Ion exchangeable glass-based articles with high fracture toughness

Abstract

The glass composition may include from 60 mol% to 69 mol% SiO2, from 10 mol% to 18 mol% Al2O3, from 2.3 mol% to 6.9 mol% Li2O, from 2.1 mol% to 6.7 mol% Na2O, and from 1.1 mol% to 9 mol% alkaline earth metal oxide. The glass composition may have a liquidus viscosity greater than or equal to 150 kP. The glass composition may include from 0.25 mol% to 1 mol% of K2O, from 0.5 mol% to 4 mol% of P2O5, and / or from 0.5 mol% to 3.6 mol% of B2O3. The glass composition may form a slanting feldspar or a solid solution of feldspar. The glass composition may include MgO + Li2O-(CaO + SrO + Na2O + K2O) in a range of from-0.5 to-4. The glass composition may include a volume resistivity greater than or equal to 2 * 1015 ohm-cm. The glass composition may have a fracture toughness greater than or equal to 0.75 MPa [square root of] m.

Description

BACKGROUND

[0001] This application claims the benefit of priority under 35 U.S.C. § 119 to U.S. Provisional Application Serial No. 63 / 523,718, filed June 28, 2023, and U.S. Provisional Application Serial No. 63 / 585,351, filed September 26, 2023, the contents of each of which are relied upon and incorporated herein by reference in their entirety. TECHNICAL FIELD

[0002] The present specification generally relates to glass-based compositions suitable for use as cover glasses for electronic devices. More specifically, the present specification relates to ion-exchangeable glass-based articles that can be formed into cover glasses for electronic devices. TECHNICAL BACKGROUND

[0003] The mobile nature of portable devices, such as smartphones, tablets, portable media players, personal computers, and cameras, makes these devices particularly susceptible to being accidentally dropped on a hard surface, such as the ground. These devices often contain a cover glass that can be damaged upon impact with a hard surface. In many such devices, the cover glass serves as a display cover and can contain touch functionality, such that when the cover glass is damaged, use of the device is negatively impacted.

[0004] There are two main failure modes for cover glasses when the associated portable device is dropped on a hard surface. One of the modes is a flexural failure, which is caused by bending of the glass upon dynamic loading of the device from impact with a hard surface. The other mode is a sharp contact failure, which is caused by introducing damage to the glass surface. Impact of the glass with a rough hard surface, such as asphalt, granite, etc., can result in noticeable indentations on the glass surface. These indentations become failure sites on the glass surface, from which cracks can initiate and propagate.

[0005] Through ion exchange techniques, glass can be made more resistant to flexural failure, which involves introducing compressive stress in the glass surface. However, ion-exchanged glass is still susceptible to dynamic sharp contact, as sharp contact can cause localized indentations on the glass, resulting in high stress concentration.

[0006] Glass makers and handheld device manufacturers have been working to improve the resistance of handheld devices to sharp contact failure. There are various solutions from coatings on the cover glass to bezels that prevent the cover glass from directly impacting a hard surface when the device is dropped on a hard surface. However, due to the limitations of aesthetic and functional requirements, it is very difficult to completely prevent the cover glass from impacting a hard surface.

[0007] It is desirable for portable devices to be as thin as possible. Therefore, in addition to strength, it is desirable for the glass used as a cover glass in portable devices to be as thin as possible. Therefore, in addition to increasing the strength of the cover glass, it is desirable for the glass to have mechanical properties that enable it to be formed by processes that enable the manufacture of thin glass-based articles, such as thin glass sheets.

[0008] Therefore, there is a need for glasses that can be strengthened, such as by ion exchange, and have mechanical properties that enable them to be formed into thin glass-based articles. SUMMARY

[0009] The lithium aluminosilicate glasses presented herein have good ion exchangeability, good glass quality, and high fracture toughness. The chemical strengthening process can be used to achieve high strength and high toughness properties of the lithium aluminosilicate glasses. Substitution of AI2O3 into the silicate glass network improves the interdiffusivity of monovalent cations during ion exchange. By chemical strengthening in a molten salt bath (e.g., KNO3 or NaNO3), glasses with high strength, high toughness, and high indentation crack resistance can be obtained. The stress profile achieved by chemical strengthening can have various shapes, thereby improving the drop performance, strength, toughness, and other attributes of the glass-based articles.

[0010] The glasses described herein can achieve high fracture toughness values (e.g., at least 0.75 MPaVm) without the inclusion of additives, such as ZrO2, Ta2O5, TiO2, HfO2, La2O3, and Y2O3, which can increase fracture toughness but are expensive and can have limited commercial availability. In this regard, the glasses disclosed herein provide comparable or improved performance while reducing manufacturing costs. Fracture toughness and depth stress are key to improving drop performance on rough surfaces. To this end, maximizing the amount of stress that can be provided in a glass-based article before reaching a fragility limit can improve depth stress and rough surface drop performance. Fracture toughness is known to control the fragility limit, and increasing fracture toughness can increase the fragility limit. The glass-based compositions disclosed herein have high fracture toughness and are able to achieve high levels of compressive stress while remaining non-fragile. These properties of the glass-based compositions enable the development of improved stress profiles designed to address specific failure modes. This ability enables ion-exchanged glass-based articles produced from the glass-based compositions described herein to be tailored to have different stress profiles to address specific failure modes of interest.

[0011] The compositions described herein are selected to achieve high fracture toughness values while also maintaining a desired degree of manufacturability. The compositions include a substantial amount of AI2O3 and Li2O to produce the desired fracture toughness while maintaining compatibility with desired manufacturing limits. The drop performance of ion exchanged glass-based articles formed from the glass-based compositions described herein is improved by increasing the depth of compression (DOC), which is at least partially achieved by selecting a high Li / Na molar ratio (e.g., 1.2-2). The glass-based compositions described herein provide improved ion exchange performance, evidenced by increased central tension capability and increased ion exchange speed, while also avoiding volatile issues at free surfaces during manufacturing that can be introduced due to excessive B2O3 and P2O5 content. When the concentration of AI2O3 and the concentration of SiO2 are balanced with the concentration of alkali metal oxides in the glass-based composition, the AI2O3 can lower the liquidus temperature of the glass melt, thereby increasing the liquidus viscosity and improving the compatibility of the glass-based composition with certain forming processes.

[0012] Contrary to conventional expectations associated with lower liquidus viscosities and higher K IC values and improved ion exchange capability, examples of the present disclosure demonstrate that high fracture toughness (e.g., K IC values and improved ion exchange capability, examples of the present disclosure demonstrate that high fracture toughness (e.g., K 15 values and improved ion exchange capability, examples of the present disclosure demonstrate that high fracture toughness (e.g., K 16 values and improved ion exchange capability, examples of the present disclosure demonstrate that high fracture toughness (e.g., K 17 values and improved ion exchange capability, examples of the present disclosure demonstrate that high fracture toughness (e.g., K

[0013] For example, providing RO can increase the volume resistivity of the glass-based substrate and / or glass-based article due to the relatively high field strength of the alkaline earth metal ions and / or the reduced mobility of the alkali metal ions. Providing a high volume resistivity (e.g., 2 x 10 15 ohm-cm or more, or 1 x 10 16 ohm-cm to 1 x 10 17Glass-based substrates and / or glass-based articles having an electrical resistivity of greater than or equal to 1010ohm-cm can reduce the incidence of electrostatic discharge that can discolor and / or otherwise damage the glass-based substrate and / or glass-based article, especially when the glass-based substrate and / or glass-based article is relatively large in size (e.g., 10 cm or greater, or 20 cm or greater).

[0014] Greater central tension (CT), depth of compression (DOC), and high compressive stress (CS) can be achieved through different ion exchange processes. However, the addition of lithium in aluminosilicate glasses can lower the melting point, softening point, or liquidus viscosity of the glass. By providing a glass-based substrate and / or ceramic-based substrate comprising a first depth of compression and / or a second depth of compression that is included in a range from about 20% to about 25% of the thickness of the substrate, good impact and / or puncture resistance can be achieved. The ratio of the depth of layer (e.g., DOL SP ) to the depth of compression (e.g., DOC) can be a property of the compositions of the present disclosure that can be different from other compositions, the value of which (e.g., 0.08 to 0.25 or 0.18 to 0.25) in combination with the ratio of the compressive stress at the depth of the compressive stress spike to the corresponding maximum compressive stress (e.g., 0.02 to 0.05).

[0015] Aspect 1. A glass-based article comprising a composition, based on the oxide basis of the glass-based article, the composition comprising:

[0016] greater than or equal to 60 mol% to less than or equal to 69 mol% Si02;

[0017] greater than or equal to 10 mol% to less than or equal to 18 mol% AI2O3;

[0018] greater than or equal to 2.3 mol% to less than or equal to 6.9 mol% Li20;

[0019] greater than or equal to 2.1 mol% to less than or equal to 6.7 mol% Na20; and

[0020] greater than or equal to 1.1 mol% to less than or equal to 9 mol% RO, where RO is the sum of the amounts of MgO, CaO, SrO, BaO, and ZnO,

[0021] wherein the liquidus viscosity of the composition is greater than or equal to 175 kilopoise.

[0022] Aspect 2. A glass-based article comprising a composition, based on the oxide basis of the glass-based article, the composition comprising:

[0023] greater than or equal to 60 mol% to less than or equal to 69 mol% Si02;

[0024] greater than or equal to 10 mol% to less than or equal to 18 mol% AI2O3;

[0025] greater than or equal to 2.3 mol% to less than or equal to 6.9 mol% Li20;

[0026] greater than or equal to 2.1 mol% to less than or equal to 6.7 mol% Na20;

[0027] greater than or equal to 0.25 mol% to less than or equal to 1 mol% K20; and

[0028] greater than or equal to 1.1 mol% to less than or equal to 9 mol% RO, where RO is the sum of the amounts of MgO, CaO, SrO, BaO, and ZnO,

[0029] wherein the liquidus viscosity of the composition is greater than or equal to 150 kilopoise.

[0030] Aspect 3. The glass-based article of Aspect 2, wherein the liquidus viscosity is greater than or equal to 175 kilopoise.

[0031] Aspect 4. The glass-based article of any one of Aspects 1 to 3, wherein the liquidus viscosity is greater than or equal to 200 kilopoise to less than or equal to 300 kilopoise.

[0032] Aspect 5. The glass-based article of any one of Aspects 1 to 4, wherein the composition crystallizes into a major crystalline phase comprising anorthite or feldspar solid solution after heating at 1050 °C for 24 hours.

[0033] Aspect 6. A glass-based article comprising a composition, based on the oxide basis of the glass-based article, the composition comprising:

[0034] greater than or equal to 60 mol% to less than or equal to 69 mol% Si02;

[0035] greater than or equal to 10 mol% to less than or equal to 18 mol% AI2O3;

[0036] greater than or equal to 2.3 mol% to less than or equal to 6.9 mol% Li20;

[0037] greater than or equal to 2.1 mol% to less than or equal to 6.7 mol% Na20; and

[0038] greater than or equal to 2.3 mol% to less than or equal to 6.9 mol% Li20;

[0039] wherein the composition crystallizes after heating at 1050 °C for 24 hours to have a primary crystalline phase comprising anorthite or a feldspar solid solution.

[0040] Aspect 7. The glass-based article of any one of Aspects 1 to 6, wherein the value in mol% of MgO + Li20 - (CaO + SrO + Na20 + K20) is greater than or equal to -4 to less than or equal to -0.5.

[0041] Aspect 8. A glass-based article comprising a composition, based on the oxide basis of the glass-based article, the composition comprising:

[0042] greater than or equal to 60 mol% to less than or equal to 69 mol% Si02;

[0043] greater than or equal to 10 mol% to less than or equal to 18 mol% Al203;

[0044] greater than or equal to 2.3 mol% to less than or equal to 6.9 mol% Li20;

[0045] greater than or equal to 2.1 mol% to less than or equal to 6.7 mol% Na20; and

[0046] greater than or equal to 1.1 mol% to less than or equal to 9 mol% RO, wherein RO is the sum of the amounts of MgO, CaO, SrO, BaO, and ZnO,

[0047] wherein the value in mol% of MgO + Li20 - (CaO + SrO + Na20 + K20) is greater than or equal to -4 to less than or equal to -0.5.

[0048] Aspect 9. The glass-based article of any one of Aspects 7 to 8, wherein the value in mol% of MgO + Li20 - (CaO + SrO + Na20 + K20) is greater than or equal to -1.5 to less than or equal to -1.0.

[0049] Aspect 10. The glass-based article of any one of Aspects 1 to 9, wherein the composition comprises:

[0050] greater than or equal to 10 mol% to less than or equal to 16 mol% Al203;

[0051] greater than or equal to 0.5 mol% to less than or equal to 4.0 mol% P2O5;

[0052] greater than or equal to 0.5 mol% to less than or equal to 3.6 mol% B2O3.

[0053] Aspect 11. A glass-based article comprising a composition, based on the oxide basis of the glass-based article, the composition comprising:

[0054] greater than or equal to 60 mol% to less than or equal to 69 mol% SiO2;

[0055] greater than or equal to 10 mol% to less than or equal to 16 mol% Al2O3;

[0056] greater than or equal to 2.3 mol% to less than or equal to 6.9 mol% Li2O;

[0057] greater than or equal to 2.1 mol% to less than or equal to 6.7 mol% Na2O;

[0058] greater than or equal to 0.5 mol% to less than or equal to 4.0 mol% P2O5;

[0059] greater than or equal to 0.5 mol% to less than or equal to 3.6 mol% B2O3; and

[0060] greater than or equal to 1.1 mol% to less than or equal to 9 mol% RO, wherein RO is the sum of the amounts of MgO, CaO, SrO, BaO, and ZnO.

[0061] Aspect 12. The glass-based article of any one of Aspects 1 to 11, wherein the composition comprises:

[0062] greater than or equal to 2 mol% to less than or equal to 3.6 mol% B2O3.

[0063] Aspect 13. The glass-based article of any one of Aspects 1 to 12, wherein the volume resistivity is greater than or equal to 2 x 1014 15 ohm-cm.

[0064] Aspect 14. A glass-based article comprising a composition, based on the oxide basis of the glass-based article, the composition comprising:

[0065] greater than or equal to 60 mol% to less than or equal to 69 mol% SiO2;

[0066] greater than or equal to 10 mol% to less than or equal to 18 mol% Al2O3;

[0067] greater than or equal to 2.3 mol% to less than or equal to 6.9 mol% Li20;

[0068] greater than or equal to 2.1 mol% to less than or equal to 6.7 mol% Na20;

[0069] greater than or equal to 1.1 mol% to less than or equal to 9 mol% RO, where RO is the sum of the amounts of MgO, CaO, SrO, BaO, and ZnO,

[0070] where the glass-based article has a volume resistivity greater than or equal to 2 x 1010 ohm-cm. 15 ohm-cm.

[0071] Aspect 15. The glass-based article of any one of Aspects 13-14, wherein the volume resistivity is greater than or equal to 1 x 1010 ohm-cm to less than or equal to 1 x 1011 ohm-cm. 16 ohm-cm. 17 ohm-cm.

[0072] Aspect 16. The glass-based article of any one of Aspects 1-15, wherein the composition comprises:

[0073] greater than or equal to 14 mol% to less than or equal to 16 mol% Al203.

[0074] Aspect 17. The glass-based article of any one of Aspects 1-16, wherein the composition comprises:

[0075] greater than or equal to 60 mol% to less than or equal to 66 mol% Si02;

[0076] greater than or equal to 14 mol% to less than or equal to 16 mol% Al203.

[0077] greater than or equal to 5 mol% to less than or equal to 6.9 mol% Li20;

[0078] greater than or equal to 4 mol% to less than or equal to 6 mol% Na20;

[0079] greater than or equal to 0.5 mol% to less than or equal to 3 mol% P205; and

[0080] greater than 0 mol% to less than or equal to 1 mol% Ti02.

[0081] Aspect 18. A glass-based article comprising a composition, based on the oxide basis of the glass-based article, the composition comprising:

[0082] greater than or equal to 60 mol% to less than or equal to 66 mol% Si02;

[0083] greater than or equal to 14 mol% to less than or equal to 16 mol% AI2O3;

[0084] greater than or equal to 5 mol% to less than or equal to 6.9 mol% Li20;

[0085] greater than or equal to 4 mol% to less than or equal to 6 mol% Na20;

[0086] greater than or equal to 0.5 mol% to less than or equal to 3 mol% P205;

[0087] greater than or equal to 0.5 mol% to less than or equal to 5 mol% B203; and

[0088] greater than 0 mol% to less than or equal to 1 mol% Ti02.

[0089] Aspect 19. The glass-based article of any one of Aspects 1 to 18, wherein the composition comprises:

[0090] greater than or equal to 4.4 mol% to less than or equal to 6.8 mol% Li20; and

[0091] greater than or equal to 3.5 mol% to less than or equal to 6.7 mol% Na20.

[0092] Aspect 20. The glass-based article of any one of Aspects 1 to 19, wherein the composition comprises:

[0093] greater than or equal to 6 mol% to less than or equal to 6.7 mol% Li20; and

[0094] greater than or equal to 5 mol% to less than or equal to 5.8 mol% Na20.

[0095] Aspect 21. The glass-based article of any one of Aspects 1 to 20, wherein the molar ratio of Li20 / Na20 is greater than or equal to 1.2 to less than or equal to 2.1.

[0096] Aspect 22. The glass-based article of any one of Aspects 1 to 21, wherein the glass-based article is substantially free of Ta205, Hf02, La203, and Y203.

[0097] Aspect 23. The glass-based article of any one of Aspects 1 to 22, wherein the composition is substantially free of ZnO.

[0098] Aspect 24. The glass-based article of any one of Aspects 1-23, wherein the composition is substantially free of ZrCh.

[0099] Aspect 25. The glass-based article of any one of Aspects 1-24, further comprising:

[0100] greater than or equal to 0.1 mol% to less than or equal to 0.5 mol% TiCh; and

[0101] greater than or equal to 0.1 mol% to less than or equal to 1 mol% K2O.

[0102] Aspect 26. The glass-based article of any one of Aspects 1-25, wherein the composition comprises:

[0103] greater than or equal to 0.25 mol% to less than or equal to 1 mol% K2O.

[0104] Aspect 27. The glass-based article of any one of Aspects 1-26, wherein the composition comprises:

[0105] greater than or equal to 1.5 mol% to less than or equal to 3.3 mol% RO.

[0106] Aspect 28. The glass-based article of any one of Aspects 1-27, wherein the composition comprises:

[0107] greater than or equal to 0.1 mol% to less than or equal to 0.9 mol% MgO.

[0108] Aspect 29. The glass-based article of any one of Aspects 1-28, wherein the composition comprises:

[0109] greater than or equal to 1 mol% to less than or equal to 2 mol% CaO.

[0110] Aspect 30. The glass-based article of any one of Aspects 1-29, wherein the composition comprises:

[0111] greater than or equal to 0.6 mol% to less than or equal to 1.5 mol% SrO.

[0112] Aspect 31. The glass-based article of any one of Aspects 1-30, wherein the composition comprises:

[0113] greater than or equal to 0 mol% to less than or equal to 0.1 mol% SnCh.

[0114] Aspect 32. The glass-based article of any one of Aspects 1 to 31, wherein the composition comprises:

[0115] greater than or equal to 64 mol% to less than or equal to 65 mol% Si02.

[0116] Aspect 33. The glass-based article of any one of Aspects 1 to 32, wherein the composition comprises:

[0117] greater than or equal to 15 mol% to less than or equal to 16 mol% Al203.

[0118] Aspect 34. The glass-based article of any one of Aspects 1 to 33, wherein the composition comprises:

[0119] greater than or equal to 0.5 mol% to less than or equal to 1.5 mol% P205.

[0120] Aspect 35. The glass-based article of any one of Aspects 1 to 34, wherein the composition comprises:

[0121] greater than or equal to 3 mol% to less than or equal to 3.5 mol% B203.

[0122] Aspect 36. The glass-based article of any one of Aspects 1 to 35, wherein the glass-based article has a K IC fracture toughness greater than or equal to 0.75 MPa-m 0.5 .

[0123] Aspect 37. The glass-based article of any one of Aspects 1 to 36, further comprising:

[0124] a compressive stress layer extending from a surface of the glass-based article to a compressive depth, the compressive stress layer comprising a maximum compressive stress; and

[0125] a central tension region comprising a maximum central tension,

[0126] wherein the composition corresponds to a material at a center of the glass-based article, and the glass-based article comprises a thickness t.

[0127] Aspect 38. The glass-based article of Aspect 37, wherein the maximum compressive stress of the compressive stress layer is greater than or equal to 500 MPa to less than or equal to 1000 MPa.

[0128] Aspect 39. The glass-based article of any one of Aspects 37-38, wherein the maximum central tension of the central tension region is greater than or equal to 50 MPa to less than or equal to 100 MPa.

[0129] Aspect 40. The glass-based article of any one of Aspects 37-39, wherein the compressive depth is greater than or equal to 0.15t to less than or equal to 0.25t, wherein t is the thickness of the glass-based article.

[0130] Aspect 41. The glass-based article of any one of Aspects 37-40, further comprising a depth of layer of one or more alkali metal ions associated with the compressive stress layer, wherein a ratio of the depth of layer to the compressive depth is greater than or equal to 0.02 to less than or equal to 0.05.

[0131] Aspect 42. The glass-based article of any one of Aspects 37-41, wherein the compressive stress layer comprises a compressive stress spike extending from the surface of the glass-based article to a depth of the compressive stress spike, and a ratio of a compressive stress at the depth of the compressive stress spike to the maximum compressive stress is greater than or equal to 0.18 to less than or equal to 0.25.

[0132] Aspect 43. The glass-based article of any one of Aspects 37-41, wherein the compressive stress layer comprises a compressive stress spike extending from the surface of the glass-based article to a depth of the compressive stress spike, and the depth of the compressive stress spike is greater than or equal to 3 pm to less than or equal to 10 pm.

[0133] Aspect 44. The glass-based article of any one of Aspects 37-43, wherein the thickness t is greater than or equal to 0.02 mm to less than or equal to 2 mm.

[0134] Aspect 45. The glass-based article of Aspect 44, wherein the thickness t is greater than or equal to 0.5 mm to less than or equal to 2 mm.

[0135] Aspect 46. A consumer electronic product comprising:

[0136] a housing having a front surface, a back surface, and side surfaces;

[0137] electrical components disposed at least partially within the housing, the electrical components including at least a controller, a memory, and a display disposed at or adjacent to the front surface of the housing; and

[0138] a cover substrate disposed over the display,

[0139] wherein at least a portion of at least one of the housing and the cover substrate comprises the glass-based article of any of aspects 1 to 45.

[0140] Aspect 47. A method of making the glass-based article of any of aspects 1 to 45, the method comprising:

[0141] ion-exchanging a glass-based substrate in a molten salt bath to form a glass-based article, wherein the glass-based article comprises a compressive stress layer extending from a surface of the glass-based article to a compressive depth, the glass-based article comprises a central tension region, and the glass-based substrate comprises the glass-based article of any of claims 1 to 40.

[0142] Aspect 48. The method of aspect 47, wherein the molten salt bath comprises NaN03.

[0143] Aspect 49. The method of any of aspects 47 to 48, wherein the molten salt bath comprises KNO3.

[0144] Aspect 50. The method of any of aspects 47 to 49, wherein the temperature of the molten salt bath is greater than or equal to 380 °C to less than or equal to 470 °C.

[0145] Aspect 51. The method of any of aspects 47 to 50, wherein the ion-exchanging is for a period of time greater than or equal to 10 minutes to less than or equal to 24 hours.

[0146] Aspect 52. The method of any of aspects 47 to 51, comprising ion-exchanging the glass-based article in a second molten salt bath.

[0147] Aspect 53. The method of any of aspects 47 to 52, wherein the second molten salt bath comprises KNO3.

[0148] Aspect 54. The method of aspect 37, wherein the maximum compressive stress of the compressive stress layer is greater than or equal to 500 MPa to less than or equal to 1500 MPa.

[0149] Aspect 55. The glass-based article of aspect 37 or aspect 54, wherein the maximum central tension of the central tension region is greater than or equal to 50 MPa to less than or equal to 100 MPa.

[0150] Aspect 56. The glass-based article of any one of Aspects 54-55, wherein the compressive depth is greater than or equal to 0.15t to less than or equal to 0.25t, wherein t is the thickness of the glass-based article.

[0151] Aspect 57. The glass-based article of any one of Aspects 37 or 54-56, further comprising a layer depth of one or more alkali metal ions associated with the compressive stress layer, wherein a ratio of the layer depth to the compressive depth is greater than or equal to 0.02 to less than or equal to 0.08.

[0152] Aspect 58. The glass-based article of Aspect 57, wherein a ratio of the layer depth to the compressive depth is greater than or equal to 0.04 to less than or equal to 0.06.

[0153] Aspect 59. The glass-based article of any one of Aspects 54-58, wherein the compressive stress layer comprises a compressive stress spike extending from the surface of the glass-based article to a depth of the compressive stress spike, and a ratio of a compressive stress at the depth of the compressive stress spike to the maximum compressive stress is greater than or equal to 0.17 to less than or equal to 0.25.

[0154] Aspect 60. The glass-based article of any one of Aspects 54-58, wherein the compressive stress layer comprises a compressive stress spike extending from the surface of the glass-based article to a depth of the compressive stress spike, and a ratio of a compressive stress at the depth of the compressive stress spike to the maximum compressive stress is greater than or equal to 0.08 to less than or equal to 0.20.

[0155] Aspect 61. The glass-based article of any one of Aspects 54-60, wherein the compressive stress layer comprises a compressive stress spike extending from the surface of the glass-based article to a depth of the compressive stress spike, and the depth of the compressive stress spike is greater than or equal to 3 µm to less than or equal to 10 µm.

[0156] Aspect 62. The glass-based article of any one of Aspects 59-61, wherein a stress at the depth of the compressive stress spike is less than or equal to 210 megapascals.

[0157] Aspect 63. The glass-based article of any one of Aspects 59-62, wherein a slope of the compressive stress spike is greater than or equal to -220 MPa / µm to less than or equal to -60 MPa / µm.

[0158] Aspect 64. The glass-based article of any one of aspects 59 to 63, wherein a slope of a deep region extending from the depth of the compressive stress spike to the compressive depth is greater than or equal to -1.8 MPa / pm to less than or equal to -1.1 MPa / pm.

[0159] Aspect 65. The glass-based article of any one of aspects 54 to 64, wherein a total stored strain energy in the glass-based article is less than or equal to 90 Joules per square meter.

[0160] Aspect 66. The glass-based article of any one of aspects 54 to 65, wherein the thickness t is greater than or equal to 0.02 mm to less than or equal to 2 mm.

[0161] Aspect 67. The glass-based article of aspect 44 or aspect 66, wherein the thickness t is greater than or equal to 0.4 mm to less than or equal to 2 mm.

[0162] Aspect 68. A method of making the glass-based article of any one of aspects 54 to 67, the method comprising:

[0163] ion-exchanging a glass-based substrate in a molten salt bath to form a glass-based article, wherein the glass-based article comprises a compressive stress layer extending from a surface of the glass-based article to a compressive depth, the glass-based article comprises a central tension region, and the glass-based substrate comprises the glass-based article of any one of claims 54 to 65.

[0164] Aspect 69. The method of aspect 68, wherein the molten salt bath comprises NaN03.

[0165] Aspect 70. The method of any one of aspects 68 to 69, wherein the molten salt bath comprises KN03.

[0166] Aspect 71. The method of any one of aspects 47 to 49 or 68 to 70, wherein a temperature of the molten salt bath is greater than or equal to 350 °C to less than or equal to 500 °C.

[0167] Aspect 72. The method of any one of aspects 68 to 70, wherein a temperature of the molten salt bath is greater than or equal to 380 °C to less than or equal to 470 °C.

[0168] Aspect 73. The method of any one of aspects 47 to 50 or 68 to 72, wherein the ion-exchanging is for a period of time greater than or equal to 5 minutes to less than or equal to 24 hours.

[0169] Aspect 74. The method of any one of Aspects 68-73, comprising ion exchanging the glass-based article in a second molten salt bath.

[0170] Aspect 75. The method of Aspect 74, wherein the second molten salt bath comprises KNO3.

[0171] Aspect 76. The method of any one of Aspects 74-75, wherein the second molten salt bath comprises K2CO3.

[0172] Aspect 77. The method of Aspect 76, wherein the amount of K2CO3 in the second molten salt bath is 1 wt% to 7 wt%.

[0173] Aspect 78. The glass-based article of any one of Aspects 59-62, wherein the slope of the compressive stress spike is greater than or equal to -300 MPa / µm to less than or equal to -60 MPa / µm.

[0174] Aspect 79. The glass-based article of any one of Aspects 59-63, wherein a slope of a deep region extending from the depth of the compressive stress spike to the compressive depth is greater than or equal to -2.0 MPa / µm to less than or equal to -1.1 MPa / µm.

[0175] Additional features and advantages will be set forth in the detailed description below, and in part will become apparent to those skilled in the art from that description, or from the practice of the aspects and / or embodiments described herein, including the detailed description and claims that follow, and the appended drawings.

[0176] It is to be understood that both the foregoing general description and the following detailed description describe various embodiments and are intended to provide an overview or framework for understanding the nature and character of the claimed subject matter. The accompanying drawings are included to provide a further understanding of the various embodiments, and are incorporated into and constitute a part of this specification. The drawings illustrate the various aspects described herein and, together with the description, serve to explain the principles and operations of the claimed subject matter. BRIEF DESCRIPTION OF DRAWINGS

[0177] Figure 1 schematically depicts a cross-section of a glass-based article having a compressive stress region according to aspects described and disclosed herein;

[0178] Figure 2 is a plan view of an exemplary electronic device including any of the glass-based articles described herein;

[0179] Figure 3 is Figure 2perspective view of an exemplary electronic device;

[0180] Figure 4 schematically illustrates a step of ion exchanging a glass-based substrate to form a glass-based article;

[0181] Figure 5 schematically illustrates an optional step of further ion exchanging a glass-based substrate to form a glass-based article;

[0182] Figure 6 is a plot of stress versus depth from the surface to the glass-based article DA of Composition 1 ;

[0183] Figure 7 is a plot of stress versus depth from the surface to the glass-based article DB of Composition 2; and

[0184] Figure 8 is a plot of stress versus depth from the surface to the glass-based articles DD, DG, DJ, and DM of Composition 9

[0185] Throughout the disclosure, the drawings are used to emphasize certain aspects. Thus, unless otherwise specifically noted, the relative size of the different regions, portions, and substrates shown in the drawings should not be considered to be proportionate to their actual relative size. DETAILED DESCRIPTION

[0186] Aspects will now be described in more detail below with reference to the accompanying drawings, in which example aspects are shown. Like reference numerals can be used throughout the different drawings to denote like parts.

[0187] Reference will now be made in detail to lithium aluminosilicate glasses in accordance with various aspects. The lithium aluminosilicate glasses have good ion exchange capability, and high strength and high toughness properties of the lithium aluminosilicate glasses are achieved using a chemical strengthening process. The lithium aluminosilicate glasses are highly ion exchangeable glasses with high glass quality. Substitution of AI2O3 into the silicate glass network improves the interdiffusivity of monovalent cations during ion exchange. Glasses with high strength, high toughness, and high indentation crack resistance can be obtained by chemical strengthening in a molten salt bath (e.g., KNO3 or NaNO3). The stress profile achieved by chemical strengthening can have various shapes, thereby improving the drop performance, strength, toughness, and other attributes of the glass-based articles.

[0188] Accordingly, lithium aluminosilicate glasses having good physical properties, chemical durability, and ion exchange properties are of interest for use as cover glasses. In particular, provided herein are lithium aluminosilicate glasses having relatively high fracture toughness (e.g., at least 0.75 MPaVm) and reasonable raw material costs. The glasses described herein can achieve these fracture toughness values without including additives, such as Zr02, Ta205, Ti02, Hf02, La203, and Y203, which can increase fracture toughness but are expensive and can have limited commercial availability. In this regard, the glasses disclosed herein provide comparable or improved performance while reducing manufacturing costs. Greater central tension (CT), depth of compression (DOC), and high compressive stress (CS) can be achieved through different ion exchange processes. However, the addition of lithium in aluminosilicate glasses can lower the glass melting point, softening point, or liquidus viscosity.

[0189] In aspects of the glass-based compositions described herein, the concentrations of constituent components (e.g., Si02, Al203, Li20, etc.) are given in mole percent (mol%) on an oxide basis, unless otherwise specified. The components of the alkali aluminosilicate glass-based compositions according to embodiments are discussed individually below. It should be understood that any one of the various recited ranges for a component can be combined individually with any one of the various recited ranges for any other component. As used herein, a trailing zero in a number is intended to indicate the significant digits of the number. For example, the number “1.0” contains two significant digits, and the number “1.00” contains three significant digits. Throughout this disclosure, the composition of the glass-based articles and / or glass-based substrates refers to the composition of the shaped article or substrate as determined by X-ray fluorescence and comparison to standard samples of aluminum oxide, phosphorous, alkaline earth metals, transition metals (e.g., ZnO, Ti02, Fe203, Sn02), sodium oxide, and potassium oxide in wt%; the amount of B203was measured using Inductively Coupled Plasma (ICP) methods; the amount of lithium oxide (Li20) was measured using flame emission spectroscopy; and the amount of Si02was taken as the balance of the material (i.e., 100% of the material measured using X-ray fluorescence, ICP, and flame emission spectroscopy) and then the composition was converted from wt% to mol% as reported herein. The composition refers to the composition of the shaped article or substrate, not the raw materials added to form the glass-based article and / or glass-based substrate.

[0190] As used herein, "glass-based substrate" refers to a glass-based sheet that has not been ion exchanged. Similarly, "glass-based article" refers to a glass-based sheet that has been ion exchanged and formed by subjecting a glass-based substrate to an ion exchange process. Thus, "glass-based substrate" and "glass-based article" are defined and encompass glass-based substrates and glass-based articles and substrates and articles made wholly or partially of glass-based materials, such as glass-based substrates that include surface coatings. While reference can be made herein generally to glass-based substrates and glass-based articles for convenience, the description of glass-based substrates and glass-based articles should be understood to apply equally to glass-based substrates and glass-based articles. Likewise, unless otherwise indicated, the claims are not necessarily limited to ion-exchanged glass-based articles or glass-based substrates that have not been ion exchanged.

[0191] As used herein, "glass-based" encompasses both glasses and glass-ceramics, where the glass-ceramics have one or more crystalline phases and an amorphous residual glass phase. Glass-based materials (e.g., glass-based substrates) can include an amorphous material (e.g., glass) and, optionally, one or more crystalline materials (e.g., ceramics). The amorphous material and glass-based materials can be strengthened. As used herein, the term "strengthened" can refer to a material that has been chemically strengthened, e.g., by exchanging larger ions for smaller ions in the surface of the substrate, as discussed below. However, other strengthening methods can also be utilized, such as thermal tempering, or utilizing a mismatch in the coefficient of thermal expansion between portions of the substrate to create a compressive stress and central tension region, thereby forming a strengthened substrate.

[0192] While scratch performance is desirable, drop performance is a primary attribute of glass-based articles incorporated into mobile electronic devices. Fracture toughness and depth stress are critical to improving drop performance on rough surfaces. To this end, maximizing the amount of stress that can be provided in a glass-based article before reaching a fragility limit can improve depth stress and rough surface drop performance. Fracture toughness is known to control the fragility limit, and increasing fracture toughness can increase the fragility limit. The glass-based compositions disclosed herein have high fracture toughness and are capable of achieving high compressive stress levels while maintaining non-fragility. These properties of the glass-based compositions enable the development of improved stress profiles designed to address specific failure modes. This ability enables glass-based articles ion exchanged from the glass-based compositions described herein to be tailored to have different stress profiles to address specific failure modes of interest.

[0193] The compositions described herein are selected to achieve high fracture toughness values while also maintaining a desired degree of manufacturability. The compositions include a high amount of AI2O3 and Li2O to produce the desired fracture toughness while maintaining compatibility with desired manufacturing limits. The drop performance of ion exchanged glass-based articles formed from the glass-based compositions described herein is improved by increasing the depth of compression (DOC), which is at least partially achieved by selecting a high Li / Na molar ratio. The glass-based compositions described herein provide improved ion exchange performance, evidenced by increased central tension capability and increased ion exchange speed, while also avoiding volatility issues at free surfaces during manufacturing that can be introduced due to excessive B2O3 and P2O5 content.

[0194] In the glass-based compositions described herein, Si02is the largest component, and thus, Si02is the primary ingredient of the glass network formed from the glass-based compositions. Pure Si02has a relatively low CTE. However, pure Si02has a high melting point. Thus, if the concentration of Si02in the glass-based composition is too high, the formability of the glass-based composition can decrease because a higher concentration of Si02increases the difficulty of melting the glass, which in turn adversely affects the formability of the composition. If the concentration of Si02in the glass-based composition is too low, the chemical durability of the glass-based material can decrease and the glass-based material can be susceptible to surface damage during post-forming processing. In aspects, the composition includes Si02in an amount of 60 mol% or more, 61 mol% or more, 62 mol% or more, 63 mol% or more, 63.5 mol% or more, 64 mol% or more, 69 mol% or less, 68 mol% or less, 67 mol% or less, 66 mol% or less, 65.5 mol% or less, 65 mol% or less, or about 64.5 mol% or less. In aspects, the composition includes Si02in a range of greater than or equal to 60 mol% to less than or equal to 69 mol%, greater than or equal to 60 mol% to less than or equal to 68 mol%, greater than or equal to 60 mol% to less than or equal to 67 mol%, greater than or equal to 60 mol% to less than or equal to 66 mol%, greater than or equal to 61 mol% to less than or equal to 65.5 mol%, greater than or equal to 62 mol% to less than or equal to 65.5 mol%, greater than or equal to 63 mol% to less than or equal to 65.5 mol%, greater than or equal to 63.5 mol% to less than or equal to 65 mol%, greater than or equal to 64 mol% to less than or equal to 65 mol%, or any range or sub-range therebetween. In preferred aspects, the composition includes Si02in an amount of greater than or equal to 60 mol% to less than or equal to 69 mol%, greater than or equal to 60 mol% to less than or equal to 66 mol%, or greater than or equal to 64 mol% to less than or equal to 65 mol%.

[0195] The glass-based composition includes AI2O3. Similar to SiO2, AI2O3 can act as a glass network structure former. Because of the tetrahedral coordination of AI2O3 in a glass melt formed from the glass-based composition, it can increase the viscosity of the glass-based composition, which can decrease the formability of the glass-based composition when the amount of AI2O3 is too high. However, when the concentration of AI2O3 is balanced with the concentration of SiO2 and the concentration of alkali metal oxide in the glass-based composition, AI2O3 can decrease the liquidus temperature of the glass melt, thereby enhancing the liquidus viscosity and improving the compatibility of the glass-based composition with certain forming processes. Inclusion of AI2O3 in the glass-based composition can achieve the high fracture toughness values described herein. In aspects, the composition includes a concentration of AI2O3 of 10 mol% or more, 11 mol% or more, 12 mol% or more, 13 mol% or more, 14 mol% or more, 14.5 mol% or more, 15 mol% or more, 18 mol% or less, 17 mol% or less, 16 mol% or less, or 15.5 mol% or less. In aspects, the composition can include AI2O3 in an amount in a range of greater than or equal to 10 mol% to less than or equal to 18 mol%, greater than or equal to 10 mol% to less than or equal to 17 mol%, greater than or equal to 10 mol% to less than or equal to 16 mol%, greater than or equal to 11 mol% to less than or equal to 16 mol%, greater than or equal to 12 mol% to less than or equal to 16 mol%, greater than or equal to 13 mol% to less than or equal to 16 mol%, greater than or equal to 14 mol% to less than or equal to 16 mol%, greater than or equal to 14.5 mol% to less than or equal to 16 mol%, greater than or equal to 15 mol% to less than or equal to 16 mol%, or any range or sub-range therebetween. In preferred aspects, the composition includes AI2O3 in an amount greater than or equal to 10 mol% to less than or equal to 18 mol%, greater than or equal to 14 mol% to less than or equal to 16 mol%, or greater than or equal to 14 mol% to less than or equal to 15 mol%.

[0196] The glass-based composition includes Li20. Inclusion of Li20 in the glass-based composition allows for better control of the ion exchange process and further reduces the softening point of the composition, thereby increasing the manufacturability of the composition. The presence of Li20 in the glass-based composition also allows for the formation of a stress profile having a parabolic shape. The Li20 in the glass-based composition can achieve the high fracture toughness values described herein. In aspects, the composition includes Li20 in an amount of 2.3 mol% or more, 3 mol% or more, 3.5 mol% or more, 4 mol% or more, 4.4 mol% or more, 5 mol% or more, 5.3 mol% or more, 5.5 mol% or more, 6 mol% or more (e.g., 6.0 mol% or more), 6.9 mol% or less, 6.8 mol% or less, 6.7 mol% or less, 6.6 mol% or less, 6.5 mol% or less, 6.3 mol% or less, or 6 mol% or less (e.g., 6.0 mol% or less). In aspects, the composition includes Li20 in an amount in a range of greater than or equal to 2.3 mol% to less than or equal to 6.9 mol%, greater than or equal to 3 mol% to less than or equal to 6.9 mol%, greater than or equal to 4 mol% to less than or equal to 6.9 mol%, greater than or equal to 4.5 mol% to less than or equal to 6.9 mol%, greater than or equal to 4.4 mol% to less than or equal to 6.8 mol%, greater than or equal to 5 mol% to less than or equal to 6.7 mol%, greater than or equal to 5.3 mol% to less than or equal to 6.7 mol%, greater than or equal to 5.5 mol% to less than or equal to 6.7 mol%, greater than or equal to 6 mol% to less than or equal to 6.7 mol% (e.g., greater than or equal to 6.0 mol% to less than or equal to 6.7 mol%), or any range or sub-range therebetween. In aspects, the composition can include greater than or equal to 5 mol% Li20 and less than or equal to 6.9 mol%, for example, in a range of greater than or equal to 5.3 mol% to less than or equal to 6.8 mol%, greater than or equal to 5.5 mol% to less than or equal to 6.8 mol%, greater than or equal to 5.5 mol% to less than or equal to 6.6 mol%, greater than or equal to 6 mol% to less than or equal to 6.5 mol%, or any range or sub-range therebetween. In preferred aspects, the composition includes Li20 in an amount in a range of greater than or equal to 2.3 mol% to less than or equal to 6.9 mol%, greater than or equal to 5 mol% to less than or equal to 6.8 mol%, or less than or equal to 6 mol% to less than or equal to 6.7 mol%.

[0197] The glass-based compositions described herein include Na2O. Na2O can contribute to the ion exchange capability of the glass-based compositions and improve the formability of the glass-based compositions, thereby improving manufacturability. However, if too much Na2O is added to the glass-based compositions, the CTE can be too low and the melting point can be too high. Additionally, if too much Na2O is included in the composition relative to the amount of Li2O, the ability of the glass-based substrate to achieve a deep depth of compression upon ion exchange can be reduced. In aspects, the composition includes Na2O in an amount of 2.1 mol% or more, 2.5 mol% or more, 3 mol% or more, 3.5 mol% or more, 4 mol% or more, 4.5 mol% or more, 5 mol% or more (e.g., 5.0 mol% or more), 5.5 mol% or more, 6.7 mol% or less, 6.5 mol% or less, 6.3 mol% or less, 6 mol% or less (e.g., 6.0 mol% or less), 5.8 mol% or less, or 5.5 mol% or less. In aspects, the composition includes Na2O in an amount in a range of greater than or equal to 2.1 mol% to less than or equal to 6.7 mol%, greater than or equal to 3 mol% to less than or equal to 6.7 mol%, greater than or equal to 3.5 mol% to less than or equal to 6.7 mol%, greater than or equal to 4 mol% to less than or equal to 6.5 mol%, greater than or equal to 4 mol% to less than or equal to 6.3 mol%, greater than or equal to 4 mol% to less than or equal to 6 mol%, greater than or equal to 4.5 mol% to less than or equal to 6 mol% (e.g., greater than or equal to 4.5 mol% to less than or equal to 6.0 mol%), greater than or equal to 5 mol% to less than or equal to 5.8 mol% (e.g., greater than or equal to 5.0 mol% to less than or equal to 5.8 mol%), or any range or sub-range therebetween. In preferred aspects, the composition includes Na2O in an amount of greater than or equal to 2.1 mol% to less than or equal to 6.7 mol% Na2O, greater than or equal to 3.5 mol% to less than or equal to 6 mol%, greater than or equal to 4 mol% to less than or equal to 5.8 mol%.

[0198] The glass-based compositions described herein can be described in terms of lithium to sodium molar ratio (Li20 / Na20). High Li20 / Na20 molar ratios allow for deep compressive depths (DOC) to be achieved when the glass compositions are ion exchanged. The increased DOC capability due to high Li20 / Na20 molar ratios results in ion exchanged articles formed from the glass-based compositions exhibiting improved drop performance, particularly on rough surfaces. In aspects, the compositions can be characterized by a molar ratio of Li20 / Na20 of 1.15 or greater, 1.2 or greater, 1.25 or greater, 1.3 or greater, 1.5 or greater, 1.6 or greater, 2.1 or less, 2 or less, 1.9 or less, 1.8 or less, 1.7 or less, 1.6 or less, 1.5 or less, 1.4 or less, 1.35 or less, or 1.3 or less (e.g., 1.30 or less). In aspects, the compositions can be characterized by a molar ratio of Li20 / Na20 in a range from greater than or equal to 1.15 to less than or equal to 2.1, from greater than or equal to 1.2 to less than or equal to 2.1, from greater than or equal to 1.2 to less than or equal to 2, from greater than or equal to 1.2 to less than or equal to 1.9, from greater than or equal to 1.25 to less than or equal to 1.8, from greater than or equal to 1.25 to less than or equal to 1.7, from greater than or equal to 1.25 to less than or equal to 1.6, from greater than or equal to 1.3 to less than or equal to 1.5, or any range or sub-range therebetween. In aspects, the compositions can be characterized by a molar ratio of Li20 / Na20 in a range from greater than or equal to 1.15 to less than or equal to 1.8, from greater than or equal to 1.2 to less than or equal to 1.7, from greater than or equal to 1.25 to less than or equal to 1.5, from greater than or equal to 1.25 to less than or equal to 1.4, from greater than or equal to 1.25 to less than or equal to 1.35, or from greater than or equal to 1.25 to less than or equal to 1.3 (e.g., from greater than or equal to 1.25 to less than or equal to 1.30), or any range or sub-range therebetween. In preferred aspects, the compositions have a molar ratio of Li20 / Na20 in a range from greater than or equal to 1.2 to less than or equal to 2.1, from greater than or equal to 1.25 to less than or equal to 1.6, or from greater than or equal to 1.25 to less than or equal to 1.30.

[0199] The glass-based compositions can include K20. Inclusion of K20 in the glass-based compositions increases the potassium diffusivity in the glass-based material, enabling deeper compressive stress peaks (DOL SPdepth. If too much K2O is included in the composition, the compressive stress imparted during the ion exchange process can be reduced. In aspects, the composition includes K2O in an amount of 0 mol% or more, 0.1 mol% or more, 0.25 mol% or more, 0.3 mol% or more, 0.35 mol% or more, 1 mol% or less, 0.75 mol% or less, 0.6 mol% or less, 0.5 mol% or less (e.g., 0.50 mol% or less), or 0.4 mol% or less. In aspects, the composition includes K2O in an amount in a range of greater than or equal to 0 mol% to less than or equal to 1 mol%, greater than or equal to 0.1 mol% to less than or equal to 1 mol%, greater than or equal to 0.25 mol% to less than or equal to 1 mol%, greater than or equal to 0.25 mol% to less than or equal to 0.75 mol%, greater than or equal to 0.25 mol% to less than or equal to 0.6 mol%, greater than or equal to 0.3 mol% to less than or equal to 0.5 mol%, greater than or equal to 0.3 mol% to less than or equal to 0.4 mol%, or any range or sub-range therebetween. In preferred aspects, the composition includes K2O in an amount in a range of greater than or equal to 0 mol% to less than or equal to 1 mol%, greater than or equal to 0.1 mol% to less than or equal to 1 mol%, or greater than or equal to 0.25 mol% to less than or equal to 0.5 mol%.

[0200] Throughout this disclosure, “RO” refers to the total amount of alkaline earth metal oxides and divalent transition metal oxides. “RO” can refer to the total amount of MgO, CaO, SrO, BaO, and ZnO. In aspects, divalent cation oxides (e.g., alkaline earth metal oxides) can improve the melting behavior of the glass composition. In aspects, divalent cation oxides can improve stress relaxation. In aspects, alkaline earth metal oxides can charge balance tetrahedral alumina. For example, providing RO can increase the volume resistivity of the glass-based substrate and / or glass-based article due to the relatively high field strength of the alkaline earth metal ions and / or the reduced mobility of the alkali metal ions. In aspects, the composition can include RO in an amount of 1.1 mol% or more, 1.3 mol% or more, 1.5 mol% or more, 1.8 mol% or more, 2 mol% or more, 2.2 mol% or more, 2.5 mol% or more, 2.8 mol% or more, 3 mol% or more (e.g., 3.00 mol% or more), 9 mol% or less, 8 mol% or less, 7 mol% or less, 6 mol% or less, 5 mol% or less, 4 mol% or less, 3.5 mol% or less (e.g., 3.50 mol% or less), 3.4 mol% or less (e.g., 3.40 mol% or less), 3.3 mol% or less (e.g., 3.30 mol% or less), 3.25 mol% or less, 3.2 mol% or less (e.g., 3.20 mol% or less), 3.15 mol% or less, or 3.1 mol% or less (e.g., 3.10 mol% or less).In aspects, the composition can include RO in an amount ranging from greater than or equal to 1.1 mol% to less than or equal to 9 mol%, greater than or equal to 1.1 mol% to less than or equal to 7 mol%, greater than or equal to 1.1 mol% to less than or equal to 5 mol%, greater than or equal to 1.3 mol% to less than or equal to 4 mol%, greater than or equal to 1.3 mol% to less than or equal to 3.5 mol%, greater than or equal to 1.5 mol% to less than or equal to 3.3 mol% (e.g., greater than or equal to 1.5 mol% to less than or equal to 3.30 mol%), greater than or equal to 1.8 mol% to less than or equal to 3.3 mol% (e.g., greater than or equal to 1.8 mol% to less than or equal to 3.30 mol%), greater than or equal to 2 mol% to less than or equal to 3.25 mol%, greater than or equal to 2.5 mol% to less than or equal to 3.25 mol%, greater than or equal to 2.8 mol% to less than or equal to 3.2 mol% (e.g., greater than or equal to 2.8 mol% to less than or equal to 3.20 mol%), greater than or equal to 3 mol% to less than or equal to 3.2 mol% (e.g., greater than or equal to 3.00 mol% to less than or equal to 3.20 mol%), greater than or equal to 3 mol% to less than or equal to 3.15 mol%, or any range or sub-range therebetween. In preferred aspects, the composition includes RO in an amount ranging from greater than or equal to 1.1 mol% to less than or equal to 9 mol% or 1.5 mol% to 3.3 mol%.

[0201] The glass-based compositions described herein can optionally include MgO. MgO can lower the viscosity of the glass, which enhances the formability and manufacturability of the composition. Inclusion of MgO in the glass-based composition can also improve the strain point and Young's modulus of the glass-based composition. However, if too much MgO is added to the glass-based composition, the liquidus viscosity can be too low to be compatible with desired forming techniques. Too much MgO can also increase the density and CTE of the glass-based composition to undesirable levels. Inclusion of MgO in the glass-based composition also contributes to achieving the high fracture toughness values described herein. In aspects, the composition includes MgO in an amount of 0 mol% or more, 0.1 mol% or more, 0.3 mol% or more, 0.4 mol% or more (e.g., 0.40 mol% or more), 0.5 mol% or more (e.g., 0.50 mol% or more), 0.9 mol% or less, 0.8 mol% or less, 0.7 mol% or less, or 0.6 mol% or less (e.g., 0.60 mol% or less). In aspects, the composition includes MgO in an amount ranging from greater than or equal to 0 mol% to less than or equal to 0.9 mol%, from greater than or equal to 0.1 mol% to less than or equal to 0.9 mol%, from greater than or equal to 0.3 mol% to less than or equal to 0.8 mol%, from greater than or equal to 0.4 mol% to less than or equal to 0.7 mol% (e.g., from greater than or equal to 0.40 mol% to less than or equal to 0.7 mol%), from greater than or equal to 0.5 mol% to less than or equal to 0.6 mol% (e.g., from greater than or equal to 0.50 mol% to less than or equal to 0.60 mol%), or any range or sub-range therebetween. In aspects, the glass-based composition can be substantially free or free of MgO. As used herein, the term "substantially free" means that the component is not added as a component of the batch material on purpose, even though the component can be present in the final glass-based composition in very small amounts (e.g., less than 0.1 mol%) as a contaminant. In preferred aspects, the composition includes MgO in an amount ranging from greater than or equal to 0 mol% to less than or equal to 1 mol%, from greater than or equal to 0.1 mol% to less than or equal to 0.9 mol%, or from greater than or equal to 0.40 mol% to less than or equal to 0.60 mol%.

[0202] The glass-based compositions described herein can include CaO. CaO can lower the viscosity of the glass, which can enhance formability, strain point, and Young’s modulus. However, if too much CaO is added to the glass-based composition, the density and CTE of the glass-based composition can increase to undesirable levels, and the ion exchange capability of the glass-based substrate can be undesirably hindered. Inclusion of CaO in the glass-based composition also contributes to achieving the high fracture toughness values described herein. In aspects, the composition can include CaO in an amount of 1 mol% or more, 1.2 mol% or more, 1.3 mol% or more, 1.4 mol% or more (e.g., 1.40 mol% or more), 2 mol% or less, 1.8 mol% or less, 1.7 mol% or less, 1.6 mol% or less (e.g., 1.60 mol% or less), or 1.5 mol% or less (e.g., 1.50 mol% or less). In aspects, the composition includes CaO in an amount in a range of greater than or equal to 1 mol% to less than or equal to 2 mol%, greater than or equal to 1.2 mol% to less than or equal to 1.8 mol%, greater than or equal to 1.3 mol% to less than or equal to 1.7 mol%, greater than or equal to 1.4 mol% to less than or equal to 1.6 mol% (e.g., greater than or equal to 1.40 mol% to less than or equal to 1.60 mol%), greater than or equal to 1.4 mol% to less than or equal to 1.5 mol% (e.g., greater than or equal to 1.40 mol% to less than or equal to 1.50 mol%), or any range or sub-range therebetween. In preferred aspects, the composition includes CaO in an amount of greater than or equal to 1 mol% to less than or equal to 2 mol% or greater than or equal to 1.40 mol% to less than or equal to 1.60 mol%.

[0203] The glass-based compositions described herein can include SrO. SrO can lower the viscosity of the glass, which can enhance formability, strain point, and Young’s modulus. However, if too much SrO is added to the glass-based composition, the density and CTE of the glass-based composition can increase to undesirable levels, and the ion exchange capability of the glass-based substrate can be undesirably hindered. Inclusion of SrO in the glass-based composition also contributes to achieving the high fracture toughness values described herein. In aspects, the composition includes SrO in an amount of 0.6 mol% or more, 0.8 mol% or more, 0.9 mol% or more (e.g., 0.90 mol% or more), 1 mol% or more, 1.5 mol% or less, 1.5 mol% or less, 1.4 mol% or less, 1.3 mol% or less, 1.2 mol% or less (e.g., 1.20 mol% or less), or 1.1 mol% or less. In aspects, the composition can include SrO in an amount ranging from greater than or equal to 0.6 mol% to less than or equal to 1.5 mol%, from greater than or equal to 0.8 mol% to less than or equal to 1.4 mol%, from greater than or equal to 0.8 mol% to less than or equal to 1.3 mol%, from greater than or equal to 0.9 mol% to less than or equal to 1.2 mol% (e.g., from greater than or equal to 0.90 mol% to less than or equal to 1.20 mol%), from greater than or equal to 1 mol% to less than or equal to 1.1 mol%, or any range or sub-range therebetween. In preferred aspects, the composition includes SrO in an amount ranging from greater than or equal to 0.6 mol% to less than or equal to 1.5 mol% or from greater than or equal to 0.90 mol% to less than or equal to 1.20 mol%.

[0204] The glass-based compositions described herein can optionally include ZnO. ZnO can decrease the viscosity of the glass, which can enhance formability, strain point, and Young’s modulus. However, if too much ZnO is added to the glass-based composition, the density and CTE of the glass-based composition can increase to undesirable levels. Including ZnO in the glass-based composition also helps to achieve the high fracture toughness values described herein and provides protection against UV-induced discoloration. In aspects, the glass-based composition includes an amount of ZnO greater than or equal to 0 mol% to less than or equal to 1 mol%, such as greater than 0 mol% to less than or equal to 1.0 mol%, greater than or equal to 0.1 mol% to less than or equal to 0.9 mol%, greater than or equal to 0.2 mol% to less than or equal to 0.8 mol%, greater than or equal to 0.3 mol% to less than or equal to 0.7 mol%, greater than or equal to 0.4 mol% to less than or equal to 0.6 mol%, greater than or equal to 0.1 mol% to less than or equal to 0.5 mol%, greater than or equal to 0 mol% to less than or equal to 0.3 mol%, and all ranges and sub-ranges between the foregoing values. Alternatively, in aspects, the glass-based composition is substantially free or free of ZnO.

[0205] The glass-based compositions described herein can include P2O5. The inclusion of P2O5 increases the diffusivity of ions in the glass base, thereby increasing the speed of the ion exchange process. If too much P2O5 is included in the composition, the compressive stress imparted in the ion exchange process can decrease, and the volatility at the free surface during manufacturing can increase to undesirable levels. In aspects, the composition includes P2O5 in an amount of 0.5 mol% or more, 0.7 mol% or more, 0.9 mol% or more, 1 mol% or more, 1.1 mol% or more, 4 mol% or less, 3.5 mol% or less, 3 mol% or less, 2.5 mol% or less, 2 mol% or less, or 1.5 mol% or less. In aspects, the composition includes P2O5 in an amount in a range of greater than or equal to 0.5 mol% to less than or equal to 4 mol%, greater than or equal to 0.5 mol% to less than or equal to 3 mol%, greater than or equal to 0.5 mol% to less than or equal to 2.5 mol%, greater than or equal to 0.5 mol% to less than or equal to 2 mol%, greater than or equal to 0.5 mol% to less than or equal to 1.5 mol%, greater than or equal to 0.7 mol% to less than or equal to 1.5 mol%, greater than or equal to 0.9 mol% to less than or equal to 1.5 mol%, greater than or equal to 1 mol% to less than or equal to 1.5 mol%, greater than or equal to 1.1 mol% to less than or equal to 1.5 mol%, or any range or sub-range therebetween. Alternatively, in aspects, the glass-based composition is substantially free or free of P2O5. In preferred aspects, the composition includes P2O5 in an amount greater than or equal to 0.5 mol% to less than or equal to 4 mol%, greater than or equal to 0.5 mol% to less than or equal to 3 mol%, or greater than or equal to 0.5 mol% to less than or equal to 1.5 mol%.

[0206] The glass-based compositions described herein can include B2O3. The inclusion of B2O3 increases the fracture toughness of the glass-based materials. In particular, the glass-based compositions include boron in a trigonal configuration, which increases the Knoop scratch threshold and fracture toughness of the glass-based articles. If too much B2O3 is included in the composition, the amount of compressive stress imparted during the ion exchange process can decrease, and the volatility at free surfaces during manufacturing can increase to undesirable levels. In aspects, the composition includes B2O3 in an amount of 0.5 mol% or more, 1 mol% or more, 1.5 mol% or more, 2 mol% or more, 2.5 mol% or more, 3 mol% or more (e.g., 3.00 mol% or more), 5 mol% or less, 4.5 mol% or less, 4 mol% or less, 3.8 mol% or less, 3.6 mol% or less, or 3.5 mol% or less (e.g., 3.50 mol% or less). In aspects, the composition includes B2O3 in an amount ranging from greater than or equal to 0.5 mol% to less than or equal to 5 mol%, greater than or equal to 0.5 mol% to less than or equal to 4 mol%, greater than or equal to 0.5 mol% to less than or equal to 3.6 mol%, greater than or equal to 1 mol% to less than or equal to 3.6 mol%, greater than or equal to 2 mol% to less than or equal to 3.6 mol%, greater than or equal to 2.5 mol% to less than or equal to 3.5 mol%, greater than or equal to 3 mol% to less than or equal to 3.5 mol% (e.g., greater than or equal to 3.00 mol% to less than or equal to 3.50 mol%), or any range or sub-range therebetween. Alternatively, in aspects, the glass-based composition is substantially free of or free of B2O3. In preferred aspects, the composition includes B2O3 in an amount ranging from greater than or equal to 0.5 mol% to less than or equal to 3.6 mol%, greater than or equal to 2 mol% to less than or equal to 3.6 mol%, or greater than or equal to 3 mol% to less than or equal to 3.5 mol%.

[0207] The glass-based compositions described herein can optionally include Ti02. Inclusion of too much Ti02in the glass-based compositions can result in the compositions being prone to devitrification and / or exhibiting undesirable coloration and undesirably changing the liquidus. Inclusion of Ti02in the glass-based compositions can prevent the glass-based materials from undergoing undesirable discoloration upon exposure to strong ultraviolet light, such as during post-processing handling. In aspects, the compositions include Ti02in an amount of 0 mol% or more, 0.1 mol% or more, 0.15 mol% or more, 1 mol% or less, 0.5 mol% or less, or 0.3 mol% or less. In aspects, the compositions include Ti02in an amount in a range of greater than or equal to 0 mol% to less than or equal to 1 mol%, greater than or equal to 0.1 mol% to less than or equal to 0.5 mol%, greater than or equal to 0.15 mol% to less than or equal to 0.3 mol%, or any range or sub-range therebetween. Alternatively, in aspects, the glass-based compositions are substantially free of or free of Ti02. In preferred aspects, the compositions include Ti02in an amount of greater than or equal to 0 mol% to less than or equal to 1 mol% or greater than or equal to 0.1 mol% to less than or equal to 0.5 mol%.

[0208] The glass-based compositions can optionally include one or more fining agents. In aspects, the fining agents can include, for example, Sn02. In aspects, Sn02may be present in the glass-based compositions in an amount of less than or equal to 0.2 mol%, such as greater than or equal to 0 mol% to less than or equal to 0.2 mol%, greater than or equal to 0 mol% to less than or equal to 0.1 mol%, greater than or equal to 0 mol% to less than or equal to 0.05 mol%, greater than or equal to 0.1 mol% to less than or equal to 0.2 mol%, and all ranges and sub-ranges therebetween. In some aspects, the glass-based compositions can be substantially free of or free of Sn02. In aspects, the glass-based compositions can be substantially free of or free of one or both of arsenic and antimony. In preferred aspects, the compositions include Sn02in an amount of greater than or equal to 0 mol% to less than or equal to 0.2 mol% or greater than or equal to 0 mol% to less than or equal to 0.1 mol%.

[0209] In all respects, the amount of Fe2O3 included in the glass-based composition may optionally be 0 mol% or more, 0.001 mol% or more, 0.005 mol% or more, 0.01 mol% or more, 0.015 mol% or more, 0.02 mol% or more, 0.1 mol% or less, 0.05 mol% or less, 0.03 mol% or less, or 0.02 mol% or less. In all respects, the amount of Fe2O3 included in the glass-based composition may optionally be within the range of: greater than or equal to 0 mol% to less than or equal to 0.1 mol%, greater than or equal to 0.001 mol% to less than or equal to 0.05 mol%, greater than or equal to 0.005 mol% to less than or equal to 0.03 mol%, greater than or equal to 0.01 mol% to less than or equal to 0.03 mol%, or any range or subrange thereof. Alternatively, in all respects, the glass-based composition may be substantially free of or contain no Fe2O3. Iron is commonly present in the raw materials used to form the glass matrix composition, and therefore can be detected in the glass matrix composition described herein even when not actively added to the glass matrix batch. In a preferred aspect, the composition comprises Fe₂O₃ in an amount greater than or equal to 0 mol% to less than or equal to 0.1 mol%, 0.0001 mol% to 0.05 mol%, or 0.01 mol% to 0.03 mol%.

[0210] The glass-based compositions described herein may be formed primarily of SiO2, Al2O3, Li2O, Na2O, K2O, MgO, CaO, SrO, P2O5, and B2O3 (i.e., each containing 0.5 mol% or more). In all respects, the glass-based compositions are substantially free of or contain no components other than SiO2, Al2O3, Li2O, Na2O, K2O, MgO, CaO, SrO, P2O5, B2O3, Fe2O3, TiO2, and / or clarifying agents (e.g., SnO2).

[0211] In aspects, the glass-based composition can be essentially free or free of Zr02. Inclusion of Zr02in the glass-based composition can result in the formation of undesirable zirconia inclusions in the glass-based material, at least in part due to the low solubility of Zr02in the glass-based material. While inclusion of Zr02in the glass-based composition can increase fracture toughness, there are cost and supply limitations and the devitrification issues described previously that can make the use of these components undesirable for commercial purposes. In other words, the ability of the glass-based compositions described herein to achieve high fracture toughness values with the inclusion of Zr02provides a cost and manufacturability advantage.

[0212] In aspects, the glass-based composition can be essentially free or free of at least one of Ta205, Hf02, La203, and Y203. In aspects, the glass-based composition can be essentially free or free of Ta205, Hf02, La203, and Y203. While these components can increase the fracture toughness of the glass-based when included, there are cost and supply limitations that make the use of these components undesirable for commercial purposes. In other words, the ability of the glass-based compositions described herein to achieve high fracture toughness values with the inclusion of Ta205, Hf02, La203, and Y203provides a cost and manufacturability advantage.

[0213] The glass-based compositions described herein have a liquidus viscosity that is compatible with manufacturing processes that are particularly suitable for forming thin glass sheets. For example, the glass compositions are compatible with down-draw processes, such as fusion draw processes or slot draw processes. Embodiments of the glass-based substrates can be described as fusion-formable (i.e., formable using a fusion draw process). Fusion processes use a draw tank that has a channel for receiving a molten glass feedstock. The channel has a weir that opens at the top along the length of the channel on both sides of the channel. When the channel is filled with molten material, the molten glass overflows the weir. Due to gravity, the molten glass flows down the outer surfaces of the draw tank in two flowing glass films. These outer surfaces of the draw tank extend downward and inward such that they join at an edge below the draw tank. The two flowing glass films join at this edge to fuse and form a single flowing glass-based article. The fusion of the glass films creates a fusion line within the glass-based substrate, and this fusion line allows the fusion-formed glass-based substrate to be identified without otherwise knowing the manufacturing history. The fusion draw method provides the advantage that the outer surfaces of the resulting glass-based article do not come into contact with any part of the equipment because the two glass films flowing through the channel fuse together. Thus, such contact does not affect the surface properties of the fusion-drawn glass-based article. The glass-based compositions described herein can be selected to have a liquidus viscosity that is compatible with fusion draw processes and / or slot draw processes. Thus, the glass-based compositions described herein are compatible with existing forming methods, which increases the manufacturability of the glass-based articles formed from the glass-based compositions.

[0214] As used herein, "liquidus viscosity" refers to the viscosity of a molten glass at the liquidus temperature, where the liquidus temperature refers to the temperature at which crystals first appear as a molten glass cools down from the melting temperature, or the temperature at which the last crystals melt away as the temperature is increased from room temperature. Unless otherwise specified, the liquidus viscosity values disclosed herein are determined by the following method. First, the liquidus temperature of the glass is measured according to ASTM C829-81 (2015), entitled "Standard Practice for Measurement of Liquidus Temperature of Glass by the Gradient Furnace Method." Next, the viscosity of the glass at the liquidus temperature is measured according to ASTM C965-96 (2012), entitled "Standard Practice for Measuring Viscosity of Glass Above the Softening Point." As used herein, the "Vogel-Fulcher-Tamman" (VFT) relationship describes the temperature dependence of viscosity and is represented by the following equation:

[0215]

[0216] where n is the viscosity. To determine the VFT A, VFT B, and VFT T o values, the viscosity of a glass composition is measured over a given temperature range. The raw data of viscosity versus temperature are then fitted to the VFT equation by a least-squares fit to obtain A, B, and T o . With these values, the viscosity points at any temperature above the softening point can be calculated (e.g., 200 poise (P) temperature, 35,000 P temperature, and 200,000 P temperature). Unless otherwise specified, the liquidus viscosity and temperature of a glass composition or article are measured prior to any ion exchange process or any other strengthening process of the composition or article. In particular, the liquidus viscosity and temperature of a glass composition or article are measured prior to exposure of the composition or article to an ion exchange solution, e.g., prior to immersion in an ion exchange solution. As reported in the examples below, the "liquidus viscosity" discussed herein corresponds to the "internal" liquidus viscosity (kP) reported in Table I.

[0217] In aspects, the glass-based composition can have a liquidus viscosity of 100 kiloPoise (kP) or more, 125 kP or more, 150 kP or more, 175 kP or more, 200 kP or more, 225 kP or more, 250 kP or more, 350 kP or less, 325 kP or less, 300 kP or less, or 275 kP or less. In aspects, the glass-based composition can have a liquidus viscosity in a range from greater than or equal to 100 kP to less than or equal to 350 kP, from greater than or equal to 125 kP to less than or equal to 350 kP, from greater than or equal to 150 kP to less than or equal to 325 kP, from greater than or equal to 175 kP to less than or equal to 325 kP, from greater than or equal to 200 kP to less than or equal to 300 kP, from greater than or equal to 225 kP to less than or equal to 300 kP, or any range or sub-range therebetween. In preferred aspects, the glass-based composition has a liquidus viscosity in a range from greater than or equal to 100 kP to less than or equal to 350 kP, from 150 kP to 300 kP, or from 200 kP to 300 kP.

[0218] Contrary to conventional expectations associated with lower liquidus viscosities and higher K IC values and improved ion exchange capabilities, examples of the present disclosure demonstrate that high fracture toughness (e.g., K IC of 0.75 MPaVm or more) and high liquidus viscosity (e.g., 100 kP or more, 150 kP or more, 175 kP or more, or 200 kP to 300 kP) can be simultaneously obtained. Without being bound by theory, it is believed that when the compositions of the present disclosure crystallize, the compositions produce a different glass network structure associated with non-lithium feldspar crystalline phases, as discussed below.

[0219] In aspects, the glass-based compositions described herein can form glass-based articles that exhibit an amorphous microstructure and can be substantially free of crystals or microcrystals. In other words, glass-based articles formed from the glass compositions described herein can exclude glass-ceramic materials. Alternatively, in aspects, the glass-based articles can form glass-ceramics. In further aspects, the glass-ceramics can be obtained by heating an amorphous glass-based article to nucleate and / or grow microcrystals. In still further aspects, the glass-ceramics can include a pericline crystalline phase and / or a feldspar solid solution crystalline phase. In even further aspects, the primary crystalline phase (i.e., the crystalline phase having the largest volume % of the glass-ceramic) can be pericline or a feldspar solid solution.

[0220] In aspects, the composition, glass-based substrate, and / or glass-based article can be crystallized by heating at 1050 °C for 24 hours to form an anorthite crystal phase or a feldspar solid solution. In further aspects, the major crystal phase (i.e., the crystal phase having the largest volume % of the glass-ceramic) after heating the composition, glass-based substrate, and / or glass-based article at 1050 °C for 24 hours can be anorthite or a feldspar solid solution.

[0221] In aspects, the value of MgO + Li20 - (CaO + SrO + Na20 + K20) of the glass-based composition in mol% can be 0 or less, -0.5 or less, -0.8 or less, -0.9 or less, -1 or less, 1.1 or less, -4 or more, -3 or more, -2.5 or more, -2 or more, -1.7 or more, -1.5 or more, or -1.2 or more. In aspects, the value of MgO + Li20 - (CaO + SrO + Na20 + K20) of the glass-based composition in mol% can be in a range from greater than or equal to -4 to less than or equal to 0, greater than or equal to -4 to less than or equal to -0.5, greater than or equal to -3 to less than or equal to -0.5, greater than or equal to -2.5 to less than or equal to -0.8, greater than or equal to -2 to less than or equal to -0.8, greater than or equal to -1.7 to less than or equal to -0.9, greater than or equal to -1.5 to less than or equal to -1, greater than or equal to -1.3 to less than or equal to -1, or any range or sub-range therebetween. In preferred aspects, the value of MgO + Li20 - (CaO + SrO + Na20 + K20) of the glass-based composition in mol% can be greater than or equal to -4 to less than or equal to 0, greater than or equal to -4 to less than or equal to -0.5, or greater than or equal to -1.5 to less than or equal to -1. Without being bound by theory, it is believed that when the value of MgO + Li20 - (CaO + SrO + Na20 + K20) in mol% is slightly negative (e.g., -4 to -0.5 or -1.5 to -1), the glass-based composition can crystallize into a non-lithium feldspar major crystal phase that can be associated with increased liquidus viscosity (e.g., 100 kP or more, 150 kP or more, 175 kP or more, 200 kP to 300 kP), as discussed above.

[0222] The glass matrix compositions described herein possess high fracture toughness. Without adhering strictly to theory, high fracture toughness can impart improved drop properties to the glass matrix compositions. The high fracture toughness of the glass matrix compositions described herein increases the damage resistance of the glass substrate and allows for the imparting of higher levels of stress, as characterized by central tension, to the resulting glass matrix articles via ion exchange without rendering them brittle. As used herein, unless otherwise stated, “fracture toughness” refers to K0 as measured by the herringbone notch bar method. IC Value. Used to measure K. IC The chevron notched short bar (CNSB) method is disclosed in Reddy, KPR et al., “Fracture Toughness Measurement of Glass and Ceramic Materials Using Chevron-Notched Specimens”, Journal of the American Ceramic Society (J. Am. Ceram. Soc.), 71 [6], C-310-C-313 (1988), the difference being that Y* m It was calculated using Equation 5 of Bubsey, RT et al., "Closed-Form Expressions for Crack-Mouth Displacement and Stress Intensity Factors for Chevron-Notched Short Bar and Short Rod Specimens Based on Experimental Compliance Measurements," NASA Technical Memorandum 83796, pp. 1-30 (October 1992). Additionally, K was measured on unreinforced glass substrate samples. IC Values, such as K measured before ion exchange of a glass substrate to form a glass-based article. IC Value. Unless otherwise stated, K discussed herein is... IC Values ​​are reported in MPa√m. In all aspects, the glass-based composition exhibits K... ICgreater than or equal to 0.75 MPaVm, such as greater than or equal to 0.76 MPaVm, greater than or equal to 0.77 MPaVm, greater than or equal to 0.8 MPaVm, or greater. In aspects, the glass-based composition exhibits a K IC greater than or equal to 0.75 MPaVmto less than or equal to 0.8 MPaVm, such as greater than or equal to 0.76 MPaVmto less than or equal to 0.79 MPaVm, greater than or equal to 0.77 MPaVmto less than or equal to 0.78 MPaVm, and all ranges and sub-ranges between the foregoing values.

[0223] Throughout the disclosure, volume resistivity is measured according to ASTM D257. Unless otherwise indicated, volume resistivity is measured using a 16008B Resistivity Cell (Agilent Technologies). In aspects, the glass-based substrate and / or glass-based article can have a volume resistivity of 2 x 10 15 ohm-cm or greater, 5 x 10 15 ohm-cm or greater, 7 x 10 15 ohm-cm or greater, 1 x 10 16 ohm-cm or greater, or 2 x 10 16 ohm-cm or greater. In aspects, the glass-based substrate and / or glass-based article can have a volume resistivity in the range of greater than or equal to 2 x 10 15 ohm-cm to less than or equal to 5 x 10 17 ohm-cm to less than or equal to 2 x 10 15 ohm-cm to less than or equal to 2 x 10 17 ohm-cm to less than or equal to 2 x 10 16 ohm-cm to 1 x 10 17 ohm-cm or any range or sub-range therebetween. In preferred aspects, the glass-based substrate can have a volume resistivity of greater than or equal to 2 x 10 15 ohm-cm to less than or equal to 5 x 10 17 ohm-cm to less than or equal to 2 x 10 16 ohm-cm to less than or equal to 2 x 10 17 ohm-cm. Glass-based substrates having a high volume resistivity (e.g., 2 x 10 15 ohm-cm or greater, or 1 x 10 16 ohm-cm to 1 x 10 17Glass substrates and / or glass articles with dimensions of ohms-cm can reduce the incidence of electrostatic discharge, which can cause discoloration or other damage to the glass substrates and / or glass articles, especially when the dimensions of the glass substrates and / or glass articles are large (e.g., 10 cm or larger, or 20 cm or larger).

[0224] like Figure 1 As shown, the glass substrate article 100 includes a first main surface 110 and a second main surface 112 opposite to the first main surface. In various aspects, the first main surface 110 and / or the second main surface 112 may include flat surfaces. In another aspect, the first main surface 110 may be parallel to the second main surface 112. As shown, the substrate thickness t of the glass substrate article 100 is defined as the average thickness between the first main surface 110 and the second main surface 112. In various aspects, the substrate thickness t may be 0.02 mm or greater, 0.05 mm or greater, 0.1 mm or greater, 0.2 mm or greater, 0.4 mm or greater, 0.5 mm or greater, 0.6 mm or greater, 0.7 mm or greater, 5 mm or less, 3 mm or less, 2 mm or less, 1.5 mm or less, 1 mm or less, 0.9 mm or less, 0.8 mm or less, 0.7 mm or less, 0.5 mm or less, or 0.2 mm or less. In all aspects, the substrate thickness t can be within the following ranges: greater than or equal to 0.02 mm and less than or equal to 5 mm, greater than or equal to 0.02 mm and less than or equal to 3 mm, greater than or equal to 0.02 mm and less than or equal to 2 mm, greater than or equal to 0.05 mm and less than or equal to 1.5 mm, greater than or equal to 0.1 mm and less than or equal to 1.5 mm, greater than or equal to 0.2 mm and less than or equal to 1 mm, greater than or equal to 0.4 mm and less than or equal to 1 mm, greater than or equal to 0.5 mm and less than or equal to 1 mm, greater than or equal to 0.6 mm and less than or equal to 0.9 mm, greater than or equal to 0.6 mm and less than or equal to 0.8 mm, or any range or subrange thereof. In a preferred aspect, the substrate thickness t of the glass-based article can be within the following ranges: greater than or equal to 0.02 mm and less than or equal to 5 mm, greater than or equal to 0.4 mm and less than or equal to 2 mm, or greater than or equal to 0.5 mm and less than or equal to 2 mm. The glass substrate used to form glass-based articles can have the same thickness as the required thickness of the glass-based articles.

[0225] As used herein, the term "Knoop Scratch Test" is used to refer to a scratch test employed on various articles including substrates, such as the articles of the present disclosure, to determine the scratch resistance of the surface under test of the substrate. The Knoop Scratch Test is conducted by sliding a Knoop indenter across an exposed surface of a sample (e.g., the first major surface 110, the second major surface 112). In particular, the test is conducted by sliding a Knoop indenter across the exposed surface at a rate of 24 mm / min under a predetermined load, as measured by a universal material tester. The Knoop indenter is a rhombohedral pyramid with diamond-tipped corners having angles of 172°30' and 130°, respectively. Further, the Knoop Scratch Test is conducted by scratching the exposed surface of a sample at progressively increasing load levels until the sample exhibits unacceptable signs of damage. According to the Knoop Scratch Test, five (5) scratch trials are conducted for each load level (e.g., in units of Newtons (N)), respectively. Also as used herein, the "Knoop Scratch Threshold" is defined as the load level (i.e., as reported in units of Newtons (N)) employed during the Knoop Scratch Test at which at least 20% of the length of the scratch is twice the width of the scratch. Further, the lowest load level (i.e., as reported in units of Newtons (N)) at which such unacceptable damage is produced on a sample is defined as the Knoop Scratch Threshold.

[0226] In aspects, the Knoop Scratch Threshold of the glass-based article 100 (see Figure 1 ) is about 9 N to about 18 N when tested using the Knoop Scratch Test. The Knoop Scratch Threshold of the glass-based article can also be greater than or equal to 18 N to less than or equal to 22 N when tested using the Knoop Scratch Test. Accordingly, the glass-based article can be characterized by a Knoop Scratch Threshold of about 9 N, 10 N, 11 N, 12 N, 13 N, 14 N, 15 N, 16 N, 17 N, 18 N, 19 N, 20 N, 21 N, 22 N, and all threshold load levels between these amounts. In further aspects, the maximum crack width of the glass-based article can be about 200 pm when tested using the Knoop Scratch Test. As used herein, the terms "maximum crack width" or "average maximum crack width" are used interchangeably and refer to the average maximum width of cracks observed in a set of samples tested using the Knoop Scratch Test at the Knoop Scratch Threshold (N). Accordingly, the average maximum crack width is measured on a set of samples at the Knoop Scratch Threshold.

[0227] The planar drop test simulates sharp contact damage in real-world conditions (e.g., damage from rough surfaces like granite or asphalt) by dropping a sample onto a 180mm coarse alumina sheet. Using a 180mm coarse alumina sheet allows for controlled test data generation, enabling fair comparisons between the sample of interest and comparison samples. The alumina sheet is replaced for each test sample to ensure consistency. The test component is mounted on a commercially available drop testing machine (Yoshida Seiki drop tester, model DT-205H, manufactured by Shinei Technology Co., Ltd., Japan) and flush with the drop surface (180mm coarse alumina sheet). Drop heights are increased in 10cm increments starting at 22cm until the test sample fails (i.e., a crack appears on the display area of ​​the screen protector), and the corresponding failure height is recorded. Ten samples are tested under each condition, and the average failure height is calculated.

[0228] In all respects, glass-based articles can withstand a surface drop test from a height of 100 cm or higher, 110 cm or higher, 120 cm or higher, 130 cm or higher, 140 cm or higher, 250 cm or lower, 220 cm or lower, 200 cm or lower, 180 cm or lower, 170 cm or lower, or 160 cm or lower. In all respects, glass-based articles can withstand a surface drop test from a height of 100 cm or higher to 250 cm or lower, 110 cm or higher to 220 cm or lower, 120 cm or higher to 200 cm or lower, 130 cm or higher to 180 cm or lower, 140 cm or higher to 170 cm or lower, or any range or subrange thereof.

[0229] As described above, in various aspects, the glass composition (e.g., glass substrate) described herein can be strengthened, such as by ion exchange, thereby producing glass-based articles that are resistant to damage for applications such as, but not limited to, display protective covers. Figure 1 As shown, the glass-based article 100 has a first compressive stress region 120 extending from a first main surface 110 to a first compression depth d1, and / or the glass-based article 100 has a second compressive stress region 122 extending from a second main surface 112 to a second compression depth d2. The first compressive stress region and / or the second compressive stress region are under compressive stress (e.g., due to ion exchange). In another aspect, such as Figure 1As shown, the glass substrate 100 may include a central tension region 130, which is under tensile stress (e.g., central tension (CT)) and positioned between a first compressive stress region 120 and a second compressive stress region 122 (e.g., extending between a first compression depth d1 from a first main surface 110 and a second compression depth d2 from a second main surface 112). As used herein, “compression depth” (DOC) refers to the depth at which stress within the glass substrate changes from compression to tension. At the DOC, the stress changes from positive (compressive) stress to negative (tensile) stress, and therefore exhibits a stress value of zero. This follows common practice in the art and... Figures 6-7 In this specification, compressive stress is expressed as positive (> 0) stress, and tensile stress is expressed as negative (< 0) stress. However, throughout this specification, both CS and CT are expressed as positive or absolute values, i.e., as listed herein, CS = |CS|. Compressive stress (CS) has a maximum value at or near the surface of the glass substrate article, and CS varies according to a function with a distance d from the surface.

[0230] In aspects, the compressive stress region can be created by chemically strengthening the glass-based substrate to form the glass-based article 100. Chemical strengthening can include an ion exchange process in which ions in the surface layer are replaced or exchanged with larger ions of the same valence or oxidation state. Methods of chemical strengthening will be discussed later. Without being bound by theory, the chemically strengthened substrate can enable small (e.g., less than about 10 mm or less) bend radii because the compressive stress from the chemical strengthening can counteract the tensile stress from bending on the outermost surface (e.g., the first major surface 110 or the second major surface 112) of the substrate. The depth of compression (DOC) can be measured by surface stress meter or scattered light polariscope (SCALP, where values reported herein were obtained using a SCALP-5 manufactured by Glasstress Co., Estonia), depending on the ion exchange treatment and the thickness of the article being measured. When stresses are created in the substrate by exchanging potassium ions into the substrate, the depth of compression is measured using a surface stress meter, such as a FSM-6000 (Orihara Industrial Co., Ltd. (Japan)). Unless otherwise specified, compressive stress (including surface CS) is measured by surface stress meter (FSM) using a commercially available instrument, such as a FSM-6000 manufactured by Orihara. Surface stress measurements rely on accurate measurement of the stress optical coefficient (SOC), which is related to the birefringence of the glass. Unless otherwise specified, SOC is measured according to Procedure C (glass disk method) of the procedure entitled “Standard Test Method for Measurement of Glass Stress-Optical Coefficient” described in ASTM Standard C770-16, the contents of which are incorporated herein in their entirety by reference. In cases where stresses are generated by exchanging sodium ions into the substrate and the thickness of the article being measured is greater than about 75 µm, the depth of compression and central tension (CT) are measured using SCALP. In cases where stresses are generated by exchanging both potassium and sodium ions into the glass and the thickness of the article being measured is less than about 75 µm, the depth of compression and CT are measured by SCALP. Without being bound by theory, the exchange depth of sodium ions can be indicative of the depth of compression, while the exchange depth of potassium ions can be indicative of a change in the magnitude of the compressive stress (rather than a change from compressive stress to tensile stress).A graphical representation of the stress profile can also be derived using a refracted near field (RNF; the RNF method is described in U.S. Patent No. 8,854,623, entitled “Systems and methods for measuring a profile characteristic of a glass sample,” which is incorporated by reference herein in its entirety) method. When deriving a graphical representation of the stress profile using the RNF method, the maximum central tension value provided by the SCALP is utilized in the RNF method. The graphical representation of the stress profile derived by the RNF is force balanced and calibrated from the maximum central tension value provided by the SCALP measurement. As used herein, “depth of layer” (DOL) means the depth of ion exchange into a substrate (e.g., sodium, potassium). Through the present disclosure, when the central tension cannot be directly measured by the SCALP (as when the article being measured is thinner than about 75 µm), the maximum central tension can be approximated by the product of the maximum compressive stress and the depth of compression divided by the difference of the substrate thickness and twice the depth of compression, where the compressive stress and the depth of compression are measured by the FSM.

[0231] In aspects, the first and / or second compression depths, as a percentage of the substrate thickness t, can be about 17% or greater, about 18% or greater, about 19% or greater, about 20% or greater, about 21% or greater, about 22% or greater, about 23% or greater, about 24% or greater, about 25% or greater, about 25% or less, about 24% or less, or about 23% or less. In even further aspects, the first and / or second compression depths, as a percentage of the substrate thickness t, can be in a range from about 17% to about 25%, about 18% to about 25%, about 19% to about 25%, about 20% to about 25%, about 21% to about 24%, about 22% to about 23%, or any range or sub-range therebetween. In aspects, the first and / or second compression depths can be about 10 pm or greater, about 30 pm or greater, about 50 pm or greater, about 100 pm or greater, about 150 pm or greater, about 200 pm or greater, about 250 pm or greater, about 500 pm or less, about 400 pm or less, about 300 pm or less, about 250 pm or less, about 200 pm or less, about 150 pm or less, or about 100 pm or less. In aspects, the first and / or second compression depths can be in a range from greater than or equal to 10 pm to less than or equal to 500 pm, greater than or equal to 30 pm to less than or equal to 400 pm, greater than or equal to 50 pm to less than or equal to 300 pm, greater than or equal to 100 pm to less than or equal to 250 pm, greater than or equal to 150 pm to less than or equal to 200 pm, or any range or sub-range therebetween. In aspects, the first and / or second compression depths can be about 150 pm or greater, for example, in a range from greater than or equal to 150 pm to less than or equal to 500 pm, greater than or equal to 200 pm to less than or equal to 400 pm, or any range or sub-range therebetween. In aspects, the first compression depth can be greater than, less than, or substantially the same as the second compression depth. By providing a glass-based substrate and / or a ceramic-based substrate comprising a first and / or second compression depth in a range from about 20% to about 25% of the substrate thickness, good impact resistance and / or puncture resistance can be achieved.

[0232] The first compressive stress region 120 includes a maximum first compressive stress, and / or the second compressive stress region 122 includes a maximum second compressive stress. In aspects, the location of the maximum first compressive stress and / or the maximum second compressive stress can be at the corresponding major surface (e.g., within about 1 pm), although the corresponding maximum compressive stress can be located more than 1 pm from the corresponding major surface. In aspects, the maximum first compressive stress and / or the maximum second compressive stress can be about 100 megapascals (MPa) or greater, about 300 MPa or greater, about 500 MPa or greater, about 600 MPa or greater, about 700 MPa or greater, about 800 MPa or greater, about 1,500 MPa or less, about 1,200 MPa or less, about 1,000 MPa or less, or about 900 MPa or less. In aspects, the maximum first compressive stress and / or the maximum second compressive stress can be in a range from greater than or equal to 100 MPa to less than or equal to 1,500 MPa, greater than or equal to 300 MPa to less than or equal to 1,200 MPa, greater than or equal to 500 MPa to less than or equal to 1,000 MPa, greater than or equal to 600 MPa to less than or equal to 1,000 MPa, greater than or equal to 800 MPa to less than or equal to 1,00 MPa, or any range or sub-range therebetween. Providing a maximum first compressive stress and / or a maximum second compressive stress in a range from about 500 MPa to about 1,500 MPa, or about 500 MPa to about 1,000 MPa, can achieve good impact resistance and / or puncture resistance.

[0233] In aspects, Na + and / or K + ions can be exchanged into the glass-based article, and Na + ions diffuse to a greater depth into the glass-based article than K + ions. The depth of penetration of K + ions, referred to herein as“potassium DOL” or“DOL,” is different from DOC because it represents the depth of potassium penetration due to the ion exchange process. For the articles described herein, potassium DOL is typically less than DOC. Potassium DOL is measured using a surface stress meter (such as the commercially available FSM-6000 surface stress meter manufactured by Orihasa Engineering Co., Ltd. (Japan)) that relies on accurate measurements of the stress optical coefficient (SOC), as described above with reference to CS measurements. Potassium DOL can be defined as the depth of the compressive stress spike (DOL SP ), where the stress profile transitions from a steep spike region to a less steep deep region. The deep region extends from the bottom of the spike to the depth of compression. In aspects, the corresponding compressive stress region of the glass-based article (e.g., DOL SPThe depth of layer of the one or more alkali metal ions associated with the corresponding compressive stress region (e.g., DOL SP The depth of layer of the one or more alkali metal ions associated with the corresponding compressive stress region (e.g., DOL SP The ratio of the depth of layer (e.g., DOL SP The ratio of the depth of layer (e.g., DOL

[0234] As described in the preceding paragraph, the compressive stress layer can include a compressive stress peak depth (DOL SP), where the stress profile transitions from a steep spike region to a less steep deep region. In aspects, the compressive stress at the compressive stress spike depth can be about 90 MPa or greater, about 100 MPa or greater, about 125 MPa or greater, about 150 MPa or greater, about 175 MPa or greater, about 300 MPa or less, about 250 MPa or less, about 225 MPa or less, about 210 MPa or less, about 200 MPa or less, about 175 MPa or less, about 150 MPa or less, or about 125 MPa or less. In aspects, the compressive stress at the compressive stress spike depth can be in a range from greater than or equal to 90 MPa to less than or equal to 300 MPa, from greater than or equal to 100 MPa to less than or equal to 250 MPa, from greater than or equal to 125 MPa to less than or equal to 225 MPa, from greater than or equal to 125 MPa to less than or equal to 210 MPa, from greater than or equal to 150 MPa to less than or equal to 200 MPa, or any range or sub-range therebetween. In aspects, the ratio of the compressive stress at the compressive stress spike depth to the corresponding maximum compressive stress can be about 0.08 or greater, about 0.10 or greater, about 0.12 or greater, about 0.15 or greater, about 0.18 or greater, about 0.19 or greater, about 0.20 or greater, about 0.21 or greater, about 0.22 or greater, about 0.25 or less, about 0.24 or less, about 0.23 or less, about 0.22 or less, or about 0.20 or less. In aspects, the ratio of the compressive stress at the compressive stress spike depth to the corresponding maximum compressive stress can be in a range from greater than or equal to 0.08 to less than or equal to 0.25, from greater than or equal to 0.10 to less than or equal to 0.25, from greater than or equal to 0.12 to less than or equal to 0.25, from greater than or equal to 0.15 to less than or equal to 0.25, from greater than or equal to 0.18 to less than or equal to 0.25, from greater than or equal to 0.19 to less than or equal to 0.24, from greater than or equal to 0.20 to less than or equal to 0.23, from greater than or equal to 0.21 to less than or equal to 0.22, or any range or sub-range therebetween. In preferred aspects, the ratio of the compressive stress at the compressive stress spike depth to the corresponding maximum compressive stress can be in a range from greater than or equal to 0.10 to less than or equal to 0.25 or from greater than or equal to 0.10 to less than or equal to 0.20. The combination of the ratio of the depth of layer (e.g., DOLSP) to the depth of compression (e.g., DOC) in one or more of the corresponding ranges in the preceding paragraph and the ratio of the compressive stress at the compressive stress spike depth to the corresponding maximum compressive stress in one or more of the ranges in the paragraph can be a property of the composition of the present disclosure that can be different from other compositions.

[0235] In aspects, the slope of the peak region (e.g., from the major surface to the depth of the compressive stress peak) can be -300 MPa / µm or greater, -250 MPa / µm or greater, -220 MPa / µm or greater, -200 MPa / µm or greater, -190 MPa / µm or greater, -100 MPa / µm or less, -130 MPa / µm or less, -150 MPa / µm or less, or -160 MPa / µm or less. In aspects, the slope of the peak region (e.g., from the major surface to the depth of the compressive stress peak) can be in a range from greater than or equal to -300 MPa / µm to less than or equal to -300 MPa / µm, greater than or equal to -250 MPa / µm to less than or equal to -100 MPa / µm, greater than or equal to -220 MPa / µm to less than or equal to -130 MPa / µm, greater than or equal to -200 MPa / µm to less than or equal to -150 MPa / µm, greater than or equal to -190 MPa / µm to less than or equal to -160 MPa / µm, or any range or sub-range therebetween. In aspects, the slope of the deep region (e.g., deeper than the compressive stress peak depth) can be about -2.0 MPa / µm or greater, -1.8 MPa / µm -1.7 MPa / µm or greater, -1.6 MPa / µm or greater, -0.8 MPa / µm or greater, -1.0 MPa / µm or greater, -1.1 MPa / µm or greater, or -1.2 MPa / µm or greater. In aspects, the slope of the deep region (e.g., deeper than the compressive stress peak depth) can be in a range from greater than or equal to -2.0 MPa / µm to less than or equal to -0.8 MPa / µm, greater than or equal to -2.0 MPa / µm to less than or equal to -1.0 MPa / µm, greater than or equal to -1.8 MPa / µm to less than or equal to -1.1 MPa / µm, greater than or equal to -1.7 MPa / µm to less than or equal to -1.1 MPa / µm, greater than or equal to -1.6 MPa / µm to less than or equal to -1.5 MPa / µm, or any range or sub-range therebetween.

[0236] The central tension region can include a maximum central tension (Max CT). The measured value of the maximum CT value is an indicator of the total amount of stress stored in the strengthened article. Thus, the ability to achieve higher CT values is related to the ability to achieve a higher degree of strengthening and improved performance. In aspects, the maximum CT can be 50 MPa or greater, 60 MPa or greater, 70 MPa or greater, 75 MPa or greater, 80 MPa or greater, 85 MPa or greater, 120 MPa or less, 100 MPa or less, 95 MPa or less, 90 MPa or less, 85 MPa or less, or 80 MPa or less. In aspects, the maximum CT can be in a range from greater than or equal to 50 MPa to less than or equal to 120 MPa, from greater than or equal to 50 MPa to less than or equal to 100 MPa, from greater than or equal to 50 MPa to less than or equal to 95 MPa, from greater than or equal to 60 MPa to less than or equal to 90 MPa, from greater than or equal to 70 MPa to less than or equal to 90 MPa, from greater than or equal to 75 MPa to less than or equal to 85 MPa, from greater than or equal to 80 MPa to less than or equal to 85 MPa, or any range or sub-range therebetween. In preferred aspects, the maximum CT can be in a range from greater than 50 MPa to less than or equal to 120 MPa, from greater than or equal to 50 MPa to less than or equal to 100 MPa, or from greater than or equal to 70 MPa to less than or equal to 100 MPa.

[0237] The high fracture toughness values of the glass compositions described herein can also enable improved performance. The fragility limit of a glass-based article produced using the glass compositions described herein depends at least in part on the fracture toughness. To this end, the high fracture toughness of the glass compositions described herein allows for a large amount of stored strain energy to be imparted to a glass-based article formed therefrom without the glass-based article becoming fragile. The increased amount of stored strain energy that can then be included in the glass-based article allows the glass-based article to exhibit increased resistance to fracture, which can be observed through the drop performance of the glass-based article. The relationship between the fragility limit and the fracture toughness is described in U.S. Patent Application Publication No. 2020 / 0079689 Al, entitled “Glass-based Articles with Improved Fracture Resistance,” published March 12, 2020, the entirety of which is incorporated by reference herein. The relationship between the fracture toughness and the drop performance is described in U.S. Patent Application Publication No. 2019 / 0369672 Al, entitled “Glass with Improved Drop Performance,” published December 5, 2019, the entirety of which is incorporated by reference herein.

[0238] Aspects of the disclosure can include a consumer electronic product. The consumer electronic product can include a front surface, a back surface, and side surfaces. The consumer electronic product can further include electrical components at least partially within a housing. The electrical components can include a controller, a memory, and a display. The display can be at the front surface of the housing or adjacent to the front surface. The consumer electronic product can include a cover substrate disposed over the display. In aspects, at least one of a portion of the housing or the cover substrate includes the coatings and / or coated articles discussed throughout the disclosure. The display can include a liquid crystal display (LCD), an electrophoretic display (EPD), an organic light emitting diode (OLED) display, or a plasma display panel (PDP). In aspects, the consumer electronic product can be a portable electronic device, such as a smartphone, a tablet, a wearable device, or a laptop computer.

[0239] The coated articles and / or coatings disclosed herein can be incorporated into another article, such as an article having a display (or display article) (e.g., a consumer electronic device, including a mobile phone, a tablet, a computer, a navigation system, a wearable device (e.g., a watch), etc.), a building article, a transportation article (e.g., an automobile, a train, an airplane, a sea vessel, etc.), an appliance article, or any article that can benefit from some degree of transparency, scratch resistance, abrasion resistance, or a combination thereof. Figure 2and 3 Exemplary articles incorporating any of the coated articles disclosed herein are shown in the Examples. In particular, Figure 2 and 3 A consumer electronic device 200 is shown that includes a housing 202 having a front surface 204, a back surface 206, and side surfaces 208. The consumer electronic device 200 can include electrical components (not shown) that are at least partially within the housing or entirely within the housing, and at least including a controller, a memory, and a display 210 at or adjacent the front surface of the housing. The consumer electronic device 200 can include a cover substrate 212 at or over the front surface of the housing, such that the cover substrate is over the display. In aspects, at least one of the cover substrate 212 or a portion of the housing 202 can include a substrate having a first major surface and / or a coated article disclosed herein.

[0240] Reference is now made to Figure 1 and 4 -5Methods of making the glass-based articles of the present disclosure are discussed. As discussed above, glass-based substrates including the compositions according to the present disclosure can be obtained by forming them with various ribbon forming processes, such as slot draw, down-draw, fusion down-draw, up-draw, press roll, redraw, or float. Alternatively, glass-based substrates including the compositions of the present disclosure can be obtained by purchase. In aspects, the glass-based substrates can be amorphous substrates or glass-ceramics. In further aspects, the glass-ceramics can be formed by heating the glass-based substrates to nucleate and / or grow crystals. As discussed above, the glass-ceramics according to the present disclosure can include a sanidine or feldspar solid solution, such as a primary crystalline phase.

[0241] In various aspects, glass substrates can be chemically strengthened by exposing them to one or more ion exchange media (e.g., molten salt solutions). The exchange media may contain, for example, molten nitrates (e.g., KNO3, NaNO3, or combinations thereof) as molten salt solutions, but other sodium and / or potassium salts, such as sodium nitrite or potassium nitrite, phosphates, or sulfates, may be used in the ion exchange media. In various aspects, the ion exchange media may contain lithium salts, such as LiNO3. Additionally, the ion exchange media may contain additives typically included when ion-exchanging glass, such as silicate. In various aspects, the ion exchange media may contain mixtures of sodium and potassium (e.g., containing both NaNO3 and KNO3). In all respects, the ion exchange medium may contain any combination of the following amounts of NaNO3 and KNO3, such as a molten salt bath containing 80 wt% NaNO3 and 20 wt% KNO3, a molten salt bath containing 70 wt% NaNO3 and 30 wt% KNO3, a molten salt bath containing 60 wt% NaNO3 and 40 wt% KNO3, a molten salt bath containing 50 wt% NaNO3 and 50 wt% KNO3, a molten salt bath containing 40 wt% NaNO3 and 60 wt% KNO3, or any range or subrange thereof.

[0242] In all respects, the ion exchange medium includes NaNO3. Sodium in the ion exchange medium exchanges with lithium ions in the glass to generate compressive stress. In all respects, the ion exchange medium may contain NaNO3 in amounts of 95 wt% or less, 90 wt% or less, 80 wt% or less, 70 wt% or less, 60 wt% or less, 50 wt% or less, 40 wt% or less, 30 wt% or less, 20 wt% or less, 10 wt% or less, 5 wt% or more, 10 wt% or more, 20 wt% or more, 30 wt% or more, 40 wt% or more, 50 wt% or more, 60 wt% or more, 70 wt% or more, 80 wt% or more, or 90 wt% or more. In all respects, the ion exchange medium may contain NaNO3 in amounts greater than or equal to 0 wt% to less than or equal to 100 wt%, greater than or equal to 10 wt% to less than or equal to 90 wt%, greater than or equal to 20 wt% to less than or equal to 80 wt%, greater than or equal to 30 wt% to less than or equal to 70 wt%, greater than or equal to 40 wt% to less than or equal to 60 wt%, or any range or subrange thereof. In all respects, the molten ion exchange medium contains 100 wt% NaNO3.

[0243] In aspects, the ion exchange medium comprises KNO3. In aspects, the ion exchange medium can comprise KNO3 in an amount of 95 wt% or less, 90 wt% or less, 80 wt% or less, 70 wt% or less, 60 wt% or less, 50 wt% or less, 40 wt% or less, 30 wt% or less, 20 wt% or less, 10 wt% or less, 5 wt% or more, 10 wt% or more, 20 wt% or more, 30 wt% or more, 40 wt% or more, 50 wt% or more, 60 wt% or more, 70 wt% or more, 80 wt% or more, or 90 wt% or more.

[0244] In aspects, the ion exchange medium can comprise KNO3 in an amount of 0 wt% to 100 wt%, greater than or equal to 10 wt% to less than or equal to 90 wt%, greater than or equal to 20 wt% to less than or equal to 80 wt%, greater than or equal to 30 wt% to less than or equal to 70 wt%, greater than or equal to 40 wt% to less than or equal to 60 wt%, or any range or sub-range therebetween. In aspects, the molten ion exchange medium comprises 98 wt% KNO3, 99 wt% KNO3, or 100 wt% KNO3.

[0245] In aspects, the ion exchange medium comprises KNO3. In aspects, the ion exchange medium can comprise KNO3 in an amount of 95 wt% or less, 90 wt% or less, 80 wt% or less, 70 wt% or more, 60 wt% or more, 50 wt% or more, 40 wt% or more, 30 wt% or more, 20 wt% or more, 10 wt% or more, 5 wt% or more, 10 wt% or more, 20 wt% or more, 30 wt% or more, 40 wt% or more, 50 wt% or more, 60 wt% or more, 70 wt% or more, 80 wt% or more, or 90 wt% or more. Figure 4As shown, the glass substrate 103 can be exposed to the molten salt solution 403 (e.g., contained in a salt bath 401), for example, by immersing the glass substrate 103 in the molten salt solution 403. Alternatively, although not shown, this may include spraying an ion exchange medium onto a glass substrate made of a glass composition, or otherwise physically applying an ion exchange medium onto a glass article to form an ion-exchanged glass article. In another aspect, the ion exchange medium (e.g., the molten salt solution 403) may be maintained at a predetermined temperature, and / or the glass substrate 103 may be in contact with the ion exchange medium (e.g., the molten salt solution 403) for a predetermined period of time. In another aspect, the predetermined temperature may be about 350°C or higher, about 360°C or higher, about 370°C or higher, about 380°C or higher, about 390°C or higher, about 400°C or higher, about 410°C or higher, about 420°C or higher, about 430°C or higher, about 440°C or higher, about 500°C or lower, about 480°C or lower, about 470°C or lower, about 460°C or lower, about 450°C or lower, about 440°C or lower, or about 430°C or lower. In another aspect, the predetermined temperature may be within the following ranges: greater than or equal to 350°C and less than or equal to 500°C, greater than or equal to 360°C and less than or equal to 500°C, greater than or equal to 370°C and less than or equal to 490°C, greater than or equal to 380°C and less than or equal to 480°C, greater than or equal to 390°C and less than or equal to 470°C, greater than or equal to 390°C and less than or equal to 460°C, greater than or equal to 400°C and less than or equal to 450°C, greater than or equal to 400°C and less than or equal to 440°C, greater than or equal to 410°C and less than or equal to 440°C, or any range or subrange thereof. In another aspect, the predetermined time period can be approximately 5 minutes or longer, 10 minutes or longer, 0.25 hours or longer, approximately 0.5 hours or longer, approximately 1 hour or longer, approximately 2 hours or longer, approximately 4 hours or longer, approximately 24 hours or less, approximately 8 hours or less, approximately 4 hours or less, approximately 3 hours or less, or approximately 2 hours or less. In all aspects, the predetermined time period can be within the following ranges: greater than or equal to 5 minutes and less than or equal to 24 hours, greater than or equal to 10 minutes and less than or equal to 24 hours, greater than or equal to 0.25 hours and less than or equal to 8 hours, greater than or equal to 0.5 hours and less than or equal to 8 hours, greater than or equal to 1 hour and less than or equal to 4 hours, or any range or subrange thereof.

[0246] In some aspects, the ion exchange process may include a second ion exchange treatment. In other aspects, the second ion exchange treatment may involve ion exchange of the glass substrate in a second molten salt bath. For example, as... Figure 5As shown in FIG. 3, the glass-based substrate 103 can be exposed to a second molten salt solution 503 (e.g., contained in a second salt bath 501) by, for example, immersing the glass-based substrate 103 in the second molten salt solution 503. The second ion exchange process can utilize any of the ion exchange media described herein. In aspects, the second ion exchange process utilizes a second molten salt bath that includes KNO3.

[0247] The ion exchange process can be conducted in an ion exchange medium under process conditions that provide, for example, an improved compressive stress profile as disclosed in U.S. Patent Application Publication No. 2016 / 0102011, which is incorporated herein by reference in its entirety. In aspects, the ion exchange process can be selected to form a parabolic stress profile in the glass-based article, such as those described in U.S. Patent Application Publication No. 2016 / 0102014, which is incorporated herein by reference in its entirety.

[0248] After the ion exchange process is conducted, it will be appreciated that the composition at the surface of the ion exchanged glass-based article can be different than the composition of the as-formed glass substrate (i.e., the glass substrate prior to being subjected to the ion exchange process). This is due to the replacement of one type of alkali metal ion (e.g., Li + or Na + ) in the as-formed glass substrate with a larger alkali metal ion (e.g., Na + or K + , respectively. However, in aspects, the glass composition at or near the depth center of the glass-based article will still have the composition of the as-formed non-ion exchanged glass substrate that was used to form the glass-based article. As used herein, the center of the glass-based article refers to any location in the glass-based article that is at least 0.5t from each surface of the glass-based article, where t is the thickness of the glass-based article.

[0249] Examples

[0250] The embodiments will be further clarified by the following examples. It should be understood that these examples do not limit the aspects described above.

[0251] Glass compositions were prepared and analyzed. The analyzed glass compositions included the components listed in Table I below, and were prepared by conventional glass forming methods. As described above, the compositions reported herein (including Table I) refer to the composition of the resulting glass-based substrate. Composition 1 was produced in a production scale manufacturing process, while compositions 2-9 were produced in a laboratory scale crucible manufacturing process. In Table I, all components are in mol% and K IC Fracture toughness was measured with a double cantilever beam (DCB) procedure, as described in the next paragraph. Alternatively, K ICFracture toughness can also be measured using the herringbone notch (CNSB) method described herein. The Poisson's ratio (ν), Young's modulus (E), and shear modulus (G) of the glass composition were measured using a general type of resonant ultrasonic spectroscopy technique as specified in ASTM E2001-13, entitled "Standard Guide for Resonant Ultrasound Spectroscopy for Defect Detection in Both Metallic and Non-metallic Parts." Table I also reports the refractive index and stress optical coefficient (SOC) of the substrate at 589.3 nm. The density of the glass composition was determined using the buoyancy method according to ASTM C693-93 (2013).

[0252] For DCB programs, Figure 7 The geometry of the DCB sample is shown, where the parameters are crack length *a*, applied load *P*, cross-sectional dimensions *w* and *2h*, and the thickness *b* of the crack guide groove. The sample is cut into rectangles with a width of *2h* = 1.25 cm and a thickness ranging from *w* = 0.3 mm to 1 mm, where the total length of the sample (which is not a critical dimension) varies from 5 cm to 10 cm. Holes are drilled at both ends with a diamond drill bit to provide means for attaching the sample to the sample holder and load. The crack "guide groove" is cut along the length of both planes of the sample using a wafer saw with a diamond blade, leaving a "mesh" material approximately half the total thickness of the plate. Figure 7 Dimension b) of the sample was used, with a height of 180 µm, consistent with the saw blade thickness. The high dimensional tolerance of the cutting saw resulted in minimal variation between samples. The cutting saw was also used to cut an initial crack of a = 15 mm. As a result of this final operation, a very thin wedge-shaped material was created near the crack tip (due to the saw blade curvature), allowing for easier crack initiation in the sample. The sample was mounted on a metal sample holder with a steel wire inserted through a hole in the bottom. Supports were also provided at the other end of the sample to keep it level under low load conditions. A spring connected in series with a load cell (FUTEK, LSB200) was hooked into the upper hole, and the hole was gradually stretched using a rope and a high-precision slider to apply the load. The crack was monitored using a 5 µm resolution microscope, a digital camera, and a computer. The applied stress intensity K was calculated using the following equation. P :

[0253]

[0254] For each sample, a crack was first initiated at the top of the web, and then the initial crack was carefully sub-critically grown until the size was greater than 1.5 to a / h to accurately calculate the stress intensity. At this point, the crack length a was measured and recorded using a traveling microscope with a resolution of 5 pm. A drop of toluene was then placed into the crack slot and wick along the length of the slot by capillary forces, arresting the crack from moving until the fracture toughness was reached. The load was then increased until the sample fractured, and the critical stress intensity K IC was calculated from the fracture load and sample dimensions. P The equivalent K IC .

[0255] As used herein, the term "annealing point" refers to the temperature at which the viscosity of the glass composition is 1 x 10 13.18 poise. As used herein, the term "strain point" refers to the temperature at which the viscosity of the glass composition is 1 x 10 14.68 poise. The strain point and annealing point of the glass composition were determined using the fiber elongation method of ASTM C336-71 (2015) or the beam bending viscosity (BBV) method of ASTM C598-93 (2013).

[0256] As used herein, the term "softening point" refers to the temperature at which the viscosity of the glass composition is 1 x 10 7.6 poise. The softening point of the glass composition was determined using the fiber elongation method of ASTM C336-71 (2015) or the parallel plate viscosity (PPV) method, which measures the viscosity of inorganic glasses from 10 7 to 10 9 poise as a function of temperature, similar to ASTM C1351M.

[0257] The coefficient of linear thermal expansion (CTE) in ppm / °C over the temperature range of 0-300 °C was determined according to ASTM E228-11 using a push-rod dilatometer.

[0258] Table I

[0259]

[0260] Table I (continued)

[0261]

[0262] Table I (continued)

[0263]

[0264]

[0265] Table I (continued)

[0266]

[0267]

[0268] Substrates of thickness 0.6 mm and 0.7 mm were formed from Composition 1 (Table I) and subsequently ion exchanged to form example articles corresponding to articles DA and DB, respectively (Table II). Substrates of thickness 0.55 mm, 0.6 mm, 0.65 mm and 0.7 mm were formed from Composition 9 (Table I) and subsequently ion exchanged to form example articles (see thickness and properties reported in Table II for articles DC-DS and EA-EN).

[0269] A two-step ion exchange process was performed on the substrates, in which the substrates were immersed in a first molten salt bath and then immersed in a second molten salt bath. To form articles DA-DB, the first molten salt bath was at a temperature of 425 °C and the second molten salt bath was at a temperature of 390 °C, with the composition of each bath and ion exchange time reported in Table II. For articles DC-DS, EA-EC and EJ-EN, the first molten salt bath was maintained at 440 °C or 450 °C and the second molten salt bath was maintained at 390 °C or 400 °C, with the composition of each bath and ion exchange time reported in Table II. For articles ED-EI, the first molten salt bath was maintained at 400 °C and the second molten salt bath was maintained at 390 °C using Composition 9 and the ion exchange times reported in Table II for each bath.

[0270] Table II also reports the properties of the resulting stress profiles, including the maximum compressive stress at the first major surface (CS 表面 ), the depth of the compressive stress peak (DOL sp ), the stress at DOL sp (CS sp ), the depth of compression (DOC) and the maximum tensile stress in the central tension region (CT). The stress profiles of articles DA and DB of Table II were measured using RNF, respectively, as shown in Figures 6-7 . In Figures 6-7 , the horizontal axes 601 and 701 are the depth from the first major surface in micrometers (pm), the vertical axes 603 and 703 are the stress measured in megapascals (MPa) and the curves 605 and 705 correspond to the stress profiles of articles DA and DB, respectively. The stress profiles of articles DD, DG, DJ and DM of Table II were measured using RNF, as shown in Figure 8 . In Figure 8In this case, the horizontal axis 801 is the depth from the first major surface in microns (pm), the vertical axis 801 is the stress measured in megaPascals (MPa), and the curves 805, 807, 809, and 811 correspond to the stress profiles of articles DD, DG, DJ, and DM, respectively.

[0271] Table II

[0272]

[0273]

[0274] Table II (continued)

[0275]

[0276]

[0277] Table II (continued)

[0278]

[0279] Table II (continued)

[0280]

[0281]

[0282] Table II (continued)

[0283]

[0284]

[0285] The article DA had a thickness of 0.7 mm and the article DB had a thickness of 0.6 mm. The glass-based substrate was ion exchanged in a first molten salt bath having a composition of 60 wt% NaN03and 40 wt% KN03at a temperature of 425 °C for a time in the range of 2 hours to 3 hours, followed by ion exchange in a second molten salt bath having a composition of 2 wt% NaN03and 98 wt% KN03at a temperature of 390 °C for a time in the range of 0.1 hours to 0.25 hours. As shown in Table II, the article DA and DB had a maximum compressive stress of 850 MPa to 1,000 MPa, a depth of layer (DOL Figures 6-7 and Table II, the article DA and DB had a maximum compressive stress of 850 MPa to 1,000 MPa, a depth of layer (DOL sp ) of 3 pm to 10 pm, a DOL sp (CS spThe stress at the point is 150 MPa to 200 MPa, the depth of compression (DOC) is 110 µm to 150 µm, and the maximum tensile stress in the center tension region (CT) is 80 MPa to 120 MPa. Further, as shown in Table II for articles DA and DB, the storage compression energy is 40 J / m². 2 Up to 60 J / m 2 Within the range, the storage tension energy is 15 J / m 2 Up to 20 J / m 2 Within the range, and the total storage energy is 60 J / m³. 2 Up to 75 J / m 2 Within the range. Furthermore, the CS of products DA and DB. sp / CS 表面 From 0.18 to approximately 0.25 (e.g., 0.18 to 0.21) and DOL sp / DOC is 0.02 to 0.05 (e.g., 0.03 to 0.05), which may be a unique characteristic of the compositions disclosed herein. Additionally, samples of article DA exhibit a Knoop scratch threshold of 10 N to 13 N. In a plane drop test, samples of article DA withstood an average height of 148 cm, and samples of article DB withstood an average height of 132 cm. Glass-based articles can withstand a certain height in a plane drop.

[0286] The thickness of product DC-DD is 0.7 mm, the thickness of product DE-DG is 0.6 mm, and the thickness of product DH-DS is 0.55 mm. The glass substrates were subjected to ion exchange in a first molten salt bath composed of 40 wt% to 60 wt% NaNO3 and 40 wt% to 60 wt% KNO3 at a temperature of 440°C or 450°C for 1.5 to 3.5 hours, followed by ion exchange in a second molten salt bath composed of 0 wt% to 1 wt% NaNO3 and 99 wt% to 100 wt% KNO3 at a temperature of 390°C or 400°C for 0.25 hours. As shown in Table II, the maximum compressive stress of product DC-DS is 1,100 MPa to 1,350 MPa, and the peak depth (DOL) is... sp ) is 5 µm to 10 µm, DOL sp (CS) sp The stress at the point is 130 MPa to 200 MPa, the depth of compression (DOC) is 105 µm to 150 µm, and the maximum tensile stress in the center tension region (CT) is 80 MPa to 95 MPa. As further shown in Table II for the DC-DS product, the total stored compressibility is 55 J / m³. 2 Up to 75 J / m 2Within the range. Furthermore, the CS of the DC-DS product... sp / CS 表面 From 0.105 to approximately 0.16 and DOL sp / DOC is 0.04 to 0.06, which may be a unique characteristic of the compositions disclosed herein.

[0287] As shown in Table II, article EA-EN underwent ion exchange in a first molten salt bath comprising 60 wt% KNO3 and 40 wt% NaNO3, held at 400°C to 450°C for 1.5 to 3.0 hours, followed by ion exchange in a second molten salt bath comprising 92 wt% to 99 wt% KNO3, 1 wt% to 5 wt% NaNO3, and (optionally) 0 wt% to 5 wt% K2CO3, held at 390°C to 400°C for 0.25 hours. As shown in Table II, the maximum compressive stress of articles EA, ED, EE, and EG was 1,100 MPa to 1,350 MPa; the peak depth (DOL) of articles EA-EC and EI-EL was... sp The diameter is 5 µm to 10 µm; the DOL of products EA-EC, EE-EK and EM-EN is... sp (CS) sp The stress at the point is 130 MPa to 200 MPa; the depth of compression (DOC) of products EA-EC, EF-EG, EI-EK, and EN-EM is 105 µm to 150 µm; and the maximum tensile stress in the center tension region (CT) of product EA-EN is 80 MPa to 95 MPa. Furthermore, the maximum compressive stress of product EA is 1,100 MPa to 1,350 MPa, and the depth of peak (DOL) is... sp ) is 5 µm to 10 µm, DOL sp (CS) sp The stress at the point is 130 MPa to 200 MPa, the depth of compression (DOC) is 105 µm to 150 µm, and the maximum tensile stress in the center tension region (CT) is 80 MPa to 95 MPa. Further, as shown in Table II, for articles EA-EC, EF-EJ, and EM, the total stored compressibility is 55 J / m³. 2 Up to 75 J / m 2 Within the scope. Furthermore, the CS of products EA and ED. sp / CS 表面 From 0.105 to approximately 0.16 and DOL spDOC of 0.04 to 0.06, which can be a unique property of the compositions of the present disclosure. With respect to the effect of K2CO3, compare articles EE, EG, and EH to Examples ED, EF, and EI, respectively, which were all chemically strengthened in the same first molten salt bath (and associated processing conditions) and treated with 0 wt% K2CO3 or 5 wt% K2CO3 in the second molten salt bath at the same time and temperature. For the pairs of articles EG vs. EF and EH vs. EI, the addition of 5 wt% K2CO3 is associated with an increase in CS 表面 , the magnitude (i.e., absolute value) of the peak slope, and total stored energy, and a decrease in DOL sp , CS sp / CS 表面 , and DOL sp / DOC.

[0288] The volume resistivity of Composition 1 (without ion exchange) and article DA (prepared as described in Table II) was also measured. The volume resistivity of Composition 1 (without ion exchange) was 1.4 x 10 16 Ω-cm, and the volume resistivity of article DA (prepared as described in Table II) was 1.7 x 10 16 Ω-cm.

[0289] The above observations can be combined to produce lithium aluminosilicate glasses with good ion exchangeability, good glass quality, and high fracture toughness. The chemical strengthening process can be used to achieve high strength and high toughness properties of lithium aluminosilicate glasses. Substitution of Al2O3 into the silicate glass network improves the interdiffusivity of monovalent cations during ion exchange. By performing chemical strengthening in a molten salt bath (e.g., KNO3 or NaNO3), glasses with high strength, high toughness, and high indentation crack resistance can be obtained. The stress profile achieved by chemical strengthening can have various shapes, thereby improving the drop performance, strength, toughness, and other attributes of the glass-based articles.

[0290] The glasses described herein can achieve high fracture toughness values (e.g., at least 0.75 MPaVm) without the inclusion of additives such as Zr02, Ta205, Ti02, Hf02, La203, and Y203, which can increase fracture toughness but are expensive and can have limited commercial availability. In this regard, the glasses disclosed herein provide comparable or improved performance while reducing manufacturing costs. Fracture toughness and depth of stress are critical to improving drop performance on rough surfaces. To this end, maximizing the amount of stress that can be provided in a glass-based article before reaching a fragility limit can improve depth of stress and rough surface drop performance. Fracture toughness is known to control the fragility limit, and increasing fracture toughness can increase the fragility limit. The glass-based compositions disclosed herein have high fracture toughness and are capable of achieving high compressive stress levels while remaining non-fragile. These characteristics of the glass-based compositions enable the development of improved stress profiles designed to address specific failure modes. This ability enables glass-based articles ion exchanged from the glass-based compositions described herein to be tailored to have different stress profiles to address specific failure modes of interest.

[0291] The compositions described herein are selected to achieve high fracture toughness values while also maintaining a desired degree of manufacturability. The compositions include high amounts of Al203and Li20 to produce the desired fracture toughness while maintaining compatibility with desired manufacturing limits. The drop performance of glass-based articles ion exchanged from the glass-based compositions described herein is improved by increasing the depth of compression (DOC), which is at least partially achieved by selecting a high Li / Na molar ratio (e.g., 1.2-2). The glass-based compositions described herein provide improved ion exchange performance, evidenced by increased central tension capability and increased ion exchange speed, while also avoiding volatility issues at free surfaces during manufacturing that can be introduced due to high B203and P205content. When the concentration of Al203and the concentration of Si02are balanced with the concentration of alkali oxides in the glass-based composition, the Al203can lower the liquidus temperature of the glass melt, thereby increasing the liquidus viscosity and improving the compatibility of the glass-based composition with certain forming processes.

[0292] In contrast to conventional expectations associated with lower liquidus viscosities with higher K IC In contrast to conventional expectations associated with lower liquidus viscosities with higher K ICand a high liquidus viscosity (e.g., 100 kP or more, 150 kP or more, 175 kP or more, or 200 kP to 300 kP). Without being bound by theory, it is believed that when the compositions of the present disclosure crystallize, the compositions produce a different glass network structure associated with a non-spodumene crystal phase. Without being bound by theory, it is believed that when the value of MgO + Li20 - (CaO + SrO + Na20 + K20) in mol% is slightly negative (e.g., -4 to -0.5 or -1.5 to -1), the glass-based composition can crystallize into a non-spodumene major crystal phase that can be associated with an increased liquidus viscosity (e.g., 100 kP or more, 150 kP or more, 175 kP or more, 200 kP to 300 kP).

[0293] For example, providing RO can increase the volume resistivity of the glass-based substrate and / or glass-based article due to the relatively high field strength of the alkaline earth metal ions and / or the reduced mobility of the alkali metal ions. Providing a glass-based substrate and / or glass-based article having a high volume resistivity (e.g., 2 x 1010 15 ohm-cm or more, or 1 x 1011 16 ohm-cm to 1 x 1011 17 ohm-cm) can reduce the incidence of electrostatic discharge that can discolor or otherwise damage the glass-based substrate and / or glass-based article, especially when the glass-based substrate and / or glass-based article is relatively large in size (e.g., 10 cm or more, or 20 cm or more).

[0294] Greater central tension (CT), depth of compression (DOC), and high compressive stress (CS) can be achieved through different ion exchange processes. However, the addition of lithium in aluminosilicate glasses can lower the melting point, softening point, or liquidus viscosity of the glass. By providing a glass-based substrate and / or ceramic-based substrate that includes a first depth of compression and / or a second depth of compression in a range from about 20% to about 25% of the thickness of the substrate, good impact and / or puncture resistance can be achieved. The ratio of the depth of layer (e.g., DOL SP ) to the depth of compression (e.g., DOC) (e.g., 0.08 to 0.25 or 0.18 to 0.25) in combination with the ratio of the compressive stress at the depth of the compressive stress spike to the corresponding maximum compressive stress (e.g., 0.02 to 0.05) can be a characteristic of the compositions of the present disclosure that can be different from other compositions.

[0295] Unless otherwise stated, all compositional components, relationships, and ratios described in this specification are provided in mol%. All scopes disclosed in this specification include any and all scopes and subscopes covered by the broadly disclosed scope, whether or not explicitly stated before or after the disclosure.

[0296] It should also be understood that, as used herein, the terms “the” and “a / an” mean “at least one” and should not be limited to “only one” unless explicitly indicated otherwise. For example, unless the context otherwise explicitly indicates otherwise, reference to “component” includes aspects having two or more such components. Similarly, “a plurality of” is intended to mean “more than one.”

[0297] As used herein, the term “about” means that a quantity, dimension, formulation, parameter, and other quantity and characteristic is not exact and need not be exact, but may be approximate and / or larger or smaller as needed, reflecting tolerances, conversion factors, rounding, measurement errors, and other factors known to those skilled in the art. In this document, a range may be expressed as from “about” one particular value and / or to “about” another particular value. When such a range is expressed, each aspect includes from said one particular value and / or to said other particular value. Similarly, when a value is expressed as an approximation using the antecedent “about,” it should be understood that said particular value forms another aspect. Regardless of whether the numerical or range endpoints in the specification are described as “about,” the numerical or range endpoints are intended to include two aspects: one modified by “about” and one not modified by “about.” It should also be understood that each endpoint of a range is meaningful relative to and independent of the other endpoint.

[0298] As used herein, the terms “significant,” “substantially,” and their variations are intended to indicate that the described feature is equal to or approximately equal to a certain value or description. For example, a “substantially flat” surface is intended to mean a flat or substantially flat surface. Furthermore, as defined above, “substantially similar” is intended to mean that two values ​​are equal or approximately equal. In various respects, “substantially similar” can mean values ​​that differ from each other by approximately 10%, such as values ​​that differ from each other by approximately 5%, or values ​​that differ from each other by approximately 2%.

[0299] Unless otherwise expressly stated, it is not intended to interpret any method described herein as requiring its steps to be performed in a particular order. Therefore, no particular order is intended to be inferred unless the method claims actually describe the order in which the steps are performed or unless the claims or description specifically specify that the steps should be limited to a particular order.

[0300] While various features, elements or steps of aspects can be disclosed using the transitional phrase "comprising," it is to be understood that alternative aspects can be described using the transitional phrases "consisting of" or "consisting essentially of." Thus, for example, an apparatus including A + B + C is implied by an apparatus comprising A + B + C, an apparatus consisting of A + B + C, and an apparatus consisting essentially of A + B + C. As used herein, the terms "comprising" and "including," and variations thereof, are synonymous and are open-ended, unless otherwise indicated.

[0301] The above aspects and features of those aspects can be provided independently or in any combination, without departing from the scope of the disclosure.

[0302] It will be apparent to those skilled in the art that various modifications and variations can be made to the present disclosure without departing from the spirit and scope of the disclosure. Thus, it is intended that the present disclosure cover the modifications and variations of this aspect of the disclosure provided such modifications and variations come within the scope of the appended claims and their equivalents.

Claims

1. A glass-based article comprising a composition, based on an oxide basis of the glass-based article, the composition comprising: greater than or equal to 60 mol% to less than or equal to 69 mol% Si02; greater than or equal to 10 mol% to less than or equal to 18 mol% AI2O3; greater than or equal to 2.3 mol% to less than or equal to 6.9 mol% Li20; greater than or equal to 2.1 mol% to less than or equal to 6.7 mol% Na20; and greater than or equal to 0.25 mol% to less than or equal to 1 mol% K20; and greater than or equal to 1.1 mol% to less than or equal to 9 mol% RO, where RO is the sum of the amounts of MgO, CaO, SrO, BaO, and ZnO, wherein the liquidus viscosity of the composition is greater than or equal to 150 kilopoise.

2. The glass-based article of claim 1, wherein the liquidus viscosity is greater than or equal to 175 kilopoise.

3. The glass-based article of any one of claims 1-2, wherein the composition crystallizes after heating at 1050 °C for 24 hours to have a primary crystalline phase comprising anorthite or a feldspar solid solution.

4. The glass-based article of any one of claims 1-3, wherein the value in mol% of MgO + Li20 - (CaO + SrO + Na20 + K20) is greater than or equal to -4 to less than or equal to -0.

5.

5. The glass-based article of claim 4, wherein the value in mol% of MgO + Li20 - (CaO + SrO + Na20 + K20) is greater than or equal to -1.5 to less than or equal to -1.

0.

6. The glass-based article of any one of claims 1-5, wherein the composition comprises: greater than or equal to 10 mol% to less than or equal to 16 mol% AI2O3; greater than or equal to 0.5 mol% to P2O5; and greater than or equal to 0.5 mol% to less than or equal to 3.6 mol% B2O3.

7. The glass-based article of any one of claims 1-6, wherein the composition comprises: greater than or equal to 2 mol% to less than or equal to 3.6 mol% B2O3.

8. The glass-based article of any of claims 1-7, wherein the volume resistivity is greater than or equal to 2 x 10 15 ohm-centimeters.

9. The glass-based article of claim 8, wherein the volume resistivity is greater than or equal to 1 x 10 16 ohm-centimeters to less than or equal to 1 x 10 17 ohm-centimeters.

10. The glass-based article of any one of claims 1-9, wherein the composition comprises: greater than or equal to 14 mol% to less than or equal to 16 mol% AI2O3.

11. The glass-based article of any one of claims 1-10, wherein the composition comprises: greater than or equal to 60 mol% to less than or equal to 66 mol% Si02; greater than or equal to 14 mol% to less than or equal to 16 mol% AI2O3; greater than or equal to 5 mol% to less than or equal to 6.9 mol% Li20; greater than or equal to 4 mol% to less than or equal to 6 mol% Na20; and greater than or equal to 0.25 mol% to less than or equal to 1 mol% K20. greater than or equal to 0.5 mol% to less than or equal to 3 mol% P2O5; and greater than 0 mol% to less than or equal to 1 mol% TiO2.

12. The glass-based article of any of Claims 1 to 11, wherein the composition comprises: greater than or equal to 6 mol% to less than or equal to 6.7 mol% Li2O; and greater than or equal to 5 mol% to less than or equal to 5.8 mol% Na2O.

13. The glass-based article of any of Claims 1 to 12, wherein: the molar ratio of Li2O / Na2O is greater than or equal to 1.2 to less than or equal to 2.

1.

14. The glass-based article of any of Claims 1 to 13, wherein the glass-based article is substantially free of Ta2O5, HfO2, La2O3, and Y2O3.

15. The glass-based article of any of Claims 1 to 14, wherein the composition is substantially free of ZnO and ZrO2.

16. The glass-based article of any of Claims 1 to 15, further comprising: greater than or equal to 0.1 mol% to less than or equal to 0.5 mol% TiO2; and greater than or equal to 0.1 mol% to less than or equal to 1 mol% K2O.

17. The glass-based article of any of Claims 1 to 16, wherein the composition comprises: greater than or equal to 0.25 mol% to less than or equal to 1 mol% K2O.

18. The glass-based article of any of Claims 1 to 17, wherein the composition comprises: greater than or equal to 1.5 mol% to less than or equal to 3.3 mol% RO.

19. The glass-based article of any of Claims 1 to 18, wherein the composition comprises: greater than or equal to 0.1 mol% to less than or equal to 0.9 mol% MgO.

20. The glass-based article of any of Claims 1 to 19, wherein the composition comprises: greater than or equal to 0.6 mol% to less than or equal to 1.5 mol% SrO.

21. The glass-based article of any of claims 1 to 20, wherein the glass has a K IC fracture toughness greater than or equal to 0.75 MPa-m 0.5 .

22. The glass-based article of any of Claims 1 to 21, further comprising: a compressive stress layer extending from a surface of the glass-based article to a compressive depth, the compressive stress layer comprising a maximum compressive stress; and a central tension region comprising a maximum central tension, wherein the composition corresponds to a material at a center of the glass-based article, and the glass-based article comprises a thickness t.

23. The glass-based article of Claim 22, wherein the maximum compressive stress of the compressive stress layer is greater than or equal to 500 MPa to less than or equal to 1500 MPa.

24. The glass-based article of any of Claims 22 to 23, wherein the maximum central tension of the central tension region is greater than or equal to 50 MPa to less than or equal to 100 MPa.

25. The glass-based article of any of claims 22 to 24, wherein the compressive depth is greater than or equal to 0.15t to less than or equal to 0.25t, wherein t is the thickness of the glass-based article.

26. The glass-based article of any of claims 22 to 25, further comprising a layer depth of one or more alkali metal ions associated with the compressive stress layer, wherein a ratio of the layer depth to the compressive depth is greater than or equal to 0.02 to less than or equal to 0.

08.

27. The glass-based article of any of claims 22 to 26, wherein the compressive stress layer comprises a compressive stress spike extending from the surface of the glass-based article to a depth of the compressive stress spike, and a ratio of a compressive stress at the depth of the compressive stress spike to the maximum compressive stress is greater than or equal to 0.08 to less than or equal to 0.

25.

28. The glass-based article of any of claims 22 to 26, wherein the compressive stress layer comprises a compressive stress spike extending from the surface of the glass-based article to a depth of the compressive stress spike, and the depth of the compressive stress spike is greater than or equal to 3 pm to less than or equal to 10 pm.

29. The glass-based article of any of claims 27 to 28, wherein a stress in the depth of the compressive stress spike is less than or equal to 210 megapascals.

30. The glass-based article of any of claims 22 to 29, wherein a slope of the compressive stress spike is greater than or equal to -220 MPa / pm to less than or equal to -60 MPa / pm.

31. The glass-based article of any of claims 22 to 29, wherein a slope of the compressive stress spike is greater than or equal to -300 MPa / pm to less than or equal to -60 MPa / pm.

32. The glass-based article of any of claims 22 to 31, wherein a slope of a deep region extending from the depth of the compressive stress spike to the compressive depth is greater than or equal to -2.0 MPa / pm to less than or equal to -1.1 MPa / pm.

33. The glass-based article of any of claims 22 to 32, wherein a total stored strain energy in the glass-based article is less than or equal to 90 joules per square meter.

34. The glass-based article of any of claims 22 to 33, wherein the thickness t is greater than or equal to 0.4 mm to less than or equal to 2 mm.

35. A consumer electronic product comprising: a housing having a front surface, a back surface, and side surfaces; electrical components disposed at least partially within the housing, the electrical components including at least a controller, a memory, and a display disposed at or adjacent to the front surface of the housing; and a cover substrate disposed over the display, ​ wherein at least a portion of at least one of the enclosure and the cover substrate comprises the glass-based article of any of claims 1-34.

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