressive stress on its surface within a very short time. In one embodiment, this compressive stress sensitivity can reach 800 MPa, or even 900 MPa, 1000 MPa, or more than 1100 MPa, under 30 minutes of chemical toughening. Despite this excellent compressive stress sensitivity, the glass has only a moderate coefficient of thermal expansion, for example, less than 9.8 ppm / K, or even less than 9.0 ppm / K. This very moderate thermal expansion allows for the production of articles with excellent dimensional characteristics. In the production of thin glass, such as in the down-drawing process, the glass undergoes rapid cooling. Typically, the cooling rate is not uniform across all parts of the glass. This leads to warping in the glass articles. For articles made of glass with a higher coefficient of thermal expansion, the warping will be greater. Due to the low coefficient of thermal expansion of the glass disclosed herein, glass articles with particularly low warping can be produced.

[0010] Furthermore, the glass disclosed herein also exhibits excellent chemical resistance, particularly acid resistance. Chemical resistance is highly useful for glass used in display applications. Existing glasses with considerable chemical strengthening characteristics typically have only moderate or insufficient chemical resistance. In one embodiment, the glass may have an acid resistance rating of 2 or better, an alkali resistance rating of 2 or better, and a hydrolysis resistance rating of at least 4 or better.

[0011] In a third aspect, this disclosure relates to a glass article comprising or composed of the glass described herein.

[0012] In a fourth aspect, this disclosure relates to a glass article having a thickness of less than 1000 µm, wherein the article comprises a glass containing at least 40.0 wt% SiO2, at least 12.0 wt% Na2O, and further containing ZrO2, wherein the weight content of ZrO2 is in a ratio of at least 1.5 to the sum of the weight contents of Al2O3 and B2O3, and the CSS of the glass is... 30µm For at least 700 MPa, and / or for acid resistance of less than 5.0 mg / dm³ 2 Or acid resistance of less than 2.5 mg / dm 2 .

[0013] In a fifth aspect, this disclosure relates to a glass article comprising or composed of the glass described herein, and having an ion-exchange layer on one or both of its main surfaces.

[0014] In a sixth aspect, this disclosure relates to an electronic device that includes the glass or glass article described herein.

[0015] In a seventh aspect, this disclosure relates to a method of manufacturing the glass or glass articles of the present disclosure. Detailed Implementation

[0016] definition coefficient of thermal expansion ( C efficient of t hermal e The coefficient of thermal expansion (CTE) is the average linear coefficient of thermal expansion in the temperature range of 20°C to 300°C. This coefficient is determined according to DIN ISO 7991:1987.

[0017] Compressive stress sensitivity ( C ompressive s tress sChemical toughness (CSS, or CSS score) is expressed in MPa. It is the value of compressive stress in a glass sample measured under specific test conditions. For this test, the sample can be a plate with a thickness of 200 µm or 30 µm. The sample is subjected to ion exchange treatment in an alkali metal nitrate bath (100%) for 30 minutes, where for thinner glass (<35 µm), the chemical toughening duration can be reduced to, for example, 15 minutes. Temperatures can be chosen to obtain the highest chemical stress. The alkali metal nitrate depends on the type of ion exchange to be performed, i.e., which ions need to be exchanged. Optionally, the alkali metal nitrate is KNO3, and the bath temperature is 440°C. The fact that CSS is determined using plate-shaped samples with a thickness of 200 µm or 30 µm does not imply limitation to plate-shaped glass articles, or even glass plates of that thickness. Rather, CSS is a property of the glass material that is measured on a glass plate made of glass. While CSS is affected by the thermal history of the glass, it is a characteristic of the glass material or glass article. It is important to note that CSS is a characteristic of unstrengthened (i.e., un-ion-exchanged) materials or articles. The different thicknesses involved in CSS values ​​are represented by an index, for example, CSS 30µm This indicates a glass plate with a thickness of 30µm.

[0018] "1000 MPa IOX time" refers to the ion exchange treatment time required for a glass to develop a compressive stress of at least 1000 MPa on its surface. The corresponding experiment is the same as the CSS measurement, using a 200 µm thick glass plate immersed in an alkali metal nitrate bath. For a sodium nitrate bath, the temperature can be 380°C; for other alkali metal nitrate baths, the temperature can be 440°C. "1000 MPa IOX time" is achieved when the compressive stress of the sample reaches at least 1000 MPa.

[0019] Compressive stress (CS) is the compression of the glass network that occurs after ion exchange in the glass surface layer. CS typically decreases from its maximum value at the glass surface (surface CS) towards the interior of the glass layer. As is customary in the art, any designation of CS in this disclosure refers to the maximum value at the corresponding surface. CS can be measured using commercially available testing instruments such as the FSM6000LE (ORIHARA INDUSTRIAL CO. LTD.) or the SLP1000 (ORIHARA Corporation, Japan).

[0020] Layer depth (DoL) is the thickness of the CS layer present on the surface of a glass product, which is essentially equivalent to the thickness of the ion exchange layer. Commercially available testing instruments, such as the FSM6000 (Luceo Co., Ltd., Tokyo, Japan), can measure DoL using a waveguide mechanism.

[0021] "Diffusion rate" (D, in µm) 2 The diffusivity (I / h) is a material property of glass that describes its ability to form an ion exchange layer during chemical tempering / ion exchange processes. This property can be calculated by measuring the depth of the ion exchange layer (DoL, µm) after a given ion exchange time (IET, in hours). Higher diffusivity results in a deeper DoL after a given ion exchange time. The corresponding formula is... In this disclosure, unless otherwise specified, any designation of D indicates chemical tempering for 30 minutes using 100% alkali metal nitrates. For thinner glasses, the chemical tempering time can be shortened, for example, to 15 minutes. The temperature of the sodium nitrate bath can be selected as 380°C, and the temperature of other alkali metal nitrates can be selected as 440°C. Alkali metal nitrates are nitrates containing alkali metal ions with the next largest diameter compared to the most abundant alkali metal oxide in the glass composition. The diameter order of alkali metal ions is Cs > K > Na > Li. For example, if the most abundant alkali metal oxide in the glass is sodium, then D indicates ion exchange with 100% KNO3 for 30 minutes at 440°C.

[0022] Central Tension (CT): When CS is generated on one or both sides of a glass plate, according to Newton's third law, a tensile stress must be generated in the central region of the glass to balance the stress; this is called central tension. CT is calculated from the measured CS and DoL.

[0023] The term "surface roughness" as used in this article refers to the average roughness R. a It is a measure of surface texture. Typically, the amplitude parameter characterizes the surface based on the perpendicular deviation of the roughness profile from the mean line. R a It is the arithmetic mean of the absolute values ​​of these vertical deviations. It can be determined according to the DIN EN ISO 4287:2010-07 standard.

[0024] Warp is the difference between the maximum and minimum distances between the mid-surface of a free, unclamped glass article and a reference plane. Warp can be measured according to the description in SEMI MF1390 standard.

[0025] Total thickness change ( t otal thickness v The thickness difference (TTV) is the difference between the maximum and minimum thickness of a glass product. It can be measured according to the SEMI MF1530 standard.

[0026] "Hydrolytic resistance" refers to the amount of Na₂O equivalent extracted. It is determined according to ISO 719:2020-09. It is a measure of the extractability of alkali metal compounds from glass in water at 98°C. The result is expressed as the amount of Na₂O equivalent extracted per gram of glass (expressed in µg).

[0027] "Alkali resistance" refers to the glass's resistance to alkali corrosion. It is determined according to ISO 695:1991-05 using a boiling aqueous solution of sodium carbonate and sodium hydroxide. This test is performed as described in Section 6.2, "Glass Materials." The result is the mass loss per unit surface area of ​​the glass sample (mg / dm³). 2 ).

[0028] "Acid resistance" refers to the glass's resistance to acid corrosion. It is determined using a boiling aqueous solution of hydrochloric acid, according to DIN 12116:2001-03. This test is performed as described in Section 6.3, "Glass Materials." The result is the mass loss per unit surface area of ​​the glass sample (mg / dm³). 2 ).

[0029] "T4" refers to a glass viscosity of 10. 4 The temperature at which dPa*s is measured. T4 can be measured using methods known to those skilled in the art for determining glass viscosity, for example, according to ISO 7884-2:1987-12. 13 "This is when the glass viscosity is 10" 13 The temperature at dPa*s. Similarly, in T n The other temperatures indicated are at a glass viscosity of 10. n The temperature at which dPa*s is measured. For example, "T5" refers to the temperature at which the glass viscosity is 10. 5 The temperature at dPa*s. "Strain point" (T) 14.5 The temperature at which all the motion of glass molecules reaches the point where no further strain is introduced into the hot glass is introduced. It is at a viscosity η=10. 14.5 The viscosity capping point (temperature value) at dPa*s. This limit value represents the highest service temperature of the glass component. "T" g "It is the transition temperature as defined in ISO 7884-8:1987."

[0030] Three-point bending strength is a test of a material's bending strength. It can be determined using the method described in ASTM C1161-13. An exemplary test setup is as follows: a cylindrical steel bearing with a radius of 2 mm; a support span of 16 mm; and sample dimensions of 28 x 28 x 0.2 mm. 3 Prepared according to standard procedure 7.2.4; loading speed is 5 mm / min.

[0031] Vickers hardness was determined using the standard Vickers indenter as specified in ASTM C 1327 (2015). The measurement parameters are as follows: Force F n (Maximum) = 1N; Approximate rate = 4µm / min; Loading rate 2N / min; Hold time 20s; Release rate 6N / min.

[0032] Typically, the Vogel-Fulcher-Tammann (VFT) equation is used to calculate the temperature required to reach a certain viscosity in a glass (see the ISO 7884 series of standards, such as ISO 7884-1:1987-12, 7884-2:1987-12; 7884-3:1987-12; 7884-4:1987-12): In the VFT equations, η represents viscosity, A and B are material parameters, T is temperature, and T0 is the Vogel temperature. For any given glass, A, B, and T0 are constants. The notation of these constants can provide more detailed information about the viscosity behavior of a particular glass composition.

[0033] The "major surfaces" of a product are the two surfaces with the largest area among all the surfaces of the product.

[0034] When this disclosure refers to glass as "free of a component" or not containing a certain component, it means that the component is only permitted to be present in the glass as an impurity. This means that the component is not added in substantial amounts. Substantial amounts refer to contents of less than 3000 ppm (by weight), less than 2500 ppm (by weight), less than 2000 ppm (by weight), less than 1500 ppm (by weight), less than 1250 ppm (by weight), particularly less than 750 ppm (by weight) or less than 500 ppm (by weight).

[0035] In the following text, the terms "chemical hardening" and "chemical strengthening" may be used interchangeably.

[0036] Composition It has been found that, in the constituent substrates of this disclosure, the disclosed compositions, proportions, and total amounts provide improved sensitivity to chemical strengthening, maintain resistance to devitrification, and exhibit good chemical resistance (especially acid resistance). Optionally, the glass compositions disclosed herein may consist substantially of the listed oxides, i.e., without any other components not mentioned in this disclosure.

[0037] In one embodiment, the glass comprises the following components: i.SiO2, ii. Al2O3 in a content of 0.0 to 6.0% by weight, ii. A content of at least 8.0% by weight of ZrO2, iii. A content of at least 12.0% by weight of Na₂O, iv. 0.0 to 5.0% by weight of B2O3, v. 0.0 to 5.0 wt% Li₂O, vi. 0.0 to 10.0 wt% K₂O; and vii. Optionally, one or more components selected from P2O5 and TiO2.

[0038] Optional, the glass contains the following components by weight percentage: In addition, optionally, it contains dyes or colorants, such as Fe2O3, CoO and / or Cr2O3.

[0039] It has been found that ZrO2 can be present in a content of at least 8.0% by weight, while the content of Al2O3 should be kept below 6.0% by weight to obtain the desired CSS, devitrification resistance and acid resistance properties.

[0040] In one embodiment, the glass comprises:

[0041] In one embodiment, the ratio of ZrO2 content to Al2O3 content by weight percentage is at least 1.5. In yet another embodiment, this ratio can be at least 2, at least 3, at least 4, at least 5, at least 10, at least 20, at least 30, at least 50, at least 65, at least 75, at least 100, at least 125, or even at least 130. Optionally, this ratio can be at most 200, at most 180, at most 150, at most 125, at most 110, or at most 75. For example, this ratio can be from 1.5 to 200, from 2 to 150, from 5 to 145, and from 10 to 135. This ratio can also include glass that is substantially free of Al2O3, i.e., contains only Al2O3 impurities or is completely free of Al2O3, wherein the ratio tends to infinity.

[0042] In one embodiment, the ratio of Al2O3 content to ZrO2 content by weight percentage is less than 0.5, less than 0.25, less than 0.20, less than 0.15, less than 0.10, less than 0.05, less than 0.025, or even less than 0.015. Optionally, this ratio can be at least 0.001, at least 0.0025, at least 0.005, or at least 0.0065. For example, the ratio can be from 0.001 to 0.5, from 0.0025 to 0.2, from 0.005 to 0.1, or from 0.0065 to 0.025. This ratio can also include glass that is substantially free of Al2O3, i.e., glass containing only Al2O3 impurities or completely free of Al2O3, wherein the ratio tends to be 0.0.

[0043] In some embodiments, the total content of Al2O3 and ZrO2 is from 8.0 wt% to 35.0 wt%, 10.0 wt% to 33.0 wt%, or 12.0 wt% to 29.0 wt%. However, the combination of high proportions of the two components leads to an increased tendency for devitrification, making it impossible to manufacture the glass using the down-drawing method. Therefore, the glass of this disclosure can have a very low Al2O3 content or be Al2O3-free, thereby allowing a higher proportion of ZrO2 to dissolve in the glass.

[0044] The glass disclosed herein may comprise ZrO2, Al2O3, and B2O3. Therefore, when B2O3 is also present, the weight percentage of ZrO2 to the sum of the weight percentages of Al2O3 and B2O3 may be at least 1.5. In another embodiment, this ratio may be at least 2, at least 3, at least 4, or even at least 5. Optionally, the weight percentage of ZrO2 to the sum of the weight percentages of Al2O3 and B2O3 is from 1.50 to 200.00, for example, 2.00 to 180, 2.50 to 155, 3.65 to 145, or 4.75 to 135. In embodiments, this ratio is at least 1.50, at least 2.00, at least 3.50, at least 4.65, or at least 5.00. This ratio can be as high as 200.00, 180.00, 150.00, 125.00, 110.00, or 75.00. This ratio can also include glass that is substantially free of Al2O3 and / or B2O3, i.e., glass containing only Al2O3 and / or B2O3 impurities or glass completely free of Al2O3 and / or B2O3, wherein this ratio tends towards infinity.

[0045] It is worth noting that conventional ZrO2-rich glasses in the prior art require a clarification step using As2O3 and / or Sb2O3. This is harmful to the environment and health. The glass of this disclosure can be produced without the use of As2O3 and / or Sb2O3 while still maintaining high quality. The clarification of the glass of this disclosure can be performed using CeO2, SnO2, Cl, or SO3, or any combination thereof. In one embodiment, the glass may not require clarification using a clarifying agent. Therefore, in one embodiment, no harmful substances, such as As2O3 and / or Sb2O3, are used in the clarification process; thus, in one embodiment, the glass composition is free of As2O3 and / or Sb2O3. 3。 In this context, the term "free of As2O3 and / or Sb2O3" means a content of less than 100 ppm by weight, less than 50 ppm by weight, less than 25 ppm by weight, less than 20 ppm by weight, less than 10 ppm by weight, less than 5 ppm by weight, or even less than 1 ppm by weight.

[0046] In some embodiments, the glass does not contain Li2O. High Li2O content leads to increased raw material costs, which the glass of this disclosure avoids.

[0047] In this disclosure, alkali metal oxides R₂O include oxides of lithium, sodium, potassium, and cesium. In some embodiments, the glass is free of lithium, potassium, and / or cesium. Alkali earth metal oxides R'O include oxides of magnesium, calcium, strontium, and barium. In some embodiments, the glass is free of magnesium, calcium, cesium, strontium, and / or barium.

[0048] In the following text, R2O represents the sum of the contents of alkali metal oxides, and R'O represents the sum of the contents of all alkaline earth metal oxides. In some embodiments, the sum of the contents of alkali metal oxides (R2O), alkaline earth metal oxides (R'O), and ZnO in the glass is not greater than 35.0 wt%, not greater than 34.0 wt%, or not greater than 33.75 wt%. Optionally, the sum of R2O + R'O + ZnO is at least 19.0 wt%, at least 20.0 wt%, or at least 21.0 wt%. For example, the sum of R2O + R'O + ZnO is from 19.0 to 35.0 wt%, from 20.0 to 34.0 wt%, or from 21.0 to 33.75 wt%.

[0049] In some embodiments, the sum of the contents of alkaline earth metal oxides (R'O) and ZnO in the glass is not greater than 12.5 wt%, not greater than 12.0 wt%, not greater than 11.5 wt%, not greater than 11.0 wt%, not greater than 10.5 wt%, not greater than 10.0 wt%, not greater than 9.5 wt%, not greater than 9.0 wt%, not greater than 8.5 wt%, or not greater than 8.25 wt%. Optionally, the sum of the contents of R'O and ZnO is at least 0.1 wt%, at least 0.5 wt%, at least 0.75 wt%, at least 1.0 wt%, or at least 1.9 wt%. For example, the total amount of R'O+ZnO is 0 to 12.5 wt%, 0 to 11.5 wt%, 0 to 10.5 wt%, 0 to 9.5 wt%, 0 to 8.5 wt%, 0.1 to 11.0 wt%, 0.5 to 10.0 wt%, 1.0 to 9.0 wt%, 1.5 to 8.5 wt%, or 1.9 to 8.25 wt%.

[0050] The glass may contain one or more alkali metal oxides (R₂O). Optionally, the weight percentage ratio of the second most abundant alkali metal oxide B to the most abundant alkali metal oxide A is less than 0.23, less than 0.22, less than 0.18, less than 0.16, less than 0.12, or less than 0.10. The “most abundant” alkali metal oxide is the oxide with the highest weight percentage in the glass. Therefore, the “second most abundant” is the oxide with the second highest weight percentage, and so on. In one embodiment, A is Na₂O and B is K₂O; in alternative embodiments, B is Na₂O and A is K₂O. In some embodiments, this ratio can be as low as below 0.10, below 0.05, or even below 0.04. In some cases, this ratio can be 0.

[0051] In one embodiment, the weight ratio of K₂O to the sum of the weight contents of Li₂O and Na₂O in the glass composition is less than 0.23, less than 0.22, less than 0.18, less than 0.16, less than 0.12, or less than 0.10. In some embodiments, this ratio can be as low as below 0.10, below 0.05, or even below 0.04. In some cases, this ratio can be 0.

[0052] In alternative embodiments, the ratio of the weight content of Na₂O to the sum of the weight contents of Li₂O and K₂O is less than 0.23, less than 0.22, less than 0.18, less than 0.16, less than 0.12, or less than 0.10. In some embodiments, this ratio can be as low as below 0.10, below 0.05, or even below 0.04. In some cases, this ratio can be 0.

[0053] In one embodiment, the ratio of the weight content of SiO2 in the glass to the sum of the weight contents of Li2O and Na2O is less than 4.5, optionally less than 4.25, or less than 4.0. Optionally, this ratio can be at least 2.0, at least 2.5, or at least 3.0. For example, the ratio can be from 2.0 to 4.5, from 3.0 to 4.25, or from 3.0 to 4.0. The inventors have found that this ratio has a positive effect on the thermal expansion and CSS properties of the glass.

[0054] The glass contains SiO2, optionally in a content of at least 40.0 wt%, at least 41.0 wt%, at least 43 wt%, at least 45 wt%, or at least 48 wt%. In some embodiments, the SiO2 content is up to 70.0 wt%, up to 68.0 wt%, up to 66.0 wt%, or up to 64.0 wt%. In some embodiments, the relative content of this component is 40.0 to 70.0 wt%, 41.0 to 68.0 wt%, 43.0 to 66.0 wt%, or 48.0 to 65.0 wt%. SiO2 contributes to achieving the desired thermal expansion behavior and chemical resistance. If the SiO2 content is too high, the viscosity increases, thereby increasing the melting and thermoforming temperatures. Furthermore, SiO2 reduces ion exchange capacity, thereby reducing surface compressive stress.

[0055] A low Al2O3 content can be used to achieve the desired acid resistance. However, excessive Al2O3 in the glass of this disclosure can lead to devitrification. Therefore, optionally, the content of this component is at least 0.1 wt%, at least 0.25 wt%, at least 0.5 wt%, at least 0.75 wt%, at least 1.25 wt%, at least 1.5 wt%, at least 1.75 wt%, or at least 1.8 wt%. In some embodiments, the Al2O3 content may be limited to at most 5.0 wt%, at most 4.5 wt%, at most 4.0 wt%, at most 3.5 wt%, at most 3.0 wt%, at most 2.5 wt%, or at most 2.0 wt%. For example, the content of this oxide can range from 0.1 to 5.0 wt%, 0.25 to 4.5 wt%, 0.5 to 4.0 wt%, 0.75 to 3.5 wt%, 1.0 to 3.0 wt%, 1.25 to 2.5 wt%, or 1.5 to 2.0 wt%. However, Al2O3 reduces the acid resistance of the glass and increases its viscosity. Furthermore, glass melts with high Al2O3 and ZrO2 contents are prone to devitrification, therefore, an Al2O3 content greater than 6.0 wt% should be avoided. In some embodiments, the glass may be Al2O3-free.

[0056] The B2O3 content in the glass can be up to 5.0 wt%, up to 4.5 wt%, or up to 3.0 wt%. In some embodiments, the content of this component is as low as below 0.75 wt%, below 0.5 wt%, or even below 0.25 wt%. In some embodiments, the B2O3 content is less than 0.1 wt%. The presence of B2O3 helps to balance any devitrification tendencies that may be caused by the use of ZrO2. Optionally, the B2O3 content is 0 to 5.0 wt%, 0 to 4.5 wt%, or 0 to 3.0 wt%. In some embodiments, the amount of B2O3 used is at least 0.25 wt% or at least 0.5 wt%. However, an excessively high proportion of B2O3 can impair chemical tempering performance, especially with short incubation times, and therefore a B2O3 content greater than 5.0 wt% should be avoided. In some embodiments, the glass may be B2O3-free. 3。

[0057] The glass may contain Al2O3 and / or B2O3 in a total content of 0.0 to 10.0% by weight, provided that the weight ratio of ZrO2 to the total weight of Al2O3 and B2O3 is at least 1.5. Optionally, the glass may contain Al2O3 and / or B2O3 in a total content of 0.0 to 9.5% by weight, 0.0 to 9.0% by weight, or 0.0 to 8.5% by weight, provided that the weight ratio of ZrO2 to the sum of the weight contents of Al2O3 and B2O3 is at least 1.5. In one embodiment, the total content of Al2O3 and B2O3 is less than 9.5% by weight, less than 9.0% by weight, less than 8.5% by weight, less than 8.0% by weight, or less than 7.0% by weight. Optionally, the total content of Al2O3 and B2O3 is at least 0.5% by weight, at least 0.75% by weight, at least 1.0% by weight, at least 1.25% by weight, or at least 1.5% by weight. In some embodiments, the glass may be free of Al2O3 and B2O3. 3。

[0058] P2O5 is an optional ingredient. It can be used in proportions of at least 0.015% by weight, at least 0.02% by weight, at least 0.025% by weight, or at least 0.03% by weight. Suitable upper limits are 10.0% by weight, 8.0% by weight, 6.0% by weight, 5.0% by weight, 4.0% by weight, and 3.5% by weight. The dosage range of P2O5 is 0 to 10.0% by weight, 0.02% to 8.0% by weight, 0.025% to 5.0% by weight, or 0.03% to 3.5% by weight.

[0059] Some embodiments include TiO2 as a glass component. The amount used can be 0.0 to 5.0 wt%, 0.0 to 4.0 wt%, 0.0 to 3.0 wt%, 0.0 to 2.0 wt%, 0.0 to 1.5 wt%, 0.0 to 1.0 wt%, or less than 100 ppm.

[0060] ZrO2 is an important component in glass compositions. It has been found that to achieve the desired anti-devitrification properties, the ZrO2 content should be at least 8.0 wt%, while the Al2O3 content needs to be kept below 6.0 wt%. Ideally, the ZrO2 content is at least 8.0 wt%, at least 9.5 wt%, at least 10.0 wt%, at least 10.5 wt%, or at least 11.0 wt%. In some embodiments, the ZrO2 content can be at least 8.1 wt%, at least 8.5 wt%, at least 8.8 wt%, at least 9.2 wt%, or at least 9.5 wt%. In some embodiments, the content of this component is up to 32.0 wt%, or up to 30 wt%. Optionally, the ZrO2 content in the glass can range from 8.0 wt% to 32.0 wt%, 9.5 wt% to 32.0 wt%, 10.0 wt% to 30.0 wt%, 10.5 wt% to 20.0 wt%, 11.0 wt% to 17.5 wt%, 8.1 wt% to 28.0 wt%, 8.5 wt% to 24.0 wt%, 8.8 wt% to 23.5 wt%, or 9.5 wt% to 22.5 wt%. In one embodiment, the ZrO2 content is at least 8.5 wt%, at least 8.7 wt%, or at least 9.0 wt%. In some embodiments, the ZrO2 content can be at least 8.0 wt%, at least 9.0 wt%, or greater than 10.0 wt%, for example, at least 10.1 wt%. Therefore, in one embodiment, the ZrO2 content can range from 8.0% to 30.0 wt%. Due to its increased bulk density, ZrO2 is an essential component for increasing surface compressive stress after ion exchange. It further improves chemical resistance and reduces the coefficient of thermal expansion (CTE). However, it has been found that if the ZrO2 content is too high, the solubility deteriorates, and devitrification and phase separation may occur, thereby reducing yield.

[0061] In some embodiments, Y₂O₃ may be present in the glass composition. The content of Y₂O₃ may be at least 5.0 wt%, at least 6.0 wt%, at least 7.0 wt%, or at least 8.5 wt%. In some embodiments, the content of this component ranges from up to 20.0 wt%, up to 15.0 wt%, up to 10.0 wt%, or up to 5.0 wt%. Optionally, the content of Y₂O₃ in the glass ranges from 0.0 to 20.0 wt%, 0.0 to 15.0 wt%, 0.0 to 10.0 wt%, or 0.0 to 5.0 wt%. In some embodiments, the glass may be free of Y₂O₃.

[0062] In some embodiments, the ratio of (a) the weight percentage content of ZrO2 to the weight percentage content of (b) SiO2 is 0.10 to 0.75, 0.15 to 0.70, or 0.19 to 0.65. In one embodiment, the ratio is at least 0.08, at least 0.10, at least 0.15, or at least 0.19. The ratio can be up to 0.70, up to 0.68, up to 0.65, up to 0.625, or up to 0.62.

[0063] Optionally, the glass comprises alkali metal oxides. The total content of alkali metal oxides R2O can be from 10.0 to 30.0% by weight. Optionally, this content is up to 25.0% by weight, up to 23.0% by weight, up to 22.0% by weight, up to 21.0% by weight, or up to 20.5% by weight. A certain amount of alkali metal oxides may be required to obtain sufficient CSS performance. Therefore, its minimum content can be 10.0% by weight, 11.0% by weight, 12.0% by weight, or even 13.0% by weight. For example, the content of R2O can be from 10.0 to 25.0% by weight, 11.0 to 24.0% by weight, 11.0 to 23.0% by weight, or 12.0 to 22.0% by weight. In some embodiments, the sum of the contents of all alkali metal oxides R2O is less than 20.5% by weight, less than 20.25% by weight, or less than 20.15% by weight.

[0064] Optionally, the ratio of (a) the sum of the weight percentage contents of all alkali metal oxides R2O to (b) the weight percentage contents of SiO2 is 0.1 to <0.4, 0.15 to <0.39, 0.2 to <0.38, or 0.25 to <0.37.

[0065] In one embodiment, the most abundant alkali metal oxide in the glass composition is Na₂O, the second most abundant alkali metal oxide, if present, is K₂O in some embodiments and Li₂O in others, and the third most abundant alkali metal oxide, if present, is Li₂O in some embodiments and K₂O in others. Alternatively, the most abundant alkali metal oxide may be K₂O, the second most abundant alkali metal oxide, if present, may be Na₂O, and the third most abundant alkali metal oxide, if present, may be Li₂O. In one embodiment, Li₂O is not the most abundant alkali metal oxide. Optionally, Na₂O or K₂O is the most abundant alkali metal oxide. For example, the abundance of Li₂O may be less than that of Na₂O and / or less than that of K₂O. Na₂O acts as a network forming agent and is an important component ensuring high compressive stress after ion exchange. It further lowers the melting and thermoforming temperatures. However, if the Na₂O content is too high, hydrolysis resistance decreases sharply.

[0066] Li₂O can be present in glass at contents up to 5.0 wt%, 3.0 wt%, 2.5 wt%, 2.25 wt%, 2.15 wt%, 2.1 wt%, 1.5 wt%, 1.0 wt%, 0.5 wt%, 0.2 wt%, or 0.1 wt%. Due to the increasing demand for Li₂O in battery production, high Li₂O content increases raw material costs; therefore, Li₂O content should be kept low, and contents exceeding 5.0 wt% should be avoided. i2 O. In some embodiments, the glass may be free of Li2O.

[0067] K2O can be present in the glass at a content of up to 7.0 wt%, up to 6.0 wt%, or up to 5.0 wt%. In some embodiments, the K2O content can be at least 4.0 wt% or at least 3.0 wt%. In one embodiment, the K2O content in the glass composition is less than 5.0 wt%, less than 4.5 wt%, less than 4.0 wt%, less than 3.5 wt%, less than 3.0 wt%, less than 2.8 wt%, less than 2.5 wt%, less than 2.0 wt%, or less than 1.5 wt%. Alternatively, it can be used at a proportion of at least 1.0 wt%, at least 2.0 wt%, or at least 3.0 wt%. However, because the network structure is too open, excessive K2O in the glass reduces its sensitivity to chemical tempering, so K2O content greater than 10.0 wt% should be avoided. In some embodiments, the glass may be K2O-free.

[0068] Na₂O may be present in the glass at a content of up to 22.0% by weight, up to 20.0% by weight, or up to 19.0% by weight. In some embodiments, the content of Na₂O may be at least 14.0% by weight or at least 15.0% by weight.

[0069] Optionally, the total content of Na2O and / or K2O may be 10.0 to 22.0% by weight, 14.0 to 21.0% by weight, or 15.0 to 20.5% by weight.

[0070] One or more oxides selected from ZnO, Li2O, Na2O, K2O, MgO, CaO, SrO, BaO, and combinations thereof may be present in the glass in a total content of 10.0 to 40.0% by weight. In most embodiments, this total content is less than 30.0% by weight, less than 25.0% by weight, or less than 22.0% by weight.

[0071] The CaO content in glass can be, for example, up to 15.0 wt%, up to 13.5 wt%, up to 12.2 wt%, up to 6.0 wt%, up to 3.0 wt%, up to 0.5 wt%, up to 0.2 wt%, or up to 0.1 wt%. Excessive CaO content can reduce the glass's sensitivity to chemical strengthening; therefore, a CaO content greater than 15.0 wt% should be avoided. Glass can also be CaO-free.

[0072] The SrO content in the glass can be, for example, up to 10.0 wt%, up to 7.0 wt%, up to 6.0 wt%, up to 5.0 wt%, up to 1.0 wt%, up to 0.5 wt%, up to 0.2 wt%, or up to 0.1 wt%. The glass may also be free of SrO.

[0073] The BaO content in the glass can be, for example, up to 10.0 wt%, up to 7.0 wt%, up to 5.0 wt%, up to 2.0 wt%, up to 1.0 wt%, up to 0.5 wt%, up to 0.2 wt%, or up to 0.1 wt%. The glass may also be free of BaO.

[0074] The sum of the contents of CaO, SrO, and BaO in the glass may be, for example, up to 20.0 wt%, up to 15.0 wt%, up to 13.0 wt%, up to 12.0 wt%, up to 11.0 wt%, up to 5.0 wt%, up to 2.0 wt%, or up to 1.0 wt%. In some embodiments, the glass may be free of CaO, SrO, and BaO.

[0075] The ZnO content in the glass can range from 0.0 to 5.0 wt%, 0.0 to 4.0 wt%, 0.0 to 3.0 wt%, or 0.0 to 2.0 wt%. In some embodiments, the ZnO content is less than 100 ppm. In some embodiments, the ZnO content can range from 0.5 to 5.0 wt%, or 1.0 to 4.0 wt%. In some embodiments, the glass may be ZnO-free.

[0076] The total content of alkaline earth metal oxides plus the content of ZnO can be 0 to 15.0 wt%, 0.0 to 10.0 wt%, 0.0 to 9.0 wt%, or 0.0 to 8.0 wt%, or 0.0 to 7.0 wt%, or 0.0 to 5.0 wt%.

[0077] Optionally, the content of alkaline earth metal oxide R'O is less than 10.0 wt%, less than 6.0 wt%, less than 4.0 wt%, or less than 2.0 wt%. Alternatively, it can be used in proportions of at least 1.0 wt%, at least 2.0 wt%, or at least 3.0 wt%.

[0078] In one embodiment, the ratio of (a) the sum of the weight percentage contents of all alkaline earth metal oxides R'O to (b) the weight percentage content of SiO2 is 0.00 to <0.06, 0.01 to <0.3, less than 0.2, <0.1, <0.05, or <0.025. Optionally, this ratio can be >0.01, >0.02, or >0.03. For example, this ratio can be >0.01 to <0.3, or >0.02 to <0.2.

[0079] In some embodiments, the glass may contain MgO in a content of 0.0 to 9.0 wt%, 0.1 to 8.5 wt%, or 0.5 to 8.0 wt%. Optionally, the MgO content is at least 0.1 wt%, at least 0.5 wt%, or at least 1.0 wt%, for example at least 1.5 wt%, at least 2.0 wt%, or at least 3.0 wt%. MgO can be advantageous in terms of resistance to devitrification. MgO can also act as a network forming agent and improve solubility. It can also improve the compressive stress on the surface after ion exchange because it additionally increases the packing density. However, if the MgO content is too high, devitrification may occur, especially due to reaction with refractive materials. Furthermore, excessively high MgO content may lead to phase separation. However, in some embodiments, the glass does not contain MgO.

[0080] Optionally, the sum of the weight percentages of MgO and the second abundant alkali metal oxide is less than 10.0 wt%, less than 9.5 wt%, or less than 9.0 wt%. In one embodiment, MgO can be used in a proportion of at least 1.5 wt%, at least 2.0 wt%, or at least 3.0 wt%. For example, the sum of the contents of MgO and CaO can be at least 1.5 wt%, at least 5.0 wt%, at least 7.5 wt%, at least 15.0 wt%, or at least 20 wt%.

[0081] An optional glass disclosed herein comprises the following components by weight percentage:

[0082] An optional glass disclosed herein comprises the following components by weight percentage:

[0083] An optional glass disclosed herein comprises the following components by weight percentage:

[0084] An optional glass disclosed herein comprises the following components by weight percentage:

[0085] An optional glass disclosed herein comprises the following components by weight percentage:

[0086] An optional glass disclosed herein comprises the following components by weight percentage:

[0087] An optional boron-containing glass disclosed herein comprises the following components by weight percentage:

[0088] An optional boron-free glass disclosed herein comprises the following components by weight percentage:

[0089] An optional Al2O3-containing glass disclosed herein comprises the following components by weight percentage:

[0090] An optional low-Al2O3 glass disclosed herein comprises the following components by weight percentage:

[0091] An optional P2O5-containing glass disclosed herein comprises the following components by weight percentage:

[0092] An optional glass with relatively high K2O disclosed herein comprises the following components by weight percentage:

[0093] An optional glass with relatively high ZrO2 content disclosed herein comprises the following components by weight percentage:

[0094] An optional glass with relatively high CaO content disclosed herein comprises the following components by weight percentage:

[0095] An optional glass with a relatively high MgO content disclosed herein comprises the following components by weight percentage:

[0096] Another optional glass of this disclosure having a relatively high ZrO2 content comprises the following components by weight percentage:

[0097] The glass may contain one or more clarifying agents, such as CeO2, SnO2, Cl, and SO3. Optionally, Fe2O3 may be used as a clarifying aid. Therefore, the glass may optionally contain Fe2O3. It is desirable to avoid the use of toxic clarifying agents arsenic and antimony, thereby the total content of arsenic and antimony may be less than 100 ppm. For toxicity reasons, the total content of lead and bismuth may be less than 100 ppm. In the embodiments, the content of F in the glass may be less than 1% by weight.

[0098] In one embodiment, the glass may contain coloring ions as dyes and / or colorants, such as iron, cobalt, chromium, copper, vanadium, nickel, manganese, neodymium, erbium, europium, molybdenum, or combinations thereof. They may be used in various oxidation states.

[0099] In one embodiment, to further improve the fusibility of this glass system, B2O3, K2O, MgO and / or CaO may be used.

[0100] parameter The coefficient of thermal expansion of glass can be less than 9.8 × 10⁻⁶. -6 K -1 Less than 9.7*10 -6 K -1 or less than 9.6*10 -6 K -1 In a particular embodiment, the coefficient of thermal expansion is as high as 10.0*10. -6 K -1 Up to 9.5*10 -6 K -1 or as high as 9.2 *10 -6 K -1 Optionally, the coefficient of thermal expansion is at least 7.0 × 10⁻⁶. -6 K -1 At least 7.5*10 -6 K -1 At least 8.0*10 -6 K -1 or at least 8.2*10 -6 K -1 In this embodiment, the coefficient of thermal expansion of the glass is 7.0*10⁻⁶. -6 K -1 Up to 9.8*10 -6 K -1 7.5*10 -6 K -1 Up to 9.7*10 -6 K -1 8.0*10 -6 K -1 Up to 9.6*10-6 K -1 or 8.2*10 -6 K -1 Up to 9.6*10 -6 K -1 Within a certain range. In some embodiments, the coefficient of thermal expansion is less than 9.59*10. -6 K -1 Even less than 9.58*10 -6 K -1 .

[0101] The Young's modulus of the glass can be at least 74 GPa, at least 75 GPa, at least 76 GPa, or at least 77 GPa. Optionally, the Young's modulus can be up to 90 GPa, up to 88 GPa, or up to 86 GPa. In embodiments, the Young's modulus of the glass ranges from 74 GPa to 90 GPa, 75 GPa to 88 GPa, or 76 GPa to 86 GPa. In some embodiments, the Young's modulus is at least 76 GPa, or even at least 77 GPa. The glass of this disclosure can have an excellent Young's modulus (in GPa) between 70 and 90.

[0102] Typically, a higher Young's modulus increases the tensile stress on the glass surface during bending. This also reduces the tendency of glass articles to form creases in the bending region. The high compressive stress at the surface can compensate for the tensile stress during bending. Since the disclosed glass exhibits improved sensitivity to chemical strengthening, it has higher CSS and CS, and thus a higher Young's modulus. The advantage of this is that, particularly in the case of foldable display covers, the tendency to form creases in the bending region of the display cover can be significantly reduced. Therefore, in one embodiment, the disclosed glass is particularly suitable for foldable display covers.

[0103] In one embodiment, the Poisson's ratio of the glass is 0.220 to 0.270, 0.225 to 0.265, or 0.230 to 0.260. Optionally, the Poisson's ratio may be less than 0.260, less than 0.259, or less than 0.258. In another embodiment, the Poisson's ratio is at least 0.220, at least 0.225, or at least 0.230.

[0104] Optionally, the density of the glass is between 2.530 and 2.850 g / cm³. 3 2.580 to 2.830 g / cm³ 3 Or 2.600 to 2.780 g / cm³ 3 The density can be at least 2.530 g / cm³. 3At least 2.580 g / cm 3 or at least 2.600 g / cm 3 In this embodiment, the density will be as high as 2.850 g / cm³. 3 Up to 2.830 g / cm³ 3 Up to 2.790 g / cm³ 3 or as high as 2.780 g / cm³ 3 .

[0105] In one embodiment, the bulk density of the glass is 0.44 to 0.58, 0.48 to 0.56, or 0.50 to 0.54. The bulk density may be at least 0.44, at least 0.48, or at least 0.50. In embodiments, the bulk density may be as high as 0.58, up to 0.56, up to 0.54, or up to 0.53.

[0106] In one embodiment, the glass transition temperature T of the glass g It can be at least 545°C, at least 550°C, or at least 555°C. In some embodiments, T g It can even be at least 560°C or at least 561°C, while in certain embodiments, T g The value can even be above 565℃. Optionally, T g It can be less than 680°C or less than 675°C. In the embodiment, T g Within the ranges of 545℃ to 680℃, 550℃ to 675℃, or 553℃ to 630℃. High T g High temperatures are permissible during ion exchange processes. It features high TL. g The stress relaxation of glass due to ion exchange at higher temperatures will be less than that at lower temperatures. g The glass. Higher temperatures accelerate the ion exchange process, thus making ion exchange more economical.

[0107] In one embodiment, the strain point of the glass can be at least 500°C, at least 525°C, at least 540°C, at least 550°C, or at least 560°C. In some embodiments, the strain point can even be at least 543°C or at least 573°C, and in certain embodiments, the strain point value can even be above 580°C. Optionally, the strain point can be less than 700°C or less than 675°C. In embodiments, the strain point is in the range of 500°C to 700°C, 525°C to 685°C, or 540°C to 675°C. A high strain point allows for the use of high temperatures during ion exchange processing. Glass with a high strain point experiences less stress relaxation during ion exchange at higher temperatures than glass with a lower strain point. Higher temperatures accelerate the ion exchange process, thereby making ion exchange more economical.

[0108] Optionally, the glass composition exhibits one or more of the following properties: Temperature T4 is at least 1065°C, at least 1075°C, at least 1080°C, at least 1085°C, at least 1095°C, or at least 1100°C; Temperature T3 is at least 1180°C, at least 1200°C, at least 1225°C, at least 1250°C, at least 1310°C, or at least 1330°C; The VFT constant A is < 0.00, optionally -5.00 to -2.00; The VFT constant B is >5000℃, optionally from 5800℃ to 8000℃; and The VFT constant T0 is 140 to 450°C, for example 145 to 300°C, or up to 255°C.

[0109] The temperature-viscosity curve of the glass disclosed herein can have a significant steepness. The steepness of this curve can be quantified by temperatures T4 and T... 7.6 The difference. For the glass of this disclosure, this difference can be at least 250K, at least 265K, at least 280K, or at least 285K. Optionally, the difference does not exceed 380K, 360K, or 340K. For example, temperatures T4 and T... 7.6 The difference can be in the range of 250 to 380K, 265 to 260K, or 280 to 340K.

[0110] All these parameters describe the viscosity behavior of the glass. The glass of this disclosure has a fairly high characteristic temperature, which makes it possible to use high temperatures during ion exchange processes, thereby accelerating the ion exchange process.

[0111] A key characteristic of the glass disclosed herein is its ability to generate high compressive stress in a very short time. This characteristic is quantified by a CSS score (or simply "CSS"), which corresponds to the compressive stress formed in the test sample. A further index is used to indicate the glass thickness used to measure the CSS. The glass compositions of this disclosure exhibit significant CSS values ​​even with small glass thicknesses.

[0112] Optionally, the CSS of the glass disclosed herein 200µm For at least 800 MPa, at least 950 MPa, at least 1000 MPa, at least 1050 MPa, or even at least 1070 MPa. This is a very significant compressive stress sensitivity, which allows very high compressive stress to be introduced into the glass over a short period of time. Optionally, CSS 200µm Up to 1700 MPa, up to 1500 MPa, or up to 1400 MPa. In the embodiment, CSS 200µmThe compressive stress ranges from 800 MPa to 1700 MPa, 1000 MPa to 1500 MPa, or 1050 MPa to 1400 MPa. Existing glass compositions require much longer ion exchange times to achieve such high compressive stresses. Typically, existing glass compositions achieve, or do not achieve, compressive stresses of 1000 MPa after more than 4 hours of ion exchange.

[0113] Optionally, the CSS of the glass disclosed herein 30µm For at least 600 MPa, at least 700 MPa, at least 800 MPa, at least 850 MPa, or even at least 900 MPa. Optional, CSS 30µm The pressure can be up to 1200 MPa, up to 1100 MPa, or up to 1000 MPa. In the embodiment, CSS... 30µm Within the range of 600 MPa to 1200 MPa, 700 MPa to 1100 MPa, or 800 MPa to 1000 MPa. In one embodiment, CSS 30µm Score refers to CSS 30µm Existing glass compositions cannot achieve such high compressive stress at such a small thickness.

[0114] Another way to express the remarkable characteristic of this glass to accept compressive stress is by using a 1000 MPa 10X-time, that is, the time required for the glass sample to undergo ion exchange treatment in an alkali metal nitrate bath when the compressive stress on its surface reaches 1000 MPa. Optionally, the 1000 MPa 10X-time for the glass of this disclosure is less than 60 minutes, less than 30 minutes, or even less than 20 minutes. In one embodiment, the 1000 MPa 10X-time is 10X-time in a potassium nitrate bath.

[0115] The diffusion rate of this glass further illustrates its superior ability to be chemically strengthened. High diffusion rate means that the glass can achieve a sufficiently deep compressive stress layer in a short time, making the glass manufacturing process more economical. In some embodiments, the diffusion rate of the glass disclosed herein is at least 8 µm. 2 / h, 10µm 2 / h, 12µm 2 / h, 14µm 2 / h, or 16µm 2 / h. Optionally, this value can range up to 45µm. 2 / h, 40µm 2 / h or 35µm 2 / h. In some embodiments, the diffusion rate is 8 to 45 µm. 2 / h, 9 to 40µm2 / h, or 10 to 31µm 2 / h.

[0116] The glass disclosed herein may have chemical resistance characterized by one or more of the following: (a) The hydrolysis resistance value in μg / g sodium equivalent is less than 320, or less than 300, or less than 280, or less than 250, or less than 225, or less than 210; (b) by mg / dm 2 The alkali resistance value of the weight loss meter is less than 25, or less than 22, or less than 20, or less than 18. (c) According to mg / dm 2 The acid resistance value of the weight loss meter is less than 5.0, or less than 2.5, or less than 2.0, or less than 1.0.

[0117] Optionally, the hydrolysis resistance value, calculated in μg / g sodium equivalent, may be at least 15, at least 50, or at least 100. In one embodiment, it is calculated in mg / dm³. 2 The alkali resistance value of the weight loss meter is at least 1, at least 5, or at least 8. In another embodiment, it is expressed in mg / dm³. 2 The acid resistance value of the weight loss meter can be at least 0.1, at least 0.2, or at least 0.3.

[0118] The glass disclosed herein exhibits significant compressive stress sensitivity (in MPa) relative to the total content of alkali metal oxide R2O and alkaline earth metal oxide R'O. Existing glass technologies require large amounts of alkali metal oxides or alkaline earth metal oxides to achieve compressive stress during ion exchange. Conversely, the compositions described herein produce high compressive stress even when the alkali metal and alkaline earth metal ratio is moderate. Optionally, The number is at least 25, at least 30, at least 40, at least 50, or at least 60. In some embodiments, For at least 70, at least 80, or at least 90. Optionally, Up to 100, up to 75, or up to 50. In some embodiments, The range is 25 to 100, 30 to 75, or 35 to 65. For readability reasons, the unit (MPa / wt.%) for this parameter is not specified.

[0119] In one embodiment, this disclosure relates to a glass having a CSS value in MPa. 200µm The ratio of the coefficient of thermal expansion in ppm / K over a temperature range of 20 to 300°C The values ​​are at least 85, at least 100, at least 110, at least 120, or at least 130. Existing glass compositions suffer from high thermal expansion, typically greater than 9.0 x 10⁻⁶. -6 K -1 The glass compositions disclosed herein exhibit high CSS at low CTE. 200µm ,For example, The range is 100 to 250, 110 to 220, or 120 to 200. For example, It can be as high as 250, 220, or 200. For readability reasons, the unit (MPa*K / ppm) for this parameter is not specified.

[0120] The refractive index of the glass used for the display screen should not be too high, as this provides limited reflectivity. Optionally, the refractive index n of the glass disclosed herein... d The refractive index is less than 1.600, less than 1.550, or even less than 1.540. In some embodiments, the refractive index is in the range of 1.520 to 1.600 or 1.530 to 1.550.

[0121] In one embodiment, the glass does not devitrify, especially at the operating point (viscosity 10). 4 dPa*s). This is advantageous for glass produced using a down-draw process. In one embodiment, glass can be produced using a down-draw process, such as slot down-draw or overflow melt down-draw. It is desirable that, at 10 4 There is no devitrification at the operating point of dPa*s. However, at slightly higher viscosities, especially at viscosity 10... 5 At dPa*s, a smaller crystal growth rate is permissible, and at a viscosity of 10... 5 Glass with a dPa*s crystal growth rate of no more than 0.5 μm / min is generally compatible with the pull-down process.

[0122] Therefore, for the purposes of this disclosure, resistance to devitrification can be expressed as at a viscosity of 10 5 Crystal growth rate at dPa*s. The lower the crystal growth rate, the higher the resistance to devitrification, and thus the higher the yield. The measurement of crystallization rate is well known. The crystallization rate is measured along the formed crystal (i.e., at its maximum extension). In particular, the crystallization rate is determined when the glass is subjected to gradient tempering (e.g., using a gradient furnace).

[0123] The so-called lower devitrification temperature (LDT) is the temperature at which devitrification begins in a heating process. Above the liquidus temperature (also known as the upper devitrification temperature (UDT)), crystallization will not occur even after a long period of time. The LDT and UDT values ​​are typically different for different glasses. Unless otherwise stated, the terms "crystallization" and "devitrification" are used synonymously herein.

[0124] If crystallization occurs, it happens at temperatures above the lower limit of the devitrification temperature (LDT) but below the upper limit of the devitrification temperature (UDT), thus falling within the range between the LDT and UDT. Typically, tests are conducted at different temperatures to determine the crystal growth rate at different viscosities. This also allows us to define the LDT and UDT as the lower and upper limits of the temperature range in which crystallization occurs, respectively.

[0125] Crystal growth rate can be determined by heat-treating glass for 16 hours in a gradient furnace with a heating scheme. A gradient furnace is a furnace with different heating zones, and therefore different temperature regions. The heating scheme means that the glass is at a lower temperature than any region of the furnace before it is placed inside. Therefore, placing the glass inside the furnace raises its temperature, regardless of which region it is placed in. Thus, devitrification can be measured by heat-treating the glass for 16 hours in a (preheated) gradient furnace with different temperature zones. Because the gradient furnace is divided into different temperature locations or regions, its gradient is a location-based gradient, not a time-based gradient.

[0126] Dividing the furnace into multiple heating zones allows for simultaneous testing of different temperatures (and thus different viscosities). This is a unique advantage of gradient furnaces. The temperature selection should ensure that the crystallization rate can be determined at different temperatures between the LDT and UDT (and thus at different viscosities). If the LDT and UDT are unknown, a relatively large range of temperatures is tested to determine them. For example, a temperature approximately 350 K lower than the glass processing temperature (operating point) can be chosen as the lowest temperature of the gradient furnace. The operating point corresponds to a viscosity of 10. 4 dPa*s.

[0127] As mentioned above, at a viscosity of 10 5 The crystal growth rate under dPa*s conditions is related to the manufacturability of the pull-down process. Optionally, the glass of this disclosure has anti-devitrification properties, such that at 10... 5At viscosities of dPa*s, crystal growth rates are at most 0.5 μm / min, at most 0.4 μm / min, at most 0.3 μm / min, at most 0.2 μm / min, at most 0.1 μm / min, at most 0.05 μm / min, at most 0.02 μm / min, or at most 0.01 μm / min, particularly when heat-treated in a gradient furnace with a heating scheme for 16 hours. In one embodiment, at 10 5 No devitrification occurs at viscosities of dPa*s. Importantly, if at 10... 5 If devitrification does not occur at a viscosity of dPa*s, then it cannot be determined whether 10 5 Crystal growth rate at dPa*s. At 10 5 The absence of devitrification at a viscosity of dPa*s can also be expressed as a crystal growth rate of 0 μm / min.

[0128] Optionally, glass particles, particularly those with a diameter of about 2 to 3 mm, are used to determine the crystallization rate. These glass particles are placed on a support, such as a platinum support used for gradient tempering. For example, the support may have recesses (each recess for accommodating the glass particles) and pores at the bottom of each recess, thereby allowing the crystallization rate to be determined under a microscope. Considering the size of the glass particles, the diameter of each recess may be 2 mm, and the diameter of each pore may be 0.9 mm.

[0129] After heat treatment, the specific temperature range and crystal growth rate within which this occurs can be determined under a microscope (thus determining the viscosity). Based on the known correlation between temperature and viscosity, the viscosity at which this occurs is determined to be 10... 5 The crystal growth rate at a viscosity of dPa*s. Based on the glass composition, it can be determined which viscosity corresponds to which temperature. LDT and UDT can be determined as the lower and upper limits of the temperature range in which crystallization occurs, respectively. Because it is known which location in the furnace has which temperature and which glass particle is located in which position within the furnace during heat treatment, different glass particles can be easily assigned to different temperatures in the gradient furnace.

[0130] Tempered products The glass article disclosed herein may have a thickness of less than 1000 μm, wherein the article comprises a glass containing at least 40.0 wt% SiO2, at least 12.0 wt% Na2O, and further containing ZrO2, wherein the weight content of ZrO2 is at least 1.5 times the sum of the weight contents of Al2O3 and B2O3, and the CSS of the glass is... 30µm The pressure resistance is at least 700 MPa, and / or the acid resistance of the glass is less than 5.0 mg / dm³. 2 or less than 2.5 mg / dm 2 .

[0131] The glass articles disclosed herein may have a thickness of less than 1000 μm and comprise or consist of the glass as described herein or glass compositions as described herein. Typically, the article may be referred to as a thin glass article or glass sheet, and its thickness may be less than 850 μm, less than 500 μm, less than 300 μm, less than 200 μm, or less than 100 μm. In some embodiments, the thickness may be as low as less than 80 μm or as low as less than 70 μm. Some articles have a thickness of less than 50 μm or less than 40 μm. Such thin glass articles have bendable and / or foldable properties. For such flexible or foldable cover glass, a desired thickness may be less than 100 μm, less than 80 μm, less than 60 μm, or less than 40 μm. To provide sufficient impact resistance, a minimum thickness may be required. The minimum thickness may be at least 5 μm, at least 10 μm, or at least 15 μm.

[0132] Due to the significant characteristic of low CTE and other desired properties, glass articles can be manufactured with warpage of less than 3.0 mm, less than 2.0 mm, or less than 1.0 mm. Typically, glass articles can be manufactured in a stretching process, where temperature differences between different parts of the glass will cause warpage. Because the glass of this disclosure has a low CTE and other desired properties, such as good viscosity characteristics, articles with low warpage can be obtained. In some embodiments, the warpage is at least 5 μm, at least 10 μm, at least 100 μm, or at least 250 μm.

[0133] Optionally, the total thickness variation of the article can be less than 15 μm, less than 10 μm, less than 7 μm, or less than 5 μm. In an embodiment, the total thickness variation (TTV) can be from 1 μm to 10 μm. In one embodiment, the TTV is ±10.0%, ±5.0%, or ±3.0% of the thickness of the glass article.

[0134] The area of ​​the article can be at least 10 cm². 2 At least 15 cm 2 or at least 20 cm 2 In this embodiment, the area of ​​the article can be less than 10,000 cm². 2 Less than 1000 cm 2 or less than 200 cm 2 .

[0135] The surface roughness R of the product on one or two of its main surfaces a The roughness can be no greater than 5.0 nm, no greater than 3.0 nm, or no greater than 1.5 nm. This very small roughness can be obtained through a pull-down process.

[0136] The article may exhibit significant chemical resistance on one or both of its main surfaces. Chemical resistance can be characterized by one or more of the following: (a) The hydrolysis resistance value, calculated in μg / g sodium equivalent, is less than 320, less than 300, less than 280, less than 250, less than 225, or less than 210. (b) by mg / dm 2 The alkali resistance value of the weight loss meter is less than 25, less than 22, less than 20, or less than 18; (c) According to mg / dm 2 The acid resistance value of the weight loss meter is less than 5.0, less than 2.5, less than 2.0, or less than 1.0.

[0137] The Vickers hardness of glass articles may be at least 580, at least 590, or at least 600. Optionally, the Vickers hardness is in the range of 580 to 800, 590 to 700, or 600 to 630.

[0138] In one embodiment, the glass article exhibits excellent three-point flexural strength, demonstrating a three-point flexural strength of at least 100 MPa, at least 200 MPa, or at least 300 MPa. Notably, such strength can be achieved even without ion exchange strengthening. With such high initial strength, the strength of the article becomes significantly more pronounced after ion exchange. Optionally, the three-point flexural strength can be in the range of 100 MPa to 600 MPa, 200 MPa to 500 MPa, or 300 MPa to 400 MPa.

[0139] Tempered products Glass articles may include ion-exchange layers on one or both of their main surfaces. The ion-exchange layers impart high strength to the glass articles. Optionally, the compressive stress on one or both of the articles' main surfaces may be at least 500 MPa, at least 600 MPa, at least 700 MPa, or at least 800 MPa. In embodiments, the compressive stress may be as high as 1800 MPa, up to 1600 MPa, up to 1500 MPa, or up to 1400 MPa. For example, the compressive stress may be in the range of 400 MPa to 1800 MPa, 700 MPa to 1600 MPa, or 800 MPa to 1400 MPa.

[0140] In one embodiment, the glass article has a thickness of 20 to 40 μm, for example 25 to 35 μm, and a compressive stress of at least 600 MPa, at least 700 MPa, at least 800 MPa, at least 850 MPa, or at least 900 MPa on one or both of its main surfaces.

[0141] Optionally, the glass article exhibits a DoL of 6 to 12 μm or 7 to 11 μm on one or both of its main surfaces. For example, the DoL can be at least 6 μm, at least 7 μm, or at least 8 μm. Alternatively or additionally, the DoL can be up to 15 μm, up to 13 μm, up to 12 μm, or up to 11 μm.

[0142] In one embodiment, DoL is 15% to 25% of the article thickness, or 16% to 20% of the article thickness. In another embodiment, DoL is at least 15%, at least 16%, or at least 17% of the article thickness. DoL can be as high as 33%, 25%, or 20% of the article thickness. In this document, DoL refers to the depth of a compressive stress layer. The total DoL of all compressive stress layers can be greater.

[0143] A striking characteristic of the articles of this disclosure is that very high compressive stress can be achieved even in thin articles. In embodiments, the ratio of compressive stress (in MPa) to article thickness (in μm) on one or both main surfaces of the glass article is at least 4.0 MPa / μm, at least 5.0 MPa / μm, at least 6.0 MPa / μm, or at least 10.0 MPa / μm. In embodiments, this value can be as high as 40.0 MPa / μm, as high as 35.0 MPa / μm, or as high as 30.0 MPa / μm. Optionally, the ratio of compressive stress (in MPa) to article thickness (in μm) is as high as 10.0 MPa / μm, as high as 8.0 MPa / μm, or as high as 7.0 MPa / μm. In some embodiments, the ratio of compressive stress (MPa) to article thickness (μm) is in the range of 4.0 MPa / μm to 40.0 MPa / μm, 5.0 MPa / μm to 35.0 MPa / μm, 5.0 MPa / μm to 30.0 MPa / μm, or 10.0 MPa / μm to 29.0 MPa / μm. In a particular embodiment, this value is in the range of 20.0 MPa / μm to 30.0 MPa / μm. In one embodiment, the ratio of compressive stress (MPa) to article thickness is at least 20.0 MPa / μm or at least 25.0 MPa / μm.

[0144] Optionally, the ratio of compressive stress (MPa) to the depth of the ion exchange layer (μm) on one or both main surfaces of the article can be at least 50 MPa / μm, at least 75 MPa / μm, or at least 90 MPa / μm. In one embodiment, the value is even at least 100 MPa / μm, at least 120 MPa / μm, or at least 140 MPa / μm. For example, the ratio of compressive stress (MPa) to the depth of the ion exchange layer (μm) can range from 50 to 400 MPa / μm, 75 to 300 MPa / μm, or 90 to 200 MPa / μm. In some embodiments, the ratio of compressive stress (MPa) to the depth of the ion exchange layer (μm) is as high as 400 MPa / μm, as high as 300 MPa / μm, or as high as 200 MPa / μm.

[0145] In one embodiment, this disclosure relates to a glass article exhibiting a three-point bending strength of at least 400 MPa, at least 500 MPa, or at least 600 MPa.

[0146] In one embodiment, the glass article exhibits excellent three-point bending strength, demonstrating a three-point bending strength of at least 400 MPa, at least 500 MPa, or at least 600 MPa. It is noteworthy that such strength is achievable. Optionally, the three-point bending strength can be in the range of 400 MPa to 1200 MPa, 500 MPa to 1000 MPa, or 600 MPa to 800 MPa.

[0147] electronic devices The glass and / or the glass article can be used in electronic devices, such as laptops, smartphones, tablets, and other handheld or wearable devices. The glass and / or the glass article can be part of a display screen.

[0148] Therefore, an electronic device according to this disclosure may include glass or glass articles according to this disclosure. The electronic device may include a display screen, wherein the display screen includes the glass and / or glass articles of this disclosure. The glass article may be a cover glass of the electronic device.

[0149] The electronic device can be a flexible and / or foldable device, such as a flexible and / or foldable smartphone or tablet.

[0150] Manufacturing method The glass can be produced by melting a batch of raw materials suitable for obtaining the compositions of this disclosure. For example, the glass can be melted in a platinum crucible. After melting, the glass melt can be clarified using one or more clarifying agents to remove air bubbles. Physical clarification methods, such as vacuum clarification, can also be used instead of chemical clarifying agents.

[0151] On an industrial scale, glass articles can be manufactured using float glass or downdraw processes (such as slot downdraw or overflow melt downdraw). Slot downdraw is preferred because it allows for very small thicknesses.

[0152] After molding, the article can be strengthened (also known as "chemically strengthened") by ion exchange. Strengthening may include immersing the article in a molten salt bath. The salt is selected according to the desired ion exchange process. In a preferred embodiment, the salt may be an alkali metal salt, such as an alkali metal nitrate. In some embodiments, the salt bath contains potassium nitrate, optionally containing about 100% KNO3.

[0153] It is well known to those skilled in the art that glass articles are chemically strengthened through ion exchange. The strengthening process can be accomplished by immersing the glass article in a salt bath containing monovalent ions to exchange with alkali metal ions within the glass. The monovalent ions in the salt bath have a higher ion concentration than the alkali metal ions (e.g., Na+) within the glass. + K + and / or Cs + Larger radius. After ion exchange, the larger ions are forced into the glass network, generating compressive stress on the glass. The strength of the glass is significantly improved after ion exchange. Furthermore, the CS produced by chemical strengthening improves the bending properties of tempered glass products and enhances their scratch resistance. Typical salts used for chemical strengthening are, for example, salts containing K. + Molten salt or a mixture of salts. An optional salt bath for chemical tempering is one containing Na. + and / or containing K + A molten salt bath or a mixture thereof. Optional salts include NaNO3, KNO3, CsNO3, NaCl, KCl, CsCl, Na2SO4, K2SO4, Cs2SO4, Na2CO3, K2CO3, Cs2CO3, and K2Si2O5. Additives, such as NaOH, KOH, and other sodium or potassium salts, are also used to better control the ion exchange rate for chemical enhancement. For example, ion exchange is carried out in KNO3 at a temperature range of 300°C to 480°C, or 340°C to 480°C, particularly 340°C to 450°C, or 390°C to 450°C. Optionally, during ion exchange, the temperature of the salt bath is maintained at T... g -400℃ to T g -100℃, or T g -250℃ to Tg The temperature range is -150℃.

[0154] Chemical strengthening is not limited to a single step. It can include multiple steps in one or more salt baths, where the salt baths contain various concentrations of alkali metal ions, and / or different ions in the salt baths, to achieve better tempering properties. Therefore, chemically tempered glass articles can be tempered in one step or in a process of multiple steps (e.g., two steps). Two-step chemical tempering is particularly suitable for Li₂O-containing glasses because lithium can be exchanged for both sodium and potassium ions.

[0155] The inventors discovered that the glass exhibits very rapid ion exchange and achieves high compressive stress within a short time. The article can be immersed in a molten salt bath at a specified temperature for a period ranging from 20 minutes to 12 hours, 25 minutes to 4 hours, or 30 minutes to 2 hours. Optionally, the time is at least 20 minutes, at least 25 minutes, or at least 30 minutes. In some embodiments, the ion exchange time is no more than 2 hours or no more than 1 hour.

[0156] In one embodiment, the method includes: A batch of raw materials is melted as needed to obtain glass according to this disclosure; Forming glass articles, such as the glass articles described herein; The product is enhanced by ion exchange treatment in an ion exchange bath.

[0157] This project is publicly disclosed. As described in detail above, each of the following items represents a specific embodiment of glass, glass articles, and other aspects of this disclosure.

[0158] The first item relates to a glass composition comprising: i.SiO2, ii. Al2O3 in a content of 0.0 to 6.0% by weight, ii. A content of at least 8.0% by weight of ZrO2, iii. A content of at least 12.0% by weight of Na₂O, iv. 0.0 to 5.0% by weight of B2O3, v. 0.0 to 5.0 wt% Li₂O, vi. 0.0 to 10.0% by weight of K₂O; and vii. Optionally, one or more components selected from P2O5 and TiO2.

[0159] The second item relates to a glass composition comprising the following components by weight percentage: In addition, optionally, it contains dyes or colorants, such as Fe2O3, CoO and / or Cr2O3.

[0160] The third item relates to a glass composition comprising the following components by weight percentage:

[0161] Item 4 relates to a glass comprising the following components by weight percentage:

[0162] Item 5 relates to a glass comprising the following components by weight percentage:

[0163] Item 6 relates to a glass comprising the following components by weight percentage:

[0164] Item 7 relates to a glass comprising the following components by weight percentage:

[0165] Item 8 relates to a glass comprising the following components by weight percentage:

[0166] Item 9 relates to a glass comprising the following components by weight percentage:

[0167] Item 10 relates to a glass comprising the following components by weight percentage:

[0168] Item 11 relates to a glass comprising the following components by weight percentage:

[0169] Item 12 relates to a glass comprising the following components by weight percentage:

[0170] Item 13 relates to a glass comprising the following components by weight percentage:

[0171] Item 14 relates to a glass with a relatively high K2O content, comprising the following components by weight percentage:

[0172] Item 15 relates to a glass with a relatively high ZrO2 content, comprising the following components by weight percentage:

[0173] Item 16 relates to a glass having a relatively high CaO content, comprising the following components by weight percentage:

[0174] Item 17 relates to a glass having a relatively high MgO content, comprising the following components by weight percentage:

[0175] Item 18 relates to a glass with a relatively high ZrO2 content, comprising the following components by weight percentage:

[0176] Item 19 relates to a glass composition according to any one of items 1 to 18, comprising SiO2 and ZrO2. 2, ZrO2 contains Al2O3 and B2O3, wherein the weight ratio of ZrO2 to the sum of the weight contents of Al2O3 and B2O3 is at least 1.5.

[0177] Item 20 relates to a glass composition according to any one of items 1 to 19, which is free of As2O3 and / or Sb2O3.

[0178] Item 21 relates to a glass composition according to any one of items 1 to 20, wherein, if present, the amounts of Al2O3, B2O3, Li2O, K2O, SrO, ZnO, SO3, Fe2O3, TiO2, SnO2 and / or Cl are less than 0.1% by weight, less than 500 ppm, less than 200 ppm, or less than 100 ppm, or even about 0.0%.

[0179] Item 22 relates to a glass composition according to any one of items 1 to 21, wherein the coefficient of thermal expansion in a temperature range of 20 to 300°C is less than 15.0 × 10⁻⁶. -6 K -1 Less than 12.0*10 -6 K -1 Less than 10.0*10 -6 K -1 or less than 9.8*10 -6 K -1 .

[0180] Item 23 relates to a glass composition according to any one of items 1 to 22, which is defined as CSS. 200µm The fractional compressive stress sensitivity is at least 900 MPa.

[0181] Item 24 relates to a glass composition according to any one of items 1 to 23, wherein the ZrO2 content is at least 10.0% by weight or at least 12.0% by weight.

[0182] Item 25 relates to a glass composition according to any one of items 1 to 24, wherein the ratio of the content of ZrO2 to the content of Al2O3 (in weight percentage) is at least 2.0 or at least 3.0.

[0183] Item 26 relates to a glass composition according to any one of items 1 to 25, wherein the 1000 MPa 1OX time is less than 60 minutes or less than 30 minutes.

[0184] Item 27 relates to a glass composition according to any one of items 1 to 26, having a glass transition temperature T. g It can be at least 540°C, at least 550°C, or at least 564°C.

[0185] Item 28 relates to a glass composition according to any one of items 1 to 27, wherein the glass composition is characterized by its temperature T4 and T5. 7.6 The steepness of the temperature-viscosity curve of the glass, characterized by the difference between the values, is 260 to 350 K.

[0186] Item 29 relates to a glass composition according to any one of items 1 to 28, wherein the glass has a diffusion rate of at least 10 μm. 2 / h or at least 15μm 2 / h.

[0187] The 30 relates to a glass composition according to any one of claims 1 to 29, wherein the total content of alkaline earth metal oxides and ZnO in the glass is not more than 15.0% by weight.

[0188] Item 31 relates to a glass composition according to any one of items 1 to 30, wherein when the glass is heat-treated in a gradient furnace having a heating scheme for 16 hours, at 10 5 At a viscosity of dPa*s, the crystal growth rate is at most 0.5 μm / min.

[0189] Item 32 relates to a glass composition according to any one of items 1 to 31, wherein the DoL is between 5 µm and 12 µm.

[0190] Item 33 relates to a glass composition according to any one of items 1 to 32, wherein the Young's modulus (in GPa) is between 70 and 90.

[0191] Item 34 relates to a glass composition according to any one of items 1 to 33, comprising one or more clarifying agents, such as CeO2, SnO2, Cl, SO3 or Fe2O3.

[0192] Item 35 relates to a glass composition according to any one of items 1 to 34, wherein the coefficient of thermal expansion of the glass is 7.0 × 10⁻⁶. -6 K -1 Up to 9.8*10 -6 K -1 .

[0193] Item 36 relates to a glass composition according to any one of items 1 to 35, having a Young's modulus of 74 GPa to 90 GPa.

[0194] Item 37 relates to a glass composition according to any one of items 1 to 36, having a Poisson's ratio of 0.220 to 0.270.

[0195] Item 38 relates to a glass composition according to any one of items 1 to 37, having a density of 2.530 to 2.900 g / cm³. 3 .

[0196] Item 39 relates to a glass composition according to any one of items 1 to 38, having a bulk density of 0.44 to 0.58.

[0197] Item 40 relates to a glass composition according to any one of items 1 to 39, having a glass transition temperature T. g The temperature ranges from 550℃ to 700℃.

[0198] Item 41 relates to a glass composition according to any one of items 1 to 40, wherein the strain point is at least 550°C to 670°C.

[0199] Item 42 relates to a glass composition according to any one of items 1 to 41, which exhibits one or more of the following: Temperature T4 is at least 960°C, at least 970°C, at least 1005°C, at least 1010°C, at least 1050°C, or at least 1070°C; Temperature T3 is at least 1180°C, at least 1200°C, at least 1225°C, at least 1250°C, at least 1310°C, or at least 1330°C; The VFT constant A is < 0.00, optionally -5.00 to -2.00; The VFT constant B is >5000℃, optionally from 5800℃ to 8000℃; and The VFT constant T0 is 140 to 450°C, for example 145 to 300°C, or up to 255°C.

[0200] Item 43 relates to a glass composition according to any one of items 1 to 42, wherein the glass composition is subjected to temperatures T4 and T... 7.6 The steepness of the temperature-viscosity curve of the glass, characterized by the difference between the values, is 200 to 400 K.

[0201] Item 44 relates to a glass composition according to any one of items 1 to 43, wherein the glass composition is formed by temperatures T4 and T5. 7.6 The steepness of the temperature-viscosity curve of the glass, characterized by the difference between the values, is 250 to 380 K.

[0202] Item 45 relates to a glass composition according to any one of items 1 to 44, wherein the CSS 200µm The pressure ranges from 800 MPa to 1700 MPa.

[0203] Item 46 relates to a glass composition according to any one of items 1 to 45, wherein the CSS 30µm The pressure ranges from 600 MPa to 1200 MPa.

[0204] Item 47 relates to a glass composition according to any one of items 1 to 46, having a diffusivity of 10 to 80 µm. 2 / h.

[0205] Item 48 relates to a glass composition according to any one of items 1 to 47, wherein the chemical resistance characteristic is one or more of the following: (a) The hydrolysis resistance value, calculated in μg / g sodium equivalent, is less than 320, less than 300, less than 280, less than 250, less than 225, or less than 210. (b) by mg / dm 2 The alkali metal resistance value of the weight loss meter is less than 25, less than 22, less than 20, or less than 18. (c) According to mg / dm 2 The acid resistance value of the weight loss meter is less than 5.0, less than 2.5, or less than 1.0.

[0206] Item 49 relates to a glass composition according to any one of items 1 to 48, wherein the compressive stress sensitivity in MPa is a ratio of the total content of alkali metal oxide R2O and alkaline earth metal oxide R'O by weight percentage. The range is 25 to 100.

[0207] Item 50 relates to a glass composition according to any one of items 1 to 49, wherein the CSS in MPa is... 200µm The ratio of the coefficient of thermal expansion in ppm / K over a temperature range of 20 to 300°C. The range is 100 to 250.

[0208] Item 51 relates to a glass composition according to any one of items 1 to 50, having a refractive index n d It ranges from 1.520 to 1.600.

[0209] Item 52 relates to a glass composition according to any one of items 1 to 51, wherein the glass composition is in the form of 10 4 There is no devitrification at the operating point of dPa*s.

[0210] Item 53 relates to a glass composition according to any one of items 1 to 52, wherein the glass composition is in the form of 10 5 At a viscosity of dPa*s, the crystal growth rate is at most 0.5 μm / min.

[0211] Item 54 relates to a type of glass comprising:

[0212] Item 55 relates to the glass composition according to Item 54, having a CTE of 8.0 ppm / K to 9.0 ppm / K, or about 8.8 ppm / K.

[0213] Item 56 relates to a glass composition according to Item 54 or 55, having a Young's modulus of 70 GPa to 85 GPa, or about 78 GPa.

[0214] Item 57 relates to a glass composition according to any one of items 54 or 55 to 56, having a Poisson constant of 0.245 to 0.255, or about 0.250.

[0215] Item 58 relates to a glass composition according to any one of items 54 or 55 to 57, wherein T g It ranges from 600°C to 625°C, or approximately 611°C.

[0216] Item 59 relates to a glass composition according to any one of items 54 or 55 to 58, having a density of 2.600 g / cm³. 3 Up to 2.725 g / cm 3 or approximately 2.644 g / cm³ 3 .

[0217] Item 60 relates to a glass composition according to any one of items 54 or 55 to 59, having a bulk density of 0.440 to 0.580, or 0.50 to 0.54.

[0218] Item 61 relates to a glass composition according to any one of items 54 or 55 to 60, wherein the VFT A is -3.200 to -3.450, or about -3.375.

[0219] Item 62 relates to a glass composition according to any one of items 54 or 55 to 61, wherein the VFT B is 6700°C to 6850°C, or about 6776°C.

[0220] Item 63 relates to a glass composition according to any one of items 54 or 55 to 62, wherein the VFT T0 is 200°C to 250°C, or about 213°C.

[0221] Item 64 relates to a glass composition according to any one of items 54 or 55 to 63, wherein T 14.5 It ranges from 580°C to 600°C, or approximately 593°C.

[0222] Item 65 relates to a glass composition according to Item 54 or any one of Items 55 to 64, wherein T 13 The temperature ranges from 615°C to 640°C, or approximately 627°C.

[0223] Item 66 relates to a glass composition according to any one of items 54 or 55 to 65, wherein T 7.6 It ranges from 815°C to 845°C, or approximately 831°C.

[0224] Item 67 relates to a glass composition according to any one of items 54 or 55 to 66, wherein the T4 is 1100°C to 1200°C, or about 1132°C.

[0225] Item 68 relates to a glass composition according to any one of items 54 or 55 to 67, wherein T3 It ranges from 1200°C to 1300°C, or approximately 1276°C.

[0226] Item 69 relates to a glass composition according to any one of items 54 or 55 to 68, wherein T2 It ranges from 1400°C to 1500°C, or approximately 1474°C.

[0227] Item 70 relates to a glass composition according to any one of items 54 to 69, wherein the CSS 200µm The pressure ranges from 800 MPa to 1700 MPa.

[0228] Item 71 relates to a glass composition according to any one of items 54 to 70, wherein the CSS 30µm The pressure ranges from 600 MPa to 1200 MPa.

[0229] Item 72 relates to a glass composition according to any one of items 54 to 71, having a diffusivity of 10 to 80 µm. 2 / h.

[0230] Item 73 relates to a glass composition according to any one of items 54 to 72, wherein its chemical resistance characteristic is one or more of the following: (a) The hydrolysis resistance value, calculated in μg / g sodium equivalent, is less than 210; (b) by mg / dm 2 The alkali metal resistance value of the weight loss meter is less than 18; (c) According to mg / dm 2 The acid resistance value of the weight loss meter is less than 2.5 or less than 1.0.

[0231] Article 74 relates to a glass composition according to any one of Articles 54 to 73, wherein its compressive stress sensitivity in MPa is a ratio of the total content of alkali metal oxide R2O and alkaline earth metal oxide R'O by weight percentage. The range is 25 to 100.

[0232] Item 75 relates to a glass composition according to any one of items 54 to 74, wherein its CSS in MPa is... 200µm The ratio of the coefficient of thermal expansion in ppm / K over a temperature range of 20 to 300°C. The range is 100 to 250.

[0233] Item 76 relates to a glass article comprising a glass composition according to any one of items 1 to 75, the thickness of which may be less than 1000 μm, less than 100 μm, less than 80 μm, less than 60 μm, or less than 40 μm.

[0234] Item 77 relates to a glass article, optionally comprising a glass composition according to any one of items 1 to 75, said article having a thickness of less than 1000 μm, said article comprising a glass containing at least 40.0 wt% SiO2, at least 12.0 wt% Na2O, and further containing ZrO2, wherein the weight content of ZrO2 is at least 1.5 times the sum of the weight contents of Al2O3 and B2O3, and said glass has a CSS 30µm For at least 700 MPa, and / or for acid resistance of less than 5.0 mg / dm³ 2 or less than 2.5 mg / dm2 .

[0235] Item 78 relates to a glass article according to Item 76 or 77, which includes an ion exchange layer on one or two of its main surfaces, said main surfaces having a compressive stress of at least 400 MPa, at least 700 MPa, or at least 800 MPa.

[0236] Item 79 relates to a glass article according to any one of items 76 to 78, wherein the ratio of compressive stress in MPa to article thickness in μm on one or both of its main surfaces is at least 4.0 MPa / µm, at least 5.0 MPa / µm, at least 10.0 MPa / µm, or at least 20.0 MPa / µm.

[0237] Item 80 relates to a glass article according to any one of items 76 to 79, wherein the ratio of compressive stress in MPa to the depth of the ion exchange layer in µm is at least 50 MPa / µm, at least 75 MPa / µm, or at least 90 MPa / µm.

[0238] Item 81 relates to a glass article according to any one of items 76 to 80, having a thickness of 1000 µm or less.

[0239] Item 82 relates to a glass article according to any one of items 76 to 81, wherein the warpage is less than 3.0 mm.

[0240] Item 83 relates to a glass article according to any one of items 76 to 82, wherein the total thickness variation is less than 15.0 µm.

[0241] Item 84 relates to a glass article according to any one of items 76 to 83, having a surface roughness R a The value is no greater than 5.0 nm.

[0242] Item 85 relates to glass articles according to any one of items 76 to 84, wherein significant chemical resistance is characterized by one or more of the following: (a) The hydrolysis resistance value, calculated in μg / g sodium equivalent, is less than 320, less than 300, less than 280, less than 250, less than 225, or less than 210. (b) by mg / dm 2 The alkali resistance value of the weight loss meter is less than 25, less than 22, less than 20, or less than 18; (c) According to mg / dm 2 The acid resistance value of the weight loss meter is less than 5.0, less than 2.5, or less than 1.0.

[0243] Item 86 relates to glass articles according to any one of items 76 to 85, having a Vickers hardness of at least 580.

[0244] Item 87 relates to a glass article according to any one of items 76 to 86, having a three-point bending strength of 300 MPa to 400 MPa.

[0245] Item 88 relates to a glass article according to any one of items 76 to 87, wherein the compressive stress is at least 400 MPa.

[0246] Item 89 relates to a glass article according to any one of items 76 to 88, having a thickness of 20 to 40 µm.

[0247] Item 90 relates to a glass article according to any one of items 76 to 89, wherein the DoL on one or both of its main surfaces is 6 to 11 µm.

[0248] Item 91 relates to a glass article according to any one of items 76 to 90, wherein the DoL is 15% to 25% of the thickness of the article.

[0249] Item 92 relates to a glass article according to any one of items 76 to 91, wherein the ratio of compressive stress in MPa to article thickness in µm is at least 4.0 MPa / µm.

[0250] Article 93 relates to a glass article according to any one of Articles 76 to 92, wherein the ratio of compressive stress in MPa to the depth of the ion exchange layer in µm on one or two of its main surfaces is at least 50.

[0251] Item 94 relates to a glass article according to any one of items 76 to 93, wherein the three-point bending strength is at least 400 MPa.

[0252] Item 95 relates to an electronic device comprising: a glass composition according to any one of items 1 to 75, and / or a glass article according to any one of items 76 to 94.

[0253] Example Exemplary compositions of glasses according to the invention are prepared by melting suitable glass raw materials. The following table provides an overview of the compositions and properties of these glasses. Please note that the values ​​in the table have been rounded to one decimal place. Therefore, small rounding errors may occur during the derivation and summation of the values.

[0254] 1. The composition to be tested Table 1 Table 2 Table 3 The packing density is determined by dividing the ion volume by the molar volume of the glass, where the ion volume is the volume occupied by one mole of ions constituting the glass, and the molar volume is the quotient of the molar weight of the glass and the measured density. To calculate the volume of each type of ion, the coordination number is calculated using the effective ion radius according to Shannon, combined with Pauling's rules.

[0255] 2. Ion exchange treatment Thin glass plates were prepared from the glass compositions in Examples 1 to 7. The plate thickness was 200 µm. Subsequently, the plates were ion-exchanged in a 100% KNO3 salt bath at 440 °C for 30 minutes. The table below lists the resulting compressive stress and ion-exchange layer depth (DoL).

[0256] Table 4 3. Chemical resistance The chemical resistance of glass sample number 2 was tested. Hydrolysis resistance was tested according to ISO 719. Alkali resistance was tested according to ISO 695, and acid resistance was tested according to DIN 12116. The test results are as follows: Hydrolysis resistance [µg / g]: 172, Alkali resistance [mg / dm] 2 ]:15, Acid resistance [mg / dm] 2 ]: 0.7.

[0257] 4. Opacity For the glass compositions of Examples 1, 2, 3 and 7, according to 10 5 Crystal growth rate (µm / min) at viscosity dPa*s is used to determine devitrification resistance. A lower crystal growth rate indicates higher devitrification resistance. The measurement of crystal growth rate is well-known. The crystal growth rate is measured along the formed crystal (i.e., at its maximum extension).

[0258] In short, the crystal growth rate was determined by heat-treating the glass in a gradient furnace using a heating scheme for 16 hours. Importantly, if at 10... 5 If no devitrification occurs at a viscosity of dPa*s, then it cannot be determined whether devitrification will occur at 10... 5 Crystal growth rate at dPa*s. No devitrification can also be expressed as crystal growth rate at 10... 5 The crystal growth rate at dPa*s is 0µm / min.

[0259] The crystallization rate was determined using glass particles with a diameter of approximately 2 to 3 mm. The glass particles were placed on a platinum support and subjected to gradient tempering. The support had recesses (each recess for accommodating the glass particles) and pores at the bottom of each recess for optical inspection, thereby allowing the crystal growth rate to be determined by microscopy. Each recess had a diameter of 2 mm, and each pore had a diameter of 0.9 mm.

[0260] The results are shown in the table below.

Claims

1. A type of glass comprising the following components: i.SiO2, ii. Al2O3 in a content of 0.0 to 6.0% by weight, ii. A content of at least 8.0% by weight of ZrO2, iii. A content of at least 12.0% by weight of Na₂O, iv. 0.0 to 5.0% by weight of B2O3, v. 0.0 to 5.0 wt% Li₂O, vi. 0.0 to 10.0% by weight of K₂O; and vii. Optionally, one or more components selected from P2O5 and TiO2.

2. The glass according to claim 1, comprising the following components by weight percentage: In addition, optionally, it contains dyes or colorants, such as Fe2O3, CoO and / or Cr2O3.

3. The glass according to any one of the preceding claims, wherein it is free of As2O3 and / or Sb2O3.

4. The glass according to any one of the preceding claims, wherein the coefficient of thermal expansion in the temperature range of 20 to 300°C is less than 15.0 × 10⁻⁶. -6 K -1 Less than 12.0*10 -6 K -1 Less than 10.0*10 -6 K - 1. Less than 9.8*10 -6 K -1 .

5. The glass according to any one of the preceding claims, having a CSS-defined... 30µm The fractional compressive stress sensitivity is at least 700 MPa.

6. The glass according to any one of the preceding claims, wherein, The ZrO2 content is greater than 10.0% by weight.

7. The glass according to any one of the preceding claims, wherein, The ratio of ZrO2 content to Al2O3 content by weight percentage is at least 1.5 or at least 2.

0.

8. The glass according to any one of the preceding claims, wherein the 1000 MPa 10X time is less than 60 minutes.

9. The glass according to any one of the preceding claims, wherein the glass transition temperature T g The temperature must be at least 540°C, at least 550°C, or at least 560°C.

10. The glass according to any one of the preceding claims, wherein the temperature T4 and T5 are... 7.6 The steepness of the temperature-viscosity curve of the glass, characterized by the difference between the values, is 250 to 350 K.

11. The glass according to any one of the preceding claims, wherein, The glass has a diffusion rate of at least 8µm. 2 / h, or at least 10µm 2 / h.

12. The glass according to any one of the preceding claims, wherein, According to mg / dm 2 The acid resistance value of the weight loss meter is less than 5.

0.

13. The glass according to any one of the preceding claims, wherein, When the glass is heat-treated in a gradient furnace using an incremental temperature scheme for 16 hours, at 10 5 At a viscosity of dPa*s, the crystal growth rate is at most 0.5µm / min.

14. The glass according to any one of the preceding claims, wherein, Young's modulus is between 70 and 90 GPa.

15. A glass article, optionally the glass according to any one of claims 1 to 15, having a thickness of less than 1000 µm, wherein the article comprises a glass containing at least 40.0 wt% SiO2, at least 12.0 wt% Na2O, and further containing ZrO2, wherein the weight ratio of the ZrO2 content to the sum of the weight contents of Al2O3 and B2O3 is at least 1.5, and the CSS of the glass... 30µm For at least 700 MPa, and / or for acid resistance of less than 5.0 mg / dm³ 2 Or acid resistance of less than 2.5 mg / dm 2 .

16. The glass article according to claim 15, wherein the thickness is less than 100µm, less than 80µm, less than 60µm, or less than 40µm.

17. The glass article according to any one of claims 15 to 16, wherein the glass comprises an ion-exchange layer on one or both of its main surfaces.

18. The glass article according to claim 17, wherein the compressive stress on one or both of its main surfaces is at least 400 MPa, at least 700 MPa, or at least 800 MPa.

19. The glass article according to claim 17 or 18, wherein the ratio of compressive stress (MPa) on one or two of its main surfaces to article thickness (µm) is at least 4.0 MPa / µm, at least 5.0 MPa / µm, at least 10.0 MPa / µm, at least 15.0 MPa / µm, or at least 20.0 MPa / µm.

20. The glass article according to at least one of claims 17 to 19, wherein the ratio of compressive stress (MPa) to ion exchange layer depth (µm) on one or both of its main surfaces is at least 50 MPa / μm, at least 75 MPa / μm, or at least 90 MPa / μm.

21. An electronic device comprising glass according to any one of claims 1 to 14 and / or glass articles according to any one of claims 15 to 20.

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