3D Shaping Of Lithium Silicate Glass Ceramic With Residual Glass Phase

Abstract

Glass ceramic compositions having at least a lithium disilicate crystal phase, a petalite crystal phase, and a residual glass phase (e.g., 15-50 wt%) are described. The glass ceramic article can have good mechanical properties. Processes for 3D forming such glass ceramic articles by making glass ceramic preforms and 3D forming them are described. In addition, the composition is capable of chemical tempering to even higher strength glass ceramics, which can be used, for example, in consumer electronic devices.

Description

[0001] This application claims the benefit of priority of U.S. Provisional Application Serial No. 63 / 416,229, filed on October 14, 2022, under 35 U.S.C. § 119, the content of which is incorporated herein by reference in its entirety. BACKGROUND OF THE INVENTION TECHNICAL FIELD

[0002] This specification generally relates to glass-ceramic articles, and more particularly to a 3D forming method of glass-ceramics for producing glass-ceramic articles. BACKGROUND OF THE INVENTION

[0004] Portable electronic devices require high-strength glass. Currently, several materials are used in the market, such as: glass, zirconia, plastics, metals, and glass-ceramics.

[0005] Glass-ceramics have certain advantages over other materials, but it may be difficult to form glass-ceramics into various shapes with the properties required for high-strength portable devices. Therefore, there is a need for glass-ceramic articles with improved properties and a manufacturing method for glass-ceramic articles. SUMMARY OF THE INVENTION

[0006] A first aspect of the present disclosure may relate to a method of forming a glass-ceramic article, the method comprising: three-dimensionally (3D) forming a glass-ceramic preform to produce a glass-ceramic article having a lithium disilicate crystal phase, a spodumene crystal phase, and a residual glass phase. Before 3D forming, the glass-ceramic preform contains a lithium disilicate crystal phase, a spodumene crystal phase, and a residual glass phase. After 3D forming, the glass-ceramic article contains a higher concentration of the residual glass phase than the glass-ceramic preform.

[0007] A second aspect of the present disclosure may include the first aspect, wherein, before 3D forming, the concentration of the residual glass phase in the glass-ceramic preform is 10 wt% to 50 wt%.

[0008] A third aspect of the present disclosure may include any one of the first or second aspects, wherein, after 3D forming, the glass-ceramic article has a residual glass phase of 15 wt% to 50 wt%.

[0009] A fourth aspect of the present disclosure may include any one of the first to third aspects, wherein, after 3D forming, the glass-ceramic article has a residual glass phase of 20 wt% to 50 wt%.

[0010] The fifth aspect of the present disclosure may include any one of the first to fourth aspects, wherein the concentration of the residual glass phase in the glass-ceramic article is at least 5% greater than the concentration of the residual glass phase in the glass-ceramic preform.

[0011] The sixth aspect of the present disclosure may include any one of the first to fifth aspects, wherein, prior to 3D shaping, the combined concentration of the lithium disilicate crystal phase and the spodumene crystal phase contained in the glass-ceramic preform is 50 wt% to 90 wt%.

[0012] The seventh aspect of the present disclosure may include any one of the first to sixth aspects, wherein the glass-ceramic article is clear and transparent.

[0013] The eighth aspect of the present disclosure may include any one of the first to seventh aspects, wherein the glass-ceramic article contains Na 2 O, K 2 O, or both of them.

[0014] The ninth aspect of the present disclosure may include the eighth aspect, wherein the molar concentrations of Na 2 O and K 2 O in the glass-ceramic article are greater than or equal to 0.5 mol% to 9 mol%.

[0015] The tenth aspect of the present disclosure may include any one of the eighth or ninth aspects, wherein the glass-ceramic article has a molar ratio of [Na 2 O + K 2 O] / [Al 2 O 3 of 0.1 to 5.

[0016] The eleventh aspect of the present disclosure may include any one of the eighth to tenth aspects, wherein the glass-ceramic article has a molar ratio of [Na 2 O + K 2 O] / [ZrO 2 of 0.3 to 5.

[0017] The twelfth aspect of the present disclosure may include any one of the first to eleventh aspects, wherein the glass-ceramic article contains one or more metal oxides selected from the group consisting of: ZnO, MgO, CaO, BaO, SrO, and combinations thereof.

[0018] The thirteenth aspect of the present disclosure may include the twelfth aspect, wherein the glass-ceramic article has a molar ratio of [MgO + CaO + BaO + SrO + ZnO] / [Al 2 O 3 of 0.05 to 5.

[0019] The 14th aspect of the present disclosure may include any one of the 12th or 13th aspects, wherein the glass-ceramic article has a molar ratio of [MgO + CaO + BaO + SrO + ZnO] / [ZrO 2 of 0.1 to 5.

[0020] The 15th aspect of the present disclosure may include any one of the 1st to 14th aspects, wherein the glass-ceramic article contains B 2 O 3 .

[0021] The 16th aspect of the present disclosure may include the 15th aspect, wherein the glass-ceramic article contains 0 mol% to 10 mol% B 2 O 3 .

[0022] The 17th aspect of the present disclosure may include any one of the 1st to 16th aspects, wherein the composition of the glass-ceramic article contains SiO 2 , Al 2 O 3 , Li 2 O, P 2 O 5 and ZrO 2 .

[0023] The 18th aspect of the present disclosure may include the 17th aspect, wherein the composition of the glass-ceramic article contains: 55 mol% to 80 mol% SiO 2 , 1 mol% to 15 mol% Al 2 O 3 , 10 mol% to 40 mol% Li 2 O, 0.2 mol% to 4 mol% P 2 O 5 , and 0.1 mol% to 10 mol% ZrO 2 .

[0024] The 19th aspect of the present disclosure may include any one of the 17th or 18th aspects, wherein the composition of the glass-ceramic article contains: 68 mol% to 71 mol% SiO 2 , 3 mol% to 5 mol% Al 2 O 3 , 18 mol% to 25 mol% Li 2 O, 0.6 mol% to 1 mol% P 2 O 5 , and 1.5 mol% to 3 mol% ZrO 2 .

[0025] The 20th aspect of the present disclosure may include any one of the 17th to 19th aspects, wherein the composition of the glass-ceramic article comprises: 68.2 mol% to 70.4 mol% SiO 2 , 3.5 mol% to 4.5 mol% Al 2 O 3 , 20 mol% to 23 mol% Li 2 O, 0.8 mol% to 1 mol% P 2 O 5 , and 1.6 mol% to 3 mol% ZrO 2 .

[0026] The 21st aspect of the present disclosure may include any one of the 17th to 20th aspects, wherein the composition of the glass-ceramic article further comprises 0 mol% to 5 mol% Na 2 O, 0 mol% to 4 mol% K 2 O, or both of them.

[0027] The 22nd aspect of the present disclosure may include the 21st aspect, wherein the composition of the glass-ceramic article comprises 0.5 mol% to 2 mol% Na 2 O, 0.5 mol% to 1.2 mol% K 2 O, or a combination of these.

[0028] The 23rd aspect of the present disclosure may include any one of the 17th to 22nd aspects, wherein the composition of the glass-ceramic article comprises: less than 0.5 mol% of Na 2 O and K 2 O, and further comprises one or more of the following: 0 mol% to 8 mol% ZnO, 0 mol% to 8 mol% MgO, 0 mol% to 8 mol% CaO, 0 mol% to 8 mol% SrO, or 0 mol% to 8 mol% BaO, wherein the total concentration of ZnO, MgO, CaO, SrO, and BaO is greater than or equal to 0.5 mol%.

[0029] The 24th aspect of the present disclosure may include any one of the 17th to 23rd aspects, wherein the composition of the glass-ceramic article further comprises one or more of the following: Fe 2 O 3 , SnO 2 , HfO 2 , TiO 2 , or a combination of these.

[0030] The 25th aspect of the present disclosure may include any one of the 1st to 24th aspects, wherein the glass-ceramic preform is ceramified before 3D forming to produce the glass-ceramic article.

[0031] The 26th aspect of the present disclosure may include any one of the 1st to 25th aspects, wherein the total concentration of the crystalline phase in the glass-ceramic preform before 3D forming is the maximum total concentration of the crystalline phases of the composition of the glass-ceramic preform.

[0032] The 27th aspect of the present disclosure may include any one of the 1st to 26th aspects, and further includes preparing a glass-ceramic preform before 3D forming the glass-ceramic preform to produce a glass-ceramic article.

[0033] The 28th aspect of the present disclosure may include the 27th aspect, wherein preparing the glass-ceramic preform includes: ceramizing a precursor glass to produce a glass-ceramic preform comprising a lithium disilicate crystalline phase, a spodumene crystalline phase, and a residual glass phase, wherein the concentration of the residual glass phase in the glass-ceramic preform is 10 wt% to 50 wt%.

[0034] The 29th aspect of the present disclosure may include the 28th aspect, wherein ceramizing the precursor glass to produce the glass-ceramic preform includes: heating the precursor glass to a nucleation temperature of 500 °C to 650 °C; maintaining the precursor glass at the nucleation temperature for a first period of 1 minute to 600 minutes; increasing the temperature of the precursor glass to a crystallization temperature of 680 °C to 800 °C; and maintaining the precursor glass at the crystallization temperature for a second period of 1 second to 600 minutes to produce the glass-ceramic preform.

[0035] The 30th aspect of the present disclosure may include the 29th aspect, and further includes cooling the glass-ceramic preform from a first temperature to room temperature.

[0036] The 31st aspect of the present disclosure may include any one of the 27th to 30th aspects, wherein after ceramizing the precursor glass to produce the glass-ceramic preform, the total concentration of the crystalline phases of the glass-ceramic preform differs from the total concentration of the crystalline phases in the glass-ceramic article after 3D forming by within 50%.

[0037] The 32nd aspect of the present disclosure may include any one of the 1st to 31st aspects, wherein the three-dimensional shape of the glass-ceramic article is different from the shape of the glass-ceramic preform.

[0038] The 33rd aspect of the present disclosure may include any one of the 1st to 32nd aspects, wherein 3D forming the glass-ceramic preform may include thermo-mechanical shaping.

[0039] The 34th aspect of the present disclosure may include any one of the 1st to 33rd aspects, wherein 3D forming the glass-ceramic preform includes: heating the glass-ceramic preform to a forming temperature; after heating, pressing the glass-ceramic preform into a mold for a period of time to produce a glass-ceramic article; and cooling the glass-ceramic article.

[0040] The 35th aspect of the present disclosure may include the 34th aspect, wherein the forming temperature is 650 °C to 850 °C.

[0041] The 36th aspect of the present disclosure may include any one of the 34th or 35th aspects, wherein the glass-ceramic preform is pressed into the mold with a pressing pressure of 0.001 MPa to 0.9 MPa.

[0042] The 37th aspect of the present disclosure may include any one of the 34th to 36th aspects, wherein the mold is a graphite mold.

[0043] The 38th aspect of the present disclosure may include any one of the 34th to 37th aspects, wherein heating and pressing the glass-ceramic preform increases the concentration of the residual glass phase in the glass-ceramic article, as compared to the glass-ceramic preform.

[0044] The 39th aspect of the present disclosure may include any one of the 1st to 38th aspects, wherein the glass-ceramic article includes a haze of less than 0.20 measured at a thickness of 0.8 mm.

[0045] The 40th aspect of the present disclosure may include any one of the 1st to 39th aspects, wherein the overall volume change of the glass-ceramic article during the forming process is less than 1% of the glass-ceramic preform before 3D forming.

[0046] The 41st aspect of the present disclosure may include any one of the 1st to 40th aspects, wherein the method does not include any active method steps after 3D forming aimed at further increasing the crystallinity of the glass-ceramic article.

[0047] The 42nd aspect of the present disclosure may include any one of the 1st to 41st aspects, and further includes strengthening the glass-ceramic article after 3D forming to produce a strengthened glass-ceramic article having a compressive stress layer extending from the first surface of the glass-ceramic article to a compressive depth.

[0048] The 43rd aspect of the present disclosure may include the 42nd aspect, wherein the strengthened glass-ceramic article has a compressive stress of the compressive stress layer greater than or equal to 200 MPa.

[0049] The 44th aspect of the present disclosure may include any one of the 42nd or 43rd aspects, wherein the compressive depth of the tempered glass article is 0*t to 0.3*t, where t is the thickness of the tempered glass-ceramic article.

[0050] The 45th aspect of the present disclosure may include any one of the 42nd to 44th aspects, wherein the tempered glass-ceramic article has a compressive depth greater than or equal to 10% of the thickness of the tempered glass-ceramic article, a central tension greater than or equal to 40 MPa, or both.

[0051] The 46th aspect of the present disclosure may include any one of the 42nd to 45th aspects, wherein strengthening the glass-ceramic article includes ion-exchanging the glass-ceramic article to produce a tempered glass-ceramic article.

[0052] The 47th aspect of the present disclosure may include the 46th aspect, wherein ion-exchanging the glass-ceramic article causes the weight per unit volume of the glass-ceramic article to increase by greater than or equal to 0.05%.

[0053] The 48th aspect of the present disclosure may relate to a glass-ceramic article comprising a lithium disilicate crystal phase, a spodumene crystal phase, and a residual glass phase, and the glass-ceramic article is prepared by the following process: 3D shaping a glass-ceramic preform to produce the glass-ceramic article, wherein, before 3D shaping, the glass-ceramic preform comprises a lithium disilicate crystal phase, a spodumene crystal phase, and a residual glass phase, and after 3D shaping, the concentration of the residual glass phase comprised in the glass-ceramic article is greater than the concentration of the residual glass phase in the glass-ceramic preform.

[0054] The 49th aspect of the present disclosure may include the 48th aspect, wherein 3D shaping the glass-ceramic preform to produce the glass-ceramic article includes thermo-mechanical shaping.

[0055] The 50th aspect of the present disclosure may include the 49th aspect, wherein 3D shaping the glass-ceramic preform produces a glass-ceramic article, wherein the concentration of the residual glass phase in the glass-ceramic article is at least 5% greater than the concentration of the residual glass phase in the glass-ceramic preform.

[0056] The 51st aspect of the present disclosure may include any one of the 48th to 50th aspects, wherein 3D shaping the glass-ceramic preform includes: heating the glass-ceramic preform to a shaping temperature; after heating, pressing the glass-ceramic preform into a mold for a period of time to produce the glass-ceramic article; and cooling the glass-ceramic article.

[0057] The 52nd aspect of the present disclosure may include the 51st aspect, wherein the forming temperature is 650 °C to 850 °C, and the pressing pressure during the pressing process is 0.001 MPa to 0.9 MPa.

[0058] The 53rd aspect of the present disclosure may include any one of the 48th to 52nd aspects, wherein, during the 3D forming process, the shrinkage exhibited by the glass-ceramic article is less than 1% of the total volume of the glass-ceramic preform.

[0059] The 54th aspect of the present disclosure may include any one of the 48th to 53rd aspects, and further includes strengthening the glass-ceramic article after 3D forming to produce a strengthened glass-ceramic article having a compressive stress layer extending from the first surface of the glass-ceramic article to a compressive depth.

[0060] The 55th aspect of the present disclosure may include the 54th aspect, wherein the strengthened glass-ceramic article has a compressive stress of the compressive stress layer greater than or equal to 200 MPa.

[0061] The 56th aspect of the present disclosure may include any one of the 54th or 55th aspects, wherein the compressive depth of the strengthened glass-ceramic article is 0*t to 0.3*t, where t is the thickness of the strengthened glass-ceramic article.

[0062] The 57th aspect of the present disclosure may include any one of the 54th to 56th aspects, wherein the strengthened glass-ceramic article has a compressive depth greater than or equal to 10% of the thickness of the strengthened glass-ceramic article, a central tension greater than or equal to 40 MPa, or both.

[0063] The 58th aspect of the present disclosure may include any one of the 54th to 57th aspects, wherein strengthening the glass-ceramic article includes ion-exchanging the glass-ceramic article to produce a strengthened glass-ceramic article.

[0064] The 59th aspect of the present disclosure may include the 58th aspect, wherein ion-exchanging the glass-ceramic article causes the weight per unit volume of the glass-ceramic article to increase by greater than or equal to 0.05%.

[0065] The 60th aspect of the present disclosure may include any one of the 48th to 59th aspects, wherein the glass-ceramic article has a refractive index of 1.5 to 1.6 for light with a wavelength of 589.3 nm.

[0066] The 61st aspect of the present disclosure may include any one of the 48th to 60th aspects, wherein the glass-ceramic article includes a haze less than 0.20 measured at a thickness of 0.8 mm.

[0067] The 62nd aspect of the present disclosure may include any one of the 48th to 61st aspects, wherein, when measured at a thickness of 0.8 mm, for electromagnetic radiation wavelengths from 450 nm to 800 nm, the glass-ceramic article includes an optical transmittance greater than 85%.

[0068] The 63rd aspect of the present disclosure may include any one of the 48th to 62nd aspects, and includes an electronic device having a transparent surface that includes the glass-ceramic article of any one of the 48th to 62nd aspects.

[0069] The 64th aspect of the present disclosure may include the 63rd aspect, wherein the glass-ceramic article has a thickness of 0.3 mm to 1 mm.

[0070] The 65th aspect of the present disclosure may include either the 63rd or 64th aspect, wherein the electronic device is a consumer electronic device.

[0071] The 66th aspect of the present disclosure may include a glass-ceramic article containing a lithium disilicate crystal phase, a spodumene crystal phase, and a residual glass phase, wherein the concentration of the residual glass phase is 15 wt% to 50 wt% and the glass-ceramic article has one or more of the following: molar ratio [Na 2 O + K 2 O] / [Al 2 O 3 is 0.1 to 5, molar ratio [Na 2 O + K 2 O] / [ZrO 2 is 0.3 to 5, molar ratio [MGO + CaO + BaO + SrO + ZnO] / [Al 2 O 3 is 0.05 to 5, molar ratio [MgO + CaO + BaO + SrO + ZnO] / [ZrO 2 is 0.1 to 5, or a combination thereof.

[0072] The 67th aspect of the present disclosure may include the 66th aspect, wherein the concentration of the lithium disilicate crystal phase and the spodumene crystal phase is greater than any other crystal phase in the glass-ceramic article.

[0073] The 68th aspect of the present disclosure may include either the 66th or 67th aspect, wherein the glass-ceramic article has a concentration of the residual glass phase of 20 wt% to 50 wt%.

[0074] The 69th aspect of the present disclosure may include any one of the 66th to 68th aspects, wherein, before 3D forming, the combined concentration of the lithium disilicate crystal phase and the spodumene crystal phase contained in the glass-ceramic preform is 50 wt% to 90 wt%.

[0075] The 70th aspect of the present disclosure may include any one of the 66th to 69th aspects, wherein the glass-ceramic article is clear and transparent.

[0076] The 71st aspect of the present disclosure may include any one of the 66th to 70th aspects, wherein the glass-ceramic article contains Na 2 O, K 2 O, or both of them.

[0077] The 72nd aspect of the present disclosure may include the 71st aspect, wherein the molar concentration of Na 2 O and K 2 O in the glass-ceramic article is greater than or equal to 0.5 mol% to 9 mol%.

[0078] The 73rd aspect of the present disclosure may include any one of the 71st or 72nd aspects, wherein the glass-ceramic article has a molar ratio of [Na 2 O + K 2 O] / [Al 2 O 3 of 0.1 to 5.

[0079] The 74th aspect of the present disclosure may include any one of the 71st to 73rd aspects, wherein the glass-ceramic article has a molar ratio of [Na 2 O + K 2 O] / [ZrO 2 of 0.3 to 5.

[0080] The 75th aspect of the present disclosure may include any one of the 66th to 74th aspects, wherein the glass-ceramic article contains one or more metal oxides selected from the group consisting of: ZnO, MgO, CaO, BaO, SrO, and combinations thereof.

[0081] The 76th aspect of the present disclosure may include the 75th aspect, wherein the glass-ceramic article has a molar ratio of [MgO + CaO + BaO + SrO + ZnO] / [Al 2 O 3 of 0.05 to 5.

[0082] The 77th aspect of the present disclosure may include any one of the 75th or 76th aspects, wherein the glass-ceramic article has a molar ratio of [Mg + CaO + BaO + SrO + ZnO] / [ZrO 2 of 0.1 to 5.

[0083] The 78th aspect of the present disclosure may include any one of the 66th to 77th aspects, wherein the glass-ceramic article contains B 2 O 3 .

[0084] The 79th aspect of the present disclosure may include the 78th aspect, wherein the glass-ceramic article contains greater than 0 mol% to 10 mol% B 2 O 3 .

[0085] The 80th aspect of the present disclosure may include any one of the 66th to 79th aspects, wherein the composition of the glass-ceramic article contains SiO 2 , Al 2 O 3 , Li 2 O, P 2 O 5 and ZrO 2 .

[0086] The 81st aspect of the present disclosure may include the 80th aspect, wherein the composition of the glass-ceramic article contains: 55 mol% to 80 mol% SiO 2 , 1 mol% to 15 mol% Al 2 O 3 , 10 mol% to 40 mol% Li 2 O, 0.2 mol% to 4 mol% P 2 O 5 , and 0.1 mol% to 10 mol% ZrO 2 .

[0087] The 82nd aspect of the present disclosure may include any one of the 80th or 81st aspects, wherein the composition of the glass-ceramic article contains: 68 mol% to 71 mol% SiO 2 , 3 mol% to 5 mol% Al 2 O 3 , 18 mol% to 25 mol% Li 2 O, 0.6 mol% to 1 mol% P 2 O 5 , and 1.5 mol% to 3 mol% ZrO 2 .

[0088] The 83rd aspect of the present disclosure may include any one of the 80th to 82nd aspects, wherein the composition of the glass-ceramic article comprises: 68.2 mol% to 70.4 mol% SiO 2 , 3.5 mol% to 4.5 mol% Al 2 O 3 , 20 mol% to 23 mol% Li 2 O, 0.8 mol% to 1 mol% P 2 O 5 , and 1.6 mol% to 3 mol% ZrO 2 .

[0089] The 84th aspect of the present disclosure may include any one of the 80th to 83rd aspects, wherein the composition of the glass-ceramic article further comprises 0 mol% to 5 mol% Na 2 O, 0 mol% to 4 mol% K 2 O, or both of them.

[0090] The 85th aspect of the present disclosure may include the 84th aspect, wherein the composition of the glass-ceramic article comprises 0.5 mol% to 2 mol% Na 2 O, 0.5 mol% to 1.2 mol% K 2 O, or a combination of these.

[0091] The 86th aspect of the present disclosure may include any one of the 84th or 85th aspects, wherein the composition of the glass-ceramic article comprises: less than 0.5 mol% of Na 2 O and K 2 O, and further comprises one or more of the following: 0 mol% to 8 mol% ZnO, 0 mol% to 8 mol% MgO, 0 mol% to 8 mol% CaO, 0 mol% to 8 mol% SrO, or 0 mol% to 8 mol% BaO, wherein the total concentration of ZnO, MgO, CaO, SrO, and BaO is greater than or equal to 0.5 mol%.

[0092] The 87th aspect of the present disclosure may include any one of the 80th to 86th aspects, wherein the composition of the glass-ceramic article further comprises one or more of the following: Fe 2 O 3 , SnO 2 , HfO 2 , TiO 2 , or a combination of these.

[0093] The 88th aspect of the present disclosure may include any one of the 66th to 87th aspects, wherein the composition of the glass-ceramic article comprises, consists of, or consists essentially of: 55 mol% to 80 mol% SiO 2, 1 mol% to 15 mol% Al 2 O 3 , 10 mol% to 40 mol% Li 2 , 0.2 mol% to 4 mol% P 2 O 5 , 0 mol% to 10 mol% B 2 O 3 , 0.1 mol% to 10 mol% ZrO 2 , 0 mol% to 5 mol% Na 2 O, 0 mol% to 4 mol% K 2 O, 0 mol% to 8 mol% MgO, 0 mol% to 8 mol% CaO, 0 mol% to 8 mol% SrO, 0 mol% to 8 mol% BaO, 0 mol% to 8 mol% ZnO, 0 mol% to 0.5 mol% Fe 2 O 3 , 0 mol% to 0.5 mol% HfO 2 , 0 mol% to 0.5 mol% SnO 2 , and 0 mol% to 2 mol% TiO 2 .

[0094] The 89th aspect of the present disclosure may include the 88th aspect, wherein the composition of the glass-ceramic article comprises: 68 mol% to 71 mol% SiO 2 , 3 mol% to 5 mol% Al 2 O 3 , 18 mol% to 25 mol% Li 2 O, 0.6 mol% to 1 mol% P 2 O 5 , 1.5 mol% to 3 mol% ZrO 2 , 0.5 mol% to 2 mol% Na 2 O, 0.5 mol% to 2 mol% K 2 O, 0 mol% to 0.1 mol% CaO, 0 mol% to 0.1 mol% Fe 2 O 3 , 0 mol% to 0.1 mol% HfO 2 , 0 mol% to 0.0.5 mol% SnO 2 , and 0 mol% to 2 mol% TiO 2 .

[0095] The 90th aspect of the present disclosure may include any one of the 66th to 89th aspects, wherein the glass-ceramic article is a component of an electronic device.

[0096] The 91st aspect of the present disclosure may include the 90th aspect, wherein the glass-ceramic article is a transparent cover plate for an electronic device.

[0097] The 92nd aspect of the present disclosure may include any one of the 66th to 91st aspects, wherein the glass-ceramic article has a Young's modulus of 90 GPa to 110 GPa.

[0098] The 93rd aspect of the present disclosure may include any one of the 66th to 92nd aspects, wherein the glass-ceramic article has a shear modulus of 35 GPa to 50 GPa.

[0099] The 94th aspect of the present disclosure may include any one of the 66th to 93rd aspects, wherein the glass-ceramic article has a Poisson's ratio of 0.19 to 0.24.

[0100] The 95th aspect of the present disclosure may include any one of the 66th to 94th aspects, wherein the glass-ceramic article has a fracture toughness of 1.0 MPa / m 0.5 to 2.0 MPa / m 0.5 of fracture toughness.

[0101] The 96th aspect of the present disclosure may include any one of the 66th to 95th aspects, wherein the glass-ceramic article has a stress optical coefficient (SOC) of 2.60 nm / mm / MPa to 2.75 nm / mm / MPa.

[0102] The 97th aspect of the present disclosure may include any one of the 66th to 96th aspects, wherein the glass-ceramic article has a refractive index of 1.5 to 1.6 for light with a wavelength of 589.3 nm.

[0103] The 98th aspect of the present disclosure may include any one of the 66th to 97th aspects, wherein the glass-ceramic article is strengthened and has a compressive stress of greater than or equal to 200 MPa.

[0104] The 99th aspect of the present disclosure may include any one of the 66th to 98th aspects, wherein the glass-ceramic article is strengthened and has a central tension of greater than or equal to 30 MPa in a thickness range of 0.5 mm to 0.6 mm.

[0105] The 100th aspect of the present disclosure may include any one of the 66th to 99th aspects, wherein the glass-ceramic article is strengthened and has a compressive depth of greater than or equal to 10% of the thickness of the glass-ceramic article or greater than or equal to 80 microns.

[0106] The 101st aspect of the present disclosure may include any one of the 66th to 100th aspects, wherein the glass-ceramic article is strengthened and has a compressive depth of 0*t to 0.3*t, where t is the thickness of the glass-ceramic article.

[0107] The 102nd aspect of the present disclosure may include any one of the 66th to 101st aspects, wherein the glass-ceramic article has a stress that delays less than 30 nm per mm of the thickness of the glass-ceramic article.

[0108] The 103rd aspect of the present disclosure may include any one of the 66th to 102nd aspects, wherein the glass-ceramic article includes a stress that delays less than 25 nm per mm of the thickness of the glass-ceramic article.

[0109] The 104th aspect of the present disclosure may include any one of the 66th to 103rd aspects, wherein the haze of the glass-ceramic article is less than 0.0994t + 0.12, in percentage (%), where t is the thickness of the glass-ceramic article in mm;

[0110] The 105th aspect of the present disclosure may include any one of the 66th to 104th aspects, wherein the glass-ceramic article has an optical transmittance greater than 0.91×10(2 - 0.03t) for electromagnetic radiation with wavelengths from 450 nm to 800 nm, in percentage (%), where t is the thickness of the glass-ceramic article in mm.

[0111] The 106th aspect of the present disclosure may include any one of the 66th to 105th aspects, wherein the glass-ceramic article includes a haze less than 0.20 measured at a thickness of 0.8 mm.

[0112] The 107th aspect of the present disclosure may include any one of the 66th to 106th aspects, wherein, when measured at a thickness of 0.8 mm, for electromagnetic radiation wavelengths from 450 nm to 800 nm, the glass-ceramic article includes an optical transmittance greater than 85%.

[0113] The 108th aspect of the present disclosure may include any one of the 66th to 107th aspects, wherein the glass-ceramic article has a thickness of 0.3 mm to 1 mm.

[0114] The 109th aspect of the present disclosure may include any one of the 66th to 108th aspects, wherein the glass-ceramic article is a component of an electronic device.

[0115] The 110th aspect of the present disclosure may include the 109th aspect, wherein the glass-ceramic article is a clear and transparent cover plate for an electronic device.

[0116] The 111th aspect of the present disclosure may include any one of the 66th to 110th aspects, including an electronic device having a transparent surface, the transparent surface including a glass-ceramic article of any one of the 66th to 110th aspects.

[0117] The 112th aspect of the present disclosure may include the 111th aspect, wherein the glass-ceramic article has a thickness of 0.3 mm to 1 mm.

[0118] The 113th aspect of the present disclosure may include any one of the 111th or 112th aspects, wherein the electronic device is a consumer electronic device.

[0119] The 114th aspect of the present disclosure may include a glass-ceramic article including a lithium disilicate crystal phase, a spodumene crystal phase, and a residual glass phase, wherein the concentration of the residual glass phase is 15 wt% to 50 wt%. The glass-ceramic article has a Young's modulus of 90 GPa to 110 GPa, a shear modulus of 35 GPa to 50 GPa, and a fracture toughness of 1.0 MPa / m 0.5 to 2.0 MPa / m 0.5 of the fracture toughness.

[0120] The 115th aspect of the present disclosure may include the 114th aspect, wherein the glass-ceramic article has a Poisson's ratio of 0.19 to 0.24.

[0121] The 116th aspect of the present disclosure may include any one of the 114th or 115th aspects, wherein the glass-ceramic article has a stress optical coefficient (SOC) of 2.60 nm / mm / MPa to 2.75 nm / mm / MPa.

[0122] The 117th aspect of the present disclosure may include any one of the 114th to 116th aspects, wherein the glass-ceramic article has a refractive index of 1.5 to 1.6 for light with a wavelength of 589.3 nm.

[0123] The 118th aspect of the present disclosure may include any one of the 114th to 117th aspects, wherein the glass-ceramic article is strengthened and has a compressive stress of greater than or equal to 200 MPa.

[0124] The 119th aspect of the present disclosure may include any one of the 114th to 118th aspects, wherein the glass-ceramic article is strengthened and has a central tension of greater than or equal to 30 MPa in a thickness range of 0.5 mm to 0.6 mm.

[0125] The 120th aspect of the present disclosure may include any one of the 114th to 119th aspects, wherein the glass-ceramic article is strengthened and has a compressive depth greater than or equal to 10% of the thickness of the glass-ceramic article or greater than or equal to 80 microns.

[0126] The 121st aspect of the present disclosure may include any one of the 114th aspects, wherein the glass-ceramic article has a molar ratio of [Na 2 O + K 2 O] / [Al 2 O 3 of 0.1 to 5.

[0127] The 122nd aspect of the present disclosure may include any one of the 114th to 121st aspects, wherein the glass-ceramic article has a molar ratio of [Na 2 O + K 2 O] / [ZrO 2 of 0.3 to 5.

[0128] The 123rd aspect of the present disclosure may include any one of the 114th to 122nd aspects, wherein the glass-ceramic article has a molar ratio of [MgO + CaO + BaO + SrO + ZnO] / [Al 2 O 3 of 0.05 to 5.

[0129] The 124th aspect of the present disclosure may include any one of the 114th to 123rd aspects, wherein the glass-ceramic article has a molar ratio of [MGO + CaO + BaO + SrO + ZnO] / [ZrO 2 of 0.1 to 5.

[0130] The 125th aspect of the present disclosure may include any one of the 114th to 124th aspects, wherein the glass-ceramic article is strengthened and has a compressive depth of 0*t to 0.3*t, where t is the thickness of the glass-ceramic article.

[0131] The 126th aspect of the present disclosure may include any one of the 114th to 125th aspects, wherein the glass-ceramic article has a stress that is less than 30 nm of delay per mm of the thickness of the glass-ceramic article.

[0132] The 127th aspect of the present disclosure may include any one of the 114th to 126th aspects, wherein the glass-ceramic article includes a stress that is less than 25 nm of delay per mm of the thickness of the glass-ceramic article.

[0133] The 128th aspect of the present disclosure may include any one of the 114th to 127th aspects, wherein the haze of the glass-ceramic article is less than 0.0994t + 0.12, in percentage (%), where t is the thickness of the glass-ceramic article, in mm.

[0134] The 129th aspect of the present disclosure may include any one of the 114th to 128th aspects, wherein the glass-ceramic article has an optical transmittance greater than 0.91×10^(2 - 0.03t) for electromagnetic radiation with wavelengths from 450 nm to 800 nm, in percentage (%), where t is the thickness of the glass-ceramic article, in mm.

[0135] The 130th aspect of the present disclosure may include any one of the 114th to 129th aspects, wherein the glass-ceramic article includes a haze less than 0.20 measured at a thickness of 0.8 mm.

[0136] The 131st aspect of the present disclosure may include any one of the 114th to 130th aspects, wherein, when measured at a thickness of 0.8 mm, for electromagnetic radiation wavelengths from 450 nm to 800 nm, the glass-ceramic article includes an optical transmittance greater than 85%.

[0137] The 132nd aspect of the present disclosure may include any one of the 114th to 131st aspects, wherein the glass-ceramic article has a thickness of 0.3 mm to 1 mm.

[0138] The 133rd aspect of the present disclosure may include any one of the 114th to 132nd aspects, wherein the glass-ceramic article includes a component of an electronic device.

[0139] The 134th aspect of the present disclosure may include any one of the 114th to 133rd aspects, wherein the glass-ceramic article is a transparent cover plate for an electronic device.

[0140] The 135th aspect of the present disclosure may include any one of the 114th to 134th aspects, including an electronic device having a transparent surface that includes the glass-ceramic article of any one of the 114th to 134th aspects.

[0141] The 136th aspect of the present disclosure may include the 135th aspect, wherein the glass-ceramic article has a thickness of 0.3 mm to 1 mm.

[0142] The 137th aspect of the present disclosure may include any one of the 135th or 136th aspects, wherein the electronic device is a consumer electronic device.

[0143] The 138th aspect of the present disclosure may include a glass-ceramic article comprising a first surface, a second surface opposite the first surface, a lithium disilicate crystal phase, a spodumene crystal phase, a residual glass phase, and a compressive stress layer extending from the first surface to a depth of compression (DOC), wherein the compressive stress of the compressive stress layer is greater than or equal to 200 MPa, the DOC is greater than or equal to 10% of the thickness of the glass-ceramic article, and the concentration of the residual glass phase is 15 wt% to 50 wt%.

[0144] The 139th aspect of the present disclosure may include the 138th aspect, wherein the glass-ceramic article has a Young's modulus of 90 GPa to 110 GPa.

[0145] The 140th aspect of the present disclosure may include any one of the 138th or 139th aspects, wherein the glass-ceramic article has a shear modulus of 35 GPa to 50 GPa.

[0146] The 141st aspect of the present disclosure may include any one of the 138th to 140th aspects, wherein the glass-ceramic article has a Poisson's ratio of 0.19 to 0.24.

[0147] The 142nd aspect of the present disclosure may include any one of the 138th to 141st aspects, wherein the glass-ceramic article has a fracture toughness as follows: 1.0 MPa / m 0.5 to 2.0 MPa / m 0.5 1.1 MPa / m 0.5 to 1.3 MPa / m 0.5 or 1.12 MPa / m 0.5 to 1.22 MPa / m 0.5 .

[0148] The 143rd aspect of the present disclosure may include any one of the 138th to 142nd aspects, wherein the glass-ceramic article has a stress optical coefficient (SOC) of 2.60 nm / mm / MPa to 2.75 nm / mm / MPa.

[0149] The 144th aspect of the present disclosure may include any one of the 138th to 143rd aspects, wherein the glass-ceramic article has a refractive index of 1.5 to 1.6 for light with a wavelength of 589.3 nm.

[0150] The 145th aspect of the present disclosure may include any one of the 138th to 144th aspects, wherein the glass-ceramic article has a thickness of 0.3 mm to 1.0 mm.

[0151] The 146th aspect of the present disclosure may include any one of the 138th to 145th aspects, wherein the glass-ceramic article has a central tension of 30 MPa or more.

[0152] The 147th aspect of the present disclosure may include any one of the 138th to 146th aspects, wherein the glass-ceramic article has one or more of the following: a molar ratio of [Na 2 O + K 2 O] / [Al 2 O 3 of 0.1 to 5, a molar ratio of [Na 2 O + K 2 O] / [ZrO 2 of 0.3 to 5, a molar ratio of [MgO + CaO + BaO + SrO + ZnO] / [Al 2 O 3 of 0.05 to 5, a molar ratio of [MgO + CaO + BaO + SrO + ZnO] / [ZrO 2 of 0.1 to 5, or a combination thereof.

[0153] The 148th aspect of the present disclosure may include any one of the 138th to 147th aspects, wherein the glass-ceramic article includes a component of an electronic device.

[0154] The 149th aspect of the present disclosure may include the 148th aspect, wherein the glass-ceramic article is a transparent cover plate for an electronic device.

[0155] The 150th aspect of the present disclosure may include any one of the 138th to 149th aspects, including an electronic device including a transparent surface, the transparent surface including the glass-ceramic article of any one of the 138th to 149th aspects.

[0156] The 151st aspect of the present disclosure may include the 150th aspect, wherein the glass-ceramic article has a thickness of 0.3 mm to 1 mm.

[0157] The 152nd aspect of the present disclosure may include any one of the 150th to 151st aspects, wherein the electronic device is a consumer electronic device.

[0158] The 153rd aspect of the present disclosure may include a glass-ceramic article including a lithium disilicate crystal phase, a spodumene crystal phase, and a residual glass phase, wherein the concentration of the residual glass phase is 15 wt% to 50 wt%, based on the total weight of the glass-ceramic article, the glass-ceramic article has a thickness of 0.3 mm to 1.0 mm, and the glass-ceramic article includes a component of an electronic device.

[0159] The 154th aspect of the present disclosure may include the 153rd aspect, wherein the glass-ceramic article includes at least one concave surface.

[0160] The 155th aspect of the present disclosure may include any one of the 153rd to 154th aspects, wherein the outer surface of the glass-ceramic article includes a flat rectangular outer surface and a convex boundary region defining the flat rectangular outer surface.

[0161] The 156th aspect of the present disclosure may include the 155th aspect, wherein the convex boundary region has a width of 10 mm.

[0162] The 157th aspect of the present disclosure may include any one of the 153rd to 156th aspects, wherein the glass-ceramic article has a rectangular shape with four rounded corners in a top view.

[0163] The 158th aspect of the present disclosure may include any one of the 156th to 157th aspects, wherein each rounded corner is congruent to an arc with a radius of 20 mm.

[0164] The 159th aspect of the present disclosure may include any one of the 153rd to 158th aspects, wherein the glass-ceramic article has a length of 100 mm to 200 mm and a width of 50 mm to 100 mm.

[0165] The 160th aspect of the present disclosure may include any one of the 153rd to 159th aspects, wherein the glass-ceramic article is a transparent cover plate for an electronic device.

[0166] The 161st aspect of the present disclosure may include any one of the 153rd to 160th aspects, including an electronic device including a transparent surface, the transparent surface including the glass-ceramic article of any one of the 153rd to 160th aspects.

[0167] The 162nd aspect of the present disclosure may include the 161st aspect, wherein the glass-ceramic article has a thickness of 0.3 mm to 1 mm.

[0168] The 163rd aspect of the present disclosure may include any one of the 161st to 162nd aspects, wherein the electronic device is a consumer electronic device.

[0169] These and other aspects, advantages, and salient features will become apparent from the following detailed description, the drawings, and the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS

[0170] Figure 1 Schematically shows a glass stack according to an embodiment disclosed and described herein;

[0171] Figure 2 Schematic cross-sectional side view showing a toughened glass-ceramic article according to an embodiment disclosed and described herein;

[0172] Figure 3 Graphical representation showing the percentage haze (y-axis) as a function of thickness (x-axis) of a glass-ceramic sheet according to an embodiment disclosed and described herein;

[0173] Figure 4A Schematic top plan view showing an electronic device incorporating any of the glass-ceramic articles disclosed herein according to an embodiment disclosed and described herein;

[0174] Figure 4B Schematic showing according to an embodiment disclosed and described herein Figure 4A elevation view of an electronic device;

[0175] Figure 5 Graphical representation showing the beam bending viscosity reports of the compositions of Examples 8, 9, and 10 and Comparative Examples 11 and 12 according to an embodiment disclosed and described herein;

[0176] Figure 6 Schematic top plan view showing a flat glass-ceramic preform according to an embodiment disclosed and described herein;

[0177] Figure 7A Schematic showing according to an embodiment disclosed and described herein by Figure 6 top plan view of a glass-ceramic article prepared by 3D shaping a flat glass-ceramic preform;

[0178] Figure 7B Schematic showing according to an embodiment disclosed and described herein along Figure 7A reference line 7B-7B in Figure 7A side cross-sectional view of a glass-ceramic article;

[0179] Figure 8A Photograph of a glass-ceramic article of Comparative Example 15 according to one or more embodiments shown and described herein, showing nucleation and then spotting after simultaneous 3D shaping and ceramization;

[0180] Figure 8B Photograph of a glass-ceramic article of Example 14 according to one or more embodiments shown and described herein, showing spotting after ceramization and then subsequent 3D shaping;

[0181] Figure 9A Photograph of a shadow generated by passing a xenon lamp through a glass-ceramic article of Comparative Example 15 according to one or more embodiments shown and described herein;

[0182] Figure 9B A photograph of the shadow produced by passing a xenon lamp through the glass-ceramic article of Example 14, according to one or more embodiments shown and described herein;

[0183] Figure 10 Illustrative display of a qualitative assessment of post-3D forming finishing of the glass-ceramic articles of Example 14 compared to that of Comparative Example 15, according to one or more embodiments shown and described herein, versus post-3D forming finishing of a glass article that has undergone 3D forming without nucleation or ceramization; and

[0184] Figure 11 Illustrative display of the concentration of the residual glass phase (left y-axis) versus the mole % of non-lithium alkali metal oxides and alkaline earth metal oxides in the glass composition, for the glass-ceramic articles of Examples 13 and 14 and Comparative Examples 16 and 17, after 3D forming, according to one or more embodiments shown and described herein. Detailed Description

[0185] Reference will now be made specifically to embodiments of glass-ceramic articles, glasses and / or glass-ceramic compositions for producing glass-ceramic articles, and methods for ceramizing and 3D forming or shaping glass-ceramic articles. Various embodiments thereof will be described herein with specific reference to the accompanying drawings. Whenever possible, the same reference numerals will be used throughout the drawings to refer to the same or like parts. In the following detailed description, in order to provide a thorough understanding of the embodiments described herein, numerous specific details may be set forth. However, it will be apparent to those skilled in the art that embodiments may be practiced without some or all of these specific details. In other instances, well-known features or processes may not be described in detail so as not to obscure the present disclosure. Additionally, like or identical reference numerals may be used to identify common or similar elements. Except as otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure pertains. In case of conflict, the present specification, including the definitions herein, will control.

[0186] Definitions and Measurement Techniques

[0187] Although other methods and materials may be used to practice or test the embodiments, certain suitable methods and materials are described herein.

[0188] Embodiments that can be used in the disclosed methods and compositions, can be used in combination with the disclosed methods and compositions, can be used for the preparation of the disclosed methods and compositions, or are materials, compounds, compositions, and components of the disclosed methods and compositions are disclosed. These and other materials are disclosed herein, and it should be understood that when combinations, subsets, interactions, groups, etc. of these materials are disclosed without specifically referring to each different individual and collective combination and the arrangement of these compounds, each of them is specifically contemplated and described herein.

[0189] Thus, if a class of substituents A, B, and C is disclosed and also a class of substituents D, E, and F and an example of the combination embodiment A-D is disclosed, each can be contemplated individually and jointly. Thus, in this example, each of the combinations A-E, A-F, B-D, B-E, B-F, C-D, C-E, and C-F is specifically contemplated and should be considered disclosed from the disclosure of A, B, and / or C, D, E, and / or F, and the exemplary combination A-D. Similarly, any subset or combination of these is also specifically anticipated and disclosed. Thus, for example, subsets such as A-E, B-F, and C-E are specifically contemplated and should be considered disclosed from the disclosure of A, B, and / or C, D, E, and / or F, and the exemplary combination A-D. This concept applies to all aspects of the present disclosure, including but not limited to any components of the composition and steps in the methods of making and using the compositions of the present disclosure. More specifically, the exemplary compositional ranges given herein are considered to be part of the specification and are considered to provide exemplary numerical range endpoints, which are equivalent in all respects to specifically including them in the text, and specifically, all combinations are considered and disclosed. In addition, if there are multiple additional steps that can be carried out, it should be understood that each of these additional steps can be carried out by any specific embodiment or combination of embodiments of the disclosed method, and each such combination can be specifically contemplated and should be considered disclosed.

[0190] Unless otherwise indicated in a particular context, the numerical ranges set forth herein include the upper and lower values, and the ranges are intended to include the endpoints as well as all integers and fractions within the ranges. The scope of the present disclosure is not limited to the specific values recited when defining the range. Further, when a quantity, concentration, or other value or parameter is stated in the form of a range, one or more preferred ranges, or preferred upper and lower numerical limits, it is to be understood that this is equivalent to specifically disclosing any range formed by combining any pair of the upper range limits or preferred values with any pair of the lower range limits or preferred values, regardless of whether such pairs are specifically disclosed. Finally, when the term "about" is used to describe a value or endpoint of a range, it is to be understood that the present disclosure includes the specific value or endpoint being referenced.

[0191] As used herein, the term "about" means that a quantity, dimension, formulation, parameter, and other variable and characteristic are not and need not be exact, but may be approximate and / or larger or smaller as desired, reflecting tolerances, conversion factors, rounding, measurement error, and other factors known to those of skill in the art. In general, whether or not expressly stated, the quantities, dimensions, formulas, parameters, or other quantities or characteristics are "about" or "approximate".

[0192] It should be noted that one or more of the claims may use the term "wherein" as a transitional phrase. For purposes of defining the present disclosure, it should be noted that this term is introduced in the claims as an open-ended transitional phrase to introduce a description of a series of structural features and should be interpreted in a manner similar to the more common open-ended introductory phrase "comprising".

[0193] As a result of the raw materials and / or equipment used to produce the glass or glass-ceramic compositions of the present disclosure, certain impurities or components that are not intentionally added may be present in the final glass or glass-ceramic composition. Such materials are present in small amounts in the glass or glass-ceramic composition and are referred to herein as "detritus".

[0194] As used herein, a glass or glass-ceramic composition having 0 wt% of a compound is defined as not intentionally adding the compound, molecule, or element to the composition, but the composition may still include the compound, typically as detritus or a trace amount. Similarly, "iron-free", "sodium-free", "lithium-free", "zirconium-free", "alkaline earth metal-free", or "heavy metal-free", etc. are defined to mean that the composition does not intentionally add the compound, molecule, or element, but the composition may still contain iron, sodium, lithium, zirconium, alkaline earth metals, or heavy metals, etc., but as an approximate trace or a trace amount.

[0195] As used herein, the term "glass-ceramic" refers to a solid prepared by controlled crystallization of a precursor glass and having one or more crystalline phases and a residual glass phase.

[0196] As used herein, "depth of compression" or "DOC" refers to the depth of the compressive stress (CS) layer and is the depth at which the stress within a glass-ceramic article changes from compressive stress to tensile stress and the stress value is zero. In accordance with common practice in the art, compressive stress (CS) is represented as a negative stress (<0) and tensile stress is represented as a positive stress (>0). However, throughout this specification, unless otherwise stated, CS is represented as a positive value or absolute value, i.e., CS as stated herein = |CS|.

[0197] The values of DOC, midpoint center tension (CT), and maximum CT are measured using a Scattered Light Polariscope (SCALP) purchased from Glasstress Ltd. located in Tallinn, Estonia. During the measurement, the laser angle of the SCALP-05 instrument is 79.3 degrees.

[0198] Surface CS is measured using a surface stress meter (FSM), such as a commercial instrument like the FSM-6000 manufactured by Orihara Industrial Co., Ltd. (Japan). Surface stress measurement relies on the accurate measurement of the stress optical coefficient (SOC), which is related to the birefringence of the glass. The SOC is then measured in accordance with Scheme C (glass disc method) described in ASTM standard C770-16, entitled "Standard Test Method for Measurement of Glass Stress-Optical Coefficient", the entire content of which is incorporated herein by reference.

[0199] The CS in the remaining CS region is measured by the refraction near-field (RNF) method described in U.S. Patent No. 8,854,623, entitled "Systems and Methods for Measuring a Profile Characteristic of a Glass Sample", the entire content of which is incorporated herein by reference. The RNF measurement is force-balanced and calibrated by the maximum CT value provided by the SCALP measurement. Specifically, the RNF method includes placing the glass article close to a reference block, generating a polarization-switching beam (which switches between orthogonal polarizations at a rate of 1 Hz to 50 Hz), measuring the amount of power in the polarization-switching beam, and generating a polarization-switching reference signal, wherein the amount of power measured in each orthogonal polarization is within 50% of each other. The method further includes passing the polarization-switching beam through the glass sample and the reference block, into different depths of the glass sample, and then using a delay optical system to delay the passed polarization-switching beam from reaching a signal light detector, which generates a polarization-switching detector signal. The method also includes dividing the detector signal by the reference signal to form a normalized detector signal, and determining the profile characteristic of the glass sample from the normalized detector signal.

[0200] The values of DOC, midpoint center tension (CT), and maximum CT are measured using a scatter light polarimeter (SCALP) purchased from Glasstress Ltd. in Tallinn, Estonia. During the measurement, the laser angle of the SCALP-05 instrument is 79.3 degrees. The SOC of the glass ceramic is set to 2.654, and the refractive index (RI) is set to 1.531. The values of SOC and RI will vary depending on the composition of the glass ceramic. The above values of the above parameters (SOC = 2.654 and RI = 1.531) represent the compositions disclosed herein.

[0201] The stress distribution can be measured by a combination of RNF for the inner CS, SCALP for the CT region, and a method for measuring the surface CS.

[0202] The stored tensile energy (in J / m 2 ) is calculated using the following equation (1):

[0203] Stored tensile energy (J / m 2 ) = [1 - ν] / E ∫(σ 2 )(dt)(1)

[0204] In equation (1), ν is the Poisson's ratio, E is the Young's modulus, σ is the stress, t is the thickness, and the integral is calculated only over the thickness of the tensile region.

[0205] The value of Poisson's ratio stated in the present disclosure refers to the value measured by the general type of resonant ultrasound spectroscopy technique described in ASTM E2001-13.

[0206] Based on X-ray diffraction (XRD), Rietveld analysis was employed to determine the crystalline phase assemblage (before ion exchange) and the weight percentages of the crystalline phase and the residual glass phase. An XRD spectrum was obtained using a D8 ENDEAVOR XRD machine purchased from Bruker Corporation and equipped with Cu radiation and a LynxEye detector. TM The Rietveld analysis based on the XRD spectrum was performed using Bruker's TOPAS TM version 6 analysis software.

[0207] The following process (referred to herein as the "fragment test") was used to determine the number of fragments into which a glass-ceramic article breaks after cracking. The ion-exchanged glass-ceramic article having dimensions of 50 mm by 50 mm by 0.8 mm was placed on a steel surface. A stylus with a tungsten carbide tip (purchased from Fisher Scientific Industries, trademarked as and having a manufacturer's identification number of #13-378 and a 60-degree conical tip) weighing 40 g was attached to a fixture on a gear-driven mechanism that moved the stylus up and down. The tip of the stylus was placed in contact with the glass-ceramic article, and then the gear mechanism was adjusted incrementally until the glass-ceramic article cracked. The number of fragments was then counted.

[0208] Fracture toughness is measured in accordance with the chevron notched short bar (CNSB) ASTM E 1304-97 method. Samples for measurement are prepared from thick disks of glass having the desired composition and ceramized through the ceramization cycle of interest (presented as “COR” in the example) in a box furnace. The fracture toughness value (Kic) is measured by the chevron notched short bar (CNSB) method, which is disclosed in Reddy, K.P.R. et al., “Fracture Toughness Measuremetn of Glass and Ceramic Materials Using Chevron-Notched Specimens”, J. Am. Ceram. Soc., 71[6], C-310-C-313 (1988), except that Equation 5 from Bubsey, R.T. 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, pages 1-30 (October 1992) is used to calculate Y* m .

[0209] The Young's modulus value stated in this disclosure refers to the value measured by the general type of resonant ultrasound spectroscopy technique described in ASTM E2001-13.

[0210] The shear modulus value stated in this disclosure refers to the value measured by the general type of resonant ultrasound spectroscopy technique described in ASTM E2001-13.

[0211] Refractive index measurements are made at 589.3 nm on a Metricon Model 2010 Prism Coupler.

[0212] The haze of the glass-ceramic article is measured using a haze meter (e.g., BYK Gardner Haze-Gard I) in accordance with, for example, ASTM D1003 or ASTM D1044. The specific test method will be described in conjunction with the recorded results.

[0213] As used herein, the transmittance refers to the total transmittance and is measured using a Perkin Elmer Lambda 950 UV / VIS / NIR spectrophotometer with a 150 mm integrating sphere. The sample is mounted at the entrance end of the sphere to enable collection of wide-angle scattered light. The total transmittance data is collected using a reference Spectralon reflectance disk at the exit end of the sphere. The percentage transmittance (%T) of the total transmittance is calculated relative to an open-beam baseline measurement.

[0214] The stress is measured by the retardance of the glass-ceramic after ceramization using a GFP1400 instrument sold by Stress Photonics Inc. in Madison, Wisconsin (GFP = gray field polarizer). Other systems, such as commercially available systems (systems sold by Axometrics, Inc.) or custom systems, can be used to perform similar measurements. The stress is typically measured on the intact sheet after ceramization. The measurement area corresponds to an area approximately 5 mm inward from the dimensions of the intact sheet (in a given example, the dimensions of the intact sheet are approximately 245 x 641 (+ / -10 mm)). Alternatively, the stress can be measured on a component cut from the intact sheet after ceramization. Release agents remaining on the sheet surface may result in higher stress values being recorded. This release agent can be removed (by brushing or cleaning the surface) before measurement.

[0215] On an optically polished sample with plane-parallel surfaces, the optical transmittance in the wavelength range of 250 - 1000 nm is measured using a Perkin Elmer Lambda 950 spectrophotometer with a data spacing of 2 nm. The transmittance is measured on the glass-ceramic article itself without any coatings or other applications.

[0216] Using a Bruker D4 ENDEAVOR equipped with Cu radiation and a LynxEye detector TM XRD measures X-ray diffraction (XRD). Rietveld analysis is completed using Bruker's Topas software package.

[0217] Raman data is measured using a Thermo Fisher DXR2 SmartRaman instrument.

[0218] The heat capacity is measured at room temperature according to the standard test method ASTM E1461.

[0219] The density is measured according to the standard test method ASTM C20.

[0220] The thermal conductivity is measured at room temperature according to the standard test method ASTM E1461.

[0221] The optical delay can be measured according to the standard test method ASTM F218-13.

[0222] Unless otherwise expressly stated, no method described herein should be construed as requiring its steps to be carried out in a specific order or as requiring any device to have a specific orientation. Thus, if a method claim does not actually recite an order to be followed by its steps, or any apparatus claim does not actually recite an order or orientation of components, or the claims or specification do not otherwise specifically state that the steps are limited to a specific order or do not recite a specific order or orientation of the components of the device, then no order or orientation should be inferred in any respect. This applies equally to any possible basis of construction not expressly stated, including: logic with respect to arrangement of steps, operational flow, order of components or orientation of components; general sense obtained from grammatical structure or punctuation; and number or type of embodiments described in the specification.

[0223] Unless the context clearly indicates otherwise, as used herein, the singular forms "a", "an" and "the" include plural referents. Thus, for example, reference to "a" component includes aspects having two or more of such components, unless the text clearly indicates otherwise.

[0224] Unless otherwise specified, directional terms used herein, such as up, down, left, right, front, back, top, bottom, longitudinal, horizontal, are only with reference to the drawings and do not denote absolute orientation.

[0225] As used herein, the terms "warpage" and "flatness" and any variations thereof are used interchangeably and have the same meaning.

[0226] Unless otherwise expressly stated, any range used herein includes all ranges and sub-ranges therebetween and any values.

[0227] Overview of the glass-ceramic article

[0228] The properties of the glass-ceramic article can be adjusted to be used as a cover substrate and / or housing of a mobile electronic device. For example, without being limited by theory, a glass-ceramic article having a high fracture toughness and / or a high Young's modulus can provide crack penetration resistance and drop performance. When such a glass-ceramic article is chemically strengthened, for example, by ion exchange, the crack penetration resistance and drop performance can be further enhanced. Also, the high fracture toughness and / or Young's modulus can further increase the stored tensile energy and the maximum central tensile force, which can be imparted to the glass-ceramic article by chemical tempering while maintaining the desired fragmentation of the glass-ceramic after breakage. Also, for example, the optical properties (e.g., transparency and haze) of the glass-ceramic article can be adjusted by adjusting the heating and / or ceramization scheme for converting the glass article into a glass-ceramic article, and by chemical strengthening (e.g., by ion exchange) to design or control the properties of the glass-ceramic article.

[0229] The glass-ceramic article of the present disclosure includes a clear and transparent glass-ceramic or a translucent lithium aluminosilicate glass-ceramic composition that includes spodumene and lithium silicate as the main crystal phases and a residual glass phase. The lithium silicate crystal phase can be lithium disilicate or lithium metasilicate. In an embodiment, the lithium silicate crystal phase can be lithium disilicate. The improved properties of the glass-ceramic composition disclosed herein include: 1) the lithium silicate (e.g., lithium disilicate) remains as the main crystal phase, which provides the glass-ceramic with inherent high mechanical strength and fracture toughness; and 3) spodumene is the second main crystal phase and has fine grains, which contributes to the transparency or translucency of the glass-ceramic and can also have additional mechanical strength after ion exchange.

[0230] Various methods can be employed to form glass and glass-ceramics into three-dimensional glass-ceramic articles. The 3D forming of glass-ceramics to produce glass-ceramic articles typically involves a two-step 3D forming process. Such a two-step 3D forming process includes a first step in which the glass composition only undergoes nucleation. Nucleation refers to heating the glass composition to a nucleation temperature at which a nucleating crystalline phase (such as a lithium phosphate crystalline phase) is formed. The nucleating crystalline phase can then act as seeds for the crystallization of the main crystalline phase during the subsequent forming of the glass or during the post-forming ceramization of the ceramic. The nucleated glass composition is cooled. In the second step, after cooling, the nucleated glass composition is 3D formed into the desired 3D shape by heating the nucleated glass composition and pressing the nucleated glass composition into a mold. During the second step of 3D forming and simultaneously pressing the glass into the mold, the ceramization of the glass is completed to produce most of the crystalline phase in the glass-ceramic. In these existing 3D forming processes, crystallization is completed in a pressing mold where most of the crystalline phase is formed while 3D forming. In another forming process, the 3D forming can include a "pre-nucleation" step, followed by a 3D forming process, and then followed by post-3D forming ceramization to complete the establishment of the main crystalline phase. In this type of process, the crystallization of the material (i.e., the formation of the collection of most of the crystalline phases present in the final product) occurs during and after the 3D forming process.

[0231] However, the ceramization of the glass composition during the 3D forming process of glass-ceramic articles to produce glass-ceramic materials can lead to significant surface defects, shrinkage, and other quality defects, which increase the post-forming finishing required to meet quality specifications.

[0232] General overview of the composition and 3D forming method

[0233] The present disclosure solves these problems of the existing 3D forming processes by disclosing such a glass-ceramic composition that enables the hot 3D forming of glass-ceramics after ceramization of the glass-ceramics to produce glass-ceramic articles. The present disclosure also relates to a method for producing glass-ceramic articles that includes 3D forming a ceramized glass-ceramic preform. In the method disclosed herein, the glass-ceramics can be 3D formed (i.e., 3D formed after using a standard ceramization process to produce a material with a high crystalline phase content) after ceramizing a precursor glass to produce a transparent glass-ceramic preform. After ceramization and before 3D forming, the glass-ceramic preform can have a total crystalline phase concentration of 50 wt% to 90 wt%, based on the total weight of the glass-ceramic preform.

[0234] These 3D forming methods for producing glass-ceramic articles are enabled by such a glass-ceramic composition that has a non-lithium alkali metal oxide (e.g., Na2 O, K 2 The concentration of O, or both of these, is greater than or equal to 0.5 mol%, and the molar ratio of non-lithium alkali metal oxide to alumina is greater than or equal to 0.1 (i.e., 2 O + K 2 O] / [Al 2 O 3 ≥ 0.1), and the molar ratio of non-lithium alkali metal oxide to zirconia is greater than or equal to 0.3 (i.e., 2 O + K 2 O] / [ZrO 2 ≥ 0.3), or a combination thereof. In an embodiment, as a supplement or alternative, the glass-ceramic composition may have an RO concentration greater than or equal to 0.5 mol%, an RO to alumina molar ratio greater than or equal to 0.05 (i.e., [RO] / [Al2O3] ≥ 0.05), a high RO to zirconia molar ratio greater than or equal to 0.1 (i.e., [RO] / [Al2O3] ≥ 0.1), or a combination thereof, where RO equals all of ZnO, MgO, CaO, BaO, and SrO.

[0235] The glass-ceramic article disclosed herein can be produced by first producing a precursor glass having the composition disclosed herein by conventional melting and glass-forming schemes for glassmaking. After cooling, the glass material can be subjected to a secondary heat treatment (i.e., a ceramization process) that consists of nucleation and crystal growth steps that are required to cause the growth of the crystalline phases of interest to produce a glass-ceramic preform. As discussed previously, the glass-ceramics disclosed herein contain relatively high concentrations of non-lithium alkaline and alkaline earth elements, including 2 O, K 2 O, and / or CaO (>0.5 mol%). In these transparent glass-ceramics, these constituent components do not enter into the crystalline phases that grow during the ceramization process and instead remain in the residual glass phase. The relatively large amounts of these non-lithium alkaline oxides and / or alkaline earth oxides contribute to an increase in the residual glass phase in the glass-ceramics after the ceramization process. In addition, the relatively large concentrations of these constituent components in the residual glass phase contribute to a lower viscosity of the ceramized material during a three-dimensional (3D) thermoforming process within the temperature range of the process.

[0236] A glass-ceramic composition and a process for producing a glass-ceramic article by 3D shaping a glass-ceramic preform after ceramization can provide improved 3D shaping of the glass-ceramic while maintaining high optical transmittance of the 3D-shaped glass-ceramic article. The ceramized glass-ceramic can be thermally formed into various three-dimensional shapes while maintaining the ceramization quality (e.g., mechanical strength, fracture toughness, transparency / translucency, etc.) and improved surface quality and chemical strengthening properties of the glass-ceramic article. A high amount of non-Li 2 O alkalinity and / or alkaline earth elements in the residual glass phase after ceramization and before 3D shaping can result in a lower viscosity of the residual glass phase and can enable 3D shaping after complete ceramization of the glass-ceramic to produce a majority crystalline phase. The 3D shaping process for the ceramized glass-ceramic can enable a scalable process for forming a glass-ceramic enclosure with improved material utilization and lower cost, as compared to a process that includes pre-nucleating the glass and then 3D shaping the glass while simultaneously ceramizing to produce a crystalline phase or as compared to a process that includes ceramizing and then machining the glass-ceramic to produce a 3D shape from a thick glass-ceramic sheet. The glass-ceramics disclosed herein contain a high concentration of crystalline phase(s) after a standard ceramization process but can still be 3D shaped due to the amount of non-lithium alkalinity (Na 2 O + K 2 O) and / or alkaline earth (e.g., CaO) (which remains in the residual glass phase surrounding the crystals and provides a dual role of increasing the amount of the residual glass phase and reducing the viscosity of the residual glass phase), which can enable 3D shaping, even for highly crystalline materials, while maintaining high transparency, low haze, and good ion-exchange properties.

[0237] The glass-ceramic articles produced from the compositions and processes disclosed herein have high optical transparency and high mechanical properties, which can improve the performance of the glass-ceramic articles used as cover glasses for handheld electronic devices. Three-dimensional shaping expands this typical two-dimensional space. The possibility of 3D shaping a highly crystalline glass-ceramic material after a complete ceramization cycle can enable the production of three-dimensional shapes with improved surface defects, thereby reducing downstream polishing required to meet quality specifications. The optical transparency of the highly crystalline glass-ceramic (>50 wt%) can be established via the presence of crystals smaller than the light wavelength (e.g., <150 nanometers (nm)) and by matching the refractive index of the existing crystalline phase with the residual glass phase. Refractive index matching results in low scattering in the composite material and, thus, lower haze and higher transmittance. The low haze of the glass-ceramic articles disclosed herein can enable the use of the glass-ceramic articles for cover glass applications that require low haze and high transparency.

[0238] The glass-ceramic compositions disclosed herein can also result in an increased concentration of the residual glass phase after 3D shaping, as compared to the ceramified glass-ceramic preform prior to 3D shaping. The concentration and composition of the residual glass phase can also improve the ion-exchange process for strengthening the post-shaped glass-ceramic article. Specifically, increasing the concentration of the residual glass phase during 3D shaping can result in an increased ion-diffusion rate of the ion-exchange ions into the surface of the glass-ceramic article, which can increase the compressive stress (CS) in the resulting compressive layer and increase the corresponding central tension (CT). The increase in the ion-diffusion coefficient into the surface of the glass-ceramic article can be affected by the amount of the residual glass phase and / or the size of the crystalline-phase islands, as well as the amount of the alkaline substances in the residual glass phase. Other benefits or advantages of the glass-ceramic compositions and processes disclosed herein may be apparent to those skilled in the art by practicing the subject matter disclosed herein.

[0239] As discussed previously, the method of manufacturing a glass-ceramic article of the present disclosure can include 3D shaping a ceramified glass-ceramic preform to produce the primary crystalline phases expected to be present in the final glass-ceramic article. In an embodiment, the method can include shaping the glass-ceramic preform to produce a glass-ceramic article having a lithium disilicate crystalline phase, a spodumene crystalline phase, and a residual glass phase. Prior to 3D shaping, the glass-ceramic preform contains a lithium disilicate crystalline phase, a spodumene crystalline phase, and a residual glass phase. After 3D shaping, the glass-ceramic article contains a concentration of the residual glass phase that is equal to or greater than the concentration of the residual glass phase in the glass-ceramic preform. In an embodiment, prior to 3D shaping, the concentration of the residual glass phase in the glass-ceramic preform can be 10 wt% to 50 wt%, the balance being crystalline phases, such as a lithium disilicate crystalline phase, a spodumene crystalline phase, or both. In an embodiment, the process of the present disclosure can also include preparing a glass comprising a glass composition and then ceramifying the glass to produce a glass-ceramic. The glass-ceramic or the glass prior to ceramification can be divided into a plurality of glass-ceramic preforms or glass preforms. After ceramification, the glass-ceramic preform can then be 3D shaped to produce a glass-ceramic article.

[0240] Composition (wt%)

[0241] Glass-ceramic preforms and glass-ceramic articles can be made from any glass composition suitable for forming a glass-ceramic article, but it should be understood that the glass composition of the glass sheet affects the mechanical and optical properties of the glass-ceramic article. In an embodiment, the glass composition is selected such that the resulting glass-ceramic article has a main crystal phase comprising a spodumene crystal phase and a lithium silicate crystal phase, and wherein the spodumene crystal phase and the lithium silicate crystal phase have a higher weight percentage compared to other crystal phases present in the glass-ceramic article. Specifically, the composition of the glass from which the glass-ceramic article is prepared comprises silicon oxide (SiO 2 ), aluminum oxide (Al 2 O 3 ), lithium oxide (LiO 2 ), phosphorus pentoxide (P 2 O 5 ), and zirconium oxide (ZrO 2 ). SiO 2 , Al 2 O 3 , LiO 2 , and P 2 O 5 can be the primary constituent components of the lithium silicate crystal phase, the spodumene crystal phase, or both, which form the glass-ceramic during the ceramization process. For example, in an embodiment, the glass-ceramic preform and the glass-ceramic article can be formed from a glass comprising a glass composition comprising: about 55 wt% to about 80 wt% SiO 2 , about 0 wt% to about 20 wt% Al 2 O 3 , about 5 wt% to about 20 wt% Li 2 O, about 0 wt% to about 6 wt% P 2 O 5 , and about 0.2 wt% to about 15 wt% ZrO 2 , but is not limited thereto.

[0242] The composition of the glass for preparing the glass-ceramic article further comprises one or more non-lithium alkali metal oxides (e.g., Na 2 O and / or K 2 O), alkaline earth metal oxides (e.g., MgO, CaO, BaO, SrO), transition metal oxides (e.g., ZnO), or combinations thereof. Specifically, the composition of the glass for preparing the glass-ceramic article can comprise one or more of the following: Na 2 O, K 2 O, ZnO, CaO, MgO, BaO, SrO, B 2 O 5, or combinations thereof. According to the methods disclosed herein, non-lithium alkali metal oxides, basic oxides, ZnO, or combinations thereof can increase the concentration of the residual glass phase in the glass-ceramic to facilitate 3D thermoforming after ceramization. In embodiments, the glass composition can include other constituent components to modify one or more properties of the glass, glass-ceramic preform, or glass-ceramic article, or to aid in the processing of the glass.

[0243] SiO 2 , an oxide involved in glass forming, which can serve to stabilize the network structure of the glass and glass-ceramic. In various glass compositions, the concentration of SiO 2 should be high enough to form a spodumene crystal phase when the glass is heat-treated during ceramization to convert the glass into a glass-ceramic. The amount of SiO 2 can be limited to control the melting temperature of the glass, since the melting temperature of pure SiO 2 and glasses with high SiO 2 concentrations is undesirably high. In embodiments, the glass or glass-ceramic composition can include from about 55 wt% to about 80 wt% SiO 2 , based on the total weight of the glass or glass-ceramic composition. In embodiments, the glass or glass-ceramic composition can include from about 69 wt% to about 80 wt% SiO 2 . In some embodiments, the SiO 2 included in the glass or glass-ceramic composition can be: from about 55 wt% to about 80 wt%, from about 55 wt% to about 77 wt%, from about 55 wt% to about 75 wt%, from about 55 wt% to about 73 wt%, from about 60 wt% to about 80 wt%, from about 60 wt% to about 77 wt%, from about 60 wt% to about 75 wt%, from about 60 wt% to about 73 wt%, from about 68 wt% to about 80 wt%, from about 68 wt% to about 77 wt%, from about 68 wt% to about 75 wt%, from about 68 wt% to about 73 wt%, from about 69 wt% to about 80 wt%, from about 69 wt% to about 77 wt%, from about 69 wt% to about 75 wt%, from about 69 wt% to about 73 wt%, from about 70 wt% to about 80 wt%, from about 70 wt% to about 77 wt%, from about 70 wt% to about 75 wt%, from about 70 wt% to about 73 wt%, from about 73 wt% to about 80 wt%, from about 73 wt% to about 77 wt%, from about 73 wt% to about 75 wt%, from about 75 wt% to about 80 wt%, from about 75 wt% to about 77 wt%, or from about 77 wt% to about 80 wt% SiO 2 , based on the total weight of the glass or glass-ceramic composition.

[0244] Al 2 O3 It can also provide network stabilization and can also provide improved mechanical properties and chemical durability. However, if the amount of Al 2 O 3 is too high, the proportion of lithium silicate crystals may decrease, possibly decreasing to the extent that an interlocking structure cannot be formed. The amount of Al 2 O 3 can be modified to control the viscosity. In addition, if the amount of Al 2 O 3 is too high, the viscosity of the melt generally also increases. In an embodiment, the glass or glass-ceramic composition can comprise from about 0 wt% (i.e., zero wt%) to about 20 wt% Al 2 O 3 , based on the total weight of the glass or glass-ceramic composition. In an embodiment, the glass or glass-ceramic composition can comprise from about 6 wt% to about 9 wt% Al 2 O 3 . In an embodiment, the amount of Al 2 O 3 contained in the glass or glass-ceramic composition can be: from about 2 wt% to about 20 wt%, from about 2 wt% to about 18 wt%, from about 2 wt% to about 15 wt%, from about 2 wt% to about 12 wt%, from about 2 wt% to about 10 wt%, from about 2 wt% to about 9 wt%, from about 2 wt% to about 8 wt%, from about 2 wt% to about 5 wt%, from about 5 wt% to about 20 wt%, from about 5 wt% to about 18 wt%, from about 5 wt% to about 15 wt%, from about 5 wt% to about 12 wt%, from about 5 wt% to about 10 wt%, from about 5 wt% to about 9 wt%, from about 5 wt% to about 8 wt%, from 6 wt% to about 20 wt%, from about 6 wt% to about 18 wt%, from about 6 wt% to about 15 wt%, from about 6 wt% to about 12 wt%, from about 6 wt% to about 10 wt%, from about 6 wt% to about 9 wt%, from 8 wt% to about 20 wt%, from about 8 wt% to about 18 wt%, from about 8 wt% to about 15 wt%, from about 8 wt% to about 12 wt%, from about 8 wt% to about 10 wt%, from 10 wt% to about 20 wt%, from about 10 wt% to about 18 wt%, from about 10 wt% to about 15 wt%, from about 10 wt% to about 12 wt%, from about 12 wt% to about 20 wt%, from about 12 wt% to about 18 wt%, or from about 12 wt% to about 15 wt%, based on the total weight of the glass or glass-ceramic composition.

[0245] In the glass-ceramics disclosed herein, Li 2 O helps to form two crystal phases, spodumene and lithium silicate. In fact, in order to obtain spodumene and lithium disilicate as the main crystal phases, the glass or glass-ceramic composition can have at least about 5 wt% Li 2O or at least about 7 wt% Li 2 O, based on the total weight of the glass or glass-ceramic composition. Further, it has been found that when the concentration of Li 2 O becomes too high (greater than about 20 wt%), the composition becomes very fluid. Thus, in an embodiment, the glass or glass-ceramic composition may comprise from about 5 wt% to about 20 wt% Li 2 O, based on the total weight of the glass or glass-ceramic composition. In an embodiment, the glass or glass-ceramic composition may comprise from about 10 wt% to about 20 wt% Li 2 O, based on the total weight of the glass or glass-ceramic composition. In an embodiment, the amount of Li 2 O comprised in the glass or glass-ceramic composition may be: from about 5 wt% to about 20 wt%, from about 5 wt% to about 18 wt%, from about 5 wt% to about 16 wt%, from about 5 wt% to about 14 wt%, from about 5 wt% to about 12 wt%, from about 5 wt% to about 10 wt%, from about 5 wt% to about 8 wt%, from about 7 wt% to about 20 wt%, from about 7 wt% to about 18 wt%, from about 7 wt% to about 16 wt%, from about 7 wt% to about 14 wt%, from about 7 wt% to about 12 wt%, from about 7 wt% to about 10 wt%, from about 8 wt% to about 20 wt%, from about 8 wt% to about 18 wt%, from about 8 wt% to about 16 wt%, from about 8 wt% to about 14 wt%, from about 8 wt% to about 12 wt%, from about 10 wt% to about 20 wt%, from about 10 wt% to about 18 wt%, from about 10 wt% to about 16 wt%, from about 10 wt% to about 14 wt%, from about 10 wt% to about 12 wt%, from about 12 wt% to about 20 wt%, from about 12 wt% to about 18 wt%, from about 12 wt% to about 16 wt%, from about 12 wt% to about 14 wt%, from about 16 wt% to about 20 wt%, from about 16 wt% to about 18 wt%, or from about 18 wt% to about 20 wt%.

[0246] The glass and glass-ceramic compositions disclosed herein may comprise P 2 O 5 . P 2 O 5 may function as a nucleating agent to produce bulk nucleation. If the concentration of P 2 O 5 is too low, the precursor glass does crystallize, but (due to the lower viscosity) only at higher temperatures and with a weak and often distorted body from the surface inwards. However, if the concentration of P 2 O 5 is too high, it may be difficult to control devitrification after cooling during the forming of the glass sheet. In an embodiment, the glass and / or glass-ceramic compositions disclosed herein may comprise from greater than 0 wt% to about 6 wt% P2 O 5 , based on the total weight of the glass or glass-ceramic composition. In embodiments, the glass and / or glass-ceramic compositions disclosed herein may comprise from about 2 wt% to about 5 wt% P 2 O 5 . In embodiments, the glass and / or glass-ceramic compositions disclosed herein may comprise from about 1.5 wt% to about 4.75 wt% P 2 O 5 . In some embodiments, the glass or glass-ceramic composition comprises P 2 O 5It can be: 0 wt% to about 6 wt%, 0 wt% to about 5.5 wt%, 0 wt% to 5 wt%, 0 wt% to about 4.5 wt%, 0 wt% to about 4 wt%, 0 wt% to about 3.5 wt%, 0 wt% to about 3 wt%, 0 wt% to about 2.5 wt%, 0 wt% to about 2 wt%, 0 wt% to about 1.5 wt%, 0 wt% to about 1 wt%, >0 wt% to about 6 wt%, >0 wt% to about 5.5 wt%, >0 wt% to 5 wt%, >0 wt% to about 4.5 wt%, >0 wt% to about 4 wt%, >0 wt% to about 3.5 wt%, >0 wt% to about 3 wt%, >0 wt% to about >2.5 wt%, 0 wt% to about 2 wt%, >0 wt% to about 1.5 wt%, >0 wt% to about 1 wt%, about 0.5 wt% to about 6 wt%, about 0.5 wt% to about 5.5 wt%, about 0.5 wt% to 5 wt%, about 0.5 wt% to about 4.5 wt%, about 0.5 wt% to about 4 wt%, about 0.5 wt% to about 3.5 wt%, about 0.5 wt% to about 3 wt%, about 0.5 wt% to about 2.5 wt%, about 0.5 wt% to about 2 wt%, about 0.5 wt% to about 1.5 wt%, about 0.5 wt% to about 1 wt%, about 1 wt% to about 6 wt%, about 1 wt% to about 5.5 wt%, about 1 wt% to about 5 wt%, about 1 wt% to about 4.5 wt%, about 1 wt% to about 4 wt%, about 1 wt% to about 3.5 wt%, about 1 wt% to about 3 wt%, about 1 wt% to about 2.5 wt%, about 1 wt% to about 2 wt%, about 1 wt% to about 1.5 wt%, about 1.5 wt% to about 6 wt%, about 1.5 wt% to about 5.5 wt, about 1.5 wt% to 5 wt%, about 1.5 wt% to about 4.5 wt%, about 1.5 wt% to about 4 wt%, about 1.5 wt% to about 3.5 wt%, about 1.5 wt% to about 3 wt%, about 1.5 wt% to about 2.5 wt%, about 1.5 wt% to about 2 wt%, about 2 wt% to about 6 wt%, about 2 wt% to about 5.5 wt%, about 2 wt% to 5 wt%, about 2 wt% to about 4.5 wt%, about 2 wt% to about 4 wt%, about 2 wt% to about 3.5 wt%, about 2 wt% to about 3 wt%, about 2 wt% to about 2.5 wt%, about 2.5 wt% to about 6 wt%, about 2.5 wt% to about 5.5 wt%, about 2.5 wt% to 5 wt%, about 2.5 wt% to about 4.5 wt%, about 2.5 wt% to about 4 wt%, about 2.5 wt% to about 3.5 wt%, about 2.5 wt% to about 3 wt%, about 3 wt% to about 6 wt%, about 3 wt% to about 5.5 wt%, about 3 wt% to 5 wt%, about 3 wt% to about 4.5 wt%, about 3 wt% to about 4 wt%, about 3 wt% to about 3.5 wt%, about 3.5 wt% to about 6 wt%, about 3.5 wt% to about 5.5 wt%, about 3.5 wt% to 5 wt%, about 3.5 wt% to about 4.5 wt%, about 3.5 wt% to about 4 wt%, about 4 wt% to about 6 wt%, about 4 wt% to about 5.5 wt%, about 4 wt% to 5 wt%, about 4 wt% to about 4.5 wt%, about 4.5 wt% to about 6 wt%, about 4.5 wt% to about 5.5 wt%, about 4.5 wt% to about 5 wt%, about 5 wt% to about 6 wt%, about 5 wt% to about 5.5 wt%, or about 5.5 wt% to about 6 wt%, based on the total weight of the glass or glass-ceramic composition.

[0247] In glass and glass-ceramic compositions, ZrO is typically found 2 The stability of Li 2 O-Al 2 O 3 -SiO 2 -P 2 O 5 glass can be improved by significantly reducing devitrification during forming and by lowering the liquidus temperature. When the concentration is higher than 8 wt%, ZrSiO 4 forms the main liquidus phase at high temperatures, which significantly reduces the liquidus viscosity. When the glass contains more than 2 wt% ZrO 2 , a transparent glass is formed. Adding ZrO 2 can also help reduce the grain size of spodumene, which helps form a transparent glass-ceramic. In an embodiment, the glass or glass-ceramic composition can comprise from about 0.2 wt% to about 15 wt% ZrO 2 , based on the total weight of the glass and / or glass-ceramic composition. In an embodiment, the glass or glass-ceramic composition can comprise from about 2 wt% to about 6 wt% ZrO 2 , based on the total weight of the glass and / or glass-ceramic composition. In an embodiment, the glass or glass-ceramic composition comprises ZrO 2It can be: about 0.2 wt% to about 15 wt%, about 0.2 wt% to about 12 wt%, about 0.2 wt% to about 10 wt%, about 0.2 wt% to about 8 wt%, about 0.2 wt% to about 6 wt%, about 0.2 wt% to about 4 wt%, about 0.5 wt% to about 15 wt%, about 0.5 wt% to about 12 wt%, about 0.5 wt% to about 10 wt%, about 0.5 wt% to about 8 wt%, about 0.5 wt% to about 6 wt%, about 0.5 wt% to about 4 wt%, about 1 wt% to about 15 wt%, about 1 wt% to about 12 wt%, about 1 wt% to about 10 wt%, about 1 wt% to about 8 wt%, about 1 wt% to about 6 wt%, about 1 wt% to about 4 wt%, about 2 wt% to about 15 wt%, about 2 wt% to about 12 wt%, about 2 wt% to about 10 wt%, about 2 wt% to about 8 wt%, about 2 wt% to about 6 wt%, about 2 wt% to about 4 wt%, about 3 wt% to about 15 wt%, about 3 wt% to about 12 wt%, about 3 wt% to about 10 wt%, about 3 wt% to about 8 wt%, about 3 wt% to about 6 wt%, about 3 wt% to about 4 wt%, about 4 wt% to about 15 wt%, about 4 wt% to about 12 wt%, about 4 wt% to about 10 wt%, about 4 wt% to about 8 wt%, about 4 wt% to about 6 wt%, about 8 wt% to about 15 wt%, about 8 wt% to about 12 wt%, about 8 wt% to about 10 wt%, about 10 wt% to about 15 wt%, about 10 wt% to about 12 wt%, or about 12 wt% to about 15 wt%, based on the total weight of the glass and / or glass-ceramic composition.

[0248] As discussed above, the disclosed glasses and glass-ceramics can include non-lithium alkali metal oxides such as Na 2 O, K 2 O, or both. As noted above, Li 2 O is commonly used to form various glass-ceramics, but other non-lithium alkaline oxides (e.g., Na 2 O, K 2 O, or both) tend to reduce the formation of glass-ceramics and instead form a residual glass phase in the glass-ceramics. These non-lithium alkali metal oxides, along with ZrO 2 are not incorporated into the crystalline phase lithium disilicate (Li 2 O 5 Si 2 ) or spodumene (LiAlSi 4 O 10 ) during the ceramization process and thus remain in the residual vitreous phase after the ceramization process. It is well known that Na 2 O and K 2O acts as a "flux" in glass chemistry, which refers to a constituent that reduces the viscosity of the glass (e.g., the residual glass phase). Conversely, alumina (Al 2 O 3 ) and zirconia (ZrO 2 ) tend to increase the viscosity of the glass (e.g., the residual glass phase). Thus, after ceramization, Na 2 O, K 2 O, and ZrO 2 do not enter the crystalline phase of the glass-ceramic. Part of the Al 2 O 3 may also remain in the residual vitreous phase. Increasing the concentration of non-lithium alkali metal oxides in the glass-ceramic composition (i.e., [Na 2 O + K 2 O]), increasing the molar ratio of non-lithium alkali metal to Al 2 O 3 , increasing the molar ratio of non-lithium alkali metal to ZrO 2 , or a combination of these can reduce the viscosity of the residual glass phase in the glass-ceramic. In addition, increasing the amount of [Na 2 O + K 2 O] and ZrO 2 can increase the concentration of the residual glass phase in the transparent glass-ceramics disclosed herein. Increasing the concentration of the residual glass phase in the glass-ceramic, reducing the viscosity of the residual glass phase in the glass-ceramic (or both simultaneously) can enable thermal 3D forming of the glass-ceramic after ceramization, as discussed previously herein.

[0249] The composition of the residual glass phase can be adjusted to: control the viscosity during the crystallization process and / or the 3D forming process, minimize deformation or undesirable thermal expansion, or control the microstructure properties. In an embodiment, the glass or glass-ceramic composition can contain from about 0 wt% to about 10 wt% non-lithium alkali metal oxides, based on the total weight of the glass and / or glass-ceramic. In an embodiment, the glass or glass-ceramic composition can contain from about 1 wt% to about 5 wt% Na 2 O, K 2 O, or both, based on the total weight of the glass and / or glass-ceramic. In an embodiment, the non-lithium alkali metal oxides (e.g., Na 2 O, K 2O or a combination thereof) can be: 0 wt% to about 10 wt%, about 0 wt% to about 7 wt%, about 0 wt% to about 5 wt%, 0 wt% to about 4 wt%, 0 wt% to about 3 wt%, 0 wt% to about 2 wt%, 0 wt% to about 1 wt%, greater than 0 wt% to about 10 wt%, greater than 0 wt% to about 7 wt%, greater than 0 wt% to about 5 wt%, greater than 0 wt% to about 4 wt%, greater than 0 wt% to about 3 wt%, greater than 0 wt% to about 2 wt%, greater than 0 wt% to about 1 wt%, about 0.5 wt% to about 10 wt%, about 0.5 wt% to about 7 wt%, about 0.5 wt% to about 5 wt%, about 0.5 wt% to about 4 wt%, about 0.5 wt% to about 3, about 0.5 wt% to about 2 wt%, about 0.5 wt% to about 1 wt%, about 1 wt% to about 5 wt%, about 1 wt% to about 4 wt%, about 1 wt% to about 3 wt%, about 1 wt% to about 2 wt%, about 2 wt% to about 5 wt%, about 2 wt% to about 4 wt%, about 2 wt% to about 3 wt%, about 3 wt% to about 5 wt%, about 3 wt% to about 4 wt%, or about 4 wt% to about 5 wt%, based on the total weight of the glass and / or glass-ceramic.

[0250] In an embodiment, the glass and / or glass-ceramic can contain Na 2 O. The Na 2 O contained in the glass and / or glass-ceramic can be: 0 wt% to about 10 wt%, about 0 wt% to about 7 wt%, about 0 wt% to about 5 wt%, 0 wt% to about 4 wt%, 0 wt% to about 3 wt%, 0 wt% to about 2 wt%, 0 wt% to about 1 wt%, about 0.5 wt% to about 10 wt%, about 0.5 wt% to about 7 wt%, about 0.5 wt% to about 5 wt%, about 0.5 wt% to about 4 wt%, about 0.5 wt% to about 3, about 0.5 wt% to about 2 wt%, about 0.5 wt% to about 1 wt%, about 1 wt% to about 5 wt%, about 1 wt% to about 4 wt%, about 1 wt% to about 3 wt%, about 1 wt% to about 2 wt%, about 2 wt% to about 5 wt%, about 2 wt% to about 4 wt%, about 2 wt% to about 3 wt%, about 3 wt% to about 5 wt%, about 3 wt% to about 4 wt%, or about 4 wt% to about 5 wt%, based on the total weight of the glass and / or glass-ceramic.

[0251] In an embodiment, the glass and / or glass-ceramic can contain K 2 O. The Na 2O can be: 0 wt% to about 10 wt%, about 0 wt% to about 7 wt%, about 0 wt% to about 5 wt%, 0 wt% to about 4 wt%, 0 wt% to about 3 wt%, 0 wt% to about 2 wt%, 0 wt% to about 1 wt%, about 0.5 wt% to about 10 wt%, about 0.5 wt% to about 7 wt%, about 0.5 wt% to about 5 wt%, about 0.5 wt% to about 4 wt%, about 0.5 wt% to about 3, about 0.5 wt% to about 2 wt%, about 0.5 wt% to about 1 wt%, about 1 wt% to about 5 wt%, about 1 wt% to about 4 wt%, about 1 wt% to about 3 wt%, about 1 wt% to about 2 wt%, about 2 wt% to about 5 wt%, about 2 wt% to about 4 wt%, about 2 wt% to about 3 wt%, about 3 wt% to about 5 wt%, about 3 wt% to about 4 wt%, or about 4 wt% to about 5 wt%, based on the total weight of the glass and / or glass-ceramic.

[0252] In addition to non-lithium alkali metal oxides, alkaline earth metal oxides and some transition metal oxides can also be included in the glass and glass-ceramic compositions and can partition into the residual glass phase. Alkaline earth metal oxides can include CaO, MgO, SrO, BaO, or combinations thereof. Transition metal oxides that can be incorporated into the glasses and / or glass-ceramics disclosed herein can include zinc oxide (ZnO). As used herein, the term "RO" refers to one or more of the following: ZnO, CaO, MgO, SrO, BaO, or combinations thereof. ZnO, CaO, MgO, SrO, BaO, or combinations thereof can be added to the glass-ceramic composition to increase the concentration of the residual glass phase, decrease the viscosity of the residual glass phase, or combinations thereof. The concentration of the residual glass phase can be increased, the viscosity of the residual glass phase can be decreased, or both, by increasing the concentration of RO (i.e., ZnO, CaO, MgO, SrO, BaO, or combinations thereof), increasing the molar ratio of RO to Al 2 O 3 (i.e., [RO] / [Al 2 O 3 )), increasing the molar ratio of RO to ZrO 2 (i.e., [RO] / [ZrO 2 ), or combinations thereof. By varying the amount of RO in the glass-ceramic composition to increase the concentration of the residual glass phase and / or decrease the viscosity of the residual glass phase, 3D shaping of the glass-ceramic after ceramization can be achieved to produce glass-ceramic articles as disclosed herein. In an embodiment, the glass and / or glass-ceramic composition can comprise ZnO and one or more alkaline earth metal oxides selected from the group consisting of CaO, MgO, BaO, SrO, and combinations thereof.

[0253] In an embodiment, the glass and / or glass-ceramic composition can comprise ZnO. In an embodiment, the glass or glass-ceramic composition can comprise from 0 wt% to about 10 wt% ZnO, based on the total weight of the glass or glass-ceramic. In an embodiment, the ZnO comprised in the glass or glass-ceramic composition can be: from 0 wt% to about 10 wt%, from 0 wt% to about 9 wt%, from 0 wt% to about 8 wt%, from 0 wt% to about 7 wt%, from 0 wt% to about 6 wt%, from 0 wt% to about 5 wt%, from 0 wt% to about 4 wt%, from 0 wt% to about 3 wt%, from 0 wt% to about 2 wt%, from 0 wt% to about 1 wt%, from about 1 wt% to about 10 wt%, from about 1 wt% to about 9 wt%, from about 1 wt% to about 8 wt%, from about 1 wt% to about 7 wt%, from about 1 wt% to about 6 wt%, from about 1 wt% to about 5 wt%, from about 1 wt% to about 4 wt%, from about 1 wt% to about 3 wt%, from about 1 wt% to about 2 wt%, from about 2 wt% to about 10 wt%, from about 2 wt% to about 9 wt%, from about 2 wt% to about 8 wt%, from about 2 wt% to about 7 wt%, from about 2 wt% to about 6 wt%, from about 2 wt% to about 5 wt%, from about 2 wt% to about 4 wt%, from about 2 wt% to about 3 wt%, from about 3 wt% to about 10 wt%, from about 3 wt% to about 9 wt%, from about 3 wt% to about 8 wt%, from about 3 wt% to about 7 wt%, from about 3 wt% to about 6 wt%, from about 3 wt% to about 5 wt%, from about 3 wt% to about 4 wt%, from about 4 wt% to about 10 wt%, from about 4 wt% to about 9 wt%, from about 4 wt% to about 8 wt%, from about 4 wt% to about 7 wt%, from about 4 wt% to about 6 wt%, from about 4 wt% to about 5 wt%, from about 5 wt% to about 10 wt%, from about 5 wt% to about 9 wt%, from about 5 wt% to about 8 wt%, from about 5 wt% to about 7 wt%, from about 5 wt% to about 6 wt%, from about 6 wt% to about 10 wt%, from about 6 wt% to about 9 wt%, from about 6 wt% to about 8 wt%, from about 6 wt% to about 7 wt%, from about 7 wt% to about 10 wt%, from about 7 wt% to about 9 wt%, from about 7 wt% to about 8 wt%, from about 8 wt% to about 10 wt%, from about 8 wt% to about 9 wt%, or from about 9 wt% to about 10 wt%, based on the total weight of the glass and / or glass-ceramic.

[0254] In an embodiment, the glass or glass-ceramic composition can comprise from 0 wt% to about 8 wt% MgO, based on the total weight of the glass and / or glass composition. In an embodiment, the MgO comprised in the glass or glass-ceramic composition can be: from 0 wt% to about 7 wt%, from 0 wt% to about 6 wt%, from 0 wt% to about 5 wt%, from 0 wt% to about 4 wt%, from 0 wt% to about 3 wt%, from 0 wt% to about 2 wt%, from 0 wt% to about 1 wt%, from 0 wt% to about 0.5 wt%, from about 0.01 wt% to about 8 wt%, from about 0.01 wt% to about 6 wt%, from about 0.01 wt% to about 4 wt%, from about 0.01 wt% to about 3 wt%, from about 0.01 wt% to about 2 wt%, from about 0.01 wt% to about 1 wt%, from about 0.1 wt% to about 8 wt%, from about 0.1 wt% to about 6 wt%, from about 0.1 wt% to about 4 wt%, from about 0.1 wt% to about 2 wt%, from about 0.1 wt% to about 1 wt%, from about 1 wt% to about 8 wt%, from about 1 wt% to about 6 wt%, from about 1 wt% to about 4 wt%, from about 1 wt% to about 2 wt%, from about 2 wt% to about 8 wt%, from about 2 wt% to about 6 wt%, from about 2 wt% to about 4 wt%, from about 4 wt% to about 8 wt%, from about 4 wt% to about 6 wt%, or from about 6 wt% to about 8 wt%, based on the total weight of the glass and / or glass-ceramic.

[0255] In an embodiment, the glass or glass-ceramic composition can comprise from 0 wt% to about 8 wt% CaO, based on the total weight of the glass and / or glass composition. In an embodiment, the CaO comprised in the glass or glass-ceramic composition can be: from 0 wt% to about 7 wt%, from 0 wt% to about 6 wt%, from 0 wt% to about 5 wt%, from 0 wt% to about 4 wt%, from 0 wt% to about 3 wt%, from 0 wt% to about 2 wt%, from 0 wt% to about 1 wt%, from 0 wt% to about 0.5 wt%, from about 0.01 wt% to about 8 wt%, from about 0.01 wt% to about 6 wt%, from about 0.01 wt% to about 4 wt%, from about 0.01 wt% to about 3 wt%, from about 0.01 wt% to about 2 wt%, from about 0.01 wt% to about 1 wt%, from about 0.1 wt% to about 8 wt%, from about 0.1 wt% to about 6 wt%, from about 0.1 wt% to about 4 wt%, from about 0.1 wt% to about 2 wt%, from about 0.1 wt% to about 1 wt%, from about 1 wt% to about 8 wt%, from about 1 wt% to about 6 wt%, from about 1 wt% to about 4 wt%, from about 1 wt% to about 2 wt%, from about 2 wt% to about 8 wt%, from about 2 wt% to about 6 wt%, from about 2 wt% to about 4 wt%, from about 4 wt% to about 8 wt%, from about 4 wt% to about 6 wt%, or from about 6 wt% to about 8 wt%, based on the total weight of the glass and / or glass-ceramic.

[0256] In an embodiment, the glass or glass-ceramic composition can comprise from 0 wt% to about 8 wt% SrO, based on the total weight of the glass and / or glass composition. In an embodiment, the SrO comprised in the glass or glass-ceramic composition can be: from 0 wt% to about 7 wt%, from 0 wt% to about 6 wt%, from 0 wt% to about 5 wt%, from 0 wt% to about 4 wt%, from 0 wt% to about 3 wt%, from 0 wt% to about 2 wt%, from 0 wt% to about 1 wt%, from 0 wt% to about 0.5 wt%, from about 0.01 wt% to about 8 wt%, from about 0.01 wt% to about 6 wt%, from about 0.01 wt% to about 4 wt%, from about 0.01 wt% to about 3 wt%, from about 0.01 wt% to about 2 wt%, from about 0.01 wt% to about 1 wt%, from about 0.1 wt% to about 8 wt%, from about 0.1 wt% to about 6 wt%, from about 0.1 wt% to about 4 wt%, from about 0.1 wt% to about 2 wt%, from about 0.1 wt% to about 1 wt%, from about 1 wt% to about 8 wt%, from about 1 wt% to about 6 wt%, from about 1 wt% to about 4 wt%, from about 1 wt% to about 2 wt%, from about 2 wt% to about 8 wt%, from about 2 wt% to about 6 wt%, from about 2 wt% to about 4 wt%, from about 4 wt% to about 8 wt%, from about 4 wt% to about 6 wt%, or from about 6 wt% to about 8 wt%, based on the total weight of the glass and / or glass-ceramic.

[0257] In an embodiment, the glass or glass-ceramic composition can comprise from 0 wt% to about 8 wt% BaO, based on the total weight of the glass and / or glass composition. In an embodiment, the BaO comprised in the glass or glass-ceramic composition can be: from 0 wt% to about 7 wt%, from 0 wt% to about 6 wt%, from 0 wt% to about 5 wt%, from 0 wt% to about 4 wt%, from 0 wt% to about 3 wt%, from 0 wt% to about 2 wt%, from 0 wt% to about 1 wt%, from 0 wt% to about 0.5 wt%, from about 0.01 wt% to about 8 wt%, from about 0.01 wt% to about 6 wt%, from about 0.01 wt% to about 4 wt%, from about 0.01 wt% to about 3 wt%, from about 0.01 wt% to about 2 wt%, from about 0.01 wt% to about 1 wt%, from about 0.1 wt% to about 8 wt%, from about 0.1 wt% to about 6 wt%, from about 0.1 wt% to about 4 wt%, from about 0.1 wt% to about 2 wt%, from about 0.1 wt% to about 1 wt%, from about 1 wt% to about 8 wt%, from about 1 wt% to about 6 wt%, from about 1 wt% to about 4 wt%, from about 1 wt% to about 2 wt%, from about 2 wt% to about 8 wt%, from about 2 wt% to about 6 wt%, from about 2 wt% to about 4 wt%, from about 4 wt% to about 8 wt%, from about 4 wt% to about 6 wt%, or from about 6 wt% to about 8 wt%, based on the total weight of the glass and / or glass-ceramic.

[0258] In an embodiment, the glass or glass-ceramic composition may contain boron. In an embodiment, the glass and / or glass-ceramic composition may contain B 2 O 3 . B 2 O 3 can reduce the melting temperature of the residual glass phase of the glass-ceramic. B 2 O 3 may also be added to reduce the viscosity of the residual glass phase. In an embodiment, the glass or glass-ceramic composition may contain from 0 wt% to about 10 wt% or from 0 wt% to about 2 wt% Ba 2 O 3 , based on the total weight of the glass and / or glass-ceramic composition. In an embodiment, the B 2 O 3 contained in the glass or glass-ceramic composition may be: 0 wt% to about 9 wt%, 0 wt% to about 8 wt%, 0 wt% to about 7 wt%, 0 wt% to about 6 wt%, 0 wt% to about 5 wt%, 0 wt% to about 4 wt%, 0 wt% to about 3 wt%, 0 wt% to about 2 wt%, 0 wt% to about 1 wt%, >0 wt% to about 10 wt%, >0 wt% to about 9 wt%, >0 wt% to about 8 wt%, >0 wt% to about 7 wt%, >0 wt% to about 6 wt%, >0 wt% to about 5 wt%, >0 wt% to about 4 wt%, >0 wt% to about 3 wt%, >0 wt% to about 2 wt%, >0 wt% to about 1 wt%, about 1 wt% to about 10 wt%, about 1 wt% to about 8 wt%, about 1 wt% to about 6 wt%, about 1 wt% to about 5 wt%, about 1 wt% to about 4 wt%, about 1 wt% to about 2 wt%, about 2 wt% to about 10 wt%, about 2 wt% to about 8 wt%, about 2 wt% to about 6 wt%, about 2 wt% to about 4 wt%, about 3 wt% to about 10 wt%, about 3 wt% to about 8 wt%, about 3 wt% to about 6 wt%, about 3 wt% to about 4 wt%, about 4 wt% to about 5 wt%, about 5 wt% to about 8 wt%, about 5 wt% to about 7.5 wt%, about 5 wt% to about 6 wt%, or about 5 wt% to about 5.5 wt%, based on the total weight of the glass and / or glass-ceramic.

[0259] In an embodiment, the glass or glass-ceramic composition may further contain one or more constituent components such as, but not limited to: TiO 2 , CeO 2 , HfO 2 , Fe 2 O 3 , SnO 2, or combinations thereof. As a supplement or alternative, an antimicrobial component can be added to the glass or glass-ceramic composition. Antimicrobial components that can be added to the glass or glass-ceramic can include, but are not limited to: Ag, AgO, Cu, CuO, and Cu 2 O, etc. In some embodiments, the glass or glass-ceramic composition can further contain a chemical clarifying agent. Such clarifying agents include, but are not limited to, SnO 2 、As 2 O 3 、Sb 2 O 3 、F, Cl, and Br. Other details of other additives or constituent components of the glass and / or glass-ceramic compositions suitable for various embodiments can be found, for example, in U.S. Patent Application Publication No. 2016 / 0102010, filed October 8, 2015, entitled "High Strength Glass-Ceramics Having Petalite and Lithium Silicate Structures", the entire text of which is incorporated herein by reference.

[0260] In an embodiment, the glass and / or glass-ceramic composition can contain one or more of the following: Fe 2 O 3 、SnO 2 、HfO 2 、TiO 2 , or combinations thereof. In an embodiment, the glass and / or glass-ceramic disclosed herein can contain from 0 to about 0.5 wt% SnO 2 , based on the total weight of the glass and / or glass-ceramic. In an embodiment, the glass or glass-ceramic composition contains SnO 2may be: 0 to about 1 wt%, 0 to about 0.5 wt%, 0 to about 0.4 wt%, 0 to about 0.3 wt%, 0 to about 0.2 wt%, 0 to about 0.1 wt%, about 0.05 wt% to about 1 wt%, about 0.05 wt% to about 0.5 wt%, about 0.05 wt% to about 0.4 wt%, about 0.05 wt% to about 0.3 wt%, about 0.05 wt% to about 0.2 wt%, about 0.05 wt% to about 0.1 wt%, about 0.1 wt% to about 1 wt%, about 0.1 wt% to about 0.5 wt%, about 0.1 wt% to about 0.4 wt%, about 0.1 wt% to about 0.3 wt%, about 0.1 wt% to about 0.2 wt%, about 0.3 wt% to about 1 wt%, about 0.3 to about 0.5 wt%, about 0.3 to about 0.4 wt%, about 0.4 wt% to 1 wt%, or about 0.5 to about 1 wt%, based on the total weight of the glass or glass-ceramic. In an embodiment, the glass or glass-ceramic composition comprises HfO 2 may be: 0 to about 3 wt%, 0 to about 2 wt%, 0 to about 1 wt%, 0 to about 0.5 wt%, 0 to about 0.1 wt%, about 0.05 wt% to about 3 wt%, about 0.05 wt% to about 2 wt%, about 0.05 wt% to about 1 wt%, about 0.05 wt% to about 0.5 wt%, about 0.05 wt% to about 0.1 wt%, about 0.1 wt% to about 3 wt%, about 0.1 wt% to about 2 wt%, about 0.1 wt% to about 1 wt%, about 0.1 wt% to about 0.5 wt%, about 0.5 wt% to about 3 wt%, about 0.5 wt% to about 2 wt%, about 0.5 wt% to about 1 wt%, about 1 wt% to about 3 wt%, about 1 wt% to about 2 wt%, or about 2 wt% to about 3 wt%, based on the total weight of the glass or glass-ceramic. In an embodiment, the glass or glass-ceramic composition comprises Fe 2 O 3can be: 0 to about 3 wt%, 0 to about 2 wt%, 0 to about 1 wt%, 0 to about 0.5 wt%, 0 to about 0.1 wt%, about 0.05 wt% to about 3 wt%, about 0.05 wt% to about 2 wt%, about 0.05 wt% to about 1 wt%, about 0.05 wt% to about 0.5 wt%, about 0.05 wt% to about 0.1 wt%, about 0.1 wt% to about 3 wt%, about 0.1 wt% to about 2 wt%, about 0.1 wt% to about 1 wt%, about 0.1 wt% to about 0.5 wt%, about 0.5 wt% to about 3 wt%, about 0.5 wt% to about 2 wt%, about 0.5 wt% to about 1 wt%, about 1 wt% to about 3 wt%, about 1 wt% to about 2 wt%, or about 2 wt% to about 3 wt%, based on the total weight of the glass or glass-ceramic. In an embodiment, the glass or glass-ceramic disclosed herein may comprise 0 to about 5 wt% TiO 2 , based on the total weight of the glass or glass-ceramic. In an embodiment, the glass or glass-ceramic composition comprises TiO 2 can be: 0 to about 5 wt%, 0 to about 4 wt%, 0 to about 3 wt%, 0 to about 2 wt%, 0 to about 1 wt%, about 1 to about 5 wt%, about 1 to about 4 wt%, about 1 to about 3 wt%, about 1 to about 2 wt%, about 2 to about 5 wt%, about 2 to about 4 wt%, about 2 to about 3 wt%, about 3 to about 5 wt%, about 3 to about 4 wt%, or about 4 to about 5 wt%, based on the total weight of the glass or glass-ceramic composition.

[0261] Composition (mol%)

[0262] In an embodiment, the glass or glass-ceramic composition may be expressed in mole percentages (mol%) rather than the wt% described above. As discussed above, the glass or glass-ceramic composition may comprise SiO 2 , Al 2 O 3 , LiO 2 , ZrO 2 and P 2 O 5 . In addition, the glass or glass-ceramic composition may comprise: one or more non-lithium alkali metal oxides (e.g., Na 2 O, K 2 O or both), one or more alkaline earth metal oxides (e.g., CaO, MgO, SrO, BaO, or combinations thereof), one or more transition metal oxides (e.g., ZnO), or combinations thereof.

[0263] In an embodiment, the glass or glass-ceramic composition may comprise about 55 mol% to about 80 mol% SiO 2, based on the total moles of the glass or glass-ceramic composition. In an embodiment, the glass or glass-ceramic composition contains SiO 2 may be: about 55 mol% to about 72 mol%, about 55 mol% to about 71 mol%, about 55 mol% to about 70 mol%, about 60 mol% to about 80 mol%, about 60 mol% to about 72 mol%, about 60 mol% to about 71 mol%, about 60 mol% to about 70 mol%, about 65 mol% to about 80 mol%, about 65 mol% to about 72 mol%, about 65 mol% to about 71 mol%, about 65 mol% to about 70 mol%, about 68 mol% to about 80 mol%, about 68 mol% to about 72 mol%, about 68 mol% to about 71 mol%, about 68 mol% to 70 mol%, about 70 mol% to about 80 mol%, about 70 mol% to about 72 mol%, or about 71 mol% to about 80 mol%, based on the total moles of the glass or glass-ceramic composition. In an embodiment, the glass or glass-ceramic composition may contain about 68.2 mol% to about 70.4 mol% SiO 2 , based on the total moles of the glass or glass-ceramic composition.

[0264] In an embodiment, the glass or glass-ceramic composition may contain about 0 to about 15 mol% Al 2 O 3 , based on the total moles of the glass or glass-ceramic composition. In an embodiment, the Al 2 O 3 contained in the glass or glass-ceramic composition may be: 0 mol% to about 6 mol%, 0 mol% to about 5 mol%, 0 mol% to about 4.5 mol%, greater than 0 mol% to about 15 mol%, greater than 0 mol% to about 6 mol%, greater than 0 mol% to about 5 mol%, greater than 0 mol% to about 4.5 mol%, about 0.01 mol% to about 15 mol%, about 0.01 mol% to about 6 mol%, about 0.01 mol% to about 5 mol%, about 0.01 mol% to about 4.5 mol%, about 1 mol% to about 15 mol%, about 1 mol% to about 6 mol%, about 1 mol% to about 5 mol%, about 1 mol% to about 4.5 mol%, about 3 mol% to about 15 mol%, about 3 mol% to about 6 mol%, about 3 mol% to about 5 mol%, about 3 mol% to about 4.5 mol%, about 3.5 mol% to about 15 mol%, about 3.5 mol% to about 6 mol%, about 3.5 mol% to about 5 mol%, about 3.5 mol% to about 4.5 mol%, about 4.5 mol% to about 15 mol%, about 4.5 mol% to about 6 mol%, about 4.5 mol% to about 5 mol%, about 5 mol% to about 15 mol%, or about 5 mol% to about 6 mol%, based on the total moles of the glass or glass-ceramic composition.

[0265] In an embodiment, the glass or glass-ceramic composition can comprise from about 10 to about 40 mole % Li 2 O, based on the total moles of the glass or glass-ceramic composition. In an embodiment, the Li 2 O comprised in the glass or glass-ceramic composition can be: from about 10 mole % to about 32 mole %, from about 10 mole % to about 27 mole %, from about 10 mole % to about 25 mole %, from about 10 mole % to about 23 mole %, from about 18 mole % to about 40 mole %, from about 18 mole % to about 32 mole %, from about 18 mole % to about 27 mole %, from about 18 mole % to about 25 mole %, from about 18 mole % to about 23 mole %, from about 20 mole % to about 40 mole %, from about 20 mole % to about 32 mole %, from about 20 mole % to about 27 mole %, from about 20 mole % to about 25 mole %, from about 20 mole % to about 23 mole %, from about 23 mole % to about 40 mole %, from about 23 mole % to about 32 mole %, from about 23 mole % to about 27 mole %, from about 23 mole % to about 25 mole %, from about 25 mole % to about 40 mole %, from about 25 mole % to about 32 mole %, from about 25 mole % to about 27 mole %, from about 27 mole % to about 40 mole %, from about 27 mole % to about 32 mole %, or from about 32 mole % to about 40 mole %, based on the total moles of the glass or glass-ceramic composition.

[0266] The glass and glass-ceramic compositions can comprise P 2 O 5 . P 2 O 5 can function as a nucleating agent to produce bulk nucleation. If the concentration of P 2 O 5 is too low, the precursor glass does crystallize, but only at a higher temperature (due to the lower viscosity), and a weak and often deformed body forms from the surface inward; however, if the concentration of P 2 O 5 is too high, it becomes difficult to control the devitrification after cooling during the formation of the precursor glass. In an embodiment, the glass or glass-ceramic composition disclosed herein can comprise from about 0.2 mole % to about 4.0 mole % P 2 O 5 , based on the total moles of the glass or glass-ceramic composition. In an embodiment, the P 2 O 5It may be: about 0.2 mol% to about 2.2 mol%, about 0.2 mol% to about 1.0 mol%, about 0.6 mol% to about 4 mol%, about 0.6 mol% to about 2.2 mol%, about 0.6 mol% to about 1.0 mol%, about 0.7 mol% to about 4 mol%, about 0.7 mol% to about 2.2 mol%, about 0.7 mol% to about 1.0 mol%, about 0.8 mol% to about 4 mol%, about 0.8 mol% to about 2.2 mol%, about 0.8 mol% to about 1.0 mol%, about 1.0 mol% to about 4 mol%, about 1.0 mol% to about 2.2 mol%, or about 2.2 mol% to about 4 mol%, based on the total moles of the glass or glass-ceramic composition.

[0267] In the glasses and glass-ceramics disclosed herein, ZrO is typically found 2 The stability of Li 2 O-Al 2 O 3 -SiO 2 -P 2 O 5 glass can be improved by significantly reducing glass devitrification during forming and by lowering the liquidus temperature. Adding ZrO 2 can also help reduce the grain size of the crystals, which aids in forming a transparent glass-ceramic. In an embodiment, the glass or glass-ceramic composition can comprise from about 0.1 mol% to about 10 mol% ZrO 2 , based on the total weight of the glass or glass-ceramic composition. In an embodiment, the glass or glass-ceramic composition comprises ZrO 2It may be: about 0.1 mol% to about 5 mol%, about 0.1 mol% to 4 mol%, about 0.1 mol% to about 3.5 mol%, about 0.1 mol% to about 3 mol%, about 1 mol% to about 10 mol%, about 1 mol% to about 5 mol%, about 1 mol% to 4 mol%, about 1 mol% to about 3.5 mol%, about 1 mol% to about 3 mol%, about 1.5 mol% to about 10 mol%, about 1.5 mol% to about 5 mol%, about 1.5 mol% to 4 mol%, about 1.5 mol% to about 3.5 mol%, about 1.5 mol% to about 3 mol%, about 1.6 mol% to about 10 mol%, about 1.6 mol% to about 5 mol%, about 1.6 mol% to 4 mol%, about 1.6 mol% to about 3.5 mol%, about 1.6 mol% to about 3 mol%, about 1.7 mol% to about 10 mol%, about 1.7 mol% to about 5 mol%, about 1.7 mol% to 4 mol%, about 1.7 mol% to about 3.5 mol%, about 1.7 mol% to about 3 mol%, about 2 mol% to about 10 mol%, about 2 mol% to about 5 mol%, about 2 mol% to 4 mol%, about 2 mol% to about 3.5 mol%, about 2 mol% to about 3 mol%, about 3 mol% to about 10 mol%, about 3 mol% to about 5 mol%, about 3 mol% to 4 mol%, about 3 mol% to about 3.5 mol%, about 3.5 mol% to about 10 mol%, about 3.5 mol% to about 5 mol%, about 3.5 mol% to 4 mol%, about 4 mol% to about 10 mol%, about 4 mol% to about 5 mol%, or about 5 mol% to 10 mol%, based on the total moles of the glass or glass-ceramic composition.

[0268] As discussed above, the disclosed glasses and glass-ceramics can include non-lithium alkali metal oxides such as Na 2 O, K 2 O, or both. Non-lithium alkaline oxides (e.g., Na 2 O, K 2 O, or both) tend to reduce the formation of the glass-ceramic and instead form a residual glass phase in the glass-ceramic. The non-lithium alkali metal oxides, as well as ZrO 2 are not incorporated into the crystalline phase lithium disilicate (Li 2 O 5 Si 2 ) or spodumene (LiAlSi 4 O 10 ) during the ceramization process and thus remain in the residual vitreous phase after the ceramization process. It is well known that Na 2 O and K 2O acts as a "flux" in glass chemistry, which refers to a constituent that reduces the viscosity of the glass (e.g., the residual glass phase). The concentration of non-lithium alkali metal oxides in the glass or glass-ceramic composition can be sufficient to: increase the concentration of the residual glass phase in the glass-ceramic, reduce the viscosity of the residual glass phase in the glass-ceramic, or both. In an embodiment, the glass or glass-ceramic composition can have Na of greater than or equal to 0 mol%, greater than or equal to about 0.5 mol% or even greater than or equal to about 1.3 mol% 2 O, K 2 O or both, based on the total moles of the glass or glass-ceramic composition. In an embodiment, the glass or glass-ceramic composition can contain from about 0 mol% (zero mol%) to about 9 mol% of total non-lithium alkali metal oxides, based on the total moles of the glass or glass-ceramic composition. In an embodiment, the non-lithium alkali metal oxides contained in the glass or glass-ceramic composition can be: 0 mol% to about 8 mol%, 0 mol% to about 7 mol%, 0 mol% to about 6 mol%, 0 mol% to about 5 mol%, about 0.5 mol% to about 9 mol%, about 0.5 mol% to about 8 mol%, about 0.5 mol% to about 7 mol%, about 0.5 mol% to about 6 mol%, about 0.5 mol% to about 5 mol%, about 1.3 mol% to about 9 mol%, about 1.3 mol% to about 8 mol%, about 1.3 mol% to about 7 mol%, about 1.3 mol% to about 6 mol%, about 1.3 mol% to about 5 mol%, about 1.3 mol% to about 3 mol%, or about 5 mol% to about 9 mol%, based on the total moles of the glass or glass-ceramic composition. In an embodiment, the glass or glass-ceramic composition can contain 0.5 mol% to 9 mol% of non-lithium alkali metal oxides, based on the total moles of the glass or glass composition, wherein the non-lithium alkali metal oxides include Na 2 O, K 2 O or a combination thereof.

[0269] In an embodiment, the glass or glass-ceramic composition can contain Na 2 O. In an embodiment, the glass or glass-ceramic composition can contain from 0 mol% to about 5 mol% Na 2 O, based on the total moles of the glass or glass-ceramic composition. In an embodiment, the Na contained in the glass or glass-ceramic composition 2O can be: 0 mol% to about 4 mol%, 0 mol% to about 3 mol%, 0 mol% to about 2 mol%, about 0.5 mol% to about 5 mol%, about 0.5 mol% to about 4 mol%, about 0.5 mol% to about 3 mol%, about 0.5 mol% to about 2 mol%, about 1 mol% to about 5 mol%, about 1 mol% to about 4 mol%, about 1 mol% to about 3 mol%, about 1 mol% to about 2 mol%, about 1.3 mol% to about 5 mol%, about 1.3 mol% to about 4 mol%, about 1.3 mol% to about 3 mol%, about 1.3 mol% to about 2 mol%, about 2 mol% to about 5 mol%, about 2 mol% to about 4 mol%, about 2 mol% to about 3 mol%, about 3 mol% to about 5 mol%, about 3 mol% to about 4 mol%, or about 4 mol% to about 5 mol%, based on the total moles of the glass or glass-ceramic composition.

[0270] In an embodiment, the glass or glass-ceramic composition may comprise K 2 O. In an embodiment, the glass or glass-ceramic composition may comprise 0 mol% to about 4 mol% K 2 O, based on the total moles of the glass or glass-ceramic composition. In an embodiment, the K 2 O comprised in the glass or glass-ceramic composition can be: 0 mol% to about 3 mol%, 0 mol% to about 2 mol%, 0 mol% to about 1.5 mol%, 0 mol% to 1.2 mol%, about 0.5 mol% to about 4 mol%, about 0.5 mol% to about 3 mol%, about 0.5 mol% to about 2 mol%, about 0.5 mol% to about 1.5 mol%, about 0.5 mol% to about 1.2 mol%, about 1 mol% to about 4 mol%, about 1 mol% to about 3 mol%, about 1 mol% to about 2 mol%, about 1 mol% to about 1.5 mol%, about 1.2 mol% to about 4 mol%, about 1.2 mol% to about 3 mol%, about 1.2 mol% to about 2 mol%, about 1.2 mol% to about 1.5 mol%, about 1.5 mol% to about 4 mol%, about 1.5 mol% to about 3 mol%, about 1.5 mol% to about 2 mol%, about 2 mol% to about 4 mol%, about 2 mol% to about 3 mol%, or about 3 mol% to about 4 mol%, based on the total moles of the glass or glass-ceramic composition.

[0271] As discussed above, adding Na 2 O and K 2 O can tend to reduce the viscosity of the residual glass phase. Conversely, alumina (Al 2 O 3 ) and zirconia (ZrO 2 ) tend to increase the viscosity of the glass (such as the residual glass phase). After ceramization, Na 2 O, K 2O and ZrO 2 The crystal phase that does not enter the glass-ceramic. Part of Al 2 O 3 may also remain in the residual vitreous phase. Therefore, increasing the molar ratio of non-lithium alkali metal oxides relative to Al 2 O 3 , ZrO 2 or the two of them can reduce the viscosity of the residual glass phase, which can make it easier to thermoform the glass-ceramic with a 3D shape during the 3D forming step.

[0272] In an embodiment, the total non-lithium alkali metal oxides ([Na 2 O + K 2 O]) in the glass or glass-ceramic composition and Al 2 O 3 The molar ratio can be sufficient such that the ceramified glass-ceramic is 3D formable without causing the glass-ceramic to break. In an embodiment, the glass or glass-ceramic composition can have a [Na 2 O + K 2 O] / [Al 2 O 3 molar ratio greater than or equal to about 0.1, greater than or equal to about 0.3, or even greater than or equal to about 0.5. In an embodiment, the glass or glass-ceramic composition has a [Na 2 O + K 2 O] / [Al 2 O 3 molar ratio can be: about 0.1 to about 5, about 0.1 to about 4, about 0.1 to about 3, about 0.1 to about 2, about 0.1 to about 1, about 0.3 to about 5, about 0.3 to about 4, about 0.3 to about 3, about 0.3 to about 2, about 0.3 to about 1, about 0.5 to about 5, about 0.5 to about 4, about 0.5 to about 3, about 0.5 to about 2, about 0.5 to about 1, about 1 to about 5, about 1 to about 4, about 1 to about 3, about 1 to about 2, about 2 to about 5, about 2 to about 4, about 2 to about 3, about 3 to about 5, or about 3 to about 4.

[0273] In an embodiment, the total non-lithium alkali metal oxides ([Na 2 O + K 2 O]) in the glass or glass-ceramic composition and ZrO 2 The molar ratio can be sufficient such that the ceramified glass-ceramic is 3D formable without causing the glass-ceramic to break. In an embodiment, the glass or glass-ceramic composition can have a [Na 2 O + K 2 O] / [ZrO2 molar ratio. In an embodiment, the glass or glass-ceramic composition has [Na 2 O + K 2 O] / [ZrO 2 molar ratio can be: about 0.3 to about 5, about 0.3 to about 4, about 0.3 to about 3, about 0.3 to about 2, about 0.3 to about 1, about 0.4 to about 5, about 0.4 to about 4, about 0.4 to about 3, about 0.4 to about 2, about 0.4 to about 1, about 0.5 to about 5, about 0.5 to about 4, about 0.5 to about 3, about 0.5 to about 2, about 0.5 to about 1, about 0.6 to about 5, about 0.6 to about 4, about 0.6 to about 3, about 0.6 to about 2, about 0.6 to about 1, about 1 to about 5, about 1 to about 4, about 1 to about 3, about 1 to about 2, about 2 to about 5, about 2 to about 4, about 2 to about 3, about 3 to about 5, or about 3 to about 4.

[0274] Increasing the concentration of non-lithium alkali metal oxides in the glass-ceramic composition (i.e., [Na 2 O + K 2 ), increasing the molar ratio of non-lithium alkali metal to Al 2 O 3 ), increasing the molar ratio of non-lithium alkali metal to ZrO 2 ), or a combination of these can reduce the viscosity of the residual glass phase in the glass-ceramic. In addition, increasing the amount of [Na 2 O + K 2 O] and ZrO 2 can increase the concentration of the residual glass phase in the transparent glass-ceramic disclosed herein. Increasing the concentration of the residual glass phase in the glass-ceramic, reducing the viscosity of the residual glass phase in the glass-ceramic (or both cases simultaneously) can enable the thermal 3D forming of the glass-ceramic after ceramization, as discussed earlier herein.

[0275] In addition to non-lithium alkali metal oxides, alkaline earth metal oxides and some transition metal oxides can also be included in the glass and glass-ceramic compositions. When included, the alkaline earth metal oxides and transition metal oxides can partition into the residual glass phase. The alkaline earth metal oxides can include CaO, MgO, SrO, BaO, or combinations thereof. The transition metal oxides that can be incorporated into the glasses and / or glass-ceramics disclosed herein can include zinc oxide (ZnO). As used herein, the term "RO" refers to one or more of the following: ZnO, CaO, MgO, SrO, BaO, or combinations thereof. ZnO, CaO, MgO, SrO, BaO, or combinations thereof can be added to the glass-ceramic composition to increase the concentration of the residual glass phase, decrease the viscosity of the residual glass phase, or combinations thereof. In embodiments, the glasses or glass-ceramic compositions disclosed herein can include one or more of the following: ZnO, CaO, MgO, SrO, BaO, or combinations thereof. As a supplement or alternative to the non-lithium alkali metal oxides, ZnO, CaO, MgO, SrO, BaO, or combinations thereof can be included. In embodiments, the total concentration of the non-lithium alkali metal oxides may not be sufficient to enable 3D shaping of the glass-ceramic after ceramization, e.g., the total concentration of the non-lithium alkali metal oxides is less than about 0.5 mole %. When the total concentration of the non-lithium alkali metal oxides is less than about 0.5 mole %, the concentration of RO can be increased to increase the concentration and decrease the viscosity of the residual glass phase to enable 3D shaping of the glass-ceramic after ceramization. In embodiments, RO can be included or the concentration increased even when the concentration of the non-alkali metal oxides is greater than 0.5 mole %.

[0276] In an embodiment, the total RO in the glass or glass-ceramic composition can be: greater than or equal to 0 mol%, greater than or equal to about 0.01 mol%, greater than or equal to about 0.1 mol%, or even greater than or equal to 0.5 mol%, based on the total moles of the glass or glass-ceramic composition, where RO is ZnO, CaO, MgO, SrO, BaO, or a combination thereof. In an embodiment, the glass or glass-ceramic composition can contain from 0 mol% (zero mol%) to about 10 mol% of total RO, based on the total moles of the glass or glass-ceramic composition. In an embodiment, the total RO contained in the glass or glass-ceramic composition can be: from 0 mol% to about 10 mol%, from 0 mol% to about 8 mol%, from 0 mol% to about 6 mol%, from 0 mol% to about 5 mol%, from about 0.01 mol% to about 10 mol%, from about 0.01 mol% to about 8 mol%, from about 0.01 mol% to about 6 mol%, from about 0.01 mol% to about 5 mol%, from about 0.1 mol% to about 10 mol%, from about 0.1 mol% to about 8 mol%, from about 0.1 mol% to about 6 mol%, from about 0.1 mol% to about 5 mol%, from about 0.5 mol% to about 10 mol%, from about 0.5 mol% to about 8 mol%, from about 0.5 mol% to about 6 mol%, or from about 0.5 mol% to about 5 mol%, based on the total moles of the glass or glass-ceramic composition. In an embodiment, the glass or glass-ceramic composition may not contain ZnO, MgO, CaO, SrO, BaO, or a combination of these.

[0277] In an embodiment, the glass or glass-ceramic composition can contain ZnO. In an embodiment, the glass or glass-ceramic composition can contain from 0 mol% to about 8 mol% ZnO, based on the total moles of the glass or glass-ceramic composition. In an embodiment, the ZnO contained in the glass or glass-ceramic composition can be: from 0 mol% to about 6 mol%, from 0 mol% to about 5 mol%, from 0 mol% to about 3 mol%, from about 0.001 mol% to about 8 mol%, from about 0.001 mol% to about 6 mol%, from about 0.001 mol% to about 5 mol%, from about 0.001 mol% to about 3 mol%, from about 0.01 mol% to about 8 mol%, from about 0.01 mol% to about 6 mol%, from about 0.01 mol% to about 5 mol%, from about 0.01 mol% to about 3 mol%, from about 0.1 mol% to about 8 mol%, from about 0.1 mol% to about 6 mol%, from about 0.1 mol% to about 5 mol%, or from about 0.5 mol% to about 3 mol%, based on the total moles of the glass or glass-ceramic composition.

[0278] In an embodiment, the glass or glass-ceramic composition may comprise MgO. In an embodiment, the glass or glass-ceramic composition may comprise from 0 mole % to about 8 mole % MgO, based on the total moles of the glass or glass-ceramic composition. In an embodiment, the amount of MgO comprised in the glass or glass-ceramic composition may be: from 0 mole % to about 6 mole %, from 0 mole % to about 5 mole %, from 0 mole % to about 3 mole %, from about 0.001 mole % to about 8 mole %, from about 0.001 mole % to about 6 mole %, from about 0.001 mole % to about 5 mole %, from about 0.001 mole % to about 3 mole %, from about 0.01 mole % to about 8 mole %, from about 0.01 mole % to about 6 mole %, from about 0.01 mole % to about 5 mole %, from about 0.01 mole % to about 3 mole %, from about 0.1 mole % to about 8 mole %, from about 0.1 mole % to about 6 mole %, from about 0.1 mole % to about 5 mole %, or from about 0.1 mole % to about 3 mole %, based on the total moles of the glass or glass-ceramic composition.

[0279] In an embodiment, the glass or glass-ceramic composition may comprise CaO. In an embodiment, the glass or glass-ceramic composition may comprise from 0 mole % to about 8 mole % CaO, based on the total moles of the glass or glass-ceramic composition. In an embodiment, the amount of CaO comprised in the glass or glass-ceramic composition may be: from 0 mole % to about 6 mole %, from 0 mole % to about 5 mole %, from 0 mole % to about 3 mole %, from about 0.001 mole % to about 8 mole %, from about 0.001 mole % to about 6 mole %, from about 0.001 mole % to about 5 mole %, from about 0.001 mole % to about 3 mole %, from about 0.01 mole % to about 8 mole %, from about 0.01 mole % to about 6 mole %, from about 0.01 mole % to about 5 mole %, from about 0.01 mole % to about 3 mole %, from about 0.1 mole % to about 8 mole %, from about 0.1 mole % to about 6 mole %, from about 0.1 mole % to about 5 mole %, or from about 0.1 mole % to about 3 mole %, based on the total moles of the glass or glass-ceramic composition.

[0280] In an embodiment, the glass or glass-ceramic composition may comprise SrO. In an embodiment, the glass or glass-ceramic composition may comprise from 0 mole % to about 8 mole % SrO, based on the total moles of the glass or glass-ceramic composition. In an embodiment, the SrO comprised in the glass or glass-ceramic composition may be: from 0 mole % to about 6 mole %, from 0 mole % to about 5 mole %, from 0 mole % to about 3 mole %, from about 0.001 mole % to about 8 mole %, from about 0.001 mole % to about 6 mole %, from about 0.001 mole % to about 5 mole %, from about 0.001 mole % to about 3 mole %, from about 0.01 mole % to about 8 mole %, from about 0.01 mole % to about 6 mole %, from about 0.01 mole % to about 5 mole %, from about 0.01 mole % to about 3 mole %, from about 0.1 mole % to about 8 mole %, from about 0.1 mole % to about 6 mole %, from about 0.1 mole % to about 5 mole %, or from about 0.1 mole % to about 3 mole %, based on the total moles of the glass or glass-ceramic composition.

[0281] In an embodiment, the glass or glass-ceramic composition may comprise BaO. In an embodiment, the glass or glass-ceramic composition may comprise from 0 mole % to about 8 mole % BaO, based on the total moles of the glass or glass-ceramic composition. In an embodiment, the BaO comprised in the glass or glass-ceramic composition may be: from 0 mole % to about 6 mole %, from 0 mole % to about 5 mole %, from 0 mole % to about 3 mole %, from about 0.001 mole % to about 8 mole %, from about 0.001 mole % to about 6 mole %, from about 0.001 mole % to about 5 mole %, from about 0.001 mole % to about 3 mole %, from about 0.01 mole % to about 8 mole %, from about 0.01 mole % to about 6 mole %, from about 0.01 mole % to about 5 mole %, from about 0.01 mole % to about 3 mole %, from about 0.1 mole % to about 8 mole %, from about 0.1 mole % to about 6 mole %, from about 0.1 mole % to about 5 mole %, or from about 0.1 mole % to about 3 mole %, based on the total moles of the glass or glass-ceramic composition.

[0282] As discussed above, adding ZnO and / or alkaline earth metal oxides may tend to increase the concentration of the residual glass phase, decrease the viscosity of the residual glass phase, or both. Conversely, alumina (Al 2 O 3 ) and zirconia (ZrO 2 ) tend to increase the viscosity of the glass (e.g., the residual glass phase). After ceramization, ZnO, CaO, MgO, BaO, SrO, and ZrO 2 do not enter the crystalline phase of the glass-ceramic. A portion of Al 2 O 3 may also remain in the residual glass phase. Thus, increasing RO relative to Al2 O 3 , ZrO 2 Alternatively, the molar ratio of these two can reduce the viscosity of the residual glass phase, which can make it easier to thermoform a glass-ceramic having a 3D shape during the 3D forming step.

[0283] In an embodiment, the total RO ([ZnO + MgO + CaO + SrO + BaO]) of the glass or glass-ceramic composition and Al 2 O 3 The molar ratio can be sufficient such that the ceramified glass-ceramic is 3D formable without causing the glass-ceramic to break. In an embodiment, the glass or glass-ceramic composition can have a [ZnO + MgO + CaO + SrO + BaO] / [Al 2 O 3 molar ratio that is greater than or equal to about 0.05, greater than or equal to about 0.1, or even greater than or equal to about 0.3. In an embodiment, the glass or glass-ceramic composition has a [ZnO + MgO + CaO + SrO + BaO] / [Al 2 O 3 molar ratio that can be: about 0.05 to about 5, about 0.05 to about 4, about 0.05 to about 3, about 0.05 to about 2, about 0.05 to about 1, about 0.1 to about 5, about 0.1 to about 4, about 0.1 to about 3, about 0.1 to about 2, about 0.1 to about 1, about 0.3 to about 5, about 0.3 to about 4, about 0.3 to about 3, about 0.3 to about 2, about 0.3 to about 1, about 1 to about 5, about 1 to about 4, about 1 to about 3, about 1 to about 2, about 2 to about 5, about 2 to about 4, about 2 to about 3, about 3 to about 5, or about 3 to about 4.

[0284] In an embodiment, the total RO ([ZnO + MgO + CaO + SrO + BaO]) of the glass or glass-ceramic composition and ZrO 2 The molar ratio can be sufficient such that the ceramified glass-ceramic is 3D formable without causing the glass-ceramic to break. In an embodiment, the glass or glass-ceramic composition can have a [ZnO + MgO + CaO + SrO + BaO] / [ZrO 2 molar ratio that is greater than or equal to about 0.1, greater than or equal to about 0.3, or even greater than or equal to about 0.5. In an embodiment, the glass or glass-ceramic composition has a [ZnO + MgO + CaO + SrO + BaO] / [ZrO 2The molar ratio can be: from about 0.1 to about 5, from about 0.1 to about 4, from about 0.1 to about 3, from about 0.1 to about 2, from about 0.1 to about 1, from about 0.3 to about 5, from about 0.3 to about 4, from about 0.3 to about 3, from about 0.3 to about 2, from about 0.3 to about 1, from about 0.5 to about 5, from about 0.5 to about 4, from about 0.5 to about 3, from about 0.5 to about 2, from about 0.5 to about 1, from about 1 to about 5, from about 1 to about 4, from about 1 to about 3, from about 1 to about 2, from about 2 to about 5, from about 2 to about 4, from about 2 to about 3, from about 3 to about 5, or from about 3 to about 4.

[0285] The concentration of RO (i.e., ZnO, CaO, MgO, SrO, BaO, or a combination thereof) can be increased, the molar ratio of RO to Al 2 O 3 (i.e., [RO] / [Al 2 O 3 ) can be increased, the molar ratio of RO to ZrO 2 (i.e., [RO] / [ZrO 2 ) can be increased, or a combination of these can be used to increase the concentration of the residual glass phase, decrease the viscosity of the residual glass phase, or both. By varying the amount of RO in the glass-ceramic composition to increase the concentration of the residual glass phase and / or decrease the viscosity of the residual glass phase, 3D shaping of the glass-ceramic after ceramization can be achieved to produce a glass-ceramic article as disclosed herein. In an embodiment, the glass and / or glass-ceramic composition can comprise ZnO and one or more alkaline earth metal oxides selected from the group consisting of CaO, MgO, BaO, SrO, and combinations thereof.

[0286] In an embodiment, the glass or glass-ceramic composition can comprise B 2 O 3 . The glass or glass-ceramic composition disclosed herein can comprise from 0 mol% to about 10 mol% B 2 O 3 , based on the total moles of the glass or glass-ceramic composition. In an embodiment, the glass or glass-ceramic composition comprises B 2 O 3It may be: 0 mol% to about 8 mol%, 0 mol% to about 6 mol%, 0 mol% to about 5 mol%, 0 mol% to about 3 mol%, about 0.01 mol% to about 10 mol%, about 0.01 mol% to about 8 mol%, about 0.01 mol% to about 6 mol%, about 0.01 mol% to about 5 mol%, about 0.01 mol% to about 3 mol%, about 0.1 mol% to about 10 mol%, about 0.1 mol% to about 8 mol%, about 0.1 mol% to about 6 mol%, about 0.1 mol% to about 5 mol%, about 0.1 mol% to about 3 mol%, about 1 mol% to about 10 mol%, about 1 mol% to about 8 mol%, about 1 mol% to about 6 mol%, about 1 mol% to about 5 mol%, about 1 mol% to about 3 mol%, about 3 mol% to about 10 mol%, about 3 mol% to about 8 mol%, about 3 mol% to about 6 mol%, about 3 mol% to about 5 mol%, about 5 mol% to about 10 mol%, about 5 mol% to about 8 mol%, or about 6 mol% to about 10 mol%, based on the total moles of the glass or glass-ceramic composition. In an embodiment, the glass or glass composition disclosed herein does not contain B 2 O 3 。

[0287] In an embodiment, the glass and / or glass-ceramic disclosed herein may contain 0 mol% to about 0.5 wt% SnO 2 ,based on the total moles of the glass or glass-ceramic composition. In an embodiment, the SnO 2 contained in the glass or glass-ceramic composition may be: 0 mol% to about 0.4 mol%, 0 mol% to about 0.3 mol%, 0 mol% to about 0.2 mol%, 0 mol% to about 0.1 mol%, about 0.05 mol% to about 0.5 mol%, about 0.05 mol% to about 0.4 mol%, about 0.05 mol% to about 0.3 mol%, about 0.05 mol% to about 0.2 mol%, about 0.05 mol% to about 0.1 mol%, about 0.1 mol% to about 0.5 mol%, about 0.1 mol% to about 0.4 mol%, about 0.1 mol% to about 0.3 mol%, about 0.1 mol% to about 0.2 mol%, about 0.2 mol% to about 0.5 mol%, about 0.2 mol% to about 0.4 mol%, about 0.2 mol% to about 0.3 mol%, about 0.3 mol% to about 0.5 mol%, about 0.3 mol% to about 0.4 mol%, about 0.4 mol% to about 0.5 mol%, and all ranges and sub-ranges therebetween, based on the total moles of the glass or glass-ceramic composition. In an embodiment, the glass or glass-ceramic composition may contain about 0, >0, 0.05, 0.1, 0.2, 0.3, 0.4, or 0.5 mol% SnO 2 。

[0288] In an embodiment, the glass and / or glass-ceramic disclosed herein may contain from 0 mol% to about 0.5 mol% HfO 2 . In an embodiment, the glass or glass-ceramic composition contains HfO 2 may be: 0 mol% to about 0.4 mol%, 0 mol% to about 0.3 mol%, 0 mol% to about 0.2 mol%, 0 mol% to about 0.1 mol%, about 0.05 mol% to about 0.5 mol%, about 0.05 mol% to about 0.4 mol%, about 0.05 mol% to about 0.3 mol%, about 0.05 mol% to about 0.2 mol%, about 0.05 mol% to about 0.1 mol%, about 0.1 mol% to about 0.5 mol%, about 0.1 mol% to about 0.4 mol%, about 0.1 mol% to about 0.3 mol%, about 0.1 mol% to about 0.2 mol%, about 0.2 mol% to about 0.5 mol%, about 0.2 mol% to about 0.4 mol%, about 0.2 mol% to about 0.3 mol%, about 0.3 mol% to about 0.5 mol%, about 0.3 mol% to about 0.4 mol%, about 0.4 mol% to about 0.5 mol%, and all ranges and sub-ranges therebetween, based on the total moles of the glass or glass-ceramic composition. In an embodiment, the glass or glass-ceramic composition may contain about 0, >0, 0.05, 0.1, 0.2, 0.3, 0.4 or 0.5 mol% HfO 2 .

[0289] In an embodiment, the glass and / or glass-ceramic composition disclosed herein may contain from 0 mol% to about 0.5 wt% Fe 2 O 3 , based on the total moles of the glass or glass-ceramic composition. In an embodiment, the Fe 2 O 3 contained in the glass or glass-ceramic composition may be: 0 mol% to about 0.4 mol%, 0 mol% to about 0.3 mol%, 0 mol% to about 0.2 mol%, 0 mol% to about 0.1 mol%, about 0.05 mol% to about 0.5 mol%, about 0.05 mol% to about 0.4 mol%, about 0.05 mol% to about 0.3 mol%, about 0.05 mol% to about 0.2 mol%, about 0.05 mol% to about 0.1 mol%, about 0.1 mol% to about 0.5 mol%, about 0.1 mol% to about 0.4 mol%, about 0.1 mol% to about 0.3 mol%, about 0.1 mol% to about 0.2 mol%, about 0.2 mol% to about 0.5 mol%, about 0.2 mol% to about 0.4 mol%, about 0.2 mol% to about 0.3 mol%, about 0.3 mol% to about 0.5 mol%, about 0.3 mol% to about 0.4 mol%, about 0.4 mol% to about 0.5 mol%, and all ranges and sub-ranges therebetween, based on the total moles of the glass or glass-ceramic composition. When Fe2 O 3 When the amount of 2 O 3 is too high, Fe 2 O 3 will affect the color of the glass-ceramic and thus affect the transparency of the glass-ceramic. In some embodiments, the glass and / or glass-ceramic composition comprises Fe

[0290] O that can be: less than 0.5 mol%, less than 0.4 mol%, less than 0.3 mol%, less than 0.2 mol%, less than 0.1 mol%, or even less than 0.05 mol%, based on the total moles of the glass or glass-ceramic composition. 2 In embodiments, the glass and / or glass-ceramic disclosed herein can comprise from 0 mol% to about 2 mol% TiO 2 . In embodiments, the TiO

[0291] comprised in the glass or glass-ceramic composition can be: from 0 mol% to about 1.75 mol%, from 0 mol% to about 1.5 mol%, from 0 mol% to about 1 mol%, from 0 mol% to about 0.8 mol%, from about 0.05 mol% to about 2 mol%, from about 0.05 mol% to about 1.75 mol%, from about 0.05 mol% to about 1.5 mol%, from about 0.05 mol% to about 1 mol%, from about 0.05 mol% to about 0.8 mol%, from about 0.1 mol% to about 2 mol%, from about 0.1 mol% to about 1.75 mol%, from about 0.1 mol% to about 1.5 mol%, from about 0.1 mol% to about 1 mol%, from about 0.1 mol% to about 0.8 mol%, from about 0.5 mol% to about 2 mol%, from about 0.5 mol% to about 1.75 mol%, from about 0.5 mol% to about 1.5 mol%, from about 0.5 mol% to about 1 mol%, from about 0.5 mol% to about 0.8 mol%, from about 0.8 mol% to about 2 mol%, from about 0.8 mol% to about 1.75 mol%, from about 0.8 mol% to about 1.5 mol%, from about 0.8 mol% to about 1 mol%, from about 1 mol% to about 2 mol%, from about 1 mol% to about 1.75 mol%, from about 1 mol% to about 1.5 mol%, from about 1.5 mol% to about 2 mol%, and all ranges and sub-ranges therebetween, based on the total moles of the glass or glass-ceramic composition. 2 , from about 1 mol% to about 15 mol% Al 2 O 3 , from about 10 mol% to about 40 mol% Li 2 O, from about 0.2 mol% to about 4 mol% P 2 O 5, and about 0.1 mole % to about 10 mole % ZrO 2 , based on the total moles of the glass and / or glass-ceramic composition. In an embodiment, the glass and / or glass-ceramic composition for preparing the glass-ceramic article disclosed herein may comprise: about 68 mole % to about 71 mole % SiO 2 , about 3 mole % to about 5 mole % Al 2 O 3 , about 18 mole % to about 25 mole % Li 2 O, about 0.6 mole % to about 1 mole % P 2 O 5 , and about 1.5 mole % to about 3 mole % ZrO 2 , based on the total moles of the glass and / or glass-ceramic composition. In an embodiment, the glass and / or glass-ceramic composition for preparing the glass-ceramic article disclosed herein may comprise: about 68.2 mole % to about 70.4 mole % SiO 2 , about 3.5 mole % to about 4.5 mole % Al 2 O 3 , about 20 mole % to about 23 mole % Li 2 O, about 0.8 mole % to about 1 mole % P 2 O 5 , and about 1.6 mole % to about 3 mole % ZrO 2 , based on the total moles of the glass and / or glass-ceramic composition. In an embodiment, the glass and / or glass-ceramic composition for preparing the glass-ceramic article disclosed herein may further comprise: about 0.5 mole % to about 5 mole % Na 2 O, K 2 O or both, based on the total moles of the glass and / or glass-ceramic composition. In an embodiment, the glass and / or glass-ceramic composition for preparing the glass-ceramic article disclosed herein may comprise: about 1 mole % to about 4 mole % or about 1 mole % to about 2 mole % Na 2 O, K 2 O or both, based on the total moles of the glass and / or glass-ceramic composition.

[0292] In an embodiment, the glass and / or glass-ceramic composition for preparing the glass-ceramic article disclosed herein may comprise, consist essentially of, or consist of: about 55 mole % to about 80 mole % SiO 2 , about 1 mole % to about 15 mole % Al 2 O 3 , about 10 mole % to about 40 mole % Li 2 O, about 0.2 mole % to about 4 mole % P 2 O 5, 0 mol% to about 10 mol% B 2 O 3 , about 0.1 mol% to about 10 mol% ZrO 2 , 0 mol% to about 5 mol% Na 2 O, 0 mol% to about 4 mol% K 2 O, 0 mol% to about 8 mol% MgO, 0 mol% to about 8 mol% CaO, 0 mol% to about 8 mol% SrO, 0 mol% to about 8 mol% BaO, 0 mol% to about 8 mol% ZnO, 0 mol% to about 0.5 mol% Fe 2 O 3 , 0 mol% to about 0.5 mol% HfO 2 , 0 mol% to about 0.5 mol% SnO 2 , and 0 mol% to about 2 mol% TiO 2 , based on the total moles of the glass and / or glass-ceramic composition, wherein, Na 2 O, K 2 O, ZnO, MgO, CaO, SrO, BaO, at least one or a combination thereof has a concentration greater than or equal to 0.5 mol%.

[0293] In an embodiment, the glass and / or glass-ceramic composition for preparing the glass-ceramic article disclosed herein may comprise, consist of, or consist essentially of: about 68 mol% to about 71 mol% SiO 2 , about 3 mol% to about 5 mol% Al 2 O 3 , about 18 mol% to about 25 mol% Li 2 O, about 0.6 mol% to about 1 mol% P 2 O 5 , about 1.5 mol% to about 3 mol% ZrO 2 , about 0.5 mol% to about 2 mol% Na 2 O, 0 mol% to about 2 mol% K 2 O, 0 mol% to about 1 mol% CaO, 0 mol% to about 1 mol% ZnO, 0 mol% to about 1 mol% MgO, 0 mol% to about 0.1 mol% Fe 2 O 3 , 0 mol% to about 0.1 mol% HfO 2 , 0 mol% to about 0.5 mol% SnO 2 , and 0 mol% to about 2 mol% TiO 2 , based on the total moles of the glass and / or glass-ceramic composition.

[0294] In an embodiment, a glass composition can be formed into a sheet by processes including, but not limited to, slot drawing, float, rolling, and other sheet forming processes known to those skilled in the art. It should be understood that unless otherwise explicitly stated, the compositions disclosed herein (whether in weight % or mole %) are the precursor glass or glass-ceramic compositions prior to the ceramization process on an oxide basis.

[0295] Heating process for producing a glass-ceramic preform from a precursor glass

[0296] Once the glass composition is prepared and formed into a precursor glass, the precursor glass can then be ceramized to form a glass-ceramic preform having one or more crystalline phases formed therein. Generally, to form a glass-ceramic, a glass stack comprising multiple sheets of precursor glass is heated to a temperature above its annealing point for a time sufficient to establish crystal nucleation (also referred to as "nucleation"). The heat treatment can be carried out, for example, in a toughening furnace or a kiln. After heating above its annealing point, the precursor glass is then further heated, typically to a higher temperature between the glass annealing point and the glass softening point, to establish the crystalline phase (also referred to as "growth" or "crystallization"). In various embodiments, the heat treatment or ceramization process includes: heating the glass stack comprising the precursor glass to a nucleation temperature, maintaining the nucleation temperature for a predetermined period of time, heating the glass stack comprising the precursor glass to a crystallization temperature, and maintaining the crystallization temperature for a predetermined period of time.

[0297] See Figure 1 , which schematically shows an embodiment of a stacking structure 100 for ceramizing a precursor glass to produce a glass-ceramic. The stacking structure 100 includes: a carrier plate 102 supporting two retainer plates 104, and a glass stack 106 placed between the retainer plates 104. In some embodiments, (not shown) thermal insulation layers can be located on the top surface of the upper retainer plate 104 and the bottom surface of the lower retainer plate 104. The thermal insulation layer can be formed of any material having a low thermal conductivity and can reduce or even eliminate the axial temperature gradient of the glass sheets 108 on the top and bottom of the glass stack 106.

[0298] As Figure 1 shown, the glass stack 106 includes multiple glass sheets 108, and each glass sheet 108 is separated from an adjacent glass sheet 108 by a release agent layer 110. The multiple glass sheets 108 can have a common shape or can be cut into specific preform shapes prior to ceramization. The release agent layer 110 reduces or even eliminates the adhesion of the glass sheets 108 in the glass stack 106 during the ceramization process. Although Figure 1Not shown in the figure, but in some embodiments, the glass stack 106 may further include a release agent layer 110 between the glass sheet 108 and the retainer plate 104. In other embodiments, the retainer plate 104 is made of a material that does not react with the glass sheet 108, and the release agent layer 110 is not required to prevent the interaction between the glass sheet 108 and the retainer plate 104. Other embodiments of the stack structure 100 related to reducing warping and haze during the ceramization process and the features of the stack structure can be found in U.S. Patent 11,014,848, entitled "Glass ceramic articles having improved properties and methods for making the same", issued on May 25, 2021, the entire content of which is incorporated herein by reference. Although shown in Figure 1 as a stack including multiple glass sheets 108, the glass can also be formed into a block, ceramized, and then cut into a preform shape after ceramization.

[0299] The processes for making glass ceramic articles disclosed herein include ceramizing a precursor glass to produce a glass ceramic having one or more crystalline phases formed therein. The precursor glass can be a crystallizable glass composition. The ceramization can include: heat treating the precursor glass at one or more predetermined temperatures for one or more predetermined periods of time to induce glass homogenization and crystallization of one or more crystalline phases (i.e., nucleation and growth) (e.g., having one or more compositions, amounts, geometric morphologies, sizes, or size distributions, etc.). In an embodiment, the heat treatment can include: (i) heating the precursor glass to a nucleation temperature (Tn) at a rate of 0.01 °C / minute to 50 °C / minute; (ii) maintaining the precursor glass at the nucleation temperature for a first predetermined period of time (tN) to produce a nucleated precursor glass; (iii) heating the nucleated precursor glass to a crystallization temperature (Tc) at a rate of about 0.01 °C / minute to about 50 °C / minute; (iv) maintaining the nucleated crystallizable glass at the crystallization temperature for a second predetermined period of time (tC) to produce a glass ceramic; and (v) cooling the glass ceramic. In the foregoing embodiment, the term "ceramized" or "ceramization" can be used to represent the collective term for steps (iii), (iv), and optionally (v).

[0300] In an embodiment, the nucleation temperature Tn can range from 500 °C to about 650 °C, such as: about 500 °C, about 510 °C, about 520 °C, about 530 °C, about 540 °C, about 550 °C, about 560 °C, about 570 °C, about 580 °C, about 590 °C, about 600 °C, about 610 °C, about 620 °C, about 630 °C, about 640 °C, or about 650 °C, and all ranges and sub-ranges therebetween. In an embodiment, the crystallization temperature Tc can be in the following ranges: about 680 °C to 900 °C, about 680 °C to about 800 °C, or about 700 °C to about 800 °C, such as: about 680 °C, about 690 °C, about 700 °C, about 710 °C, about 720 °C, about 730 °C, about 740 °C, about 750 °C, about 760 °C, about 770 °C, about 780 °C, about 790 °C, or about 800 °C, and all ranges and sub-ranges therebetween.

[0301] In an embodiment, the first predetermined time for maintaining the nucleation temperature can be from 1 minute to 6 hours, such as but not limited to: about 1 minute, about 5 minutes, about 10 minutes, about 20 minutes, about 30 minutes, about 40 minutes, about 50 minutes, about 1 hour, about 1.5 hours, about 2 hours, about 2.5 hours, about 3 hours, about 3.5 hours, about 4 hours, about 4.5 hours, about 5 hours, about 5.5 hours, or about 6 hours, and all ranges and sub-ranges therebetween. In an embodiment, the second predetermined time for maintaining the crystallization temperature can be from 1 minute to 8 hours, such as: from 1 minute to 7 hours or even from 1 minute to 4 hours, and all ranges and sub-ranges therebetween. In an embodiment, the second predetermined time for maintaining the crystallization temperature can be: about 1 minute, about 5 minutes, about 10 minutes, about 20 minutes, about 30 minutes, about 40 minutes, about 50 minutes, about 1 hour, about 1.5 hours, about 2 hours, about 2.5 hours, about 3 hours, about 3.5 hours, or about 4 hours, about 4.5 hours, about 5 hours, about 5.5 hours, about 6 hours, about 6.5 hours, about 7 hours, about 7.5 hours, or about 8 hours, and all ranges and sub-ranges therebetween. In an embodiment, the crystallization temperature can be selected to produce a transparent glass-ceramic, a translucent glass-ceramic, or an opaque glass-ceramic. In some embodiments, a crystallization temperature of about 750 °C or lower can produce a transparent glass-ceramic. In an embodiment, a crystallization temperature greater than 750 °C can produce a translucent or opaque glass-ceramic. In an embodiment, the precursor glass can be heated from room temperature to the nucleation temperature of about 560 °C to about 580 °C at a rate of about 5 °C / minute, maintained at the nucleation temperature for about 4 hours, then heated to the crystallization temperature of about 720 °C to about 750 °C at a rate of about 5 °C / minute, and maintained at the crystallization temperature for about 1 hour to about 7 hours.

[0302] In an embodiment, there may be one of a plurality of additional temperature holds between the nucleation temperature and the crystallization temperature. Thus, in some embodiments, after maintaining the precursor glass at the nucleation temperature, the nucleated precursor glass can be heated to one or more intermediate temperatures (where the intermediate temperature is between the nucleation temperature and the crystallization temperature), and held at the one or more intermediate temperatures for a predetermined time (e.g., 1 hour to 4 hours, and all ranges and sub-ranges therebetween), and then heated to the crystallization temperature.

[0303] In an embodiment, once the precursor glass is heated to the nucleation temperature, the precursor glass is not maintained at the nucleation temperature, but instead, is continuously heated to one or more intermediate temperatures until the crystallization temperature is reached (i.e., the temperature is not maintained at either the intermediate temperature or the nucleation temperature). In an embodiment, the heating rate from room temperature to the nucleation temperature, the heating rate from the nucleation temperature to the intermediate temperature, and the heating rate from the intermediate temperature to the crystallization temperature can be changed and can all be different. In embodiments where there are multiple intermediate temperatures, the heating rate between individual intermediate temperatures may also vary. In some embodiments, the heating rate can be changed and the range can be from about 0.01 °C / minute to about 50 °C / minute, e.g.: about 0.01 °C / minute, about 0.1 °C / minute, about 0.5 °C / minute, about 1 °C / minute, about 2 °C / minute, about 3 °C / minute, about 4 °C / minute, about 5 °C / minute, about 10 °C / minute, about 15 °C / minute, about 20 °C / minute, about 25 °C / minute, about 30 °C / minute, about 40 ° / minute, about 45 °C / minute, about 50 °C / minute, and all ranges and sub-ranges therebetween. In an embodiment, the heating rate can increase from one heating rate to another. In other embodiments, the heating rate can decrease from one heating rate to another. Methods for determining the ceramization cycle to control crystal growth and viscosity during the ceramization process, strategies for minimizing warping of the glass-ceramic during the ceramization process, and systems and methods for maintaining thermal uniformity during the ceramization process can be found in U.S. Patent No. 11,014,848, which is hereby incorporated by reference into the present disclosure.

[0304] In an embodiment, after holding the crystallization temperature and before 3D forming, the glass-ceramic is cooled. In an embodiment, the cooling of the glass-ceramic material to room temperature can be: a constant cooling rate in a single stage; in two stages with different cooling rates respectively; or in three or more stages with different cooling rates respectively. In an embodiment, the glass-ceramic material can be cooled from the crystallization temperature at a controlled rate, thereby minimizing the temperature gradient on the glass-ceramic and minimizing the residual stress on the glass-ceramic. Differences in the temperature gradient and residual stress in the glass-ceramic can cause warping in the glass-ceramic during the cooling process. Therefore, the cooling is controlled to control the temperature gradient and residual stress, which can also reduce the warping of the glass-ceramic preform.

[0305] In an embodiment, the cooling can be performed in two cooling stages. In such embodiments, in the first cooling stage, the temperature of the glass-ceramic is cooled from the maximum temperature (i.e., T C , the crystallization temperature) to an intermediate cooling temperature (T1) at a first cooling rate. In the second cooling stage, the temperature is cooled from the intermediate cooling temperature to approximately room temperature (Troom) at a second cooling rate. In an embodiment, the first cooling rate is slower than the second cooling rate. During the first stage, the first cooling rate is slow, thereby minimizing the temperature gradient on the glass-ceramic. In an embodiment, the intermediate cooling temperature at which the transition from the first cooling stage to the second cooling stage occurs is determined based on such a temperature (below which the glass-ceramic behaves as an elastic material). Without being limited to theory, it is believed that the slower cooling rate in the first cooling stage only needs to control the temperature gradient until the glass-ceramic reaches such a temperature (below which it behaves as an elastic material). In an embodiment, the intermediate cooling temperature can be from 450 °C to 550 °C, and all ranges and sub-ranges therebetween. In an embodiment, the intermediate cooling temperature can be less than or equal to 550 °C, 540 °C, 530 °C, 520 °C, 510 °C, 500 °C, 490 °C, 480 °C, 470 °C, 460 °C, or 450 °C. In an embodiment, the temperature drop (Tmax - T1) in the first cooling stage is less than the temperature drop (T1 - Troom) in the second cooling stage. Without being limited to theory, it is believed that the temperature gradient established in the first cooling stage has a greater impact (in the form of optical retardation) on the residual stress (and thus on warping) of the glass-ceramic after reaching room temperature than the temperature gradient established in the second cooling stage. Therefore, in some embodiments, after the controlled cooling in the first cooling stage, the glass-ceramic can be allowed to cool to room temperature in an uncontrolled cooling environment.

[0306] In an embodiment, for a total of three cooling stages, the cooling cycle may have an intermediate cooling stage between the first cooling stage and the second cooling stage. In such embodiments, in the first cooling stage, the temperature is cooled from the maximum temperature (i.e., TC, the crystallization temperature) to the first intermediate cooling temperature (T1) at a first cooling rate. In the intermediate cooling stage, the temperature is cooled from T1 to the second intermediate cooling temperature T2 at an intermediate cooling rate. In the second cooling stage, the temperature is cooled from T2 to approximately room temperature (Troom) at a third cooling rate. The cooling rate of each successive stage may be increasing such that: (i) the first cooling rate during the first cooling stage is less than the second cooling rate during the intermediate cooling stage and the third cooling rate during the second cooling stage; and (ii) the second cooling rate during the intermediate cooling stage is less than the third cooling rate during the second cooling stage. In some embodiments, (i) the temperature drop (TC - T1) in the first cooling stage is less than the temperature drop (T1 - T2) in the intermediate cooling stage and the temperature drop (T2 - Troom) in the second cooling stage, and (ii) the temperature drop (T1 - T2) in the intermediate cooling stage is less than the temperature drop (T2 - Troom) in the second cooling stage. The intermediate cooling stage enables a faster cooling cycle while still minimizing the temperature gradient and residual stress. In some embodiments, Tmax can be from about 720 °C to about 750 °C, T1 can be about 640 °C, and T2 can be about 580 °C.

[0307] In some embodiments, when there are multiple cooling stages in the cooling cycle, during the first cooling stage, the temperature gradient on the glass-ceramic can be: less than about 15 °C, less than about 14 °C, less than about 13 °C, less than about 12 °C, less than about 11 °C, less than about 10 °C, less than about 9 °C, less than about 8 °C, less than about 7 °C, less than about 6 °C, less than about 5 °C, less than about 4 °C, or less than about 3 °C. In an embodiment, the optical retardation of the glass-ceramic at room temperature can be: less than a thickness of about 15 nm / mm, less than a thickness of about 14 nm / mm, less than a thickness of about 13 nm / mm, less than a thickness of about 12 nm / mm, less than a thickness of about 11 nm / mm, less than a thickness of about 10 nm / mm, less than a thickness of about 9 nm / mm, less than a thickness of about 8 nm / mm, less than a thickness of about 7 nm / mm, less than a thickness of about 6 nm / mm, less than a thickness of about 5 nm / mm, less than a thickness of about 4 nm / mm, or less than a thickness of about 3 nm / mm. The optical retardation can be measured according to ASTM F218-13.

[0308] After the above heat treatment of the precursor glass, the resulting glass-ceramic has one or more crystalline phases and a residual glass phase. In an embodiment, the glass-ceramic contains lithium disilicate and spodumene crystalline phases. In addition to lithium disilicate and spodumene, the glass-ceramic may further contain one or more of the following exemplary crystalline phases as secondary crystalline phases: β-spodumene solid solution, β-quartz solid solution, lithium metasilicate, virgilite, cristobalite, lithium phosphate, zircon, zirconia, and any combination thereof. In an embodiment, after ceramization, the glass-ceramic may contain at least a disilicate crystalline phase, a spodumene crystalline phase, and a residual glass phase. In an embodiment, after ceramization and before 3D forming, the glass-ceramic may contain a combined concentration of lithium disilicate crystalline phase and spodumene crystalline phase that is greater than or equal to 50 wt%, such as 50 wt% to 90 wt%, and all ranges and sub-ranges therebetween, based on the total weight of the glass-ceramic. In an embodiment, the combined concentration of lithium disilicate crystalline phase and spodumene crystalline phase contained in the glass-ceramic may be: 50 wt% to 85 wt%, 50 wt% to 80 wt%, 50 wt% to 75 wt%, 50 wt% to 70 wt%, 50 wt% to 65 wt%, 50 wt% to 60 wt%, 55 wt% to 90 wt%, 55 wt% to 85 wt%, 55 wt% to 80 wt%, 55 wt% to 75 wt%, 55 wt% to 70 wt%, 55 wt% to 65 wt%, 55 wt% to 60 wt%, 60 wt% to 90 wt%, 60 wt% to 85 wt%, 60 wt% to 80 wt%, 60 wt% to 75 wt%, 60 wt% to 70 wt%, 60 wt% to 65 wt%, 65 wt% to 90 wt%, 65 wt% to 85 wt%, 65 wt% to 80 wt%, 65 wt% to 75 wt%, 65 wt% to 70 wt%, 70 wt% to 90 wt%, 70 wt% to 85 wt%, 70 wt% to 80 wt%, 70 wt% to 75 wt%, 75 wt% to 90 wt%, 75 wt% to 85 wt%, 75 wt% to 80 wt%, 80 wt% to 90 wt%, 80 wt% to 85 wt%, or 85 wt% to 90 wt%, based on the total weight of the glass-ceramic.

[0309] In an embodiment, lithium disilicate may be the crystalline phase having the highest weight percentage in the glass-ceramic. Lithium disilicate (Li 2 Si 2 O 5 ) is based on {Si 2 O 5}Orthogonal crystals of the corrugated sheets of the tetrahedral array. The crystals are generally in the form of plates or slats and have distinct cleavage planes. Due to their microstructure of randomly oriented interlocking crystals (a crystal structure that forces cracks to propagate through the material via a tortuous path around these crystals), the lithium disilicate-based glass-ceramics offer highly desirable mechanical properties, including high bulk strength and fracture toughness. In an embodiment, after ceramization, the weight percentage of the lithium disilicate crystalline phase in the glass-ceramic composition can be in the following ranges: about 20 to about 60 wt%, about 20 to about 55 wt%, about 20 to about 50 wt%, about 20 to about 45 wt%, about 20 to about 40 wt%, about 20 to about 35 wt%, about 20 to about 30 wt%, about 20 to about 25 wt%, about 25 to about 60 wt%, about 25 to about 55 wt%, about 25 to about 50 wt%, about 25 to about 45 wt%, about 25 to about 40 wt%, about 25 to about 35 wt%, about 25 to about 30 wt%, about 30 to about 60 wt%, about 30 to about 55 wt%, about 30 to about 50 wt%, about 30 to about 45 wt%, about 30 to about 40 wt%, about 30 to about 35 wt%, about 35 to about 60 wt%, about 35 to about 55 wt%, about 35 to about 50 wt%, about 35 to about 45 wt%, about 35 to about 40 wt%, about 40 to about 60 wt%, about 40 to about 55 wt%, about 40 to about 50 wt%, about 40 to about 45 wt%, about 45 to about 60 wt%, about 45 to about 55 wt%, about 45 to about 50 wt%, about 50 to about 60 wt%, about 50 to about 55 wt%, or about 55 to about 60 wt%, based on the total weight of the glass-ceramic. In an embodiment, the glass-ceramic has 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59 or 60 wt% of the lithium disilicate crystalline phase, based on the total weight of the glass-ceramic.

[0310] In an embodiment, spodumene can be the crystalline phase with the highest weight percentage. Spodumene (LiAlSi 4 O 10 ) is a monoclinic crystal with a three-dimensional framework structure and has a layered structure, with folded Si 2 O 5The layers are tetrahedrally linked by Li and Al. Li is tetrahedrally coordinated to oxygen. The mineral spodumene is the lithium source and is used as a low thermal expansion phase to improve the thermal downshock resistance of glass-ceramic or ceramic components. In addition, glass-ceramic materials based on the spodumene phase can be chemically strengthened in a salt bath, during which Na + (and / or K + ) replaces Li in the spodumene structure +, which results in surface compression and strengthening. In an embodiment, after ceramization, the weight percentage of the spodumene crystal phase in the glass-ceramic composition can be in the following ranges: about 20 to about 70 wt%, about 20 to about 65 wt%, about 20 to about 60 wt%, about 20 to about 55 wt%, about 20 to about 50 wt%, about 20 to about 45 wt%, about 20 to about 40 wt%, about 20 to about 35 wt%, about 20 to about 30 wt%, about 20 to about 25 wt%, about 25 to about 70 wt%, about 25 to about 65 wt%, about 25 to about 60 wt%, about 25 to about 55 wt%, about 25 to about 50 wt%, about 25 to about 45 wt%, about 25 to about 40 wt%, about 25 to about 35 wt%, about 25 to about 30 wt%, about 30 to about 70 wt%, about 30 to about 65 wt%, about 30 to about 60 wt%, about 30 to about 55 wt%, about 30 to about 50 wt%, about 30 to about 45 wt%, about 30 to about 40 wt%, about 30 to about 35 wt%, about 35 to about 70 wt%, about 35 to about 65 wt%, about 35 to about 60 wt%, about 35 to about 55 wt%, about 35 to about 50 wt%, about 35 to about 45 wt%, about 35 to about 40 wt%, about 40 to about 70 wt%, about 40 to about 65 wt%, about 40 to about 60 wt%, about 40 to about 55 wt%, about 40 to about 50 wt%, about 40 to about 45 wt%, about 45 to about 70 wt%, about 45 to about 65 wt%, about 45 to about 60 wt%, about 45 to about 55 wt%, about 45 to about 50 wt%, about 50 to about 70 wt%, about 50 to about 65 wt%, about 50 to about 60 wt%, about 50 to about 55 wt%, about 55 to about 70 wt%, about 55 to about 65 wt%, about 55 to about 60 wt%, about 60 to about 70 wt%, about 60 to about 65 wt%, or about 65 to about 70 wt%, based on the total weight of the glass-ceramic. In an embodiment, the glass-ceramic has about 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69 or 70 wt% of the spodumene crystal phase, based on the total weight of the glass-ceramic.

[0311] Thus, in an embodiment, after ceramization and before 3D forming, the combined weight % of lithium disilicate and spodumene crystal phases contained in the glass-ceramic can be greater than or equal to 40 wt%, such as: greater than or equal to 42 wt%, greater than or equal to 44 wt%, greater than or equal to 46 wt%, greater than or equal to 48 wt%, greater than or equal to 50 wt%, greater than or equal to 52 wt%, greater than or equal to 54 wt%, greater than or equal to 56 wt%, greater than or equal to 58 wt%, greater than or equal to 60 wt%, greater than or equal to 62 wt%, greater than or equal to 64 wt%, greater than or equal to 66 wt%, greater than or equal to 68 wt%, greater than or equal to 70 wt%, greater than or equal to 72 wt%, greater than or equal to 74 wt%, greater than or equal to 76 wt%, greater than or equal to 78 wt%, greater than or equal to 80 wt%, greater than or equal to 82 wt%, greater than or equal to 84 wt%, or greater than or equal to 85 wt%, based on the total weight of the glass-ceramic. In an embodiment, the total weight % in the glass-ceramic preform of crystal phases other than lithium disilicate and spodumene is: less than 5 wt%, less than 4 wt%, less than 3 wt%, less than 2 wt%, or less than 1 wt%, based on the total weight of the glass-ceramic.

[0312] In an embodiment, after the ceramization process, the glass-ceramic can have a crystal weight % in the following ranges: greater than 20 wt% to 90 wt%, greater than 20 wt% to 80 wt%, greater than 20 wt% to 70 wt%, 30 wt% to 100 wt%, 30 wt% to 90 wt%, 30 wt% to 80 wt%, 30 wt% to 70 wt%, 40 wt% to 90 wt%, 40 wt% to 80 wt%, 40 wt% to 70 wt%, 50 wt% to 90 wt%, 50 wt% to 80 wt%, 50 wt% to 70 wt%, and all ranges and sub-ranges therebetween. In an embodiment, after the ceramization process, the glass-ceramic can have a crystal weight % greater than 50 wt% to 90 wt%. In an embodiment, the inner region can have a crystal weight % as follows: greater than 20 wt%, greater than or equal to 25 wt%, greater than or equal to 30 wt%, greater than or equal to 35 wt%, greater than or equal to 40 wt%, greater than or equal to 45 wt%, greater than or equal to 50 wt%, greater than or equal to 55 wt%, greater than or equal to 60 wt%, greater than or equal to 65 wt%, greater than or equal to 70 wt%, greater than or equal to 75 wt%, greater than or equal to 80 wt%, or greater than or equal to 85 wt%.

[0313] After ceramization and before 3D forming, the glass-ceramic further comprises a residual glass phase. After ceramization, the concentration of the residual glass phase in the glass-ceramic can be sufficient such that the glass-ceramic can be 3D formed according to the methods disclosed herein by heating and pressing into a mold. In an embodiment, before 3D forming, the glass-ceramic preform can have a concentration of the residual glass phase of from about 5 wt% to about 50 wt%, from about 5 wt% to about 40 wt%, from about 5 wt% to 35 wt%, from about 5 wt% to about 30 wt%, from about 5 wt% to about 25 wt%, from about 5 wt% to about 20 wt%, from about 5 wt% to about 15 wt%, from about 5 wt% to about 10 wt%, from about 10 wt% to about 50 wt%, from about 10 wt% to about 45 wt%, from about 10 wt% to about 40 wt%, from about 10 wt% to about 35 wt%, from about 10 wt% to about 30 wt%, from about 10 wt% to about 25 wt%, from about 10 wt% to about 20 wt%, from about 10 wt% to about 15 wt%, from about 15 wt% to about 50 wt%, from about 15 wt% to about 45 wt%, from about 15 wt% to about 40 wt%, from about 15 wt% to about 35 wt%, from about 15 wt% to about 30 wt%, from about 15 wt% to about 25 wt%, from about 15 wt% to about 20 wt%, from about 20 wt% to about 50 wt%, from about 20 wt% to about 45 wt%, from about 20 wt% to about 40 wt%, from about 20 wt% to about 35 wt%, from about 20 wt% to about 30 wt%, from about 20 wt% to about 25 wt%, from about 25 wt% to about 30 wt%, and all ranges and sub-ranges therebetween, wherein the weight percentages are based on the total weight of the glass-ceramic. In an embodiment, the concentration of the residual glass phase in the glass-ceramic can be less than or equal to 50, 45, 40, 35, 30, 25, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7 or 6 wt%, based on the total weight of the glass-ceramic. In an embodiment, before 3D forming, the glass-ceramic preform can have a residual glass phase concentration of 10 wt% to 50 wt%, based on the total weight of the glass-ceramic preform.

[0314] In an embodiment, the phase assemblage and heat treatment conditions during the ceramization process are selected to produce a glass-ceramic sheet or preform having suitable optical properties (e.g., high transparency and low haze). In some embodiments, for a glass-ceramic sheet or preform having a thickness of 1 mm, the glass-ceramic sheet or preform is transparent to light in the wavelength range of 450 nm to 600 nm, and has an average transmittance (including surface reflection loss) of 85% or greater, 86% or greater, 87% or greater, 88% or greater, 89% or greater, 90% or greater, 91% or greater, 92% or greater, 93% or greater. In an embodiment, the glass-ceramic may be translucent in the wavelength range of 450 nm to 600 nm. In an embodiment, for a glass-ceramic sheet or preform having a thickness of 1 mm, the translucent glass-ceramic may have an average transmittance of about 20% to less than about 85% for light in the wavelength range of about 450 nm to about 800 nm. In an embodiment, before 3D forming, the glass-ceramic sheet or preform may have a haze of less than 0.2, less than 0.19, less than 0.18, less than 0.17, less than 0.16, less than 0.15, less than 0.14, less than 0.13, less than 0.12, less than 0.11, or less than 0.1 at a thickness of 0.8 mm.

[0315] After ceramization, a stack comprising multiple glass-ceramic sheets can be separated into individual glass-ceramic sheets. In an embodiment, the glass sheets can be cut into preform shapes before ceramization and then assembled into a stack comprising multiple glass sheets, so as to produce multiple glass-ceramic preforms after the ceramization process. The preform shape can be the shape of a flat sheet of glass-ceramic, which, when 3D formed by heating and pressing the glass-ceramic preform into a mold, produces a glass-ceramic article of the desired shape. In an embodiment, the glass sheets in the stack can have a common shape, such as square and rectangular, etc., and then the glass-ceramic sheets produced from ceramization can be cut or otherwise divided into one or more glass-ceramic preforms.

[0316] 3D forming process

[0317] After the precursor glass is ceramified to produce a glass-ceramic preform, the glass-ceramic preform is then subjected to a 3D shaping process to shape the glass-ceramic into a 2.5D or 3D shape that is different from the shape of the glass-ceramic preform. The 3D shaping of the glass-ceramic preform to produce the glass-ceramic article of the present disclosure may include a thermo-mechanical 3D shaping process, wherein the glass-ceramic preform is heated to a 3D shaping temperature, and then the heated glass-ceramic preform is pressed into a mold to produce the glass-ceramic article. 3D shaping after the formation of the crystalline phase via a ceramification process is enabled by the precursor glass composition, which provides a greater concentration of residual glass phase, a lower viscosity of the residual glass phase (or both), as compared to other glass-ceramics that cannot be 3D shaped after ceramification. The 3D shaping process disclosed herein in combination with the composition of the glass-ceramic results in an increased concentration of the residual glass phase in the glass-ceramic article (as compared to the concentration of the residual glass phase in the glass-ceramic preform). In addition, the composition of the glass-ceramic in combination with the 3D shaping process may further improve the ion exchange of the glass-ceramic article to produce a strengthened glass article having a greater depth of compression, a greater compressive stress in the compression layer, and a greater central tension.

[0318] The 3D shaping process for shaping a glass-ceramic preform into a glass-ceramic article may include heating the glass-ceramic preform to a shaping temperature, and after heating, pressing the glass-ceramic preform into a mold for a period of time sufficient to produce the glass-ceramic article. In an embodiment, the 3D shaping process may further include cooling the glass-ceramic article from the 3D shaping temperature back to room temperature. In an embodiment, the heating, pressing, and cooling steps may be performed on a multi-station hot forming machine, the multi-station hot forming machine including a plurality of heating stations, a plurality of pressing stations downstream of the heating stations, and a plurality of cooling stations downstream of the pressing stations. The glass-ceramic preform may be displaced sequentially through each processing station to heat the glass-ceramic preform, press the glass-ceramic preform into a mold, and cool the glass-ceramic article.

[0319] During the heating step of the 3D forming process, the glass-ceramic preform can be heated at a 3D temperature high enough so that the glass-ceramic preform can be pressed into a mold without cracking the glass-ceramic preform. In an embodiment, the glass-ceramic preform can be heated to a 3D forming temperature of about 650 °C to about 850 °C, such as: about 650 °C to about 825 °C, about 650 °C to about 800 °C, about 650 °C to about 775 °C, about 650 °C to about 750 °C, about 675 °C to about 850 °C, about 675 °C to about 825 °C, about 675 °C to about 800 °C, about 675 °C to about 775 °C, about 675 °C to about 750 °C, about 700 °C to about 850 °C, about 700 °C to about 825 °C, about 700 °C to about 800 °C, about 700 °C to about 775 °C, about 700 °C to about 750 °C, about 725 °C to about 850 °C, about 725 °C to about 825 °C, about 725 °C to about 800 °C, about 725 °C to about 775 °C, about 725 °C to about 750 °C, about 750 °C to about 850 °C, about 750 °C to about 825 °C, about 750 °C to about 800 °C, about 775 °C to about 850 °C, about 775 °C to about 825 °C, or about 800 °C to about 850 °C. In an embodiment, the 3D forming temperature can be: about 650 °C, about 660 °C, about 670 °C, about 680 °C, about 690 °C, about 700 °C, about 710 °C, about 720 °C, about 730 °C, about 740 °C, about 750 °C, about 760 °C, about 770 °C, about 780 °C, about 790 °C, about 800 °C, about 810 °C, about 820 °C, about 830 °C, about 840 °C or about 850 °C.

[0320] The pressing step may include pressing a glass-ceramic preform into a mold at a 3D forming temperature and a 3D forming pressure. In an embodiment, the mold may be a graphite mold. Molds made of other materials are contemplated. The 3D forming pressure may be sufficient to cause the glass-ceramic preform to conform to the contour of the mold. In an embodiment, the 3D forming pressure may be from about 0.001 MPa to about 0.9 MPa, such as: from about 0.001 MPa to about 0.8 MPa, from about 0.001 MPa to about 0.6 MPa, from about 0.001 MPa to about 0.4 MPa, from about 0.001 MPa to about 0.2 MPa, from about 0.001 MPa to about 0.1 MPa, from about 0.01 MPa to 0.9 MPa, from about 0.01 MPa to about 0.8 MPa, from about 0.01 MPa to about 0.6 MPa, from about 0.01 MPa to about 0.4 MPa, from about 0.01 MPa to about 0.2 MPa, from about 0.01 MPa to about 0.1 MPa, from about 0.1 MPa to about 0.9 MPa, from about 0.1 MPa to about 0.8 MPa, from about 0.1 MPa to about 0.6 MPa, from about 0.1 MPa to about 0.4 MPa, from about 0.1 MPa to about 0.2 MPa, from about 0.2 MPa to about 0.9 MPa, from about 0.2 MPa to about 0.8 MPa, from about 0.2 MPa to about 0.6 MPa, from about 0.2 MPa to about 0.4 MPa, from about 0.4 MPa to about 0.9 MPa, from about 0.4 MPa to about 0.8 MPa, from about 0.4 MPa to about 0.6 MPa, from about 0.6 MPa to about 0.9 MPa, from about 0.6 MPa to about 0.8 MPa, or from about 0.8 MPa to about 0.9 MPa.

[0321] After pressing the glass-ceramic to produce a glass-ceramic article, the glass-ceramic article may be cooled back to room temperature. In an embodiment, the glass-ceramic article may be cooled to room temperature at a constant cooling rate in a single stage, or in multiple stages each having a different cooling rate. In an embodiment, the glass-ceramic article may be cooled back to room temperature from the 3D forming temperature at a controlled rate, thereby minimizing the temperature gradient across the glass-ceramic article and minimizing the residual stress in the glass-ceramic article.

[0322] The compositions and processes for 3D forming a glass-ceramic preform after ceramization disclosed herein can maintain or increase the concentration of the residual glass phase in the glass-ceramic article, as compared to the glass-ceramic preform prior to 3D forming. In conventional compositions and 3D forming processes, ceramization is typically done concurrently with or after 3D forming, during which time the crystallinity increases to transform the nucleated precursor glass into a glass-ceramic. Thus, in conventional 3D forming processes, the total concentration of the crystalline phase increases while the concentration of the residual glass phase decreases. Additionally, since the 3D forming temperature range disclosed herein overlaps with the crystallization temperature range for ceramization to transform the precursor glass into a glass-ceramic, one skilled in the art would expect the crystalline phase concentration to increase when 3D forming is done after ceramization. However, as demonstrated by the examples, it was found that the compositions and 3D forming processes disclosed herein produced glass-ceramic articles in which the concentration of the residual glass phase was constant or increased, as compared to the glass-ceramic preform prior to 3D forming. Thus, unexpectedly, the compositions and 3D forming processes of the present disclosure result in a constant or increased concentration of the residual glass phase during 3D forming. Without being limited to theory, it is believed that an increased concentration of the glass-ceramic composition (e.g., an increased concentration of non-lithium alkali metal oxides, alkaline earth metal oxides, ZnO, or combinations thereof and / or a greater molar ratio of these constituent components compared to Al 2 O 3 and ZrO 2 in combination with the conditions of 3D forming may cause at least some of the constituent components in the crystalline phase to migrate back into the residual glass phase, thereby increasing the concentration of the residual glass phase in the glass-ceramic article.

[0323] The concentration of the residual glass phase in the glass-ceramic article can be equal to or greater than the concentration of the residual glass phase in the glass-ceramic preform prior to 3D forming. In an embodiment, heating and pressing of the glass-ceramic preform during the 3D forming process can increase the concentration of the residual glass phase. After 3D forming, the concentration of the residual glass phase in the glass-ceramic article can be at least 1% greater than the concentration of the residual glass phase in the glass-ceramic preform prior to 3D forming. In an embodiment, the concentration of the residual glass phase in the glass-ceramic article can be at least 3% greater, at least 5% greater, at least 7% greater, at least 10% greater, at least 15% greater, at least 20% greater, at least 25% greater, or even at least 30% greater than the concentration of the residual glass phase in the glass-ceramic preform prior to 3D forming. In an embodiment, after 3D forming, the difference in the concentration of the residual glass phase in the glass-ceramic article and the concentration of the residual glass phase in the glass-ceramic preform (i.e., [glass phase] 制品 – [glass phase] 预制件) can be 0% greater than or equal to the concentration of the residual glass phase in the glass-ceramic preform, 1% greater than or equal to the concentration of the residual glass phase in the glass-ceramic preform, 3% greater than or equal to the concentration of the residual glass phase in the glass-ceramic preform, 5% greater than or equal to the concentration of the residual glass phase in the glass-ceramic preform, 7% greater than or equal to the concentration of the residual glass phase in the glass-ceramic preform, 10% greater than or equal to the concentration of the residual glass phase in the glass-ceramic preform, 15% greater than or equal to the concentration of the residual glass phase in the glass-ceramic preform, 20% greater than or equal to the concentration of the residual glass phase in the glass-ceramic preform, 25% greater than or equal to the concentration of the residual glass phase in the glass-ceramic preform, or even 30% greater than or equal to the concentration of the residual glass phase in the glass-ceramic preform. The difference in the concentration of the residual glass phase in the glass-ceramic article and the concentration of the residual glass phase in the glass-ceramic preform (i.e., 制品 – 预制件 ) can be less than 100% of the concentration of the residual glass phase in the glass-ceramic preform, less than 75% of the concentration of the residual glass phase in the glass-ceramic preform, or even less than 50% of the concentration of the residual glass phase in the glass-ceramic preform.

[0324] In an embodiment, the concentration of the residual glass phase in the glass-ceramic article after 3D forming can be 15 wt% to 55 wt%, such as: 15 wt% to 50 wt%, 15 wt% to 45 wt%, 15 wt% to 40 wt%, 15 wt% to 35 wt%, 15 wt% to 30 wt%, 15 wt% to 25 wt%, 20 wt% to 55 wt%, 20 wt% to 50 wt%, 20 wt% to 45 wt%, 20 wt% to 40 wt%, 20 wt% to 35 wt%, 20 wt% to 30 wt%, 20 wt% to 25 wt%, 25 wt% to 55 wt%, 25 wt% to 50 wt%, 25 wt% to 45 wt%, 25 wt% to 40 wt%, 25 wt% to 35 wt%, 25 wt% to 30 wt%, 30 wt% to 55 wt%, 30 wt% to 50 wt%, 30 wt% to 45 wt%, 30 wt% to 40 wt%, 30 wt% to 35 wt%, 35 wt% to 55 wt%, 35 wt% to 50 wt%, 35 wt% to 45 wt%, 35 wt% to 40 wt%, 40 wt% to 55 wt%, 40 wt% to 50 wt%, 40 wt% to 45 wt%, 45 wt% to 55 wt%, 45 wt% to 50 wt%, or 50 wt% to 55 wt%, based on the total weight of the glass-ceramic article. An increase in the concentration of the residual glass phase in the glass-ceramic article compared to the glass-ceramic preform can improve the ion-exchange strengthening of the glass-ceramic article to produce a strengthened glass-ceramic article, as will be further discussed herein.

[0325] Performing a 3D forming process on the glass-ceramic preform after ceramization to produce a glass-ceramic article can also reduce the shrinkage of the glass-ceramic article during the 3D forming process. In an embodiment, the overall volume change of the glass-ceramic article compared to the volume of the glass-ceramic preform before 3D forming is less than 1% of the volume of the glass-ceramic preform before 3D forming, for example: less than 0.5% of the volume of the glass-ceramic preform before 3D forming, less than 0.3% of the volume of the glass-ceramic preform before 3D forming, or even less than 0.1% of the volume of the glass-ceramic preform before 3D forming. Without being limited to any specific case, it is believed that by ceramizing the precursor glass to produce the glass-ceramic preform before 3D shaping, the glass-ceramic preform has been densified to form various crystal phases before 3D forming. Therefore, there is very little further densification during the 3D forming process, thereby reducing the shrinkage of the glass-ceramic article compared to the glass-ceramic preform.

[0326] The glass-ceramic article produced by the method disclosed herein is clear and transparent. In addition, the glass-ceramic article can exhibit less staining from mechanical interaction with the mold during pressing, as compared to glass-ceramic articles formed by a process that includes ceramization either simultaneously with or after 3D forming, such as a process that involves only nucleating the glass precursor and then crystallizing the glass precursor while 3D forming to produce the glass-ceramic.

[0327] Aesthetically, glass-ceramic articles produced by 3D forming a glass-ceramic preform after ceramization can exhibit significantly fewer surface defects and flaws compared to glass-ceramic articles produced by processes where ceramization occurs concurrently with or after 3D forming. Specifically, glass-ceramic articles produced by 3D forming a glass-ceramic preform after ceramization can exhibit fewer blemishes compared to glass-ceramic articles produced by processes where ceramization occurs concurrently with or after 3D forming. Blemishes refer to surface defects caused by movement of the glass-ceramic relative to the surface of the mold, such as movement caused by shrinkage of the glass-ceramic during 3D forming. Without being limited to any particular theory, it is believed that blemishes are caused by movement or shrinkage of the glass-ceramic relative to the mold during 3D forming. In the blemish region, the glass-ceramic physically moves relative to the mold, which creates friction at the interface between the glass-ceramic and the mold. This friction and movement causes the glass-ceramic to scrape against the mold surface, which causes defect distribution into the surface of the glass-ceramic. These defects can be removed by downstream polishing processes. Since most of the crystallization has occurred during the ceramization step prior to 3D forming, the glass-ceramic articles disclosed herein undergo very little densification and shrinkage during the 3D forming process. Thus, glass-ceramic articles produced by the methods disclosed herein can exhibit fewer surface defects caused by blemishes. As a result, the glass-ceramic articles disclosed herein can require less post-forming processing (e.g., polishing) downstream of the 3D forming process to remove surface defects to meet quality specifications.

[0328] In an embodiment, the methods disclosed herein do not include any active method steps after 3D forming that are intended to further increase the crystalline phase concentration of the glass-ceramic article.

[0329] By a 3D forming process, a glass-ceramic preform can be shaped into a glass-ceramic article, which can have any desired 2.5D or 3D shape. In an embodiment, the glass-ceramic article can be 3D formed into the shape of a component of an electronic device, such as a cover glass for a personal handheld electronic device.

[0330] Ion exchange strengthening

[0331] In an embodiment, one or more ion exchange techniques can be employed to chemically strengthen a glass-ceramic article. After a 3D forming process, the glass-ceramic article can be strengthened by ion exchange to produce a strengthened glass-ceramic article. As discussed above, the glass-ceramic compositions and 3D forming processes disclosed herein can increase the concentration of the residual glass phase in the glass-ceramic article (compared to the glass-ceramic preform), which can improve the ion exchange process, e.g., by increasing the compressive stress, central tension, and compressive depth in the strengthened glass-ceramic article (compared to the strengthening of a glass-ceramic preform without 3D forming). Without being limited to any particular theory, it is believed that these effects can be attributed to the greater concentration of the residual glass phase in the 3D formed glass-ceramic article and / or greater lithium availability in the residual glass phase of the 3D formed glass-ceramic article (compared to a glass-ceramic that has only been ceramified). The improved ion exchange can be attributed to the diffusion coefficient of potassium and sodium ions into the surface of the glass-ceramic article being faster due to the greater concentration of the residual glass phase in the ceramified and 3D formed glass-ceramic article, which can enable component size expansion to facilitate ion exchange. The concentration of the residual glass phase increases after 3D forming, the smaller size and total volume of the crystalline phase islands in the glass-ceramic article decrease, and / or the concentration of alkaline substances in the residual glass phase of the ceramified and 3D formed glass-ceramic article is believed to be attributed to an increase in the diffusion coefficient of sodium (Na) and potassium (K) ions into the surface of the glass-ceramic article.

[0332] The processes disclosed herein can include: after 3D forming, strengthening the glass-ceramic article to produce a strengthened glass-ceramic article having a compressive stress layer extending from a first surface of the glass-ceramic article to a compressive depth. In an embodiment, ion exchange can be performed by subjecting one or more surfaces of the glass-ceramic article to one or more ion exchange media (e.g., a molten salt bath) having a specific composition and temperature for a specific period of time such that the one or more surfaces have a compressive stress layer. In an embodiment, the ion exchange medium is a molten bath containing ions (e.g., alkali metal ions, e.g.: Na + 、K + 、Rb + and / or Cs + ) that are greater than the ions present in the glass-ceramic article (e.g., alkali metal ions, e.g.: Li + 、Na + and / or K + ), wherein the larger ions from the molten bath exchange with the smaller ions in the glass-ceramic article, imparting compressive stress in the glass-ceramic article and thereby increasing the strength of the glass-ceramic article.

[0333] In an embodiment, a single-step ion exchange process can be used, while in other embodiments, a multi-step ion exchange process can be used. In an embodiment, for both the single-step and multi-step ion exchange processes, the ion exchange medium (e.g., a molten bath) can comprise 100 wt% of a sodium salt (e.g., NaNO 3 ) or can comprise a mixed salt bath (e.g., a combination of a sodium salt (e.g., NaNO 3 ) and a potassium salt (e.g., KNO 3 ). In an embodiment, the ion exchange medium can comprise a small amount of a lithium salt (e.g., LiNO 3 ). In an embodiment, the molten salt bath can contain a sodium salt (e.g., NaNO 3), and its range is: 3% to 100% by weight, 3% to 95% by weight, 3% to 90% by weight, 3% to 85% by weight, 3% to 80% by weight, 3% to 75% by weight, 3% to 70% by weight, 3% to 60% by weight, 3% to 50% by weight, 3% to 40% by weight, 5% to 100% by weight, 5% to 95% by weight, 5% to 90% by weight, 5% to 85% by weight, 5% to 80% by weight, 5% to 75% by weight, 5% to 70% by weight, 5% to 60% by weight, 5% to 50% by weight, 5% to 40% by weight, 10% to 100% by weight, 10% to 95% by weight, 10% to 90% by weight, 10% to 85% by weight, 10% to 80% by weight, 10% to 75% by weight, 10% to 70% by weight, 10% to 60% by weight, 10% to 50% by weight, 10% to 40% by weight, 15% to 100% by weight, 15% to 95% by weight, 15% to 90% by weight, 15% to 85% by weight, 15% to 80% by weight, 15% to 75% by weight, 15% to 70% by weight, 15% to 60% by weight, 15% to 50% by weight, 15% to 40% by weight, 10% to 100% by weight, 10% to 95% by weight, 10% to 90% by weight, 10% to 85% by weight, 10% to 80% by weight, 10% to 75% by weight, 10% to 70% by weight, 10% to 60% by weight, 10% to 50% by weight, 10% to 40% by weight, 25% to 100% by weight, 25% to 95% by weight, 25% to 90% by weight, 25% to 85% by weight, 25% to 80% by weight, 25% to 75% by weight, 25% to 70% by weight, 25% to 60% by weight, 25% to 50% by weight, 25% to 40% by weight, 30% to 100% by weight, 30% to 95% by weight, 30% to 90% by weight, 30% to 85% by weight, 30% to 80% by weight, 30% to 75% by weight, 30% to 70% by weight, 30% to 60% by weight, 30% to 50% by weight, 30% to 40% by weight, and all ranges and sub-ranges therebetween, based on the total weight of the molten salt bath.

[0334] In an embodiment, the molten salt bath may contain a potassium salt (e.g., KNO 3), and the range is: 3 wt% to 100 wt%, 3 wt% to 95 wt%, 3 wt% to 90 wt%, 3 wt% to 85 wt%, 3 wt% to 80 wt%, 3 wt% to 75 wt%, 3 wt% to 70 wt%, 3 wt% to 60 wt%, 10 wt% to 100 wt%, 10 wt% to 95 wt%, 10 wt% to 90 wt%, 10 wt% to 85 wt%, 10 wt% to 80 wt%, 10 wt% to 75 wt%, 10 wt% to 70 wt%, 10 wt% to 60 wt%, 20 wt% to 100 wt%, 20 wt% to 95 wt%, 20 wt% to 90 wt%, 20 wt% to 85 wt%, 20 wt% to 80 wt%, 20 wt% to 75 wt%, 20 wt% to 70 wt%, 3 wt% to 60 wt%, 30 wt% to 100 wt%, 30 wt% to 95 wt%, 30 wt% to 90 wt%, 30 wt% to 85 wt%, 30 wt% to 80 wt%, 30 wt% to 75 wt%, 30 wt% to 70 wt%, 30 wt% to 60 wt%, 40 wt% to 100 wt%, 40 wt% to 95 wt%, 40 wt% to 90 wt%, 40 wt% to 85 wt%, 40 wt% to 80 wt%, 40 wt% to 75 wt%, 40 wt% to 70 wt%, 40 wt% to 60 wt%, 50 wt% to 100 wt%, 50 wt% to 95 wt%, 50 wt% to 90 wt%, 50 wt% to 85 wt%, 50 wt% to 80 wt%, 50 wt% to 75 wt%, 50 wt% to 70 wt%, 50 wt% to 60 wt%, 60 wt% to 100 wt%, 60 wt% to 95 wt%, 60 wt% to 90 wt%, 60 wt% to 85 wt%, 60 wt% to 80 wt%, 60 wt% to 75 wt%, 60 wt% to 70 wt%, 70 wt% to 100 wt%, 70 wt% to 95 wt%, 70 wt% to 90 wt%, 70 wt% to 85 wt%, 70 wt% to 80 wt%, 70 wt% to 75 wt%, 75 wt% to 100 wt%, 75 wt% to 90 wt%, 80 wt% to 100 wt%, 80 wt% to 95 wt%, or 80 wt% to 90 wt%, based on the total weight of the molten salt bath. In an embodiment, other sodium salts and potassium salts can be used in the ion exchange solution, for example, sodium nitrite or potassium, sodium phosphate or potassium, or sodium sulfate or potassium. In an embodiment, the molten salt bath can include a lithium salt (e.g., LiNO 3 ). When present, the concentration of the lithium salt in the molten salt bath can be less than 5 wt%, less than 1 wt%, or less than or equal to 0.5 wt%, based on the total weight of the molten salt bath.

[0335] Strengthening a glass-ceramic article by ion exchange can include contacting the glass-ceramic article with a molten salt bath at an ion exchange temperature for an ion exchange time sufficient to produce a strengthened glass-ceramic article. The ion exchange temperature can be from about 335 °C to about 600 °C, such as: from about 335 °C to about 550 °C, from about 335 °C to about 500 °C, from about 350 °C to about 600 °C, from about 350 °C to about 550 °C, from about 350 °C to about 500 °C, from about 400 °C to about 600 °C, from about 400 °C to about 550 °C, from about 400 °C to about 500 °C, from about 450 °C to about 600 °C, from about 450 °C to about 550 °C, from about 450 °C to about 500 °C, or from about 500 °C to about 600 °C. In an embodiment, the ion exchange temperature can be about 500 °C. In an embodiment, the ion exchange time can be: 0.5 hour to 5 hours, 0.5 hour to 4.5 hours, 0.5 hour to 4 hours, 0.5 hour to 3.5 hours, 1 hour to 5 hours, 1 hour to 4.5 hours, 1 hour to 4 hours, 1 hour to 3.5 hours, 1.5 hours to 5 hours, 1.5 hours to 4.5 hours, 1.5 hours to 4 hours, 1.5 hours to 3.5 hours, 1.75 hours to 5 hours, 1.75 hours to 4.5 hours, 1.75 hours to 4 hours, or 1.75 hours to 3.5 hours. After ion exchange, the strengthened glass article can be cleaned to remove the reagent from the surface of the strengthened glass article.

[0336] After the ion exchange process has been carried out, it should be understood that the composition at the surface of the glass-ceramic can be different from the composition of the as-formed glass-ceramic article (i.e., the glass-ceramic before undergoing the ion exchange process). This results from one type of alkali metal ion in the as-formed glass-ceramic article (e.g., Li + or Na + ) being replaced by a larger alkali metal ion (e.g., Na + or K + ), respectively. However, in an embodiment, the composition of the glass-ceramic article at or near the center of the depth of the glass article still has the composition of the as-formed glass-ceramic article after 3D forming and before ion exchange.

[0337] In an embodiment, the glass-ceramic article can be strengthened to have a compressive stress layer on one or more of its surfaces. Now refer to Figure 2 , a schematic cross-sectional side view showing an exemplary strengthened glass-ceramic article 150, which has a first surface 152 and an opposite second surface 154 separated by a thickness (t). In an embodiment, the strengthened glass-ceramic article 150 has been ion exchanged and has a compressive stress (CS) layer 156 (or first region) extending from the first surface 152 to a compressive depth (DOC). In an embodiment, as Figure 2As shown, the glass-ceramic article 150 may also have a compressive stress (CS) layer 158 extending from the second surface 154 to a compressive depth DOC'. There is also a central tension region 160 in tension stress between DOC and DOC'.

[0338] In some embodiments, DOC, DOC', or both can be in the following ranges: greater than 0*t to 0.3*t, 0*t to 0.25*t, 0*t to 0.2*t, 0*t to 0.15*t, 0*t to 0.1*t, 0*t to 0.05*t, 0.05*t to 0.3*t, 0.05*t to 0.25*t, 0.05*t to 0.2*t, 0.05*t to 0.15*t, 0.05*t to 0.1*t, 0.1*t to 0.3*t, 0.1*t to 0.25*t, 0.1*t to 0.2*t, 0.1*t to 0.15*t, and all ranges and sub-ranges therebetween, where t is the thickness of the glass-ceramic article 150. In an embodiment, the depth of the compressive stress layer (DOC, DOC', or both) can be: greater than 0.05*t, greater than 0.06*t, greater than 0.07*t, greater than 0.08*t, greater than 0.09*t, greater than 0.1*t, greater than 0.11*t, greater than 0.12*t, greater than 0.13*t, greater than 0.14*t, greater than 0.15*t, greater than 0.16*t, greater than 0.17*t, greater than 0.18*t, greater than 0.19*t, greater than 0.2*t, greater than 0.21*t, greater than 0.22*t, greater than 0.23*t, greater than 0.24*t, greater than 0.25*t, greater than 0.26*t, greater than 0.27*t, greater than 0.28*t, greater than 0.29*t, or greater than 0.3*. In an embodiment, the depth of the compressive stress layer (DOC, DOC') can be in the following ranges: 0.01 mm to 0.6 mm, 0.01 mm to 0.5 mm, 0.01 mm to 0.4 mm, 0.01 mm to 0.3 mm, 0.01 mm to 0.2 mm, 0.01 mm to 0.1 mm, 0.05 mm to 0.6 mm, 0.05 mm to 0.5 mm, 0.05 mm to 0.4 mm, 0.05 mm to 0.3 mm, 0.05 mm to 0.2 mm, 0.05 mm to 0.1 mm, 0.1 mm to 0.6 mm, 0.1 mm to 0.5 mm, 0.1 mm to 0.4 mm, 0.1 mm to 0.3 mm, 0.2 mm to 0.6 mm, 0.2 mm to 0.5 mm, 0.2 mm to 0.4 mm, and all ranges and sub-ranges therebetween.In an embodiment, the depth of the compressive stress layer (DOC, DOC') is: greater than or equal to 0.01 mm, greater than or equal to 0.05 mm, greater than or equal to 0.06 mm, greater than or equal to 0.07 mm, greater than or equal to 0.08 mm, greater than or equal to 0.09 mm, greater than or equal to 0.1 mm, greater than or equal to 0.15 mm, greater than or equal to 0.2 mm, greater than or equal to 0.25 mm, greater than or equal to 0.3 mm, greater than or equal to 0.35 mm, greater than or equal to 0.4 mm, greater than or equal to 0.45 mm, greater than or equal to 0.5 mm, greater than or equal to 0.55 mm, or greater than or equal to 0.6 mm. In an embodiment, DOC may be equal to DOC'. In other embodiments, DOC may be different from DOC'.

[0339] In an embodiment, the toughened glass-ceramic article can have a compressive stress (CS) greater than 175 MPa at the surface, such as: greater than 180 MPa, greater than 185 MPa, greater than 190 MPa, greater than 195 MPa, greater than 200 MPa, greater than 205 MPa, greater than 210 MPa, greater than 215 MPa, greater than 220 MPa, greater than 225 MPa, greater than 230 MPa, greater than 235 MPa, greater than 240 MPa, greater than 245 MPa, greater than 250 MPa, or even greater than 300 MPa.In an embodiment, the toughened glass-ceramic article can have a CS at the surface of: 175 MPa to 500 MPa, 175 MPa to 450 MPa, 175 MPa to 400 MPa, 175 MPa to 350 MPa, 175 MPa to 300 MPa, 175 MPa to 250 MPa, 180 MPa to 500 MPa, 180 MPa to 450 MPa, 180 MPa to 400 MPa, 180 MPa to 350 MPa, 180 MPa to 300 MPa, 180 MPa to 250 MPa, 185 MPa to 500 MPa, 185 MPa to 450 MPa, 185 MPa to 400 MPa, 185 MPa to 350 MPa, 185 MPa to 300 MPa, 185 MPa to 250 MPa, 190 MPa to 500 MPa, 190 MPa to 450 MPa, 190 MPa to 400 MPa, 190 MPa to 350 MPa, 190 MPa to 300 MPa, 190 MPa to 250 MPa, 195 MPa to 500 MPa, 195 MPa to 450 MPa, 195 MPa to 400 MPa, 195 MPa to 350 MPa, 195 MPa to 300 MPa, 195 MPa to 250 MPa, 200 MPa to 500 MPa, 200 MPa to 450 MPa, 200 MPa to 400 MPa, 200 MPa to 350 MPa, 200 MPa to 300 MPa, 200 MPa to 250 MPa, 210 MPa to 500 MPa, 210 MPa to 450 MPa, 210 MPa to 400 MPa, 210 MPa to 350 MPa, 210 MPa to 300 MPa, 210 MPa to 250 MPa, 220 MPa to 500 MPa, 220 MPa to 450 MPa, 220 MPa to 400 MPa, 220 MPa to 350 MPa, 220 MPa to 300 MPa, 220 MPa to 250 MPa, 230 MPa to 500 MPa, 230 MPa to 450 MPa, 230 MPa to 400 MPa, 230 MPa to 350 MPa, 230 MPa to 300 MPa, 230 MPa to 250 MPa, 250 MPa to 500 MPa, 250 MPa to 450 MPa, 250 MPa to 400 MPa, 250 MPa to 350 MPa, 250 MPa to 300 MPa, 300 MPa to 500 MPa, 300 MPa to 450 MPa, 300 MPa to 400 MPa, or 300 MPa to 350 MPa.

[0340] In an embodiment, the toughened glass-ceramic article can have a maximum center tension (CT) greater than 30 MPa to 180 MPa. In an embodiment, the maximum CT is: greater than or equal to 30 MPa, greater than or equal to 35 MPa, greater than or equal to 40 MPa, greater than or equal to 45 MPa, greater than or equal to 50 MPa, greater than or equal to 55 MPa, greater than or equal to 60 MPa, greater than or equal to 70 MPa, greater than or equal to 80 MPa, or greater than or equal to 100 MPa. In some embodiments, the maximum CT can be in the following ranges: greater than 30 MPa to 180 MPa, greater than 30 MPa to 170 MPa, greater than 30 MPa to 160 MPa, greater than 30 MPa to 150 MPa, greater than 30 MPa to 140 MPa, greater than 35 MPa to 100 MPa, greater than 35 MPa to 80 MPa, 35 MPa to 180 MPa, 35 MPa to 170 MPa, 35 MPa to 160 MPa, 35 MPa to 150 MPa, 35 MPa to 140 MPa, 35 MPa to 100 MPa, 35 MPa to 80 MPa, 40 MPa to 180 MPa, 40 MPa to 170 MPa, 40 MPa to 160 MPa, 40 MPa to 150 MPa, 40 MPa to 140 MPa, 40 MPa to 100 MPa, 40 MPa to 80 MPa, 45 MPa to 180 MPa, 45 MPa to 170 MPa, 45 MPa to 160 MPa, 45 MPa to 150 MPa, 45 MPa to 140 MPa, 45 MPa to 100 MPa, 45 MPa to 80 MPa, 50 MPa to 180 MPa, 50 MPa to 170 MPa, 50 MPa to 150 MPa, 50 to 120, 50 MPa to 100 MPa, 50 MPa to 80 MPa, or any range and sub-range therebetween.

[0341] In an embodiment, the stored tensile energy of the toughened glass-ceramic article is in the following range: about 5 J / m 2 to about 50 J / m 2 about 5 J / m 2 to about 45 J / m 2 about 5 J / m 2 to about 40 J / m 2 about 5 J / m 2 to about 35 J / m 2 about 5 J / m 2 to about 30 J / m 2 about 5 J / m 2 to about 25 J / m 2 about 5 J / m 2 to about 20 J / m 2 about 5 J / m 2to about 15 J / m 2 about 5 J / m 2 to about 10 J / m 2 about 10 J / m 2 to about 50 J / m 2 about 10 J / m 2 to about 45 J / m 2 about 10 J / m 2 to about 40 J / m 2 about 10 J / m 2 to about 35 J / m 2 about 10 J / m 2 to about 30 J / m 2 about 10 J / m 2 to about 25 J / m 2 about 10 J / m 2 to about 20 J / m 2 about 10 J / m 2 to about 15 J / m 2 about 15 J / m 2 to about 50 J / m 2 about 15 J / m 2 to about 45 J / m 2 about 15 J / m 2 to about 40 J / m 2 about 15 J / m 2 to about 35 J / m 2 about 15 J / m 2 to about 30 J / m 2 about 15 J / m 2 to about 25 J / m 2 about 15 J / m 2 to about 20 J / m 2 about 20 J / m 2 to about 50 J / m 2 about 20 J / m 2 to about 45 J / m 2 about 20 J / m 2 to about 40 J / m 2 about 20 J / m 2 to about 35 J / m 2 about 20 J / m 2 to about 30 J / m 2 about 20 J / m 2 to about 25 J / m 2 about 25 J / m 2 to about 50 J / m 2 about 25 J / m 2 to about 45 J / m 2 about 25 J / m 2to about 40 J / m 2 ,about 25 J / m 2 to about 35 J / m 2 ,about 25 J / m 2 to about 30 J / m 2 ,about 30 J / m 2 to about 50 J / m 2 ,about 30 J / m 2 to about 45 J / m 2 ,about 30 J / m 2 to about 40 J / m 2 ,about 30 J / m 2 to about 35 J / m 2 ,about 35 J / m 2 to about 50 J / m 2 ,about 35 J / m 2 to about 45 J / m 2 ,about 35 J / m 2 to about 40 J / m 2 ,about 40 J / m 2 to about 50 J / m 2 ,about 40 J / m 2 to about 45 J / m 2 ,about 45 J / m 2 to 50 J / m 2 ,and all ranges and sub - ranges therebetween. In an embodiment, the stored tensile energy can be: greater than or equal to 5 J / m 2 ,greater than or equal to 10 J / m 2 ,greater than or equal to 15 J / m 2 ,greater than or equal to 20 J / m 2 ,greater than or equal to 25 J / m 2 ,greater than or equal to 30 J / m 2 ,greater than or equal to 35 J / m 2 ,greater than or equal to 40 J / m 2 ,or greater than or equal to 45 J / m 2 。

[0342] In an embodiment, the ion - exchange process can cause a weight increase in the strengthened glass - ceramic article compared to the glass - ceramic article prior to the ion - exchange process. The weight increase may be due to smaller alkali metal ions (Li + 、Na + ) being exchanged for larger alkali metal ions with a greater molecular weight (e.g., Na + 、K + 、Cs + 、Rb +)Results of the exchange. In embodiments, the strengthened glass-ceramic article can have a weight change of greater than or equal to 0.05%, greater than or equal to 0.1%, greater than or equal to 0.2%, greater than or equal to 0.3%, or even greater than or equal to 0.4% relative to the weight of the glass-ceramic article prior to ion exchange.

[0343] Properties of the glass-ceramic article

[0344] In embodiments, after 3D shaping, the glass-ceramic article can have a thickness range of: 0.2 mm to 4 mm, 0.2 mm to 3 mm, 0.2 mm to 2 mm, 0.2 mm to 1.5 mm, 0.2 mm to 1 mm, 0.2 mm to 0.9 mm, 0.2 mm to 0.8 mm, 0.2 mm to 0.7 mm, 0.2 mm to 0.6 mm, 0.2 mm to 0.5 mm, 0.3 mm to 4 mm, 0.3 mm to 3 mm, 0.3 mm to 2 mm, 0.3 mm to 1.5 mm, 0.3 mm to 1 mm, 0.3 mm to 0.9 mm, 0.3 mm to 0.8 mm, 0.3 mm to 0.7 mm, 0.3 mm to 0.6 mm, 0.3 mm to 0.5 mm, 0.4 mm to 4 mm, 0.4 mm to 3 mm, 0.4 mm to 2 mm, 0.4 mm to 1.5 mm, 0.4 mm to 1 mm, 0.4 mm to 0.9 mm, 0.4 mm to 0.8 mm, 0.4 mm to 0.7 mm, 0.4 mm to 0.6 mm, 0.5 mm to 4 mm, 0.5 mm to 3 mm, 0.5 mm to 2 mm, 0.5 mm to 1.5 mm, 0.5 mm to 1 mm, 0.5 mm to 0.9 mm, 0.5 mm to 0.8 mm, 0.5 mm to 0.7 mm, 0.8 mm to 4 mm, 0.8 mm to 3 mm, 0.8 mm to 2 mm, 0.8 mm to 1.5 mm, 0.8 mm to 1 mm, 1 mm to 2 mm, 1 mm to 1.5 mm, and all ranges and sub-ranges therebetween. In some embodiments, the glass-ceramic article can be substantially planar and flat. In other embodiments, the glass-ceramic article can be shaped, e.g., the glass-ceramic article can have a 2.5D or 3D shape. In embodiments, the glass-ceramic article can have a uniform thickness, while in other embodiments, the glass-ceramic article can not have a uniform thickness.

[0345] In an embodiment, the fracture toughness of the glass-ceramic article is in the following ranges: 1.0 MPa√m to 2.0 MPa√m, 1.1 MPa√m to 2.0 MPa√m, 1.2 MPa√m to 2.0 MPa√m, 1.3 MPa√m to 2.0 MPa√m, 1.4 MPa√m to 2.0 MPa√m, 1.5 MPa√m to 2.0 MPa√m, 1.0 MPa√m to 1.9 MPa√m, 1.1 MPa√m to 1.9 MPa√m, 1.2 MPa√m to 1.9 MPa√m, 1.3 MPa√m to 1.9 MPa√m, 1.4 MPa√m to 1.9 MPa√m, 1.5 MPa√m to 1.9 MPa√m, 1.0 MPa√m to 1.8 MPa√m, 1.1 MPa√m to 1.8 MPa√m, 1.2 MPa√m to 1.8 MPa√m, 1.3 MPa√m to 1.8 MPa√m, 1.4 MPa√m to 1.8 MPa√m, 1.5 MPa√m to 1.8 MPa√m, and all ranges and sub-ranges therebetween. In an embodiment, the fracture toughness of the glass-ceramic article can be: greater than or equal to 1.0 MPa√m, greater than or equal to 1.1 MPa√m, greater than or equal to 1.2 MPa√m, greater than or equal to 1.3 MPa√m, greater than or equal to 1.4 MPa√m, greater than or equal to 1.5 MPa√m, greater than or equal to 1.6 MPa√m, greater than or equal to 1.7 MPa√m, greater than or equal to 1.8 MPa√m, or greater than or equal to 1.9 MPa√m.

[0346] In an embodiment, the Young's modulus of the glass-ceramic article can be in the following ranges: 90 GPa to 110 GPa, 90 GPa to 105 GPa, 90 GPa to 103 GPa, 90 GPa to 100 GPa, 95 GPa to 110 GPa, 95 GPa to 105 GPa, 95 GPa to 103 GPa, 95 GPa to 100 GPa, 100 GPa to 110 GPa, 100 GPa to 105 GPa, 100 GPa to 103 GPa, 103 GPa to 110 GPa, 103 GPa to 105 GPa, or 105 GPa to 110 GPa, and all ranges and sub-ranges therebetween. In an embodiment, the Young's modulus of the glass-ceramic is: greater than or equal to 90 GPa, greater than or equal to 91 GPa, greater than or equal to 92 GPa, greater than or equal to 93 GPa, greater than or equal to 94 GPa, greater than or equal to 95 GPa, greater than or equal to 96 GPa, greater than or equal to 97 GPa, greater than or equal to 98 GPa, greater than or equal to 99 GPa, greater than or equal to 100 GPa, greater than or equal to 101 GPa, greater than or equal to 102 GPa, greater than or equal to 103 GPa, greater than or equal to 104 GPa, greater than or equal to 105 GPa, greater than or equal to 106 GPa, greater than or equal to 107 GPa, greater than or equal to 108 GPa, or greater than or equal to 109 GPa.

[0347] In an embodiment, the glass-ceramic article can have a shear modulus in the following ranges: 35 GPa to 50 GPa, 35 GPa to 45 GPa, 35 GPa to 43 GPa, 35 GPa to 41 GPa, 38 GPa to 50 GPa, 38 GPa to 45 GPa, 38 GPa to 43 GPa, 38 GPa to 41 GPa, 41 GPa to 50 GPa, 41 GPa to 45 GPa, 41 GPa to 43 GPa, 43 GPa to 105 GPa, 90 GPa to 103 GPa, 90 GPa to 100 GPa, 95 GPa to 110 GPa, 95 GPa to 105 GPa, 43 GPa to 50 GPa, 43 GPa to 45 GPa, or 45 GPa to 50 GPa, and all ranges and sub-ranges therebetween. In an embodiment, the glass-ceramic can have a shear modulus of: greater than or equal to 35 GPa, greater than or equal to 36 GPa, greater than or equal to 37 GPa, greater than or equal to 38 GPa, greater than or equal to 39 GPa, greater than or equal to 40 GPa, greater than or equal to 41 GPa, greater than or equal to 42 GPa, greater than or equal to 43 GPa, greater than or equal to 44 GPa, greater than or equal to 45 GPa, greater than or equal to 46 GPa, greater than or equal to 47 GPa, greater than or equal to 48 GPa, or greater than or equal to 49 GPa.

[0348] In an embodiment, the glass-ceramic article can have a Poisson's ratio of from about 0.19 to about 0.24, such as about 0.19, 0.20, 0.21, 0.22, 0.23, or 0.24, and all ranges and sub-ranges therebetween.

[0349] In an embodiment, after applying the fragmentation test (based on a 50 mm by 50 mm by 0.8 mm sample) described above, the glass-ceramic article can break into fewer than 5 fragments, fewer than 4 fragments, or fewer than 3 fragments.

[0350] In an embodiment, by using the ceramization cycle, glass precursor composition, fixture configuration, stacking configuration, and 3D forming process disclosed and described herein, the formed glass-ceramic article can have a stress of less than 30 nm delay per mm of sheet thickness, such as: less than 28 nm delay per mm of sheet thickness, less than 26 nm delay per mm of sheet thickness, less than 25 nm delay per mm of sheet thickness, less than 24 nm delay per mm of sheet thickness, less than 22 nm delay per mm of sheet thickness, less than 20 nm delay per mm of sheet thickness, less than 18 nm delay per mm of sheet thickness, less than 16 nm delay per mm of sheet thickness, or less than 15 nm delay per mm of sheet thickness. In an embodiment, the stress of the formed glass-ceramic article can be from 15 nm to 30 nm delay per mm of sheet thickness, such as: from 18 nm to 30 nm delay per mm of sheet thickness, from 20 nm to 30 nm delay per mm of sheet thickness, from 22 nm to 30 nm delay per mm of sheet thickness, from 24 nm to 30 nm delay per mm of sheet thickness, or from 28 nm to 30 nm delay per mm of sheet thickness. In an embodiment, the stress of the formed glass-ceramic article can be: from 15 nm to 25 nm delay per mm of sheet thickness, from 18 nm to 25 nm delay per mm of sheet thickness, from 20 nm to 25 nm delay per mm of sheet thickness, or from 22 nm to 25 nm delay per mm of sheet thickness.

[0351] In an embodiment, the glass-ceramic article exhibits transparency in the visible light range (i.e., the glass-ceramic is transparent). In an embodiment, a transparent glass-ceramic article having a thickness of 1 mm can have a light transmittance of ≥90% (including surface reflection loss) in the wavelength range of about 400 nm to about 1000 nm or about 400 nm to about 600 nm. In an embodiment, for a glass-ceramic article with a thickness of 1 mm, for light in the wavelength range of about 400 nm to about 1000 nm, the average transmittance of the transparent glass-ceramic article disclosed herein can be: about 85% or greater, about 86% or greater, about 87% or greater, about 88% or greater, about 89% or greater, about 90% or greater, about 91% or greater, about 92% or greater, about 93% or greater (including surface reflection loss). In an embodiment, the glass-ceramic article can be translucent in the visible light range. In an embodiment, for a glass-ceramic article with a thickness of 1 mm, for light in the wavelength range of about 400 nm to about 600 nm, the average transmittance of the transparent glass-ceramic article disclosed herein can be: about 85% or greater, about 86% or greater, about 87% or greater, about 88% or greater, about 89% or greater, about 90% or greater, about 91% or greater, about 92% or greater, about 93% or greater (including surface reflection loss).

[0352] In an embodiment, by adopting the ceramization cycle, glass precursor composition, setter configuration, stacking configuration, and 3D forming process disclosed and described herein, the haze of the formed glass-ceramic article can comply with the following formula:

[0353] Haze (%) < 0.0994t + 0.12

[0354] In the above formula, t is the thickness (mm) of the glass-ceramic article.

[0355] As Figure 3As shown, the above formula is determined through experiments. According to the embodiments, by using the ceramization cycle, glass precursor composition, setter configuration, stacking configuration, and 3D forming process disclosed and described herein, the formed glass-ceramic article can have a haze of less than 0.30 at a thickness of 0.8 mm, for example: less than 0.28 at a thickness of 0.8 mm, less than 0.26 at a thickness of 0.8 mm, less than 0.24 at a thickness of 0.8 mm, less than 0.22 at a thickness of 0.8 mm, less than 0.20 at a thickness of 0.8 mm, less than 0.18 at a thickness of 0.8 mm, less than 0.16 at a thickness of 0.8 mm, less than 0.14 at a thickness of 0.8 mm, less than 0.12 at a thickness of 0.8 mm, or less than 0.10 at a thickness of 0.8 mm. In an embodiment, the haze of the formed glass-ceramic article can be from 0.10 to 0.28 at a thickness of 0.8 mm, for example: from 0.10 to 0.26 at a thickness of 0.8 mm, from 0.10 to 0.24 at a thickness of 0.8 mm, from 0.10 to 0.22 at a thickness of 0.8 mm, from 0.10 to 0.20 at a thickness of 0.8 mm, from 0.10 to 0.18 at a thickness of 0.8 mm, from 0.10 to 0.16 at a thickness of 0.8 mm, from 0.10 to 0.14 at a thickness of 0.8 mm, or from 0.10 to 0.12 at a thickness of 0.8 mm. In an embodiment, the haze of the formed glass-ceramic article can be from 0.10 to 0.20 at a thickness of 0.8 mm. The haze of the glass-ceramic article is measured on the glass-ceramic article itself without a coating or other substitutes.

[0356] In an embodiment, by adopting the ceramization cycle, glass precursor composition, setter configuration, stacking configuration, and 3D forming disclosed and described herein, the haze of the formed glass-ceramic article can conform to the following formula:

[0357] Transmittance (%) > 0.91×10(2 - 0.03t)

[0358] In the above formula, t is the thickness of the glass-ceramic article (in mm).

[0359] According to an embodiment, by using the ceramization cycle, glass precursor composition, former configuration, stack configuration, and 3D forming process disclosed and described herein, when measured at a thickness of 0.8 mm, the formed glass-ceramic article can have an optical transmittance for electromagnetic radiation wavelengths from 450 nm to 800 nm as follows: greater than 85%, greater than 88%, greater than 90%, greater than 93%, greater than 95%, or greater than 98%. In an embodiment, when measured at a thickness of 0.8 mm, the formed glass-ceramic article can have an optical transmittance greater than 75% to 95% for electromagnetic radiation wavelengths from 450 nm to 800 nm, such as: greater than 75% to 93%, greater than 75% to 90%, greater than 75% to 88%, greater than 75% to 85%, greater than 75% to 83%, greater than 75% to 80%, or greater than 75% to 78%. As described above, the transmittance of the glass-ceramic article is measured on the glass-ceramic article itself without a coating or other substitute. In addition, the transmittance percentages disclosed herein are the transmittance percentages of electromagnetic radiation at each wavelength within the range of 450 nm to 800 nm.

[0360] In an embodiment, when measured according to the test method provided herein and using light with a wavelength of 589.3 nm, the glass-ceramic article can have a refractive index (RI) of about 1.5 to about 1.6 or about 1.54 to about 1.55, and all ranges and sub-ranges therebetween. In an embodiment, for light with a wavelength of 589.3 nm, the glass-ceramic article can have an RI as follows: about 1.50, about 1.51, about 1.52, about 1.53, about 1.54, about 1.55, about 1.56, about 1.57, about 1.58, about 1.59, or about 1.60.

[0361] In an embodiment, the glass-ceramic article can have a stress optical coefficient (SOC) of about 2.60 nm / mm / MPa to 2.75 nm / mm / MPa, such as: about 2.60 nm / mm / MPa to about 2.74 nm / mm / MPa, about 2.60 nm / mm / MPa to about 2.73 nm / mm / MPa, about 2.60 nm / mm / MPa to about 2.72 nm / mm / MPa, about 2.60 nm / mm / MPa to about 2.71 nm / mm / MPa, about 2.63 nm / mm / MPa to about 2.75 nm / mm / MPa, about 2.63 nm / mm / MPa to about 2.74 nm / mm / MPa, about 2.63 nm / mm / MPa to about 2.73 nm / mm / MPa, about 2.63 nm / mm / MPa to about 2.72 nm / mm / MPa, or about 2.63 nm / mm / MPa to about 2.71 nm / mm / MPa, and all ranges and sub-ranges therebetween.

[0362] Final product

[0363] The glass-ceramic articles disclosed herein can be incorporated into another article, such as an article having a display screen (or display article) (e.g., consumer electronics, including mobile phones, tablets, computers, navigation systems, and wearable devices (e.g., watches), etc.), building articles, transportation articles (e.g., vehicles, trains, aircraft, marine vessels, etc., e.g., used as an internal display cover, window, or windshield), electrical articles, or any article that requires partial transparency, scratch resistance, abrasion resistance, or a combination thereof. Exemplary articles incorporating any of the strengthened glass-ceramic articles disclosed herein are shown in Figure 4A and 4B as shown. Specifically, Figure 4A and 4B show a consumer electronic device 200, which includes: a housing 202 having a front surface 204, a rear surface 206, and side surfaces 208; electronic components (not shown) that are at least partially located or fully located within the housing and at least include a controller, a memory, and a display 210 located on or adjacent to the front surface of the housing; and a cover substrate 212 located on or above the front surface of the housing such that it is located above the display. In some embodiments, at least one of the cover substrate 212 or a portion of the housing 202 may include any of the strengthened glass-ceramic articles disclosed herein.

[0364] Thus, compared to glass articles ceramified according to conventional techniques, the various embodiments described herein can be used to produce glass-ceramic articles having excellent optical quality without negative impacts or even improving the stress in the glass-ceramic articles. Such glass-ceramic articles can be particularly well-suited for portable electronic devices due to their strength properties and high transmission values.

[0365] Examples

[0366] The embodiments of the glass-ceramic articles and the production methods of the glass-ceramic articles of the present disclosure will be further illustrated by the following examples.

[0367] Examples 1-10 and Comparative Examples 11 and 12

[0368] Examples of glass-ceramic precursors for implementing the transparent glass-ceramic articles of the present disclosure (in wt%) and ceramization conditions are shown in Table 1 and are determined according to conventional techniques in the glass art. Precursors glasses with glass compositions 1-10 listed in Table 1 are formed. Then the precursor glasses are subjected to a ceramization cycle having a glass homogenization hold and a crystallization hold. Table 1 provides the homogenization hold temperature and time period and the crystallization hold temperature and time period for each of Examples 1-10. The following nomenclature is used in Table 1 to describe the ceramization cycle: nucleation temperature - hold time / crystallization temperature - hold time.

[0369] In addition, two comparative glass-ceramic compositions were prepared. The comparative glass-ceramics of Comparative Examples 11 and 12 contain less than 0.5 mol% of alkali metal oxides (Na 2 O and K 2 O), an alkali metal oxide to alumina (Al 2 O 3 ) molar ratio of less than 0.1, and an alkali metal oxide to zirconia (Zr 2 O) molar ratio of less than 0.3. In addition, the comparative glass-ceramics of Comparative Examples 11 and 12 contain less than 0.1 mol% of RO (ZnO, CaO, MgO, SrO, and BaO), an RO to alumina molar ratio of less than 0.05, and an RO molar ratio of less than 0.1.

[0370] Table 1

[0371]

[0372]

[0373]

[0374] Table 1 (continued)

[0375]

[0376]

[0377] After ceramization, several tests are performed on the glass-ceramics in Table 1 to determine various properties of the glass-ceramics of Examples 1-10 and Comparative Examples 11 and 12. Specifically, according to the test methods described above in the present disclosure, the glass-ceramics of Examples 1-10 and Comparative Examples 11 and 12 are tested to determine: density, elastic modulus, shear modulus, Poisson's ratio, fracture toughness (K1c), SOC, and refractive index (RI) at 589.3 nm, and the results are recorded in Table 1.

[0378] As can be seen from Table 1, the glass-ceramics of the present disclosure include Na in the parent glass in an amount greater than 0.5 mol% or even greater than 1.3 mol% 2 O and K 2 O. These alkali metal constituent components and ZrO 2 are not incorporated into the crystalline phase lithium disilicate (Li 2 O 5 Si 2 ) or spodumene (LiAlSi 4 O 10 ), and thus remain in the residual vitreous phase after the ceramization process. Na 2 O and K 2 O are constituent components that lower the glass viscosity, while Al 2 O 3 and ZrO 2 tend to increase the viscosity. Therefore, after ceramization, since Na 2 O, K 2 O and ZrO 2 do not enter the crystalline phases in these glass-ceramics, and part of Al 2 O 3 can also remain in the residual glass phase, the precursor glass with a greater concentration of alkali metal oxides ([Na 2 O + K 2 O]) and a greater molar ratio [Na 2 O + K 2 O] / [Al 2 O 3 produces glass-ceramics in which the residual glass phase exhibits a lower concentration. In addition, increasing the amount of Na 2 O + K 2 O and ZrO 2 results in an increase in the concentration of the glass phase formed in the transparent glass-ceramics produced in Examples 1-3.

[0379] In the temperature range of 700 °C to 800 °C, using the beam bending viscosity method (BBV), according to the standard method of ASTM C598-93 (the full text of which is incorporated herein by reference), the viscosities of the glass-ceramics of Examples 8-10 and the comparative glass-ceramics of Comparative Examples 11 and 12 were measured. See Figure 5 , which illustratively shows the BBV viscosity results of the glass-ceramics of Examples 8-10 and Comparative Examples 11 and 12. The glass-ceramics of Examples 8-10 and Comparative Examples 11 and 12 have different contents of Na 2 O and [Na 2 O + K 2 O] / [Al 2 O 3 and [Na2 O + K 2 O] / [ZrO 2 of different molar ratios. As Figure 5 shown, having the maximum amount of Na 2 O and the maximum [Na 2 O + K 2 O] / [Al 2 O 3 and [Na 2 O + K 2 O] / [ZrO 2 molar ratio of the glass-ceramics shows the lowest viscosity. After ceramization, the glass-ceramics of Examples 8-10 exhibit a viscosity at 780 °C (~10 -11 ) that is up to two orders of magnitude lower than that of the glass-ceramics of Comparative Example 11 without Na 2 O or K 2 O (~10 13.2 ). The glass-ceramics of Comparative Example 12 have a small amount of Na 2 O (0.06 mol%) and K 2 O (0.07 mol%), and these small amounts of Na 2 O and K 2 O enable the glass-ceramics of Comparative Example 12 to exhibit a viscosity at 780 °C (~10 12.2 ) that is about one order of magnitude lower than that of the glass-ceramics of Comparative Example 11.

[0380] In addition, according to the method described herein, the crystal phase assemblage and the weight percentages of the crystal phase and the residual glass phase of Examples 1-10 and the glass-ceramics (before ion exchange) are determined by Rietveld analysis using X-ray diffraction (XRD). Table 2 provides the phase assemblage results and weight percentages of the main crystal phase and the residual glass phase.

[0381] Table 2

[0382]

[0383]

[0384] Forming process

[0385] For Examples 7 and 8 and Comparative Examples 11 and 12, certain glass-ceramics were subjected to a 3D forming process after ceramization to transform the glass-ceramic sheets into glass-ceramic articles having a shape different from that of the glass-ceramic sheets. The 3D forming process includes establishing a high-temperature hot-forming press to manufacture reproducible and production-quality glass-ceramic articles. The hot-forming press used for the Examples is a model DTK-DGP-3D12S covering glass forming press manufactured by Daeho Technology Korea Co., Ltd. in Gyeongsangnam-do, Korea. The multi-zone hot-forming press operates in an inert atmosphere and uses a pre-forming die (e.g., a graphite die). The multi-zone hot-forming press sequentially heats the glass-ceramic, presses the glass-ceramic into the graphite die, and then cools the glass-ceramic article. The 9-zone hot-forming process includes: 1°C temperature control, a maximum die size of 120 mm x 180 mm x a thickness of 25 mm to 50 mm, a maximum forming temperature of 850°C, and a positive pressing pressure range of 0.001 MPa to 0.9 MPa.

[0386] Now refer to Figure 6 , after ceramization and before 3D forming, the glass-ceramic has a preform shape 600, which includes a rectangle with rounded corners 602. The graphite die is shaped to 3D-form the glass-ceramic preform into a glass-ceramic article having a general shape for a cover glass of a personal electronic device. Now refer to Figure 7A and 7B , which schematically shows a glass-ceramic article 700 having a 3D shape of a general cover glass.

[0387] A double-die, 14-zone sequential pressing and forming process was used to manufacture sample glass-ceramic articles, with each zone having a set temperature, time taken for each sample, and pressure applied. The first 4 zones are intended to heat the glass-ceramic preform sheet to an appropriate temperature (e.g., ~780°C) at which shaping will be achieved. The subsequent 3 zones are used for forming, by applying pressure to the heated glass-ceramic preform such that the glass-ceramic conforms to the die and has a specified three-dimensional shape. The subsequent zones are used to cool the glass-ceramic article and reduce the forming pressure. The total processing time for 3D forming is approximately 40 minutes.

[0388] Examples 13 and 14

[0389] For Examples 13 and 14, glass-ceramic articles were prepared from the compositions of the glass-ceramics of Examples 7 and 8. Glass-ceramic articles of Examples 13 and 14 were prepared by producing a glass composition containing the compositions of Examples 7 and 8 in Table 1. Then, the glass was ceramized according to the ceramization temperature and duration of Examples 7 and 8 in Table 1 to produce glass-ceramic sheets (in which most of the crystalline phase was formed). Then, the glass-ceramic sheets were cut into Figure 6The shaped body schematically shown is used to produce a ceramized glass-ceramic preform. Then, the ceramized glass-ceramic preform is 3D formed according to the shaping process described in the foregoing embodiments to produce the glass-ceramic articles of Examples 13 and 14.

[0390] Comparative Example 15

[0391] For Comparative Example 15, a glass-ceramic article is prepared from the composition of Example 8 by nucleating the crystalline phase and then 3D forming the glass-ceramic article. In Comparative Example 15, the glass composition is only nucleated to initiate the formation of the crystalline phase, but is not ceramized to form the main crystalline phase before 3D forming. Thus, before 3D forming, the nucleated glass preform is mainly a glass phase with very little crystalline phase. For Comparative Example 15, crystallization occurs during the 3D forming process, specifically, during the heating and pressing of the glass preform to produce the glass-ceramic article of Comparative Example 15. The 3D forming is carried out according to the method discussed previously in these embodiments.

[0392] Comparative Example 16

[0393] In Comparative Example 16, a glass-ceramic article is prepared from the composition of Comparative Example 12 by ceramizing the glass composition containing the constituent components of Comparative Example 12 listed in Table 1 to produce a glass-ceramic preform, and then 3D forming the glass-ceramic preform to produce the glass-ceramic article. The composition of Comparative Example 12 contains Na 2 O and K 2 O, but the total concentration of Na 2 O and K 2 O is less than 0.5 mol%, the molar ratio of [Na 2 O + K 2 O] / [Al 2 O 3 is less than 0.1, and the molar ratio of [Na 2 O + K 2 O] / [ZrO 2 is less than 0.1. Similar to Examples 13 and 14, the glass-ceramic preform in Comparative Example 16 is ceramized to form the main crystalline phase before 3D forming, so that most of the crystalline phase is formed before 3D forming.

[0394] Comparative Example 17

[0395] For Comparative Example 17, the composition of Comparative Example 11 is ceramized and then subjected to the temperature and pressure conditions of the 3D forming process to evaluate the change in the phase assemblage under the process conditions. The composition of Comparative Example 11 does not have any alkali metal oxides, alkaline earth metal oxides, or B 2 O 5Therefore, the composition of Comparative Example 11 does not have a low enough viscosity at the forming temperature to be 3D formed according to the methods described previously in these examples. As a result, as an alternative to 3D forming, for Comparative Example 17, flat sheets of the glass-ceramic having the composition of Comparative Example 11 were subjected to temperature and pressure conditions (without a mold) to study the change in the phase assemblage.

[0396] Comparative Examples 13 and 14 are compared with Comparative Examples 15 - 17

[0397] The phase assemblage of each glass-ceramic article of Examples 13 and 14 and Comparative Examples 15 - 17 was evaluated using the Rietveld analysis based on X-ray diffraction, as discussed in this disclosure. The evaluation of the phase assemblage of Examples 13 and 14 and Comparative Example 16 was carried out again after the ceramization step (2D ceramization) and after the 3D forming step (2D ceramization + 3D forming). For Comparative Example 15, the phase assemblage was evaluated only after the 3D forming and crystallization steps. As previously discussed, Comparative Example 17 is not 3D formable, so the phase assemblage was evaluated after the ceramization step (2D ceramization) and again after subjecting the glass-ceramic sheet to the forming temperature and pressure (2D ceramization + forming temperature and pressure). Table 3 below provides the weight percentages of the residual glass phase and each crystalline phase of the glass-ceramic articles of Examples 13 and 14 and Comparative Examples 15 - 17.

[0398] Table 3

[0399]

[0400] As shown in Table 3, for each glass-ceramic article of Examples 13 and 14, the concentration of the residual glass phase increased and the crystalline phase decreased during the 3D forming step, which was carried out after the glass composition was ceramized to produce a glass-ceramic preform. The glass-ceramic article of Comparative Example 15 has a greater concentration of the residual glass phase. However, the glass-ceramic article of Comparative Example 15 exhibits other defects not exhibited by the glass-ceramic articles of Examples 13 and 14, as discussed in further detail herein. For the glass-ceramic articles of Comparative Examples 16 and 17, during the 3D forming process, the concentration of the residual glass phase remained the same or decreased and the concentration of the crystalline phase changed, which is different from the effect verified in the glass-ceramic articles of Examples 13 and 14. Therefore, when the total concentration of Na 2 O and K 2 O is greater than or equal to 0.5, the molar ratio of [Na 2 O + K 2 O] / [Al 2 O 3 is greater than or equal to 0.1 and / or [Na 2 O + K 2O] / [ZrO 2 When the molar ratio of ] is greater than or equal to 0.3, when exposed to the temperature and pressure of the 3D forming process, the concentration of the residual glass phase increases. This effect was not shown in the glass-ceramic articles of Comparative Examples 16 and 17, and the concentration of their residual glass phase remained the same or decreased during the 3D forming process. As in Examples 13 and 14, the increase in the concentration of the residual glass phase can provide additional benefits during the subsequent ion-exchange process of the 3D formed glass-ceramic article, as further studied in these examples.

[0401] Physical measurements of the glass-ceramic articles of Example 14 and Comparative Example 15 were obtained after the 3D forming process and compared with the CAD specifications of the fabricated articles. The glass-ceramic article of Example 14 was well formed in a double-die pressing process with a forming temperature of 780 °C and a holding time of 180 seconds in a mold at a pressure of 0.9 MPa. The glass-ceramic article of Example 14 exhibited a deviation range of approximately 0.08 mm relative to the CAD specifications. The glass-ceramic article of Comparative Example 15 was also well formed in the double-die pressing process under the same conditions and exhibited a deviation range of approximately 0.08 mm relative to the CAD specifications.

[0402] Table 4

[0403] Example Example 14 Comparative Example 15 Process 2D Ceramization + 3D Forming 2D Nucleation + 3D Forming / Crystallization Minimum Shape Deviation from CAD (mm) -0.05 -0.05 Maximum Shape Deviation from CAD (mm) 0.03 0.03 Shape Deviation Range from CAD (mm) 0.08 0.08 Flatness 0.08 0.08 Long Axis Sag 0.03 0.03 Short Axis Sag -0.02 -0.02 Center to Corner Sag 0.05 0.05

[0404] Evaluate the aesthetic defects of the glass-ceramic articles of Example 14 (2D ceramization + 3D forming) and Comparative Example 15 (2D nucleation + 3D forming / crystallization). Aesthetically, the glass-ceramic article of Example 14 prepared by complete 2D ceramization followed by 3D forming exhibited significantly fewer surface defects and flaws compared to the glass-ceramic article of Comparative Example 15 prepared by 2D nucleation followed by simultaneous 3D forming and ceramization. Now refer to Figure 8A and 8B , the glass-ceramic article of Comparative Example 15 ( Figure 8A ) showed more stains compared to the glass-ceramic article of Example 14 ( Figure 8B ), which was almost invisible in Figure 8B due to the transparency of the glass-ceramic article. Figure 8AThe dark regions in [reference] are stain regions generated during the process of simultaneous 3D forming and ceramization. Without being limited to any particular theory, it is believed that the stains are caused by the movement or shrinkage of the glass-ceramic during the process of simultaneous 3D forming and ceramization steps of Comparative Example 15. In the stain regions, the glass-ceramic undergoes physical movement relative to the mold, which generates friction at the interface between the glass-ceramic and the graphite mold. This friction and movement cause the glass-ceramic to scrape against the mold surface, which allows defect distribution to enter the surface of the glass-ceramic. These defects can be removed by downstream polishing processes. The stains further indicate some shrinkage of the glass-ceramic article of Comparative Example 15.

[0405] See Figure 8B , the glass-ceramic article of Example 14, which is manufactured by first ceramizing the glass-ceramic preform and then performing 3D forming, exhibits very few stains. This indicates that during the 3D forming process of the glass-ceramic article of Example 14, there is less shrinkage or physical movement of the glass-ceramic article relative to the mold, which results in less friction between the glass-ceramic and the mold surface. Therefore, the process of ceramizing the glass composition to produce a ceramized glass-ceramic preform and then performing 3D forming on the glass-ceramic preform to produce a glass-ceramic article can reduce shrinkage and stains during the 3D forming process, as compared to the case of only nucleating and completing ceramization during the 3D forming process. The 2D-ceramized 3D-shaped glass-ceramic article of Example 14 contains some stains, but the stains are much cleaner and require much less downstream polishing to meet the quality specifications.

[0406] The surface quality of the glass-ceramic articles of Example 14 and Comparative Example 16 is further evaluated by using a xenon lamp to project shadows on the glass-ceramic surface and by any deformation of the bulk glass-ceramic. Figure 9A is a shadow image generated by passing a xenon lamp through the glass-ceramic article of Comparative Example 15. As Figure 9A shown, the shadows generated by passing a xenon lamp through the glass-ceramic article of Comparative Example 16 indicate a significant amount of surface defects in the glass-ceramic article. In contrast, now see Figure 9B , passing a xenon lamp through the glass-ceramic article of Example 14 results in very few shadows, indicating fewer quality defects on the surface of the glass-ceramic article of Example 14 as compared to Comparative Example 16.

[0407] The difficulty of post-3D forming finishing of the glass-ceramic articles of Example 14 and Comparative Example 15 is evaluated. The post-3D forming finishing process can include polishing to remove surface defects. Now see Figure 10 , showing a qualitative evaluation of the post-3D forming finishing comparison of the glass-ceramic articles of Example 14 and Comparative Example 15 with the post-3D forming finishing of a glass article that has undergone 3D forming without nucleation or ceramization. AsFigure 10 As shown, after the 3D forming process required for the glass-ceramic article of Example 14, the finishing (e.g., downstream polishing) workload of the glass-ceramic article is less, compared to the glass-ceramic article of Comparative Example 15 and compared to the 3D formed glass article.

[0408] As previously referenced Figure 8A and 8B discussed above, compared to glass-ceramics that have been ceramized prior to 3D forming, pre-nucleated glass will have a significant amount of movement or shrinkage during the final ceramization crystal growth stage. For glass-ceramic articles produced by 3D forming and crystallization after pre-nucleation (such as Comparative Example 15), crystal growth and shrinkage effects occur simultaneously during the 3D forming process. In this case, the glass is restricted, and thus the friction between the glass and the mold increases. This increase in friction, along with the shrinkage naturally present during the crystallization process, induces scratch-like effects, resulting in various defects embedded in the surface of the glass-ceramic. This spotting can be removed by a downstream polishing process, but this scratching effect also reduces the expected quality life of the mold.

[0409] Now refer to Figure 11 , which illustratively shows the concentration of the residual glass phase (left y-axis) after 3D forming for the glass-ceramic articles of Examples 13 and 14 and Comparative Examples 16 and 17, and the mole % (right y-axis) of non-lithium alkali metal oxides (e.g., Na 2 O, K 2 O) and alkaline earth metal oxides (e.g., CaO, MgO, BaO, SrO) in the glass composition. As Figure 11 shown, as the concentration of non-lithium alkali metal oxides, alkaline metal oxides (or both) increases, the weight percentage of the residual glass phase after 3D forming increases.

[0410] An increase in the residual glass phase in a glass-ceramic article and an increase in the concentration of non-lithium alkali metal oxides can increase the 3D formability of the glass-ceramic after full ceramization. Specifically, increasing the concentration of the residual glass phase can reduce the viscosity of the glass-ceramic, which improves the 3D formability of the glass-ceramic. For the glass-ceramic article of Example 13 that contains approximately 14 wt% residual glass phase in the glass-ceramic preform, the maximum 3D forming temperature is 800 °C, while for the glass-ceramic article of Example 14 that contains approximately 20 wt% residual glass phase in the glass-ceramic preform, the maximum 3D forming temperature is approximately 780 °C. Thus, increasing the concentration of the residual glass phase in the glass-ceramic preform can achieve a reduction in the 3D forming temperature. Additionally, the glass-ceramic article of Comparative Example 16 requires a higher 3D forming temperature of 815 °C, whereas the maximum 3D forming temperature for the glass-ceramic articles of Examples 13 and 14 is 800 °C. As discussed above, the glass-ceramic preform of Comparative Example 17 that does not contain any non-lithium alkali metal oxides or alkaline metal oxides is not 3D formable, and the glass-ceramic preform cracks. Without being limited to any particular theory, it is believed that 0.71 mol% CaO in the composition of the glass-ceramic article of Comparative Example 16 is sufficient to help reduce the viscosity in the residual glass phase to allow 3D forming of the glass-ceramic preform of Comparative Example 16, whereas the glass-ceramic of Comparative Example 17 is not 3D formable and contains only 0.03 mol% CaO (primarily from impurities).

[0411] Without being limited to any particular theory, it is believed that a greater concentration of non-lithium alkali metal oxides (i.e., [Na 2 O + K 2 O]), a greater molar ratio of [Na 2 O + K 2 O] / [Al 2 O 3 , and [Na 2 O + K 2 O] / [ZrO 2 , and / or a greater concentration of alkaline earth metal oxides reduces the viscosity of the residual glass phase and of the glass-ceramic as a whole within the 3D forming temperature range, which enables 3D forming of the ceramified glass-ceramic preform. Having little or no non-lithium alkali metal oxides or alkaline metal oxides and / or a low or zero [Na 2 O + K 2 O] / [Al 2 O 3 and [Na 2 O + K 2 O] / [ZrO 2A glass-ceramic having a molar ratio of (e.g., the glass-ceramic of Comparative Example 17) cannot achieve 3D forming of the glass-ceramic after glass-ceramic crystallization to produce a majority of the crystalline phase. In the absence of non-lithium alkali metal oxides and / or alkaline earth metal oxides, the viscosity of the residual glass phase and the glass-ceramic as a whole is too high, and the preform cannot be thermoformed to the desired shape without cracking.

[0412] Example 18: Ion Exchange of the Glass-Ceramic Article of Example 14

[0413] In Example 18, before and after 3D forming, the glass-ceramic article of Example 14 was ion-exchanged to study the effect of an increase in the concentration of the residual glass phase during the 3D forming process on the ion-exchange process and the resulting properties of the strengthened glass article produced thereby. In Example 18, the glass-ceramic article of Example 14 having the composition of Example 8 was subjected to an ion-exchange process before and after 3D forming, wherein the glass-ceramic article was placed in a molten salt bath containing NaNO 3 , LiNO 3 and KNO 3 . Table 5 provides the concentration of each constituent component of the molten salt bath. The samples had a thickness of 0.5 mm or 0.6 mm, as shown in Table 5. Before and after 3D forming, the glass-ceramic article was ion-exchanged at an ion-exchange temperature of 500 °C for the period specified in Table 5. After ion-exchange, the strengthened glass article was evaluated for FSM compressive stress (CS), FSM compressive depth (DOC), direct CS, count, weight gain, SCALP midpoint center tension (CT), and SCALP maximum CT, the values of which are provided in Table 5 below.

[0414] Table 5

[0415]

[0416]

[0417] Table 5 (continued)

[0418]

[0419]

[0420] As shown in Table 5, for the two thicknesses of 0.5 mm and 0.6 mm, the glass-ceramic articles that are ceramized and then 3D formed (e.g., Examples 18B, 18D, and 18G) have greater weight gain and greater central tension (CT) compared to the glass-ceramics that are only ceramized without 3D forming and are ion-exchanged under the same conditions (Examples 18A, 18C, 18F). Without being limited to any particular theory, it is believed that these effects can be attributed to a greater residual glass phase concentration in the 3D formed glass-ceramic articles and / or a greater lithium availability in the residual glass phase of the 3D formed glass-ceramic articles (compared to the glass-ceramics that are only ceramized).

[0421] Example 19: Ion Exchange of the Glass-Ceramic Article of Example 13

[0422] In Example 19, before and after 3D forming, the glass-ceramic article of Example 13 was ion-exchanged to study the effect of the increased concentration of the residual glass phase during the 3D forming process on the ion-exchange process and the resulting properties of the strengthened glass article thus produced. In Example 19, the glass-ceramic article of Example 13 having the composition of Example 7 was subjected to an ion-exchange process before and after 3D forming, wherein the glass-ceramic article was placed in a molten salt bath containing NaNO 3 , LiNO 3 and KNO 3 . Table 6 provides the concentration of each constituent component of the molten salt bath. The samples had a thickness of 0.4 mm, as shown in Table 6. Before and after 3D forming, the glass-ceramic articles were ion-exchanged at an ion-exchange temperature of 500 °C for 1.75 hours. After ion-exchange, the strengthened glass articles were evaluated for FSM compressive stress (CS), FSM compressive depth (DOC), direct CS, weight gain, SCALP midpoint central tension (CT), and SCALP maximum CT, and the values are provided in Table 6 below.

[0423] Table 6

[0424]

[0425]

[0426] As shown in Table 6, glass-ceramic articles that have been ceramized and then 3D formed (e.g., Examples 19D, 19E, and 19F) have greater CS, greater weight gain, and greater depth of compression, as compared to glass-ceramics that have been only ceramized without 3D forming and that have been ion-exchanged under the same conditions (Examples 19A, 19B, and 19C). Without being limited to any particular theory, it is believed that these effects can be attributed to a greater residual glass phase concentration in the 3D formed glass-ceramic article and / or a greater lithium availability in the residual glass phase of the 3D formed glass-ceramic article (as compared to glass-ceramics that have been only ceramized). As shown by Sample 19E of Example 19, the glass-ceramic article can be ion-exchanged to produce a CS that is greater than 300 MPa or even greater than or equal to 325 MPa.

[0427] While embodiments and examples have been given for purposes of illustration, the foregoing description should not be regarded as limiting the scope of this specification or the appended claims. Accordingly, various improvements, modifications, and alternative forms may occur to those skilled in the art without departing from the spirit and scope of this specification or the appended claims.

Claims

1. A method for forming a glass-ceramic article, the method comprising: performing three-dimensional (3D) forming on a glass-ceramic preform to produce a glass-ceramic article having a lithium disilicate crystal phase, a spodumene crystal phase, and a residual glass phase, wherein: before 3D forming, the glass-ceramic preform contains a lithium disilicate crystal phase, a spodumene crystal phase, and a residual glass phase; and after 3D forming, the glass-ceramic article contains a residual glass phase at a concentration greater than that of the residual glass phase in the glass-ceramic preform.

2. The method according to claim 1, wherein, before 3D forming, the concentration of the residual glass phase in the glass-ceramic preform is 10 wt% to 50 wt%.

3. The method according to claim 1, wherein, after 3D forming, the glass-ceramic article has a residual glass phase of 15 wt% to 50 wt%.

4. The method according to claim 1, wherein, after 3D forming, the glass-ceramic article has a residual glass phase of 20 wt% to 50 wt%.

5. The method according to claim 1, wherein, the concentration of the residual glass phase in the glass-ceramic article is at least 5% greater than that of the residual glass phase in the glass-ceramic preform.

6. The method according to claim 1, wherein, before 3D forming, the combined concentration of the lithium disilicate crystal phase and the spodumene crystal phase in the glass-ceramic preform is 50 wt% to 90 wt%.

7. The method according to claim 1, wherein, the glass-ceramic article is clear and transparent.

8. The method according to claim 1, wherein, the glass-ceramic article contains Na2O, K2O, or both.

9. The method according to claim 8, wherein, the molar concentration of Na2O and K2O in the glass-ceramic article is greater than or equal to 0.5 mol% to 9 mol%.

10. The method according to claim 8, wherein, the glass-ceramic article has a molar ratio [Na2O + K2O] / [Al2O3] of 0.1 to 5.

11. The method according to claim 8, wherein, the glass-ceramic article has a molar ratio [Na2O + K2O] / [ZrO2] of 0.3 to 5.

12. The method according to claim 1, wherein, the glass-ceramic article contains one or more metal oxides selected from the group consisting of ZnO, MgO, CaO, BaO, SrO, and combinations thereof.

13. The method according to claim 12, wherein, the glass-ceramic article has a molar ratio [MgO + CaO + BaO + SrO + ZnO] / [Al2O3] of 0.05 to 5.

14. The method according to claim 12, wherein, the glass-ceramic article has a molar ratio [MgO + CaO + BaO + SrO + ZnO] / [ZrO2] of 0.1 to 5.

15. The method according to claim 1, wherein, the glass-ceramic article contains B2O3.

16. The method according to claim 15, wherein, The glass-ceramic product contains 0 mol% to 10 mol% of B 2 O 3 .

17. The method according to claim 1, wherein, the composition of the glass-ceramic article contains SiO2, Al2O3, Li2O, P2O5, and ZrO2.

18. The method according to claim 17, Among them, the composition of the glass-ceramic product includes: 55 mol% to 80 mol% SiO2, 1 mol% to 15 mol% Al2O3, 10 mol% to 40 mol% Li2O, 0.2 mol% to 4 mol% P2O5, and 0.1 mol% to 10 mol% ZrO2.

19. The method according to claim 17, wherein, the composition of the glass-ceramic product includes: 68 mol% to 71 mol% SiO2, 3 mol% to 5 mol% Al2O3, 18 mol% to 25 mol% Li2O, 0.6 mol% to 1 mol% P2O5, and 1.5 mol% to 3 mol% ZrO2.

20. The method according to claim 17, wherein, the composition of the glass-ceramic product includes: 68.2 mol% to 70.4 mol% SiO2, 3.5 mol% to 4.5 mol% Al2O3, 20 mol% to 23 mol% Li2O, 0.8 mol% to 1 mol% P2O5, and 1.6 mol% to 3 mol% ZrO2.

21. The method according to claim 17, wherein, the composition of the glass-ceramic further includes 0 mol% to 5 mol% Na2O, 0 mol% to 4 mol% K2O, or both.

22. The method according to claim 21, wherein, the composition of the glass-ceramic includes 0.5 mol% to 2 mol% Na2O, 0.5 mol% to 1.2 mol% K2O, or a combination of these.

23. The method according to claim 17, wherein, the composition of the glass-ceramic product includes less than 0.5 mol% of Na2O and K2O, and further includes one or more of the following: 0 mol% to 8 mol% ZnO; 0 mol% to 8 mol% MgO; 0 mol% to 8 mol% CaO; 0 mol% to 8 mol% SrO; or 0 mol% to 8 mol% BaO, wherein the total concentration of ZnO, MgO, CaO, SrO, and BaO is greater than or equal to 0.5 mol%.

24. The method according to claim 17, wherein, the composition of the glass-ceramic product further includes one or more of the following: Fe2O3, SnO2, HfO2, TiO2, or a combination of these.

25. The method according to claim 1, wherein, before the glass-ceramic preform is 3D formed to produce the glass-ceramic product, the glass-ceramic preform is ceramized.

26. The method according to claim 1, wherein, the total concentration of the crystalline phase in the glass-ceramic preform before 3D forming is the maximum total concentration of the crystalline phase of the composition of the glass-ceramic preform.

27. The method according to claim 1 further includes preparing a glass-ceramic preform before the glass-ceramic preform is 3D formed to produce the glass-ceramic product.

28. The method according to claim 27, wherein, preparing the glass-ceramic preform includes: ceramizing the precursor glass to produce a glass-ceramic preform containing a lithium disilicate crystal phase, a spodumene crystal phase, and a residual glass phase, wherein the concentration of the residual glass phase in the glass-ceramic preform is 10 wt% to 50 wt%.

29. The method according to claim 28, wherein, Ceramifying a precursor glass to produce a glass-ceramic preform includes: Heating the precursor glass to a nucleation temperature of 500 °C to 650 °C; Maintaining the precursor glass at the nucleation temperature for a first period of 1 minute to 600 minutes; Increasing the temperature of the precursor glass to a crystallization temperature of 680 °C to 800 °C; and Maintaining the precursor glass at the crystallization temperature for a second period of 1 second to 600 minutes to produce a glass-ceramic preform.

30. The method according to claim 29, further comprising cooling the glass-ceramic preform from a first temperature to room temperature.

31. The method according to claim 27, wherein, after the ceramification of the precursor glass to produce a glass-ceramic preform, the total concentration of the crystalline phases in the glass-ceramic preform differs from the total concentration of the crystalline phases in the glass-ceramic article after 3D shaping by within 50%.

32. The method according to claim 1, wherein, the three-dimensional shape of the glass-ceramic article is different from the shape of the glass-ceramic preform.

33. The method according to claim 1, wherein, performing 3D shaping on the glass-ceramic preform includes thermo-mechanical shaping.

34. The method according to claim 1, wherein, performing 3D shaping on the glass-ceramic preform includes: Heating the glass-ceramic preform to a shaping temperature; After heating, pressing the glass-ceramic preform into a mold for a period of time to produce a glass-ceramic article; and Cooling the glass-ceramic article.

35. The method according to claim 34, wherein, the shaping temperature is 650 °C to 850 °C.

36. The method according to claim 34, wherein, pressing the glass-ceramic preform into the mold with a pressing pressure of 0.001 MPa to 0.9 MPa.

37. The method according to claim 34, wherein, the mold is a graphite mold.

38. The method according to claim 34, wherein, the heating and pressing of the glass-ceramic preform increase the concentration of the residual glass phase in the glass-ceramic article, as compared to the glass-ceramic preform.

39. The method according to claim 1, wherein, measured at a thickness of 0.8 mm, the glass-ceramic article includes a haze of less than 0.

20.

40. The method according to claim 1, wherein, the overall volume change of the glass-ceramic article during the shaping process is less than 1% of the glass-ceramic preform before 3D shaping.

41. The method according to claim 1, wherein, the method does not include any active method steps aimed at further increasing the crystallinity of the glass-ceramic article after 3D shaping.

42. The method according to claim 1, further comprising, after 3D shaping, strengthening the glass-ceramic article to produce a strengthened glass-ceramic article having a compressive stress layer extending from a first surface of the glass-ceramic article to a compressive depth.

43. The method according to claim 42, wherein, the strengthened glass-ceramic article has a compressive stress of the compressive stress layer greater than or equal to 200 MPa.

44. The method according to claim 42, wherein, the compressive depth of the strengthened glass-ceramic article is 0*t to 0.3*t, where t is the thickness of the strengthened glass-ceramic article.

45. The method according to claim 42, wherein, the strengthened glass-ceramic article has a compressive depth greater than or equal to 10% of the thickness of the strengthened glass-ceramic article, a central tension greater than or equal to 40 MPa, or both.

46. The method according to claim 42, wherein, strengthening the glass-ceramic article includes ion-exchanging the glass-ceramic article to produce the strengthened glass-ceramic article.

47. The method according to claim 46, wherein, ion-exchanging the glass-ceramic article causes the weight per unit volume of the glass-ceramic article to increase by greater than or equal to 0.05%.

48. A glass-ceramic article comprising a lithium disilicate crystal phase, a spodumene crystal phase, and a residual glass phase, the glass-ceramic article being prepared by a process including 3D shaping a glass-ceramic preform to produce the glass-ceramic article, wherein: before 3D shaping, the glass-ceramic preform comprises a lithium disilicate crystal phase, a spodumene crystal phase, and a residual glass phase; and after 3D shaping, the glass-ceramic article comprises a residual glass phase having a concentration greater than the concentration of the residual glass phase in the glass-ceramic preform.

49. The glass-ceramic article according to claim 48, wherein, 3D shaping the glass-ceramic preform to produce the glass-ceramic article includes thermo-mechanical shaping.

50. The glass-ceramic article according to claim 49, wherein, 3D shaping the glass-ceramic preform produces a glass-ceramic article, wherein the concentration of the residual glass phase in the glass-ceramic article is at least 5% greater than the concentration of the residual glass phase in the glass-ceramic preform.

51. The glass-ceramic article according to claim 48, wherein, 3D shaping the glass-ceramic preform includes: heating the glass-ceramic preform to a shaping temperature; after heating, pressing the glass-ceramic preform into a mold for a period of time to produce the glass-ceramic article; and cooling the glass-ceramic article.

52. The glass-ceramic article according to claim 51, wherein, the shaping temperature is 650 °C to 850 °C, and the pressing pressure during the pressing process is 0.001 MPa to 0.9 MPa.

53. The glass-ceramic article according to claim 48, wherein, during 3D shaping, the glass-ceramic article exhibits a shrinkage of less than 1% of the total volume of the glass-ceramic preform.

54. The glass-ceramic article according to claim 48, further comprising, after 3D shaping, strengthening the glass-ceramic article to produce a strengthened glass-ceramic article having a compressive stress layer extending from a first surface of the glass-ceramic article to a compressive depth.

55. The glass-ceramic article according to claim 54, wherein, the strengthened glass-ceramic article has a compressive stress of the compressive stress layer greater than or equal to 200 MPa.

56. The glass-ceramic article according to claim 54, wherein, the compressive depth of the strengthened glass-ceramic article is 0*t to 0.3*t, where t is the thickness of the strengthened glass-ceramic article.

57. The glass-ceramic article according to claim 54, wherein, The toughened glass-ceramic article has a compressive depth greater than or equal to 10% of the thickness of the toughened glass-ceramic article, a central tension greater than or equal to 40 MPa, or both.

58. The glass-ceramic article according to claim 54, wherein, toughening the glass-ceramic article includes ion-exchanging the glass-ceramic article to produce a toughened glass-ceramic article.

59. The glass-ceramic article according to claim 58, wherein, ion-exchanging the glass-ceramic article causes the weight per unit volume of the glass-ceramic article to increase by greater than or equal to 0.05%.

60. The glass-ceramic article according to claim 48, wherein, for light with a wavelength of 589.3 nm, the glass-ceramic article has a refractive index of 1.5 to 1.

6.

61. The glass-ceramic article according to claim 48, wherein, measured at a thickness of 0.8 mm, the glass-ceramic article includes a haze of less than 0.

20.

62. The glass-ceramic article according to claim 48, wherein, measured at a thickness of 0.8 mm, for electromagnetic radiation wavelengths from 450 nm to 800 nm, the glass-ceramic article includes an optical transmittance of greater than 85%.

63. An electronic device, which includes a transparent surface, and the transparent surface includes the glass-ceramic article according to claim 48.

64. The electronic device according to claim 63, wherein, the glass-ceramic article has a thickness of 0.3 mm to 1 mm.

65. The electronic device according to claim 63, wherein, the electronic device is a consumer electronic device.

66. A glass-ceramic article, which includes: a lithium disilicate crystal phase; a spodumene crystal phase; and a residual glass phase, wherein: the concentration of the residual glass phase is 15 wt% to 50 wt%; and the glass-ceramic article has one or more of the following: the molar ratio [Na2O + K2O] / [Al2O3] is 0.1 to 5; the molar ratio [Na2O + K2O] / [ZrO2] is 0.3 to 5; the molar ratio [MGO + CaO + BaO + SrO + ZnO] / [Al2O3] is 0.05 to 5; the molar ratio [MgO + CaO + BaO + SrO + ZnO] / [ZrO2] is 0.1 to 5; or a combination thereof.

67. The glass-ceramic article according to claim 66, wherein, the concentrations of the lithium disilicate crystal phase and the spodumene crystal phase are greater than any other crystal phase in the glass-ceramic article.

68. The glass-ceramic article according to claim 66, wherein, the glass-ceramic article has a residual glass phase concentration of 20 wt% to 50 wt%.

69. The glass-ceramic article according to claim 66, wherein, before 3D forming, the combined concentration of the lithium disilicate crystal phase and the spodumene crystal phase in the glass-ceramic preform is 50 wt% to 90 wt%.

70. The glass-ceramic article according to claim 66, wherein, the glass-ceramic article is clear and transparent.

71. The glass-ceramic article according to claim 66, wherein, the glass-ceramic article includes Na2O, K2O, or both.

72. The glass-ceramic article according to claim 71, wherein, The molar concentrations of Na2O and K2O in the glass-ceramic product are greater than or equal to 0.5 mol% to 9 mol%.

73. The glass-ceramic product according to claim 71, wherein, the glass-ceramic product has a molar ratio [Na2O + K2O] / [Al2O3] of 0.1 to 5.

74. The glass-ceramic product according to claim 71, wherein, the glass-ceramic product has a molar ratio [Na2O + K2O] / [ZrO2] of 0.3 to 5.

75. The glass-ceramic product according to claim 66, wherein, the glass-ceramic product contains one or more metal oxides selected from the group consisting of ZnO, MgO, CaO, BaO, SrO, and combinations thereof.

76. The glass-ceramic product according to claim 75, wherein, the glass-ceramic product has a molar ratio [MgO + CaO + BaO + SrO + ZnO] / [Al2O3] of 0.05 to 5.

77. The glass-ceramic product according to claim 75, wherein, the glass-ceramic product has a molar ratio [MgO + CaO + BaO + SrO + ZnO] / [ZrO2] of 0.1 to 5.

78. The glass-ceramic product according to claim 66, wherein, the glass-ceramic product contains B2O3.

79. The glass-ceramic product according to claim 78, wherein, the glass-ceramic product contains 0 mol% to 10 mol% B2O3.

80. The glass-ceramic product according to claim 66, wherein, the composition of the glass-ceramic product contains SiO2, Al2O3, Li2O, P2O5, and ZrO2.

81. The glass-ceramic product according to claim 80, wherein, the composition of the glass-ceramic product contains: 55 mol% to 80 mol% SiO2, 1 mol% to 15 mol% Al2O3, 10 mol% to 40 mol% Li2O, 0.2 mol% to 4 mol% P2O5, and 0.1 mol% to 10 mol% ZrO2.

82. The glass-ceramic product according to claim 80, wherein, the composition of the glass-ceramic product contains: 68 mol% to 71 mol% SiO2, 3 mol% to 5 mol% Al2O3, 18 mol% to 25 mol% Li2O, 0.6 mol% to 1 mol% P2O5, and 1.5 mol% to 3 mol% ZrO2.

83. The glass-ceramic product according to claim 80, wherein, the composition of the glass-ceramic product contains: 68.2 mol% to 70.4 mol% SiO2, 3.5 mol% to 4.5 mol% Al2O3, 20 mol% to 23 mol% Li2O, 0.8 mol% to 1 mol% P2O5, and 1.6 mol% to 3 mol% ZrO2.

84. The glass-ceramic product according to claim 80, wherein, the composition of the glass-ceramic further contains 0 mol% to 5 mol% Na2O, 0 mol% to 4 mol% K2O, or both.

85. The glass-ceramic product according to claim 84, wherein, The composition of the glass-ceramic contains 0.5 mol% to 2 mol% of Na2O, 0.5 mol% to 1.2 mol% of K2O, or a combination thereof.

86. The glass-ceramic article according to claim 84, wherein, the composition of the glass-ceramic contains less than 0.5 mol% of Na2O and K2O, and further contains one or more of the following: 0 mol% to 8 mol% of ZnO; 0 mol% to 8 mol% of MgO; 0 mol% to 8 mol% of CaO; 0 mol% to 8 mol% of SrO; or 0 mol% to 8 mol% of BaO, wherein the total concentration of ZnO, MgO, CaO, SrO, and BaO is greater than or equal to 0.5 mol%.

87. The glass-ceramic article according to claim 80, wherein, the composition of the glass-ceramic article further contains one or more of the following: Fe2O3, SnO2, HfO2, TiO2, or a combination thereof.

88. The glass-ceramic article according to claim 66, wherein, the composition of the glass-ceramic article contains, consists of, or consists essentially of: 55 mol% to 80 mol% of SiO2; 1 mol% to 15 mol% of Al2O3; 10 mol% to 40 mol% of Li2O; 0.2 mol% to 4 mol% of P2O5; 0 mol% to 10 mol% of B2O3; 0.1 mol% to 10 mol% of ZrO2; 0 mol% to 5 mol% of Na2O; 0 mol% to 4 mol% of K2O; 0 mol% to 8 mol% of MgO; 0 mol% to 8 mol% of CaO; 0 mol% to 8 mol% of SrO; 0 mol% to 8 mol% of BaO; 0 mol% to 8 mol% of ZnO; 0 mol% to 0.5 mol% of Fe2O3; 0 mol% to 0.5 mol% of HfO2; 0 mol% to 0.5 mol% of SnO2; and 0 mol% to 2 mol% of TiO2.

89. The glass-ceramic article according to claim 88, wherein, the composition of the glass-ceramic article contains: 68 mol% to 71 mol% of SiO2; 3 mol% to 5 mol% of Al2O3; 18 mol% to 25 mol% of Li2O; 0.6 mol% to 1 mol% of P2O5; 1.5 mol% to 3 mol% of ZrO2; 0.5 mol% to 2 mol% of Na2O; 0.5 mol% to 2 mol% of K2O; 0 mol% to 0.1 mol% of CaO; 0 mol% to 0.1 mol% of Fe2O3; 0 mol% to 0.1 mol% of HfO2; 0 mol% to 0.0.5 mol% of SnO2; and 0 mol% to 2 mol% of TiO2.

90. The glass-ceramic article according to claim 66, wherein, the glass-ceramic article is a component of an electronic device.

91. The glass-ceramic article according to claim 90, wherein, the glass-ceramic article is a transparent cover plate of an electronic device.

92. The glass-ceramic article according to claim 66, wherein, the glass-ceramic article has a Young's modulus of 90 GPa to 110 GPa.

93. The glass-ceramic article according to claim 66, wherein, the glass-ceramic article has a shear modulus of 35 GPa to 50 GPa.

94. The glass-ceramic article according to claim 66, wherein, the glass-ceramic article has a Poisson's ratio of 0.19 to 0.

24.

95. The glass-ceramic article according to claim 66, wherein, The glass-ceramic product has a fracture toughness of 1.0 MPa / m 0.5 to 2.0 MPa / m 0.5 .

96. The glass-ceramic article according to claim 66, wherein, the glass-ceramic article has a stress optical coefficient (SOC) of 2.60 nm / mm / MPa to 2.75 nm / mm / MPa.

97. The glass-ceramic article according to claim 66, wherein, for light with a wavelength of 589.3 nm, the glass-ceramic article has a refractive index of 1.5 to 1.

6.

98. The glass-ceramic article according to claim 66, wherein, the glass-ceramic article is strengthened and has a compressive stress of greater than or equal to 200 MPa.

99. The glass-ceramic article according to claim 66, wherein, the glass-ceramic article is strengthened and has a central tension of greater than or equal to 30 MPa over a thickness range of 0.5 mm to 0.6 mm.

100. The glass-ceramic article according to claim 66, wherein, the glass-ceramic article is strengthened and has a compressive depth of greater than or equal to 10% of the thickness of the strengthened glass-ceramic article or greater than or equal to 80 microns.

101. The glass-ceramic article according to claim 66, wherein, the glass-ceramic article is strengthened and has a compressive depth of 0*t to 0.3*t, where t is the thickness of the glass-ceramic article.

102. The glass-ceramic article according to claim 66, wherein, the glass-ceramic article has a stress with a delay of less than 30 nm per mm of the thickness of the glass-ceramic article.

103. The glass-ceramic article according to claim 66, wherein, the glass-ceramic article includes a stress with a delay of less than 25 nm per mm of the thickness of the glass-ceramic article.

104. The glass-ceramic article according to claim 66, wherein, the glass-ceramic article has a haze of less than 0.0994t + 0.12, in percentage (%), where t is the thickness of the glass-ceramic article in mm; 105. The glass-ceramic article according to claim 66, wherein, The glass-ceramic article has an optical transmittance greater than 0.91×10 (2-0.03t) for electromagnetic radiation having a wavelength from 450 nm to 800 nm, in percent (%), where t is the thickness of the glass-ceramic article in mm.

106. The glass-ceramic article according to claim 66, wherein, measured at a thickness of 0.8 mm, the glass-ceramic article includes a haze of less than 0.

20.

107. The glass-ceramic article according to claim 66, wherein, measured at a thickness of 0.8 mm, for an electromagnetic radiation wavelength of 450 nm to 800 nm, the glass-ceramic article includes an optical transmittance of greater than 85%.

108. The glass-ceramic article according to claim 66, wherein, the glass-ceramic article has a thickness of 0.3 mm to 1 mm.

109. The glass-ceramic article according to claim 66, wherein, the glass-ceramic article is a component of an electronic device.

110. The glass-ceramic article according to claim 109, wherein, the glass-ceramic article is a clear and transparent cover plate for an electronic device.

111. An electronic device, comprising a transparent surface, the transparent surface comprising the glass-ceramic article according to claim 66.

112. The electronic device according to claim 111, wherein, the glass-ceramic article has a thickness of 0.3 mm to 1 mm.

113. The electronic device according to claim 111, wherein, the electronic device is a consumer electronic device.

114. A glass-ceramic article, comprising: a lithium disilicate crystal phase; a spodumene crystal phase; and a residual glass phase, wherein: the concentration of the residual glass phase is 15 wt% to 50 wt%; and The glass-ceramic product has a Young's modulus of 90 GPa to 110 GPa, a shear modulus of 35 GPa to 50 GPa, and a fracture toughness of 1.0 MPa / m 0.5 to 2.0 MPa / m 0.5 .

115. The glass-ceramic article according to claim 114, wherein, the glass-ceramic article has a Poisson's ratio of 0.19 to 0.

24.

116. The glass-ceramic article according to claim 114, wherein, the glass-ceramic article has a stress optical coefficient (SOC) of 2.60 nm / mm / MPa to 2.75 nm / mm / MPa.

117. The glass-ceramic article according to claim 114, wherein, for light with a wavelength of 589.3 nm, the glass-ceramic article has a refractive index of 1.5 to 1.

6.

118. The glass-ceramic article according to claim 114, wherein, the glass-ceramic article is strengthened and has a compressive stress greater than or equal to 200 MPa.

119. The glass-ceramic article according to claim 114, wherein, the glass-ceramic article is strengthened and has a central tension greater than or equal to 30 MPa in a thickness range of 0.5 mm to 0.6 mm.

120. The glass-ceramic article according to claim 114, wherein, the glass-ceramic article is strengthened and has a compressive depth greater than or equal to 10% of the thickness of the strengthened glass-ceramic article or greater than or equal to 80 microns.

121. The glass-ceramic article according to claim 114, wherein, the glass-ceramic article has a molar ratio of [Na2O + K2O] / [Al2O3] of 0.1 to 5.

122. The glass-ceramic article according to claim 114, wherein, the glass-ceramic article has a molar ratio of [Na2O + K2O] / [ZrO2] of 0.3 to 5.

123. The glass-ceramic article according to claim 114, wherein, the glass-ceramic article has a molar ratio of [MgO + CaO + BaO + SrO + ZnO] / [Al2O3] of 0.05 to 5.

124. The glass-ceramic article according to claim 114, wherein, the glass-ceramic article has a molar ratio of [MGO + CaO + BaO + SrO + ZnO] / [ZrO2] of 0.1 to 5.

125. The glass-ceramic article according to claim 114, wherein, the glass-ceramic article is strengthened and has a compressive depth of 0*t to 0.3*t, where t is the thickness of the glass-ceramic article.

126. The glass-ceramic article according to claim 114, wherein, the glass-ceramic article has a stress of less than 30 nm delay per mm of the thickness of the glass-ceramic article.

127. The glass-ceramic article according to claim 114, wherein, the glass-ceramic article includes a stress of less than 25 nm delay per mm of the thickness of the glass-ceramic article.

128. The glass-ceramic article according to claim 114, wherein, The glass-ceramic article has a haze of less than 0.0994t + 0.12, where the unit is percentage (%), and in the formula, t is the thickness of the glass-ceramic article, and the unit is mm.

129. The glass-ceramic article according to claim 114, wherein, The glass-ceramic article has an optical transmittance greater than 0.91×10 (2-0.03t) for electromagnetic radiation having a wavelength from 450 nm to 800 nm, in percent (%), where t is the thickness of the glass-ceramic article in mm.

130. The glass-ceramic article according to claim 114, wherein, Measured at a thickness of 0.8 mm, the glass-ceramic article has a haze of less than 0.

20.

131. The glass-ceramic article according to claim 114, wherein, Measured at a thickness of 0.8 mm, for the electromagnetic radiation wavelength from 450 nm to 800 nm, the glass-ceramic article has an optical transmittance of greater than 85%.

132. The glass-ceramic article according to claim 114, wherein, The glass-ceramic article has a thickness of 0.3 mm to 1 mm.

133. The glass-ceramic article according to claim 114, wherein, The glass-ceramic article includes components of an electronic device.

134. The glass-ceramic article according to claim 114, wherein, The glass-ceramic article is a transparent cover plate of an electronic device.

135. An electronic device, which includes a transparent surface, and the transparent surface includes the glass-ceramic article according to claim 114.

136. The electronic device according to claim 135, wherein, The glass-ceramic article has a thickness of 0.3 mm to 1 mm.

137. The electronic device according to claim 135, wherein, The electronic device is a consumer electronic device.

138. A glass-ceramic article, which includes a first surface, a second surface opposite to the first surface, a lithium disilicate crystal phase, a petalite crystal phase, a residual glass phase, and a compressive stress layer extending from the first surface to the depth of compression (DOC), wherein, The compressive stress of the compressive stress layer is greater than or equal to 200 MPa, the DOC is greater than or equal to 10% of the thickness of the glass-ceramic article, and the concentration of the residual glass phase is 15 wt% to 50 wt%.

139. The glass-ceramic article according to claim 138, wherein, The glass-ceramic article has a Young's modulus of 90 GPa to 110 GPa.

140. The glass-ceramic article according to claim 138, wherein, The glass-ceramic article has a shear modulus of 35 GPa to 50 GPa.

141. The glass-ceramic article according to claim 138, wherein, The glass-ceramic article has a Poisson's ratio of 0.19 to 0.

24.

142. The glass-ceramic article according to claim 138, wherein, The glass-ceramic product has a fracture toughness of 1.0 MPa / m 0.5 to 2.0 MPa / m 0.5 .

143. The glass-ceramic article according to claim 138, wherein, The glass-ceramic article has a stress optical coefficient (SOC) of 2.60 nm / mm / MPa to 2.75 nm / mm / MPa.

144. The glass-ceramic article according to claim 138, wherein, For light with a wavelength of 589.3 nm, the glass-ceramic article has a refractive index of 1.5 to 1.

5.

145. The glass-ceramic article according to claim 138, wherein, The glass-ceramic article has a thickness of 0.3 mm to 1.0 mm.

146. The glass-ceramic article according to claim 138, wherein, The glass-ceramic article has a central tension greater than or equal to 30 MPa.

147. The glass-ceramic article according to claim 138, wherein, the glass-ceramic article has one or more of the following: The molar ratio [Na2O + K2O] / [Al2O3] is 0.1 to 5; The molar ratio [Na2O + K2O] / [ZrO2] is 0.3 to 5; The molar ratio [MgO + CaO + BaO + SrO + ZnO] / [Al2O3] is 0.05 to 5; The molar ratio [MgO + CaO + BaO + SrO + ZnO] / [ZrO2] is 0.1 to 5; or a combination thereof.

148. The glass-ceramic article according to claim 138, wherein, the glass-ceramic article comprises a component of an electronic device.

149. The glass-ceramic article according to claim 148, wherein, the glass-ceramic article is a transparent cover plate of an electronic device.

150. An electronic device comprising a transparent surface, the transparent surface comprising the glass-ceramic article according to claim 138.

151. The electronic device according to claim 150, wherein, the glass-ceramic article has a thickness of 0.3 mm to 1 mm.

152. The electronic device according to claim 150, wherein, the electronic device is a consumer electronic device.

153. A glass-ceramic article comprising a lithium disilicate crystal phase, a spodumene crystal phase and a residual glass phase, wherein, the concentration of the residual glass phase is 15 wt% to 50 wt%, based on the total weight of the glass-ceramic article, the glass-ceramic article has a thickness of 0.3 mm to 1.0 mm, and the glass-ceramic article comprises a component of an electronic device.

154. The glass-ceramic article according to claim 153, wherein, the glass-ceramic article comprises at least one concave surface.

155. The glass-ceramic article according to claim 153, wherein, the outer surface of the glass-ceramic article comprises a flat rectangular outer surface and a convex boundary region defining the flat rectangular outer surface.

156. The glass-ceramic article according to claim 155, wherein, the convex boundary region has a width of 10 mm.

157. The glass-ceramic article according to claim 153, wherein, the glass-ceramic article has a rectangular shape with four rounded corners in a top view.

158. The glass-ceramic article according to claim 156, wherein, the glass-ceramic article has a length of 100 mm to 200 mm and a width of 50 mm to 100 mm.

159. The glass-ceramic article according to claim 156, wherein, each rounded corner is congruent to an arc with a radius of 20 mm.

160. The glass-ceramic article according to claim 153, wherein, the glass-ceramic article is a transparent cover plate of an electronic device.

161. An electronic device comprising a transparent surface, the transparent surface comprising the glass-ceramic article according to claim 153.

162. The electronic device according to claim 161, wherein, the glass-ceramic article has a thickness of 0.3 mm to 1 mm.

163. The electronic device according to claim 161, wherein, the electronic device is a consumer electronic device.

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