HK40108767A - Precursor glasses and glass-ceramics comprising a crystalline phase having a jeffbenite crystalline structure - Google Patents

Description

Precursor glasses and glass-ceramics containing crystalline phases with a Jeffbenite crystalline structure

This case is a divisional application of the patent application filed on February 13, 2023, with application number 2023800113030 and invention title "Precursor glass and glass-ceramic containing a crystalline phase having a Jeffbenite crystalline structure".

Cross-references to related applications

This specification claims the benefits of U.S. Provisional Application Serial No. 63/309,667, filed February 14, 2022, entitled “Precursor Glasses and Glass-Ceramics Comprising a Crystalline Phase having a Jeffbenite Crystalline Structure,” and U.S. Non-Provisional Application Serial No. 17/887,012, filed August 12, 2022, entitled “Precursor Glasses and Glass-Ceramics Comprising a Crystalline Phase having a Jeffbenite Crystalline Structure,” the entire contents of which are incorporated herein by reference.

Technical Field

This specification relates to precursor glass and glass-ceramic articles made therefrom.

Background Technology

Glassware, such as cover glass, glass back panels, and housings, is used in both consumer and commercial electronic devices, including smartphones, tablets, portable media players, personal computers, and cameras. The mobile nature of these portable devices makes them and their contained glassware particularly vulnerable to accidental drops onto hard surfaces like the ground. Furthermore, glassware such as cover glass may incorporate touch functionality, requiring contact with various objects, including user fingers and/or stylus devices. Therefore, glassware must be robust enough to withstand accidental drops and regular contact without damage, such as scratches. In fact, scratches introduced into the surface of glassware can reduce its strength, as scratches can act as initiation points for cracks, leading to catastrophic failure of the glass.

Therefore, alternative materials with improved mechanical properties compared to glass are needed.

Summary of the Invention

The features and advantages of the precursor glass and glass-ceramic described herein will be set forth in the following detailed description, and will be apparent in part to those skilled in the art from the description or to be recognized by practice of the embodiments described herein, including the following detailed description, claims, and drawings.

The applicant has discovered, as explained herein, that the Jeffbenite crystalline structure associated with inclusions in “ultra-deep” diamond can provide numerous useful advantages and properties if formed as a glass-ceramic crystalline phase within glass. The applicant believes that a crystalline phase having a Jeffbenite crystalline structure has never before grown or otherwise formed in glass-ceramics. The applicant also believes that a crystalline phase having a Jeffbenite crystalline structure has never before been formed or otherwise incorporated into glass-ceramic articles such as glass-ceramic sheets, glass-ceramic containers, windows, panels, shells, plates, counters, kitchenware, rods, fibers, or other such articles. Furthermore, compared to jeffbenite in (anisotropic) diamond or isolated jeffbenite, the applicant argues that a crystalline phase with a jeffbenite crystalline structure has never been included in articles possessing isotropic material properties (e.g., maintaining the same properties such as tensile strength, elasticity, and fracture toughness when tested in different directions). This can be effectively achieved by including relatively small grains, as disclosed herein, randomly oriented and uniformly distributed within a residual glass to form a glass-ceramic, or randomly oriented and uniformly distributed within another isotropic solid medium (e.g., a polymer). The applicant believes that glass-ceramics with a crystalline phase having a jeffbenite crystalline structure have never been manufactured before, even in nature; never grown from a precursor glass; and never formed at temperatures (e.g., <1600 K, <1400 K) and pressures (e.g., <12 GPa, such as <10 GPa, <8 GPa, <1 GPa, such as even 1 atm) as disclosed herein. Supported by the current findings, it is now possible to produce large quantities of crystals with the jeffbenite crystalline structure in a single batch, partly because the extreme temperatures and pressures associated with ultra-deep strata within the mantle are not required.

Furthermore, the glass-ceramics described in this paper can achieve excellent hardness and stiffness values, thus enabling thin and lightweight mobile phone and tablet display surfaces. These same characteristics allow for the use of opaque or colored glass-ceramics in phone and tablet casings. Additionally, these glass-ceramics may be lithium-free but can still be strengthened through ion exchange, thereby reducing the demand for this scarce resource.

Aspect 1 includes a glass-ceramic article comprising a first surface; a second surface opposite to the first surface; a periphery defining the shape of the glass-ceramic article; and a phase collection comprising one or more crystalline phases and a glassy phase, said one or more crystalline phases comprising a jeffbenite crystalline structure.

Aspect 2 includes the glass-ceramic articles of aspect 1, wherein one or more crystalline phases containing a jeffbenite crystalline structure are the main crystalline phase.

Aspect 3 includes any glass-ceramic articles of the foregoing aspects, wherein one or more crystalline phases comprising the jeffbenite crystalline structure have a composition according to the following formula: (Mg,R ²⁺ ) _3+x (Zr,R ⁴⁺ ) _x Al _2-2x Si ₃ O ₁₂ , wherein R ²⁺ is a divalent metal cation, R ⁴⁺ is a tetravalent metal cation, and x is greater than or equal to 0 and less than 1.

Aspect 4 includes glass-ceramic articles of aspect 1 or aspect 2, wherein the crystalline phase containing the jeffbenite crystalline structure has a composition according to the following formula: (Mg,R ²⁺ ) _3+x (Zr,R ⁴⁺ ) _x Al _2-2x Si ₃ O ₁₂ , wherein R ²⁺ is a divalent metal cation, R ⁴⁺ is a tetravalent metal cation, and x is greater than or equal to 0 and less than or equal to 1.

Aspect 5 includes the glass-ceramic article of aspect 4, wherein R ²⁺ is one or more divalent metal cations selected from Ca ²⁺ , Mn ²⁺ , Fe ²⁺ , and wherein R ⁴⁺ is one or more tetravalent metal cations selected from Ti ⁴⁺ , Sn ⁴⁺ , Hf ⁴⁺ .

Aspect 6 includes any glass-ceramic articles of the foregoing aspects, wherein one or more crystalline phases comprising the jeffbenite crystalline structure have a composition according to the following formula: (Mg,Fe,Mn,Zn) _3+x (Zr,Ti, _{Sn ) xAl2-2xSi3O12} , where x is _greater than or equal to 0 and less than 1.

Aspect 7 includes any glass-ceramic articles of the foregoing aspects, wherein one or more crystalline phases comprising the jeffbenite crystalline structure have a composition according to the following formula: Mg _3+x Zr _x Al _2-2x Si ₃ O ₁₂ , where x is greater than or equal to 0 and less than 1.

Aspect 8 includes any glass-ceramic articles of the foregoing aspects, wherein the one or more crystalline phases comprise one or more secondary crystalline phases.

Aspect 9 includes the glass-ceramic articles of aspect 8, wherein one or more secondary crystalline phases comprise the _ZrO2 crystalline phase.

Aspect 10 includes the glass-ceramic articles of aspect 8, wherein the one or more secondary crystalline phases comprise the _ZrTiO4 crystalline phase.

Aspect 11 includes any glass-ceramic article of the foregoing aspects, wherein the phase set comprises more than or equal to 25% by weight of the one or more crystalline phases and less than or equal to 75% by weight of a glass phase.

Aspect 12 includes any glass-ceramic article of the foregoing aspects, wherein at least some grains of the at least one crystalline phase containing the jeffbenite crystalline structure have a size greater than or equal to 20 nm to less than or equal to 100 nm.

Aspect 13 includes any glass-ceramic article of the foregoing aspects, wherein the glass-ceramic article has an average transmittance of at least 75% for light in the wavelength range of 400 nm to 800 nm at an article thickness of 0.6 mm.

Aspect 14 includes the glass-ceramic articles of aspects 1-12, wherein the glass-ceramic articles have an average transmittance of 20% to less than 75% for light in the wavelength range of 400 nm to 800 nm at an article thickness of 0.6 mm.

Aspect 15 includes the glass-ceramic articles of aspects 1-12, wherein the glass-ceramic articles have an average transmittance of less than 20% for light in the wavelength range of 400 nm to 800 nm at an article thickness of 0.6 mm.

Aspect ₁₆ includes any glass-ceramic articles of the foregoing aspects comprising: greater than or equal to 35 mol% to less than or equal to 65 mol% of _SiO2 ; greater than or equal to 5 mol% to less than or equal to 20 mol% of _Al2O3 ; greater than or equal to 10 mol% to less than or equal to 45 mol% of MgO; greater than or equal to 1 mol% to less than or equal to 7 mol% of _ZrO2 ; greater than or equal to 0 mol% to less than or equal to 15 mol% of _Na2O ; greater than or equal to 0 mol% to less than or equal to 15 mol% of _K2O ; greater than or equal to 0 mol% to less than or equal to 9 mol% of FeO; greater than or equal to 0 mol% to less than or equal to 1 mol% of _MnO2 ; and greater than or equal to 0 mol% to less than or equal to 12 mol% of ZnO.

Aspect 17 includes glass-ceramic articles of aspects 1-15, comprising: greater than or equal to 35 mol% to less than or equal to 65 mol% of _SiO2 ; greater than or equal to 5 mol% to less than or equal to 20 mol _% of _Al2O3 ; greater than or equal to 7 mol% to less than or equal to 65 mol% of MgO; greater than or equal to 0 mol% to less than or equal to 7 mol% of _ZrO2 ; greater than or equal to 0 mol% to less than or equal to 15 mol% of _Na2O ; greater than or equal to 0 mol% to less than or equal to 15 mol% of _K2O ; greater than or equal to 0 mol% to less than or equal to 9 mol% of FeO; greater than or equal to 0 mol% to less than or equal to 10 mol% of _MnO2 ; and greater than or equal to 0 mol% to less than or equal to 15 mol% of ZnO, wherein the glass-ceramic comprises a phase set comprising one or more crystalline phases and a glassy phase, the one or more crystalline phases comprising a crystalline phase comprising a jeffbenite crystalline structure.

Aspect 18 includes any glass-ceramic articles of the foregoing aspects containing 48 mol% to 54 mol% _SiO2 .

Aspect 19 includes any glass-ceramic articles of the foregoing aspects containing more than or equal to 9 mol% and less than or equal to 13 mol% _{of Al₂O₃} .

Aspect 20 includes any glass-ceramic articles of the foregoing aspects containing greater than or equal to 1 mol% to less than or equal to 15 mol% _Na₂O .

Aspect 21 includes any glass-ceramic articles of the foregoing aspects containing more than or equal to 1 mol% and less than or equal to 15 mol% _K2O .

Aspect 22 includes any glass-ceramic articles of the foregoing aspects, wherein the concentration of _Na₂O (mol%) + _K₂O (mol%) is greater than or equal to 2 mol% and less than or equal to 15 mol%.

Aspect 23 includes any glass-ceramic articles of the foregoing aspects, wherein _Na₂O (mol%)/( _Na₂O (mol%) + _K₂O (mol%)) is greater than or equal to 0.3.

Aspect 24 includes glass-ceramic articles of aspects 1-22, wherein _Na₂O (mol%)/( _Na₂O (mol%) + _K₂O (mol%)) is greater than or equal to 0.2.

Aspect 25 includes any glass-ceramic articles of the foregoing aspects, which further contain greater than or equal to 0.3 mol% to less than or equal to 7 mol% _TiO2 .

Aspect 26 includes any glass-ceramic articles of the foregoing aspects, wherein the _ZrO2 (mol%) + _TiO2 (mol%) is greater than or equal to 2 mol%.

Aspect 27 includes any glass-ceramic articles of the foregoing aspects, wherein _ZrO2 (mol%)/( _ZrO2 (mol%)+ _TiO2 (mol%)) is greater than or equal to 0.3.

Aspect 28 includes any glass-ceramic articles of the foregoing aspects containing more than or equal to 1 mol% to less than or equal to 12 mol% of ZnO.

Aspect 29 includes any glass-ceramic articles of the foregoing aspects, which also contain less than or equal to 3 mol% _Li₂O .

Aspect 30 includes any of the glass-ceramic articles of the foregoing aspects, wherein the glass-ceramic articles are substantially free of _Li₂O .

Aspect 31 includes any glass-ceramic articles of the foregoing aspects, which also contain more than or equal to 1 mol% and less than or equal to 8 mol% of BaO.

Aspect 32 includes any glass-ceramic article of the foregoing aspects, which further comprises at least one of CaO and SrO in an amount greater than or equal to 0.2 mol% and less than or equal to 1.7 mol%.

Aspect 33 includes any glass-ceramic articles of the foregoing aspects, wherein the glass-ceramic articles are substantially _free of _P2O5 .

Aspect 34 includes the glass-ceramic articles of aspects 1-32, wherein the glass-ceramic articles contain greater than 0 mol% to less than or equal to 4 mol% of P ₂ O ₅ .

Aspect 35 includes any glass-ceramic articles of the foregoing aspects, wherein the glass-ceramic articles contain more than or equal to 1.5 mol% and less than or equal to 3 mol% of _ZrO2 .

Aspect 36 includes any glass-ceramic article of the foregoing aspects, wherein the glass-ceramic article contains _HfO2 at a concentration greater than or equal to 0 mol% and less than or equal to 12 mol%, wherein the sum of _ZrO2 and _HfO2 is greater than 1 mol%.

Aspect 37 includes any glass-ceramic article of the foregoing aspects, wherein the glass-ceramic article contains more than 0 mol% to less than or equal to 15 mol% CaO.

Aspect 38 includes any glass-ceramic articles of the foregoing aspects, wherein the glass-ceramic articles contain greater than 0 mol% to less than or equal to 7 mol% _{of La₂O₃} .

Aspect 39 includes a glass-ceramic article comprising: 35 mol% to 65 mol% of _SiO₂ ; 5 mol% to 20 mol% of _Al₂O₃ ; 10 mol% to 45 mol% of MgO; 1 mol% to 7 mol% of _ZrO₂ ; 0 mol% to 15 mol% of _Na₂O ; 0 mol% to 15 mol% of _K₂O ; 0 mol% to 9 mol% of FeO; 0 mol% to 1 mol% of _MnO₂ ; and 0 mol% to 12 mol% of _ZnO , wherein the glass-ceramic article comprises a glassy phase and a crystalline phase having a jeffbenite crystal structure.

Aspect 40 includes a glass-ceramic article comprising: 35 mol% to 65 mol% of _SiO2 ; 5 mol% to 20 mol% of _Al2O3 ; 7 mol% to 65 mol% of MgO; 0 mol% to 7 mol% of _ZrO2 ; 0 mol% to 15 mol% of _Na2O ; 0 mol% to 15 mol% of _K2O ; 0 mol% to 9 mol% of FeO; 0 mol% to 10 mol% of _MnO2 ; and 0 mol% to 15 mol% of _ZnO , wherein the glass-ceramic article comprises a glassy phase and a crystalline phase having a jeffbenite crystal structure.

Aspect 41 includes the glass-ceramic articles of aspect 39 or aspect 40, wherein the crystalline phase comprising the jeffbenite crystalline structure has a composition according to the following formula: (Mg,R ²⁺ ) _3+x (Zr,R ⁴⁺ ) _x Al _2-2x Si ₃ O ₁₂ , wherein R ²⁺ is a divalent metal cation, R ⁴⁺ is a tetravalent metal cation, and x is greater than or equal to 0 and less than 1.

Aspect 42 includes the glass-ceramic articles of aspect 39 or aspect 40, wherein the crystalline phase comprising the jeffbenite crystalline structure has a composition according to the following formula: (Mg,R ²⁺ ) _3+x (Zr,R ⁴⁺ ) _x Al _2-2x Si ₃ O ₁₂ , wherein R ²⁺ is a divalent metal cation, R ⁴⁺ is a tetravalent metal cation, and x is greater than or equal to 0 and less than or equal to 1.

Aspect 43 includes the glass-ceramic article of aspect 42, wherein ^R²⁺ is one or more divalent metal cations selected from ^Ca²⁺ , ^Mn²⁺ , and ^Fe²⁺ , and wherein ^R⁴⁺ is one or more tetravalent metal cations selected from ^Ti⁴⁺ , ^Sn⁴⁺ , and ^Hf⁴⁺.

Aspect 44 includes the glass-ceramic articles of aspects 39-43, wherein the crystalline phase comprising the jeffbenite crystalline structure has a composition according to the following formula: (Mg,Fe,Mn,Zn) _3+x (Zr,Ti,Sn _{) xAl2-2xSi3O12 ,} where x is _greater than or equal to 0 and less than 1.

Aspect 45 includes the glass-ceramic articles of aspects 39-44, wherein the crystalline phase comprising the jeffbenite crystalline structure has a composition according to the following formula: Mg _3+x Zr _x Al _2-2x Si ₃ O ₁₂ , where x is greater than or equal to 0 and less than 1.

Aspect 46 includes glass-ceramic articles of aspects 39-45, wherein the crystalline phase comprising the crystalline structure of jeffbenite is the main crystalline phase.

Aspect 47 includes the glass-ceramic articles of aspects 39-46, which contain greater than or equal to 48 mol% and less than or equal to 54 mol% of _SiO2 .

Aspect 48 includes the glass-ceramic articles of aspects 39-47, which contain greater than or equal to 9 mol% and less than or equal to 13 mol% _{of Al₂O₃} .

Aspect 49 includes the glass-ceramic articles of aspects 39-48, which contain greater than or equal to 1 mol% and less than or equal to 15 mol% of _Na₂O .

Section 50 includes the glass-ceramic articles of sections 39-49, which contain greater than or equal to 2 mol% and less than or equal to 5 mol% _Na₂O .

Aspect 51 includes the glass-ceramic articles of aspects 49-50, which contain greater than or equal to 1 mol% and less than or equal to 15 mol% of _K₂O .

Aspect 52 includes the glass-ceramic articles of aspects 39-51, which contain greater than or equal to 1 mol% to less than or equal to 5 mol% _K2O .

Section 53 includes glass-ceramic articles of sections 39-52, wherein the content of _Na₂O (mol%) + _K₂O (mol%) is greater than or equal to 2 mol% and less than or equal to 15 mol%.

Aspect 54 includes glass-ceramic articles of aspects 39-53, wherein the ratio of _Na₂O (mol%)/( _Na₂O (mol%) + _K₂O (mol%)) is greater than or equal to 0.3.

Section 55 includes glass-ceramic articles of sections 39-53, wherein the ratio of _Na₂O (mol%)/( _Na₂O (mol%) + _K₂O (mol%)) is greater than or equal to 0.2.

Aspect 56 includes the glass-ceramic articles of aspects 39-55, which further contain greater than or equal to 0.3 mol% to less than or equal to 7 mol% _TiO2 .

Section 57 includes glass-ceramic articles of sections 39-56, wherein the content of _ZrO2 (mol%) + _TiO2 (mol%) is greater than or equal to 2 mol%.

Section 58 includes the glass-ceramic articles of sections 39-57, wherein _ZrO2 (mol%)/( _ZrO2 (mol%)+ _TiO2 (mol%)) is greater than or equal to 0.3.

Aspect 59 includes the glass-ceramic articles of aspects 39-58, which contain more than or equal to 1 mol% and less than or equal to 12 mol% of ZnO.

Section 60 includes the glass-ceramic articles of sections 39-59, which also contain less than or equal to 3 mol% _Li₂O .

Aspect 61 includes the glass-ceramic articles of aspects 39-60, wherein the glass-ceramic articles are substantially free of _Li₂O .

Aspect 62 includes the glass-ceramic articles of aspects 39-61, which further contain greater than or equal to 1 mol% and less than or equal to 8 mol% of BaO.

Aspect 63 includes the glass-ceramic articles of aspects 39-62, which further contain at least one of CaO and SrO in amounts greater than or equal to 0.2 mol% to less than or equal to 1.7 mol%.

Aspect 64 includes the glass-ceramic articles of aspects 39-63, wherein the glass-ceramic articles are substantially _free of _P2O5 .

Aspect 65 includes the glass-ceramic articles of aspects 39-63, wherein the glass-ceramic articles contain greater than 0 mol% to less than or equal to 4 mol% _{of P₂O₅} .

Aspect 66 includes the glass-ceramic articles of aspects 39-65, wherein the glass-ceramic articles contain more than or equal to 1.5 mol% to less than or equal to 3 mol% of _ZrO2 .

Aspect 67 includes the glass-ceramic articles of aspects 39-66, wherein the glass-ceramic articles contain more than 0 mol% to less than or equal to 7 mol% of _HfO2 .

Aspect 68 includes the glass-ceramic articles of aspects 39-67, wherein the glass-ceramic articles contain more than 0 mol% to less than or equal to 15 mol% CaO.

Aspect 69 includes the glass-ceramic articles of aspects 39-68, wherein the glass-ceramic articles contain greater than 0 mol% to less than or equal to 7 mol% _{of La₂O₃} .

Aspect 70 includes the glass-ceramic articles of aspects 39-69, wherein the glass-ceramic articles have a density greater than or equal to 2.65 g/ ^cm³ to less than or equal to 2.95 g/ ^cm³ .

Aspect 71 includes the glass-ceramic articles of aspects 39-69, wherein the glass-ceramic articles have a density greater than or equal to 2.50 g/ ^cm³ to less than or equal to 3.70 g/ ^cm³ .

Aspect 72 includes the glass-ceramic articles of aspects 39-71, which also contain the _ZrO2 crystalline phase.

Aspect 73 includes the glass-ceramic articles of aspects 39-72, which also contain the _ZrTiO4 crystalline phase.

Aspect 74 includes the glass-ceramic articles of aspects 39-73, wherein at least some grains of the crystalline phase having a jeffbenite crystalline structure have a size greater than or equal to 20 nm to less than or equal to 100 nm.

Aspect 75 includes a consumer electronic device comprising: a housing having a front surface, a rear surface, and a side surface; electrical components provided at least partially within the housing, the electrical components including at least a controller, a memory, and a display located at or adjacent to the front surface of the housing; and a glass-ceramic article of any of the foregoing aspects, at least one disposed above the display and forming part of the housing.

Aspect 76 includes a method of manufacturing a glass-ceramic article, the method comprising: heat-treating a precursor glass comprising _SiO2 , _Al2O3 , _MgO and _ZrO2 to nucleate one or more crystalline phases in the precursor glass, wherein the one or more crystalline phases comprise a jeffbenite crystalline structure and the precursor glass optionally comprises one or more of FeO, _MnO2 and ZnO; and growing the one or more crystalline phases in the glass phase.

Aspect 77 includes a method for manufacturing a glass-ceramic article, the method comprising: heat-treating a precursor glass comprising _SiO2 , _Al2O3 and _MgO to nucleate one or more crystalline phases in the precursor glass, wherein the one or more crystalline phases comprise a jeffbenite crystalline structure; and growing the one or more crystalline phases in the glass phase.

Aspect 78 includes a method of manufacturing a glass-ceramic article according to aspect 76 or 77, wherein the heat treatment includes: heating a precursor glass to a first temperature greater than or equal to 700°C and less than or equal to 950°C; and holding the precursor glass at the first temperature for a first time greater than or equal to 0.25 hours and less than or equal to 6 hours.

Aspect 79 includes the method of manufacturing a glass-ceramic article of aspect 78, wherein the heat treatment further includes: heating the precursor glass to a second temperature greater than or equal to 750°C and less than or equal to 950°C; and holding the precursor glass at the second temperature for a second time greater than or equal to 0.25 hours and less than or equal to 6 hours.

Aspect 80 includes the methods of manufacturing glass-ceramic articles of aspects 76-79, wherein the crystalline phase having a jeffbenite crystalline structure is the main crystalline phase.

Aspect 81 includes the method of manufacturing glass-ceramic articles of aspects 76-80, wherein the jeffbenite crystalline phase has a composition according to the following formula: (Mg,R ²⁺ ) _3+x (Zr,R ⁴⁺ ) _x Al _2-2x Si ₃ O ₁₂ , where x is greater than or equal to 0 and less than 1.

Aspect 82 includes the method of manufacturing glass-ceramic articles of aspects 76-81, wherein the crystalline phase having a jeffbenite crystalline structure has a composition according to the following formula: (Mg,R ²⁺ ) _3+x (Zr,R ⁴⁺ ) _x Al _2-2x Si ₃ O ₁₂ , where x is greater than or equal to 0 and less than or equal to 1.

Aspect 83 includes the method of manufacturing glass-ceramic articles of aspects 76-82, wherein the jeffbenite crystalline phase has _a composition according to the following formula: (Mg,Fe,Mn,Zn) _3+x (Zr,Ti,Sn) _{xAl2-2xSi3O12 ,} where x is greater than or equal to 0 and less than ₁ .

Aspect 84 includes the method of manufacturing glass-ceramic articles of aspects 76-83, wherein the jeffbenite crystalline phase has a composition according to the following formula: Mg _3+x Zr _x Al _2-2x Si ₃ O ₁₂ , where x is greater than or equal to 0 and less than 1.

Aspect 85 includes the method of manufacturing a glass-ceramic article of aspects 76-84, wherein the glass-ceramic article comprises a phase set, the phase set comprising one or more crystalline phases and a glass phase.

Aspect 86 includes the method of manufacturing glass-ceramic articles of aspect 85, wherein the one or more crystalline phases comprise one or more secondary crystalline phases.

Aspect 87 includes the method of manufacturing glass-ceramic articles of aspect 86, wherein the one or more secondary crystalline phases comprise _ZrO2 .

Aspect 88 includes the method of manufacturing glass-ceramic articles of aspect 86, wherein the one or more secondary crystalline phases comprise _ZrTiO4 .

Aspect 89 includes the method of manufacturing glass-ceramic articles of aspects 85-88, wherein the phase set comprises more than or equal to 25% by weight of the one or more crystalline phases and less than or equal to 75% by weight of a glass phase.

Aspect 90 includes the method of manufacturing glass-ceramic articles of aspects 85-89, wherein at least some grains of the crystalline phase having a jeffbenite crystalline structure have a size greater than or equal to 20 nm to less than or equal to 100 nm.

Aspect 91 includes a glass-ceramic article comprising: a first main surface and a second main surface opposing the first main surface, an edge forming a periphery of the first and second main surfaces and extending between the first and second main surfaces; wherein the thickness of the article is defined as the distance between the first and second main surfaces, the width of the article is defined as a distance orthogonal to the thickness and extending along the first main surface between the edges, and the length of the article is defined as a distance orthogonal to the width and thickness and extending along the first main surface between the edges; wherein the width is greater than or equal to the thickness; wherein the length is greater than or equal to the width; and a body between the first main surface, the second main surface, and the edge, wherein the body comprises glass-ceramic, wherein the glass-ceramic comprises a crystalline phase having a jeffbenite crystalline structure.

Aspect 92 includes the glass-ceramic article of aspect 91, wherein the glass-ceramic article comprises glass-ceramic sheet.

Aspect 93 includes the glass-ceramic article of aspect 91 or aspect 92, wherein the grains of the crystalline phase having a jeffbenite crystalline structure are uniformly distributed throughout the glass-ceramic body.

Aspect 94 includes the glass-ceramic articles of aspects 91-93, wherein the grains of the crystalline phase having a jeffbenite crystalline structure are randomly oriented within the glass-ceramic body.

Aspect 95 includes the glass-ceramic articles of aspects 91-94, wherein the grains of the crystalline phase having a jeffbenite crystalline structure overlap and interlock with each other within the glass-ceramic body to such a degree that its fracture toughness is 0.75 MPa·m ^1/2 or higher.

Aspect 96 includes the glass-ceramic articles of aspects 91-95, wherein the glass-ceramic has isotropic material properties.

Aspect 97 includes the glass-ceramic articles of aspects 91-96, wherein the thickness is greater than or equal to 200 μm and less than or equal to 5 mm.

Aspect 98 includes the glass-ceramic articles of aspects 91-97, wherein both the length and width are greater than 5 mm.

Aspect 99 includes the glass-ceramic articles of aspects 91-98, wherein the first primary surface has an area greater than or equal to 25 ^mm² .

Aspect 100 includes the glass-ceramic articles of aspects 91-99, wherein the volume of the glass-ceramic in the body is greater than or equal to 25 ^mm³ .

Aspect 101 includes the glass-ceramic articles of aspects 91-100, wherein the body is substantially composed of glass-ceramic, and wherein the body is at least partially translucent, such that at least 20% of light of wavelengths of 400 to 800 nanometers directed into the sheet thickness passes through the body.

Aspect 102 includes a method of manufacturing a glass-ceramic, comprising: heat-treating a precursor glass containing nucleation sites to grow grains of a crystalline phase having a Jeffbenite crystal structure from the nucleation sites within the precursor glass to form a glass-ceramic comprising a crystalline phase having a Jeffbenite crystal structure and residual glass; and growing grains of the crystalline phase having a Jeffbenite crystal structure during heat treatment such that at least some of the grains of the crystalline phase having a Jeffbenite crystal structure have a size greater than or equal to 20 nm.

Aspect 103 includes the method of aspect 102, wherein the growth is carried out under atmospheric pressure.

Aspect 104 includes the methods of aspects 102-103, wherein the temperature of the precursor glass is kept below 1500K during the heat treatment process.

Aspect 105 includes the methods of aspects 102-104, wherein, after growth, at least some grains of the crystalline phase having the jeffbenite crystalline structure overlap and interlock with each other within the glass-ceramic residual glass.

Aspect 106 includes the methods of aspects 102-105, wherein, after growth, at least some grains of the crystalline phase having the jeffbenite crystalline structure have a size of less than or equal to 5 μm.

Aspect 107 includes the methods of aspects 102-106, wherein the nucleation sites are located within the precursor glass such that the grains of the crystalline phase having the jeffbenite crystalline structure are uniformly distributed within the glass-ceramic.

Aspect 108 includes the methods of aspects 102-107, wherein the heat treatment causes grains of the crystalline phase having the jeffbenite crystalline structure to grow throughout the glass-ceramic.

Aspect 109 includes the methods of aspects 102-108, wherein the grains of the crystalline phase having the jeffbenite crystalline structure grow relative to each other in a random orientation and are dispersed within the glass-ceramic residual glass.

Aspect 110 includes the methods of aspects 102-109, wherein the crystalline phase having a jeffbenite crystalline structure is the main crystalline phase of a glass-ceramic material.

Aspect 111 includes the methods of aspects 102-110, wherein the glass-ceramic has isotropic material properties after growth.

Aspect 112 includes a glass-ceramic article comprising: a stoichiometric crystal of pyrope-almandine garnet having a tetragonal structure; and an amorphous glass surrounding and encapsulating the crystal, such that the crystal and the glass together form a glass-ceramic article.

Aspect 113 includes the glass-ceramic article of aspect 112, wherein the tetragonal structure falls within the space group I-42d.

Aspect 114 includes a glass-ceramic article comprising: an “a” lattice parameter greater than or equal to and less than or equal to; a “c” lattice parameter greater than or equal to and less than or equal to; and an X-ray diffraction pattern comprising: a first peak with a 2θ angle between 30° and 32°; a second peak with a 2θ angle between 33° and 35°; a third peak with a 2θ angle between 40° and 42°; and a fourth and fifth peak with a 2θ angle between 55° and 58°, wherein the first, second, third, fourth, and fifth peaks correspond to jeffbenite.

Aspect 115 includes a glass-ceramic containing jeffbenite.

Aspect 116 includes an article comprising: a surface; and a body within the surface, wherein the body comprises the glass-ceramic of aspect 115.

Aspect 117 includes an article of article according to aspect 116, wherein the surface is a first surface, the article further includes a second surface opposite to the first surface, and the body is located between the first and second surfaces such that the article is a sheet.

Aspect 118 includes a method of manufacturing a material comprising growing jeffbenite under pressure below 10 GPa.

Aspect 119 includes the method of aspect 118, wherein the growth is carried out at a temperature below 1400K.

Aspect 120 includes the method of aspect 118, wherein the jeffbenite is grown as a crystalline phase within a glass to form a glass-ceramic.

It should be understood that both the foregoing general description and the following detailed description depict various embodiments and are intended to provide an overview or framework for understanding the nature and characteristics of the claimed subject matter. The accompanying drawings are included to provide a further understanding of the various embodiments and are incorporated in and form a part of this specification. The drawings illustrate the various embodiments described herein and, together with the description, serve to explain the principles and operation of the claimed subject matter.

Attached Figure Description

Figure 1 is a top view of an electronic device including glass-ceramic articles;

Figure 2 is a perspective view of an electronic device including glass-ceramic products;

Figure 3 is a SEM micrograph of the crystal structure of a glass-ceramic containing a crystalline phase with a jeffbenite crystal structure;

Figure 4 is a SEM micrograph of the crystal structure of a glass-ceramic containing a crystalline phase with a jeffbenite crystal structure;

Figure 5 shows the 2θ X-ray diffraction pattern at high temperature, which illustrates the temperature variation of the stability range of various crystalline phases in glass-ceramics containing crystalline phases with jeffbenite crystal structure and tetragonal zirconia crystalline phase.

Figure 6A is a SEM micrograph of the crystal structure of a glass-ceramic containing a crystalline phase with a jeffbenite crystal structure;

Figure 6B is a SEM micrograph of the crystal structure of a glass-ceramic containing a crystalline phase with a jeffbenite crystal structure;

Figure 6C is a SEM micrograph of the crystal structure of a glass-ceramic containing a crystalline phase with a jeffbenite crystal structure;

Figure 6D is a SEM micrograph of the crystal structure of a glass-ceramic containing a crystalline phase with a jeffbenite crystal structure;

Figure 6E is a SEM micrograph of the crystal structure of a glass-ceramic containing a crystalline phase with a jeffbenite crystal structure;

Figure 6F is a SEM micrograph of the crystal structure of a glass-ceramic containing a crystalline phase with a jeffbenite crystal structure;

Figure 7 is an X-ray diffraction 2θ pattern, which shows the crystalline phase with a jeffbenite crystalline structure in an example glass-ceramic article;

Figure 8A schematically illustrates a glass-ceramic product;

Figure 8B schematically illustrates a cross-section of the glass-ceramic article;

Figure 9 schematically illustrates a glass-ceramic product;

Figure 10 illustrates the variation of total transmittance of a glass-ceramic article containing a crystalline phase with a jeffbenite crystalline structure as a function of wavelength.

Figure 11 illustrates the change in diffuse transmittance of a glass-ceramic article containing a crystalline phase with a jeffbenite crystalline structure as a function of wavelength.

Figure 12 illustrates the axial transmittance of a glass-ceramic article containing a crystalline phase with a jeffbenite crystalline structure as a function of wavelength.

Figure 13 illustrates the scattering ratio of a glass-ceramic article containing a crystalline phase with a jeffbenite crystalline structure as a function of wavelength;

Figure 14 illustrates the window of the MDI Jade software used to characterize glass-ceramic articles;

Figure 15 shows the window of the MDI Jade software used to characterize glass-ceramic articles;

Figure 16 illustrates the window of the MDI Jade software used to characterize glass-ceramic articles;

Figure 17 shows the window of Bruker Topas software used to characterize glass-ceramic articles;

Figure 18 illustrates the window of Bruker Topas software used to characterize glass-ceramic articles;

Figure 19 illustrates the window of Bruker Topas software used to characterize glass-ceramic articles;

Figure 20 illustrates the window of Bruker Topas software used to characterize glass-ceramic articles;

Figure 21 shows the XRD pattern of a glass-ceramic article containing a crystalline phase with a jeffbenite crystalline structure;

Figure 22 shows the XRD pattern of a glass-ceramic article containing a crystalline phase with a jeffbenite crystalline structure;

Figure 23 shows the XRD pattern of a glass-ceramic article containing a crystalline phase with a jeffbenite crystalline structure;

Figure 24 shows the XRD pattern of a glass-ceramic article containing a crystalline phase with a jeffbenite crystalline structure;

Figure 25 shows the XRD pattern of a glass-ceramic article containing a crystalline phase with a jeffbenite crystalline structure;

Figure 26 shows the XRD pattern of a glass-ceramic article containing a crystalline phase with a jeffbenite crystalline structure;

Figure 27 shows the XRD pattern of a glass-ceramic article containing a crystalline phase with a jeffbenite crystalline structure;

Figure 28 shows the XRD pattern of a glass-ceramic article containing a crystalline phase with a jeffbenite crystalline structure;

Figure 29 shows the XRD pattern of a glass-ceramic article containing a crystalline phase with a jeffbenite crystalline structure;

Figure 30 is a photograph of a transparent glass-ceramic article containing a crystalline phase with a jeffbenite crystalline structure;

Figure 31 illustrates the variation of total transmittance of a glass-ceramic article containing a crystalline phase with a jeffbenite crystalline structure as a function of wavelength.

Figure 32 illustrates the diffuse transmittance of a glass-ceramic article containing a crystalline phase with a jeffbenite crystalline structure as a function of wavelength; and

Figure 33 illustrates the scattering ratio of a glass-ceramic article containing a crystalline phase with a jeffbenite crystalline structure as a function of wavelength.

Detailed Implementation

Various embodiments of precursor glasses and glass-ceramic articles made therefrom will now be described in detail. According to one embodiment, the glass-ceramic article includes a first surface, a second surface opposite the first surface, and a periphery defining the shape of the glass-ceramic article. The glass-ceramic article may also include a phase set comprising one or more crystalline phases and a glassy phase, the one or more crystalline phases including a crystalline phase comprising a jeffbenite crystalline structure. Various embodiments of precursor glasses, glass-ceramic articles made therefrom, and methods of manufacturing glass-ceramic articles will be described herein with specific reference to the accompanying drawings.

In this document, a range can be expressed as "about" a particular value and/or "about" another particular value. Another embodiment of expressing such a range includes from one particular value and/or to another particular value. Similarly, when a value is expressed as an approximation using the antecedent "about," it should be understood that the particular value forms another embodiment. It should also be understood that the endpoints of each range are significant relative to and independent of the other endpoint.

As used in this article, directional terms—such as up, down, right, left, front, back, top, bottom—are used only with reference to the accompanying drawings and are not intended to imply absolute orientation.

Unless otherwise expressly stated, no method described herein is intended to be construed as requiring its steps to be performed in a particular order, nor is it intended to require any particular orientation of any apparatus. Therefore, in any instance where a method claim does not actually describe the order in which its steps will be followed, or any apparatus claim does not actually describe the order or orientation of the components, or where the claims or description do not expressly state that the steps will be limited to a particular order, or where a particular order or orientation of the apparatus components is not described, no inference shall be made about the order or orientation. This applies to any possible non-explicit basis of interpretation, including: logical questions concerning the arrangement of steps, the flow of operations, the order of components, or the orientation of components; obvious meanings arising from grammatical organization or punctuation; and the number or type of embodiments described in the description.

As used herein, unless the context clearly indicates otherwise, the singular forms “a,” “an,” and “the” include plural referents. Thus, for example, a reference to a “one” component includes aspects having two or more such components, unless the context clearly indicates otherwise.

The term "substantially absent," when used to describe the concentration and/or absence of a specific constituent component in a precursor glass or glass-ceramic composition, means that the constituent component was not intentionally added to the precursor glass or glass-ceramic composition. However, the precursor glass or glass-ceramic composition may contain trace constituent components, which are contaminants or impurities, in amounts less than 0.05 mol%.

In embodiments of the precursor glass or glass-ceramic composition described herein, the concentration of the constituent components (e.g., _SiO2 , _Al2O3 , _etc. ) is specified as a mole percentage (mol%) based on the oxide, unless otherwise specified.

Transmittance data (total transmittance) were measured using a Lambda 950UV/Vis spectrophotometer manufactured by PerkinElmer Inc. (Waltham, MA, USA). The Lambda 950 is equipped with a 150 mm integrating sphere. Data were collected using an open beam baseline and a reference reflector. For total transmittance (total Tx), the sample was fixed at the entrance point of the integrating sphere. For diffuse transmittance (diffuse Tx), the reference reflector was removed above the sphere's exit port to allow coaxial light to exit the sphere and enter the optical trap. Zero-offset measurements of the diffuse portion were performed without a sample to determine the efficiency of the optical trap. To correct for diffuse transmittance measurements, the zero-offset contribution was subtracted from the sample measurement using the following formula: Diffuse Tx = Diffuse Reflectance _Measurement - (Zero Offset * (Total Tx / 100)). For all wavelengths, scattering was measured as follows: (%diffuse Tx / %total Tx).

The term "transparent," when used to describe the article herein, means an article having an average transmittance of at least 75% for light in the wavelength range of 400 nm to 800 nm (inclusive) at a thickness of 0.6 mm.

The term "semi-transparent," unless otherwise specified in the claims, when used to describe the article herein, means an article having an average transmittance in the range of 20% to less than 75% for light in the wavelength range of 400 nm to 800 nm (inclusive) at an article thickness of 0.6 mm.

The term "opaque" when used to describe glass-ceramic articles formed from the glass-ceramic composition herein refers to an average transmittance of less than 20% for light in the wavelength range of 400 nm to 800 nm (inclusive) at an article thickness of 0.6 mm when measured under normal incidence.

As used herein, the term "CIELAB color space" refers to the color space defined by the International Commission on Illumination (CIE) in 1976. It represents colors as three values: L*, representing luminance from black (0) to white (100); a*, representing luminance from green (-) to red (+); and b*, representing luminance from blue (-) to yellow (+). Unless otherwise specified, the L*, a*, and b* values indicate the thickness of an article of 0.4 mm to 5 mm (inclusive) in the thickness direction of the sample under F2 illumination and a 10° standard observer angle. Unless otherwise specified, this means that each thickness within this range has L*, a*, and b* coordinates falling within the specified range of L*, a*, and b* coordinates. For example, colored glass articles with L* values in the range of 55 to 96.5 mean that each thickness in the range of 0.4 mm to 5 mm (e.g., 0.6 mm, 0.9 mm, 2 mm, etc.) has an L* value in the range of 55 to 96.5.

The grain size of one or more crystalline phases of the glass-ceramic described in this article was measured using a scanning electron microscope.

As used herein, the term “melting point” refers to the temperature at which the viscosity of the precursor glass or glass-ceramic composition is 200 poise (20 Pa*s).

As used herein, the term "softening point" refers to the temperature at which the viscosity of the precursor glass or glass-ceramic composition is 1 x ^10⁷.6 poise (1 x ^10⁶.6 Pa*s). The softening point is measured according to the parallel plate viscometry method, which measures the viscosity of inorganic glasses from ^10⁷ to ^10⁹ poise ( ^10⁶ to ^10⁸ Pa*s) as a function of temperature, similar to ASTM C1351M.

As used herein, the term “liquidline viscosity” refers to the viscosity of a glass-ceramic at the onset of devitrification (i.e., at the liquidus temperature, as determined by the gradient furnace method according to ASTM C829-81).

The elastic modulus (also known as Young's modulus) of glass-based products is given in gigapascals (GPa). The elastic modulus of glass is determined according to ASTM C623 by resonant ultrasonic spectroscopy on a block sample of each glass-based product.

Vickers hardness can be measured using ASTM C1326 and C1327 (and their successors, all incorporated herein by reference) "Standard Test Methods for Vickers Indentation Hardness of Advanced Ceramics," ASTM International, Conshohocken, PA, US. In some implementations, glass-ceramics exhibit such Vickers indentation crack initiation load values after ion-exchange chemical strengthening.

Fracture toughness can be measured using a herringbone notched short beam prior to glass-ceramic ion exchange strengthening, according to ASTM C1421-10 "Standard Test Methods for Determination of Fracture Toughness of Advanced Ceramics at Ambient Temperature".

Compressive stress (including surface compressive stress) was measured using a surface stress meter (FSM) such as the commercially available FSM-6000 manufactured by Orihara Industrial Co., Ltd. (Japan). Surface stress measurement relies on the measurement of the stress optical coefficient (SOC), which is related to the birefringence of the glass-ceramic. The SOC was then measured according to Procedure C (the glass disk method) described in ASTM standard C770-16 entitled "Standard Test Method for Measurement of Glass Stress-Optical Coefficient," the contents of which are incorporated herein by reference in their entirety. Depth of compression (DOC) was also measured using an FSM. The maximum center tension (CT) value was measured using the Scattered Light Polarizer (SCALP) technique known in the art.

The terms "depth of compression" and "DOC" refer to the location in a glass-ceramic structure where compressive stress is transformed into tensile stress.

As used herein, the term "glass precursor" or "precursor glass" refers to a glass or glass article containing one or more nucleating agents and/or nucleation sites (e.g., within the bulk of a material, which may be uniformly distributed therein and throughout the bulk) that, during heat treatment, cause (e.g., promote) at least partially the nucleation of at least one crystalline phase in the glass.

As used herein, the term "glass-ceramic" refers to a material or article formed by nucleation of at least one crystalline phase in a precursor glass material, wherein the nucleation results in the glass-ceramic containing a residual glass phase and at least one crystalline phase (see generally Figure 9 and related disclosures).

As used herein, the term "major crystalline phase" refers to a crystalline phase in a glass-ceramic whose amount (in weight percent of the glass-ceramic) is greater than the amount (in weight percent of the glass-ceramic) of any other individual crystalline phase present in the glass-ceramic. For example, if a glass-ceramic contains crystalline phases A, B, and C, and crystalline phase A is the major crystalline phase, then the amount of crystalline phase A in the glass-ceramic is greater than the amount of crystalline phase B and greater than the amount of crystalline phase C in the glass-ceramic.

Articles formed from glass-ceramics typically exhibit improved fracture toughness compared to articles formed from glass. This improvement may be attributed to the presence of crystalline grains in the glass-ceramic, which can potentially hinder crack propagation. The fracture toughness of glass-ceramics can be improved by reducing the number of grains per unit volume—that is, by increasing the grain size. However, the transparency or optical transmittance of glass-ceramics may decrease with increasing grain size. In particular, the visible light transparency of glass-ceramics may decrease significantly when the grain size is greater than 300 nm. Therefore, some glass-ceramics may have relatively good mechanical properties (such as fracture toughness) and relatively poor optical properties (such as optical transparency or optical transmittance), or relatively poor mechanical properties and relatively good optical properties, but not both simultaneously.

Additionally, some glass-ceramics can be strengthened through an ion exchange process, in which smaller alkali metal ions in the glass-ceramic are exchanged for larger alkali metal ions from, for example, a molten alkali metal salt bath. As an example, lithium-containing glass-ceramics can be strengthened by ion exchange by placing the glass-ceramic in a bath of molten alkali metal salts (such as sodium and/or potassium salts), thereby promoting the exchange of lithium ions in the glass-ceramic with sodium and/or potassium ions in the bath. However, recent demand for lithium in various applications has increased the cost and reduced the availability of lithium raw materials, thus increasing the overall cost of producing lithium-containing glass-ceramics that can be strengthened through ion exchange. The glass-ceramics described herein do not require lithium to promote the desired ion exchange properties.

This article discloses a precursor glass that can alleviate the aforementioned problems and a glass-ceramic formed therefrom.

For example, referring now to Figure 9, a glass-ceramic article 810 is schematically illustrated according to one or more embodiments shown and described herein. As stated herein, the term "glass-ceramic" refers to a material or article formed from a precursor glass material after nucleation of at least one crystalline phase in the precursor glass, such that the glass-ceramic comprises a residual glass phase and at least one crystalline phase. Thus, the glass-ceramic article 810 comprises both a glass phase 812 (e.g., amorphous glass; single-phase glass or multiphase glass) and a polycrystalline ceramic phase (e.g., grains of the main crystalline phase 814, optionally having grains of the secondary crystalline phase 816). The glass phase 812 may be referred to as "residual glass" or "residual glass phase". It is conceivable that the grains of crystalline phases 814 and 816 can be unevenly distributed or directionally grown, such as by localizing heat through laser, or by guiding the growth of grains of crystalline phases 814 and 816 by locating and/or orienting nucleation sites, and foreseeable embodiments include such properties; however, typically in the glass-ceramics disclosed herein, the grains of crystalline phases 814 and 816 can be uniformly or homogeneously distributed and randomly oriented within the glass phase 812, such as throughout some, most, or all of the glass phase of the glass-ceramic article 810. Furthermore, once nucleated from the precursor glass, the grains of crystalline phases 814 and 816 can be grown to contact, overlap, interlock, and/or fill a greater volume of the glass-ceramic article 810. Growing the grains of crystalline phases 814 and 816 to different sizes can affect the properties of the glass-ceramic article 810, and when the grains of crystalline phases 814 and 816 have the grain sizes disclosed herein and the article has the dimensions disclosed herein, such properties can be isotropic, wherein the grains of crystalline phases 814 and 816 are uniformly and homogeneously positioned and randomly oriented. After the nucleation and growth of the grains of crystalline phases 814 and 816, the glass phase 812 will surround (e.g., contact, encapsulate, package) the individual or clustered grains of crystalline phases 814 and 816. The glass-ceramic article 810 may have more than one glass phase 812 and/or more than one crystalline phase, as shown with crystalline phases 814 and 816.

The glass-ceramic embodiments described herein, as illustrated in Figure 9, have a phase set comprising one or more crystalline phases and a glassy phase. At least one crystalline phase contains a Jeffbenite crystalline structure. A crystalline phase containing a Jeffbenite crystalline structure refers to a crystalline phase identified as Jeffbenite by X-ray diffraction (XRD) analysis. For example, XRD data (e.g., XRD spectra) collected from a sample of the glass-ceramic material, along with general compositional information about the sample composition (e.g., the batch composition of the sample preparation), can be input into the MDI Jadepowder XRD analysis software from Materials Data Inc. This software uses the input information and the International Data Center for Powder Diffraction Documents Version 4 (ICDD PDF-4) database to identify the crystalline phase in the sample based on the sample compositional information and the crystalline structure of the phase as determined from the XRD data. In the embodiments, the glass-ceramic phase set may have at least one crystalline phase containing a Jeffbenite crystalline structure, as determined by this method.

Based on the foregoing, unless otherwise specified or further clarified herein as in the claims or elsewhere, the expression "jeffbenite crystalline structure" refers to a crystalline phase or crystalline phase grain identified by XRD analysis as jeffbenite as described herein, and further characterization provided herein may help clarify various embodiments and forms of crystalline phases having a jeffbenite crystalline structure that may be included and claimed.

In the implementation scheme, the crystalline phase having a Jeffbenite crystalline structure is the main crystalline phase in the glass-ceramic. The crystalline phase having a Jeffbenite crystalline structure may possess properties common to Jeffbenite (e.g., compositional properties, molecular structure properties, microstructure properties).

Jeffbenite, named by Jeffrey Harris and Ben Harte, is a mineral recently observed as an inclusion in diamonds from “ultra-deep” (e.g., depths > 300 km) sources within the mantle. Prior to its naming, Jeffbenite was called the tetragonal-almandine-pyrope-magnesium-petroleum-phase (“TAPP”). Jeffbenite can contain _{tetragonal Mg3Al2Si3O12} . The term “ _tetragonal ” refers to an originally cubic lattice stretched along one of its lattice vectors into a rectangular prism with a square base (“a x a”) and height (“c”, different from “a”), as in space group _I42d . The tetragonal crystal structure of Jeffbenite can include a cell edge parameter α of about 6.5, such as 6.5231(1), as within plus or minus 0.1, and a parameter c of about 18.2, such as 18.1756(3) Å, as within plus or minus 0.1. Crystallized phases with the crystalline structure of jeffbenite can have a tetragonal structure as described herein.

The density of Jeffbenite (itself) can be about 3.6 g/ ^cm³ , such as 3.576 g/ ^cm³ , or within 0.1 g/ ^cm³ . The microhardness of Jeffbenite (itself) can be about 7, or within 1. Jeffbenite (itself) can be uniaxial (-), with a refractive index ω of about 1.7, such as 1.733(5), or within 0.1, and ε of about 1.7, such as 1.721, or within 0.1.

While _Mg3Al2Si3O12 is the ideal form of jeffbenite, _jeffbenite is generally described as a stoichiometric garnet composition similar to pyrope ( _{Mg3Al2 ( SiO4} ) ₃ )–almandine ( _Fe3Al2 (SiO4) ₃ ), but with _a tetragonal crystalline structure and may contain other elements. In other words, structurally, jeffbenite and crystals with a jeffbenite crystalline structure can be described as (M1)(M2) ₂ (M3) ₂ ( _T1 )(T2) _2O12 , where _M1 contains magnesium (e.g. _, predominantly magnesium), M2 contains aluminum (e.g., predominantly aluminum), M3 contains magnesium (e.g., predominantly magnesium), and T1 and T2 contain silicon (both predominantly silicon), and the _two tetrahedra of such a crystalline structure do not share any oxygen with each other. Jeffbenite can be classified as a type of silicate, such as silicates containing tetrahedral _SiO4 groups, in which the ratio of silicon to oxygen is 1:4.

In _{the glass-ceramic embodiments described herein, the crystalline phase comprising the jeffbenite crystalline structure may comprise at least tetragonal Mg3Al2Si3O12, be primarily composed of tetragonal Mg3Al2Si3O12 ( > 50 wt % ) , substantially composed} of _{tetragonal Mg3Al2Si3O12} , or _{be tetragonal Mg3Al2Si3O12 .}

In the glass-ceramic embodiments described herein, the crystalline phase comprising a jeffbenite crystalline structure (or a portion thereof) can be modified by adding zirconium oxide ( _ZrO₂ ). While not intended to be bound by any particular theory, in the jeffbenite crystalline structure, alumina (i.e., the aluminum contributor) can be at least partially replaced by magnesia (i.e., the magnesium contributor) and zirconium oxide (i.e., the zirconium contributor). In such embodiments, the crystalline phase comprising a jeffbenite crystalline structure (or a portion thereof) may have a composition according to the formula: _{Mg³⁺xZr⁻xAl²⁻2xSi³O¹²} , where x is greater than _or equal to 0 _{and less} than or equal to 1. In embodiments, x may _be greater than or equal to 0 and less than or equal to 0.6. _{For example , but not limited to , crystalline phases} having _{a jeffbenite crystalline} structure _{( or a portion thereof ) may have the following compositions : Mg3Al2Si3O12 , Mg3.1Zr0.1Al1.8Si3O12 , Mg3.2Zr0.2Al1.6Si3O12 , Mg3.3Zr0.3Al1.4Si3O12 , Mg3.4Zr0.4Al1.2Si3O12 , Mg3.5Zr0.5AlSi3O12 , Mg3.6Zr0.6Al0.8Si3O12 , Mg3.7Zr0.7Al0.6Si3O12 , Mg3.8Zr0.8Al0.4Si3O12 , or Mg3.9Zr0.9Al 0.2} Si ₃ O ₁₂ .

In the glass-ceramic embodiments described herein, the crystalline phase comprising a Jeffbenite crystalline structure (or a portion thereof) can be further modified by adding titanium dioxide, tin oxide, iron oxide (FeO), manganese oxide, and/or zinc oxide. For example, titanium dioxide (i.e., titanium contributor) and/or tin oxide (i.e., tin contributor) can replace up to 50% of the zirconium in the Jeffbenite crystalline structure. Similarly, iron oxide (i.e., iron contributor), manganese oxide (i.e., manganese contributor), and/or zinc oxide (i.e., zinc contributor) can replace a portion of the magnesium in the Jeffbenite crystalline structure. In such embodiments, the crystalline phase comprising a Jeffbenite crystalline structure (or a portion thereof) may have _a composition according to the formula: (Mg _, Fe,Mn,Zn) _{³ + x} (Zr,Ti,Sn) _{xAl²⁻²⁻²xSi³O¹²} , where x is _greater than or equal to 0 and less than or equal to 1. In embodiments, x may be greater than or equal to 0 and less than or equal to 0.6. For example, but not limited to _{, crystalline phases having a jeffbenite crystalline structure (or a portion thereof) may have the following compositions: (Mg,Fe,Mn,Zn)3Al2Si3O12 , ( Mg} ,Fe,Mn,Zn) _3.1 ( _Zr ,Ti,Sn _{) 0.1Al1.8Si3O12} , (Mg,Fe,Mn,Zn) _3.2 ( _{Zr,Ti,Sn)0.2Al1.6Si3O12 , (} Mg,Fe,Mn,Zn) _3.3 ( _{Zr,Ti,Sn)0.3Al1.4Si3O12 , ( Mg} ,Fe,Mn, _{Zn)3.4(Zr,Ti,Sn)0.4Al1.2Si3O12 , ( Mg , Fe ,} Mn,Zn) _3.5 (Zr,Ti,Sn) _0.5AlSi The formulas are: ₃ O ₁₂ , (Mg,Fe,Mn,Zn) _3.6 (Zr,Ti,Sn) _0.6 Al _0.8 Si ₃ O ₁₂ , (Mg,Fe,Mn,Zn) _3.7 (Zr,Ti,Sn) _0.7 Al _0.6 Si ₃ O ₁₂ , (Mg,Fe,Mn,Zn) _3.8 (Zr,Ti,Sn) _0.8 Al _0.4 Si ₃ O ₁₂ , or (Mg,Fe,Mn,Zn) _3.9 (Zr,Ti,Sn) _0.9 Al _0.2 Si ₃ O _12. In these embodiments, it should be understood that the Fe, Mn, Zn, Ti, and Sn components in the formula are each optional and the composition can be formed without one or more of these elements. For example, the composition may be Fe-free but may contain Mn, Ti, and Sn, or Sn-free but may contain Fe, Mn, Zn, and Ti. Therefore, it should be understood that the above reference formula may be written without one or more of Fe, Mn, Zn, Ti and Sn.

It should be understood that other substitutions and modifications to crystalline phases containing the Jeffbenite structure are contemplated and possible. For example, in the glass-ceramic embodiments described herein, a crystalline phase containing the Jeffbenite crystalline structure (or a portion thereof) can be modified by adding a metal oxide to the composition as a source of divalent metal cations (denoted as " ^R²⁺ ") to replace a portion of the magnesium in the Jeffbenite crystalline structure. Examples of divalent metal cations include, but are not limited to, ^Ca²⁺ , ^Mn²⁺ , ^Fe²⁺ , etc. In these embodiments, the divalent metal cations may have an ionic radius of less than 1 angstrom (0.1 nm). Similarly, a crystalline phase containing the Jeffbenite crystalline structure (or a portion thereof) can be modified by adding a metal oxide to the composition as a source of tetravalent metal cations (denoted as " ^R⁴⁺ ") to replace a portion of the zirconium in the Jeffbenite crystalline structure. Examples of tetravalent metal cations include ^Ti⁴⁺ , ^Sn⁴⁺ , ^Hf⁴⁺ , etc. In such an embodiment, the crystalline phase comprising the jeffbenite crystalline structure ( _or a portion thereof) may have a composition according to the following formula: (Mg, ^R²⁺ ) _³⁺x (Zr, ^R⁴⁺ ) _{xAl²⁻²xSi³O¹²} , where x _is greater than or equal to 0 and less than or equal to 1. In an embodiment, x may _be greater than or equal to 0 and less than or equal to 0.6. For example, but not limited to, crystalline phases having a jeffbenite crystalline structure (or a _portion ^thereof ) _{may have the following compositions: (Mg,R²⁺)³Al₂Si₃O₁₂ , (} Mg, ^R²⁺ ) _³.1 ( _Zr , ^R⁴⁺ ) _{⁰.1Al₁.8Si₃O₁₂} , (Mg, ^R²⁺ _{) ³.2 (Zr,R⁴⁺)⁰.2Al₁.6Si₃O₁₂} ^, _{( Mg} , _R²⁺ ) _³.3 (Zr _, ^R⁴⁺ _{) ⁰.3Al₁.4Si₃O₁₂ ,} (Mg _{, R²⁺} ) _{³.4 (} ^{Zr,R⁴⁺ )} _{⁰.4Al₁.2Si₃O₁₂} ^, _{( Mg ,R²⁺)³.5} ⁽ _Zr , ^R⁴⁺ ) _{⁰.5AlSi₃O₁₂ The formulas are: (Mg,R²⁺) 3.6 (Zr,R⁴⁺) 0.6 Al 0.8 Si³O¹², (Mg,R²⁺) 3.7 (Zr,R⁴⁺) 0.7 Al 0.6} ^Si³O¹² _, ⁽ _{Mg , R²⁺} ⁾ _3.8 ⁽ _{Zr , R⁴⁺} ⁾ _0.8 ^Al _{0.4 Si³O¹² ,} or (Mg, _R²⁺ ) _3.9 ( ^{Zr,R⁴⁺ )} _0.9 Al _{0.2 Si³O¹²} . In these embodiments, it should be understood _that the ^R²⁺ and ^R⁴⁺ components are each optional and the composition _can be formed without one or the other of these elements. Therefore, it should be understood that the above reference formulas can be written without one or the other of ^R²⁺ and ^R⁴⁺ .

In embodiments, the one or more crystalline phases of the phase set may include one or more secondary crystalline phases. These secondary crystalline phases may be present in the glass-ceramic in an amount less than that of the primary crystalline phase. In embodiments, the one or more secondary crystalline phases may include tetragonal zirconia ( _ZrO₂ ), _ZrTiO₄ , or combinations thereof. However, it should be understood that other secondary crystalline phases may also be present in the resulting glass-ceramic. In embodiments, one or more of the secondary crystalline phases may enter the structure of the crystalline phase having a Jeffbenite crystalline structure (e.g., a second phase may exist within the lattice of a Jeffbenite crystalline phase).

In embodiments, the glass-ceramic phase set described herein comprises, by weight of the glass-ceramic article (i.e., wt%), greater than or equal to 25 wt% of the one or more crystalline phases and less than or equal to 75 wt% of the glass phase, greater than or equal to 30 wt% of the one or more crystalline phases and less than or equal to 70 wt% of the glass phase, greater than or equal to 40 wt% of the one or more crystalline phases and less than or equal to 60 wt% of the glass phase, greater than or equal to 50 wt% of the one or more crystalline phases and less than or equal to 50 wt% of the glass phase, greater than or equal to 60 wt% of the one or more crystalline phases and less than or equal to 40 wt% of the glass phase, greater than or equal to 70 wt% of the one or more crystalline phases and less than or equal to 30 wt% of the glass phase, greater than or equal to 80 wt% of the one or more crystalline phases and less than or equal to 20 wt% of the glass phase, as determined by Rietveld analysis of XRD spectra. It should be understood that the crystalline phase content or glass content can be within a subrange formed by any and all of the foregoing endpoints. In the embodiments, the one or more crystalline phases and glassy phases can be uniformly distributed throughout the glass-ceramic. It should also be noted that at least some, most (>50% by weight), or substantially all of such crystalline phases can have a jeffbenite crystalline structure (e.g., as identified by XRD; tetragonal, _{stoichiometric} garnet, _Mg3Al2Si3O12 , and _{its variants} ).

_SiO₂ can be the primary glass-forming agent in the precursor glass and glass-ceramic compositions described herein and can play a role in stabilizing the network structure of the glass-ceramic. The concentration of _SiO₂ in the precursor glass and glass-ceramic compositions should be sufficiently high (e.g., greater than or equal to 35 mol%) to form a crystalline phase during heat treatment of the precursor glass, thereby transforming the precursor glass into a glass-ceramic. The amount of _SiO₂ can be limited (e.g., to less than or equal to 65 mol%) to control the melting point of the precursor glass or glass-ceramic composition, as the melting temperature of pure _SiO₂ or high _-SiO₂ glasses is undesirably high. Therefore, limiting the concentration of _SiO₂ can help improve the meltability and formability of the precursor glass or glass-ceramic composition.

In embodiments, the precursor glass or glass-ceramic composition may contain a positive amount of silicon dioxide, such as greater than the amount of impurities (0.05 mol% or more), such as greater than or equal to 35 mol% to less than or equal to 65 mol% of _SiO2 . In embodiments, the precursor glass or glass-ceramic composition may contain greater than or equal to 35 mol% to less than or equal to 62 mol%, greater than or equal to 35 mol% to less than or equal to 59 mol%, greater than or equal to 35 mol% to less than or equal to 56 mol%, greater than or equal to 35 mol% to less than or equal to 53 mol%, greater than or equal to 35 mol% to less than or equal to 50 mol%, greater than or equal to 35 mol% to less than or equal to 47 mol%, or greater than or equal to 35 mol% to less than or equal to 44 mol%. ≥35 mol% to ≤41 mol%, ≥35 mol% to ≤38 mol%, ≥38 mol% to ≤65 mol%, ≥41 mol% to ≤65 mol%, ≥42 mol% to ≤65 mol%, ≥43 mol% to ≤65 mol%, ≥44 mol% to ≤65 mol%, ≥45 mol% to ≤65 mol%, and so on. 46 mol% or less than or equal to 65 mol%, 47 mol% or more than or equal to 65 mol%, 48 mol% or more than or equal to 65 mol%, 49 mol% or more than or equal to 65 mol%, 50 mol% or more than or equal to 65 mol%, 51 mol% or more than or equal to 65 mol%, 52 mol% or more than or equal to 65 mol%, 53 mol% or more than or equal to 65 mol%, and so on. The SiO2 content may be 54 mol% to less than or equal to 65 mol%, greater than or equal to 55 mol% to less than or equal to 65 mol%, greater than or equal to 56 mol% to less than or equal to 65 mol%, greater than or equal to 57 mol% to less than or equal to 65 mol%, greater than or equal to 58 mol% to less than or equal to 65 mol%, greater than or equal to 59 mol% to less than or equal to 65 mol%, greater than or equal to 60 mol% to less than or equal to 65 mol%, greater than or equal to 61 mol% _to less than or equal to 65 mol%, or any and all subranges formed by any of these endpoints. In some embodiments, the precursor glass or glass-ceramic composition may contain greater than or equal to 48 mol% to less than or equal to 54 mol% of _SiO2 . In embodiments, the concentration of _SiO2 may be greater than or equal to 40 mol%, 45 mol%, or 50 mol%. In embodiments, the concentration of _SiO2 may be less than or equal to 65 mol%, 60 mol%, or 55 mol%.

Similar to _SiO2 , _Al2O3 can stabilize the glass network and additionally provide improved _mechanical properties and chemical durability to the glass-ceramic. The amount _{of Al2O3} can also be adjusted to control the viscosity of the precursor glass or glass-ceramic composition. However, if the amount of _{Al2O3 is} too high, the viscosity of the glass melt may increase. In embodiments, the precursor glass or glass-ceramic composition may contain greater than or equal to 5 mol% to less than or equal to ₂₀ mol% _Al2O3 . In embodiments, _Al2O3 in the precursor glass or glass-ceramic composition... The concentration of ₃ can be positive, such as greater than the amount of impurities (0.05 mol% or more), such as greater than or equal to 5 mol% to less than or equal to 20 mol%, greater than or equal to 5 mol% to less than or equal to 19 mol%, greater than or equal to 5 mol% to less than or equal to 18 mol%, greater than or equal to 5 mol% to less than or equal to 17 mol%, greater than or equal to 5 mol% to less than or equal to 16 mol%, greater than or equal to 5 mol% to less than or equal to 15 mol%, greater than or equal to 5 mol% to less than or equal to 14 mol%, greater than or equal to 5 mol% to less than or equal to 13 mol%, greater than or equal to 5 mol% to less than or equal to 12 mol%, greater than or equal to 5 mol% to less than or equal to 11 mol%, greater than or equal to 5 mol% to less than or equal to 10 mol%, greater than or equal to 5 mol% to less than or equal to 9 mol%, greater than or equal to 5 mol% to less than or equal to 8 mol%, greater than or equal to 5 mol% to less than or equal to 7 mol%, greater than or equal to 5 mol% to less than 7 mol%. The range is 6 mol% or more, greater than or equal to 6 mol% to less than or equal to 20 mol%, greater than or equal to 7 mol% to less than or equal to 20 mol%, greater than or equal to 8 mol% to less than or equal to 20 mol%, greater than or equal to 9 mol% to less than or equal to 20 mol%, greater than or equal to 10 mol% to less than or equal to 20 mol%, greater than or equal to 11 mol% to less than or equal to 20 mol%, greater than or equal to 12 mol% to less than or equal to 20 mol%, greater than or equal to 13 mol% to less than or equal to 20 mol%, greater than or equal to 14 mol% to less than or equal to 20 mol%, greater than or equal to 15 mol% to less than or equal to 20 mol%, greater than or equal to 16 mol% to less than or equal to 20 mol%, greater than or equal to 17 mol% to less than or equal to 20 mol%, greater than or equal to 18 mol% to less than or equal to 20 mol%, greater than or equal to 19 mol% to less than or equal to 20 mol%, or any and all subranges formed by any of these endpoints. In embodiments, the concentration _{of Al₂O₃} in the precursor glass or glass-ceramic composition can be greater than or equal to 9 mol% to less than or equal to 13 mol%. In embodiments, the concentration of _Al₂O₃ in the precursor glass or glass-ceramic composition can be greater than or equal to 5 mol%, 7 mol%, or 10 mol%. In embodiments, the concentration _{of Al₂O₃} can be less than or equal to 20 _mol %, 15 mol%, 12 mol%, or 10 mol%.

In embodiments, the precursor glass or glass-ceramic composition may contain a positive amount of MgO, such as greater than the amount of impurities (0.05 mol% or more), such as greater than or equal to 10 mol% to less than or equal to 45 mol% of MgO. In embodiments, the precursor glass or glass-ceramic composition may contain greater than or equal to 7 mol% to less than or equal to 65 mol% of MgO. The addition of MgO can increase the elastic modulus of the precursor glass and the resulting glass-ceramic. _MgO can also replace _Al₂O₃ in the glass network and produce a more open network structure, thereby improving the ion mobility in the glass network. While not intended to be theoretically rigorous, the addition of MgO can increase the crystallinity of the glass-ceramic composition. In embodiments, the concentration of MgO in the precursor glass or glass-ceramic composition may be greater than or equal to 7 mol% and less than or equal to 65 mol%, greater than or equal to 7 mol% and less than or equal to 60 mol%, greater than or equal to 7 mol% and less than or equal to 55 mol%, greater than or equal to 7 mol% and less than or equal to 50 mol%, greater than or equal to 7 mol% and less than or equal to 48 mol%, greater than or equal to 7 mol% and less than or equal to 46 mol%, greater than or equal to 7 mol% and less than or equal to 44 mol%, greater than or equal to 7 mol% and less than or equal to 42 mol%, greater than or equal to 7 mol% and less than or equal to 40 mol%, greater than or equal to 7 mol% and less than or equal to 38 mol%, greater than or equal to 7 mol% and less than or equal to 36 mol%, greater than or equal to 7 mol% and less than or equal to 34 mol%, greater than or equal to 7 mol% and less than or equal to 32 mol%, greater than or equal to 7 mol% and less than or equal to 32 mol%, greater than or equal to 7 mol% and less than or equal to 35 mol%, greater than or equal to 7 mol% and less than or equal to 36 mol%, greater than or equal to 7 mol% and less than or equal to 34 mol%, greater than or equal to 7 mol% and less than or equal to 32 ... 30 mol% or more, greater than or equal to 7 mol% to less than or equal to 28 mol%, greater than or equal to 7 mol% to less than or equal to 26 mol%, greater than or equal to 7 mol% to less than or equal to 24 mol%, greater than or equal to 7 mol% to less than or equal to 22 mol%, greater than or equal to 7 mol% to less than or equal to 20 mol%, greater than or equal to 7 mol% to less than or equal to 18 mol%, greater than or equal to 7 mol% to less than or equal to 16 mol%, greater than or equal to 7 mol% to less than or equal to 14 mol%, greater than or equal to 7 mol% to less than or equal to 12 mol%, greater than or equal to 7 mol% to less than or equal to 10 mol%, greater than or equal to 9 mol% to less than or equal to 50 mol%, greater than or equal to 10 mol% to less than or equal to 65 mol%, greater than or equal to 10 mol% to less than or equal to 60 mol%, greater than or equal to 10 mol% to less than or equal to 55 mol%, greater than or equal to 10 mol% to less than or equal to 45 mol%, greater than or equal to 10 mol% to less than or equal to 42 mol%, greater than or equal to 10 mol% to less than or equal to 40 mol%, greater than or equal to 10 mol% to less than or equal to 38 mol%, greater than or equal to 10 mol% to less than or equal to 36 mol%, greater than or equal to 10 mol% to less than or equal to 34 mol%, greater than or equal to 10 mol% to less than or equal to 32 mol%, greater than or equal to 10 mol% to less than or equal to 30 mol%, greater than or equal to 10 mol% to less than or equal to 28 mol%, greater than or equal to 10 mol% to less than or equal to 26 mol%, greater than or equal to 10 mol% to less than or equal to 24 mol%, greater than or equal to 10 mol% to less than or equal to 22 mol%, greater than or equal to 10 mol% to less than or equal to 20 mol%, greater than or equal to 10 mol% to less than or equal to 18 mol%, greater than or equal to 10 mol% to less than 16 mol% or more, greater than or equal to 10 mol% and less than or equal to 14 mol%, greater than or equal to 10 mol% and less than or equal to 12 mol%, greater than or equal to 11 mol% and less than or equal to 50 mol%, greater than or equal to 12 mol% and less than or equal to 60 mol%, greater than or equal to 12 mol% and less than or equal to 45 mol%, greater than or equal to 13 mol% and less than or equal to 65 mol%, greater than or equal to 13 mol% and less than or equal to 50 mol%, greater than or equal to 14 mol% and less than or equal to 60 mol%, greater than or equal to 14 mol% and less than or equal to 45 mol%, greater than or equal to 15 mol% and less than or equal to 65 mol%, greater than or equal to 15 mol% and less than or equal to 50 mol%, greater than or equal to 16 mol% and less than or equal to 65 mol%, greater than or equal to 16 mol% and less than or equal to 45 mol%, greater than or equal to 17 mol% and less than or equal to 65 mol%. 17 mol% to 50 mol%, 18 mol% to 60 mol%, 18 mol% to 45 mol%, 19 mol% to 65 mol%, 20 mol% to 65 mol%, 21 mol% to 65 mol%, 22 mol% to 65 mol%, 23 mol% to 65 mol%, 24 mol% to 60 mol%, and so on. 24 mol% to less than or equal to 45 mol%, 25 mol% to less than or equal to 65 mol%, 25 mol% to less than or equal to 50 mol%, 26 mol% to less than or equal to 60 mol%, 26 mol% to less than or equal to 45 mol%, 27 mol% to less than or equal to 65 mol%, 27 mol% to less than or equal to 50 mol%, 28 mol% to less than or equal to 60 mol%, 28 mol% to less than or equal to 45 mol%, 29 mol% to less than or equal to 65 mol%, 29 mol% to less than or equal to 50 mol%, 30 mol% to less than or equal to 60 mol%, 30 mol% to less than or equal to 45 mol%, 31 mol% to less than or equal to 65 mol%, 31 mol% to less than or equal to 65 mol%, 31 mol% to less than or equal to 65 mol%. 32 mol% to 50 mol%, 32 mol% to 60 mol%, 32 mol% to 45 mol%, 33 mol% to 65 mol%, 34 mol% to 60 mol%, 35 mol% to 65 mol%, 35 mol% to 65 mol%, 35 mol% to 65 mol%, 36 mol% to 45 mol%, 37 mol% to 65 mol%, 37 mol% to 50 mol%, 38 mol% to 50 mol%. The range is equal to 60 mol%, greater than or equal to 38 mol% to less than or equal to 45 mol%, greater than or equal to 39 mol% to less than or equal to 65 mol%, greater than or equal to 39 mol% to less than or equal to 50 mol%, greater than or equal to 40 mol% to less than or equal to 60 mol%, greater than or equal to 40 mol% to less than or equal to 45 mol%, greater than or equal to 41 mol% to less than or equal to 65 mol%, greater than or equal to 41 mol% to less than or equal to 50 mol%, greater than or equal to 42 mol% to less than or equal to 60 mol%, greater than or equal to 42 mol% to less than or equal to 45 mol%, greater than or equal to 43 mol% to less than or equal to 65 mol%, greater than or equal to 43 mol% to less than or equal to 50 mol%, greater than or equal to 45 mol% to less than or equal to 50 mol%, greater than or equal to 47 mol% to less than or equal to 50 mol%, or any and all subranges formed by any of these endpoints. In embodiments, the concentration of MgO in the precursor glass or glass-ceramic composition can be greater than or equal to 7 mol%, 10 mol%, 20 mol%, 25 mol%, or 30 mol%. In embodiments, the concentration of MgO can be less than or equal to 65 mol%, 60 mol%, 55 mol%, 50 mol%, 45 mol%, 40 mol%, 35 mol%, or 30 mol%. While not intended to be theoretically rigorous, it is generally true that as the concentration of MgO in the glass-ceramic composition increases, the opacity of the glass-ceramic may increase. Similarly, as the concentration of MgO in the glass-ceramic composition decreases, the transparency may improve. However, if the concentration of MgO in the glass-ceramic composition is too low, the glass-ceramic composition may become cloudy.

In embodiments, the precursor glass or glass-ceramic composition may contain _Na₂O . The addition of _Na₂O can reduce the liquidus viscosity of the glass, which in turn can facilitate the formation or shaping of the precursor glass. _Na₂O can also promote ion exchange strengthening of the resulting glass-ceramic because most of the _Na₂O present in the precursor glass will be separated into the residual glass phase after heat treatment (e.g., ceramization). In embodiments, the concentration of Na₂O in the precursor glass or glass-ceramic composition can be greater than or equal to 0 mol% (if positive, such as greater than the amount of impurities (0.05 mol% or greater)) to less than or equal to ₁₅ mol%, greater than or equal to 0 mol% to less than or equal to 13 mol%, greater than or equal to 0 mol% to less than or equal to 11 mol%, greater than or equal to 0 mol% to less than or equal to 9 mol%, greater than or equal to 0 mol% to less than or equal to 7 mol%, greater than or equal to 0 mol% to less than or equal to 5 mol%, greater than or equal to 0 mol% to less than or equal to 3 mol%, greater than or equal to 0 mol% to less than or equal to 5 mol%, greater than or equal to 0 mol% to less than or equal to 3 mol%, greater than or equal to 0 mol% to less than or equal to 5 mol%, and so on. 1 mol%, greater than or equal to 1 mol% to less than or equal to 15 mol%, greater than or equal to 1 mol% to less than or equal to 13 mol%, greater than or equal to 1 mol% to less than or equal to 11 mol%, greater than or equal to 1 mol% to less than or equal to 9 mol%, greater than or equal to 1 mol% to less than or equal to 7 mol%, greater than or equal to 1 mol% to less than or equal to 5 mol%, greater than or equal to 1 mol% to less than or equal to 3 mol%, greater than or equal to 2 mol% to less than or equal to 15 mol%, greater than or equal to 2 mol% to less than or equal to 13 mol%. ≥2 mol% to ≤11 mol% ≥2 mol% ≥9 mol% ≥2 mol% ≥7 mol% ≥2 mol% ≥5 mol% ≥2 mol% ≥3 mol% ≥3 mol% ≥15 mol% ≥4 mol% ≥15 mol% ≥5 mol% ≥6 mol% ≥15 mol% ≥6 mol% ≥15 mol% ≥6 mol% ≥15 mol% ≥6 mol% ≥15 mol% ≥6 mol% ≥15 mol% ≥6 mol% ≥15 mol% ≥6 mol% ≥15 mol% ≥6 mol% ≥15 mol% ≥6 mol% ≥15 mol% ≥6 mol% ≥15 mol% ≥2 ... The concentration of Na₂O in the precursor glass or glass-ceramic composition may be greater than or equal to 7 mol% and less than or equal to 15 mol%, greater than or equal to 8 mol% and less than or equal to 15 mol%, greater than or equal to 9 mol% and less than or equal to 15 mol%, greater than or equal to 10 mol% and less than or equal to 15 mol%, greater than or equal to 11 mol% and less than or equal to 15 mol%, greater than or equal to 12 mol% and less than or equal to 15 mol%, greater than or equal to 13 mol% and less than or equal to 15 mol%, greater than or equal to ₁₄ mol% and less than or equal to 15 mol%, or any and all subranges formed by any of these endpoints. In embodiments, the concentration of Na₂O in the precursor glass or glass-ceramic composition may be greater than or equal to 0 mol%, 5 mol%, or 10 mol%. In embodiments, the concentration of _Na₂O may be less than or equal to 15 mol%, 10 mol%, or 5 mol%. In embodiments, the precursor glass or glass-ceramic composition may be substantially free of _Na₂O .

In embodiments, the precursor glass or glass-ceramic composition may contain _K₂O . The addition of _K₂O can reduce the liquidus viscosity of the glass, which in turn can facilitate the formation or molding of the precursor glass. _K₂O can also promote ion exchange strengthening of the resulting glass-ceramic because most of the _K₂O will be separated into the glass phase after ceramization. In embodiments, the concentration of _K₂O in the precursor glass or glass-ceramic composition may be greater than or equal to 0 mol% (if positive, such as greater than the amount of impurities (0.05 mol% or greater)) to less than or equal to 15 mol%, greater than or equal to 0 mol% to less than or equal to 13 mol%, greater than or equal to 0 mol% to less than or equal to 11 mol%, greater than or equal to 0 mol% to less than or equal to 9 mol%, greater than or equal to 0 mol% to less than or equal to 7 mol%, greater than or equal to 0 mol% to less than or equal to 5 mol%, greater than or equal to 0 mol% to less than or equal to 3 mol%, greater than or equal to 0 mol% to less than or equal to 5 mol%, greater than or equal to 0 mol% to less than or equal to 3 mol%, greater than or equal to 0 mol% to less than or equal to 5 mol%, and so on. 1 mol%, greater than or equal to 1 mol% to less than or equal to 15 mol%, greater than or equal to 1 mol% to less than or equal to 13 mol%, greater than or equal to 1 mol% to less than or equal to 11 mol%, greater than or equal to 1 mol% to less than or equal to 9 mol%, greater than or equal to 1 mol% to less than or equal to 7 mol%, greater than or equal to 1 mol% to less than or equal to 5 mol%, greater than or equal to 1 mol% to less than or equal to 3 mol%, greater than or equal to 2 mol% to less than or equal to 15 mol%, greater than or equal to 2 mol% to less than or equal to 13 mol%. %, greater than or equal to 2 mol% to less than or equal to 11 mol%, greater than or equal to 2 mol% to less than or equal to 9 mol%, greater than or equal to 2 mol% to less than or equal to 7 mol%, greater than or equal to 2 mol% to less than or equal to 5 mol%, greater than or equal to 2 mol% to less than or equal to 3 mol%, greater than or equal to 3 mol% to less than or equal to 15 mol%, greater than or equal to 4 mol% to less than or equal to 15 mol%, greater than or equal to 5 mol% to less than or equal to 15 mol%, greater than 5 mol% to less than or equal to 15 mol%, greater than The concentration of K₂O in the precursor glass or glass-ceramic composition may be greater than or equal to 6 mol% and less than or equal to 15 mol%, greater than or equal to 7 mol% and less than or equal to 15 mol%, greater than or equal to 8 mol% and less than or equal to 15 mol%, greater than or equal to 9 mol% and less than or equal to 15 mol%, greater than or equal to 10 mol% and less than or equal to 15 mol%, greater than or equal to 11 mol% and less than or equal to 15 mol%, greater than or equal to 12 mol% and less than or equal to 15 mol%, greater than or equal to 13 mol% and less than or equal to 15 mol%, or any and all subranges formed by any of these endpoints. In embodiments, the concentration of _K₂O in the precursor glass or glass-ceramic composition may be greater than or equal to 0 mol%, 5 mol%, or 10 mol%. In embodiments, the concentration of _K₂O may be less than or equal to 15 mol%, 10 mol%, or 5 mol%. In embodiments, the precursor glass or glass-ceramic composition may be substantially free of _K₂O .

In embodiments, the _Na₂O (mol%) + _K₂O (mol%) content in the precursor glass or glass-ceramic composition described herein may be greater than or equal to 0 mol% and less than or equal to 15 mol%. In embodiments, the Na₂O (mol%) + _K₂O (mol%) content in the precursor glass or glass-ceramic composition described herein may be greater than or equal to ₀ mol% and less than or equal to 15 mol%. O (mol%) can be greater than or equal to 0 mol% to less than or equal to 15 mol%, greater than or equal to 0 mol% to less than or equal to 13 mol%, greater than or equal to 0 mol% to less than or equal to 11 mol%, greater than or equal to 0 mol% to less than or equal to 9 mol%, greater than or equal to 0 mol% to less than or equal to 7 mol%, greater than or equal to 0 mol% to less than or equal to 5 mol%, greater than or equal to 1 mol% to less than or equal to 15 mol%, greater than or equal to 1 mol% to less than or equal to 13 mol%, greater than or equal to 1 mol% to less than or equal to 11 mol%, greater than or equal to 1 mol% to less than or equal to 9 mol%, greater than or equal to 1 mol% to less than or equal to 7 mol%, greater than or equal to 1 mol% to less than or equal to 5 mol%, greater than or equal to 2 mol% to less than or equal to 15 mol%, greater than or equal to 2 mol% to less than or equal to 13 mol%, greater than or equal to 2 mol% to less than or equal to 11 mol%, greater than or equal to 2 mol% to less than or equal to 9 mol%, greater than or equal to 2 mol% to less than or equal to 7 mol%, greater than or equal to 2 mol% to less than or equal to 5 mol%, greater than or equal to 3 mol% to less than or equal to 15 mol%, greater than or equal to 3 mol% to less than or equal to 13 mol%, greater than or equal to 3 mol% to less than or equal to 11 mol%, greater than or equal to 3 mol% to less than or equal to 9 mol%, greater than or equal to 3 mol% to less than or equal to 7 mol%, greater than or equal to 3 mol% to less than or equal to 5 mol%, greater than or equal to 4 mol% to less than or equal to 15 mol%, greater than or equal to 4 mol% to less than or equal to 13 mol%, greater than or equal to 4 mol% to less than or equal to 11 mol%, greater than or equal to 4 mol% to less than or equal to 9 mol%, greater than or equal to 4 mol% to less than or equal to 7 mol%, greater than or equal to 4 mol% to less than or equal to 5 mol%, greater than or equal to 5 mol% to less than or equal to 15 mol%, greater than or equal to 5 mol% to less than or equal to 13 mol%, greater than or equal to 5 mol% to less than or equal to 11 mol%, greater than or equal to 5 mol% to less than or equal to 9 mol%, greater than or equal to 5 mol% to less than or equal to 7 mol%, greater than or equal to 6 mol% to less than or equal to 15 mol%, greater than or equal to 6 mol% to less than or equal to 13 mol%, greater than or equal to 6 mol% to less than or equal to 11 mol%, greater than or equal to 6 mol% to less than or equal to 9 mol%, greater than or equal to 6 mol% to less than or equal to 7 mol%, greater than or equal to 7 mol% to less than or equal to 15 mol%, greater than or equal to 7 mol% to less than or equal to 13 mol%, greater than or equal to 7 mol% to less than or equal to 11 mol%, greater than or equal to 7 mol% to less than or equal to 15 mol%. 9 mol%, greater than or equal to 8 mol% to less than or equal to 15 mol%, greater than or equal to 8 mol% to less than or equal to 13 mol%, greater than or equal to 8 mol% to less than or equal to 11 mol%, greater than or equal to 8 mol% to less than or equal to 9 mol%, greater than or equal to 9 mol% to less than or equal to 15 mol%, greater than or equal to 9 mol% to less than or equal to 13 mol%, greater than or equal to 9 mol% to less than or equal to 11 mol%, greater than or equal to 10 mol% to less than or equal to 15 mol%, greater than or equal to 10 mol% to less than or equal to 13 mol%, greater than or equal to 10 mol% to less than or equal to 11 mol%, greater than or equal to 11 mol% to less than or equal to 15 mol%, greater than or equal to 11 mol% to less than or equal to 13 mol%, greater than or equal to 13 mol% to less than or equal to 15 mol%, or any and all subranges formed by any of these endpoints. In embodiments, the concentration of _Na₂O (mol%) + _K₂O (mol%) in the precursor glass or glass-ceramic composition may be greater than or equal to 2 mol%, 3 mol%, 5 mol%, or 10 mol%. In embodiments, the concentration of _Na₂O (mol%) + _K₂O (mol%) may be less than or equal to 15 mol%, 10 mol%, or 5 mol%. In embodiments, _Na₂O (mol%)/( _Na₂O (mol%) + _K₂O (mol%)) may be greater than or equal to 0.2 or even greater than or equal to 0.3 to improve the ion exchange properties of the resulting glass-ceramic.

In embodiments, the ratio of _Na₂O (mol%) to _K₂O (mol%) can be about 1:3, about 2:5, or about 1:1, such as in a particular composition disclosed herein, where the amount of _Na₂O , in mol%, is at least 33% or more of the amount of _K₂O , or vice versa (i.e., the amount of _K₂O , in mol%) is at least 33% or more of the amount of _Na₂O ), as illustrated in the examples, such as the amount of _Na₂O , in mol%, is at least 40% or more of the amount of _K₂O , or vice versa, such as the amount of _Na₂O , in mol%, is at least 50% or more of the amount of _K₂O , or vice versa, such as the amount of Na₂O, in mol%, is at least 60% or more of the amount of _K₂O , or vice versa, such as the amount of _Na₂O , in mol%, is at least 70% or more of the amount of _K₂O , or vice versa, such as the amount of _Na₂O , in mol%, is at least 80% or more of the amount of _K₂O , or vice versa, such as the amount of _Na₂O , in mol%, is at least 1:3, about 2:5, or about ₁ :1, or vice versa. The amount of _Na₂O is at least 90% or more, or vice versa. Without being bound by theory, it is believed that the ratio of _Na₂O (mol%) to _K₂O (mol%) can be adjusted to improve the transparency of the glass-ceramic composition.

In embodiments, the precursor glass or glass-ceramic composition may contain _ZrO2 . Not wishing to be bound by theory, _ZrO2 is believed to act as a nucleating agent, promoting the nucleation of crystalline phases with a jeffbenite crystalline structure during heat treatment at ambient atmospheric pressure (i.e., ~100 kPa). In embodiments, _ZrO2 may be tetragonal _ZrO2 . In embodiments, the concentration of _ZrO2 in the precursor glass or glass-ceramic composition may be greater than or equal to 0 mol% (if positive, such as greater than the amount of impurities (0.05 mol% or greater)) to less than or equal to 7 mol% ZrO2 _. 0 mol% to 7 mol% or less, 0 mol% to 6 mol% or less, 0 mol% to 5 mol% or less, 0 mol% to 4 mol% or less, 0 mol% to 3 mol% or less, 0 mol% to 2 mol% or less, 0 mol% to 1 mol% or less, 1 mol% to 7 mol% or less Or equal to 6 mol%, greater than or equal to 1 mol% to less than or equal to 5 mol%, greater than or equal to 1 mol% to less than or equal to 4 mol%, greater than or equal to 1 mol% to less than or equal to 3 mol%, greater than or equal to 1 mol% to less than or equal to 2 mol%, greater than 1.5 mol% to less than or equal to 7 mol%, greater than 1.5 mol% to less than or equal to 6 mol%, greater than 1.5 mol% to less than or equal to 5 mol%, greater than 1.5 mol% to less than or equal to 4 mol%, greater than 1.5 mol% to less than 6 mol%, greater than 1.5 mol% to less than or equal to 5 mol%, greater than 1.5 mol% to less than 4 mol%, greater than 1.5 mol% to less than 6 ... The range is 3 mol% or more, greater than 1.5 mol% to less than or equal to 2 mol%, greater than or equal to 2 mol% to less than or equal to 7 mol%, greater than or equal to 2 mol% to less than or equal to 6 mol%, greater than or equal to 2 mol% to less than or equal to 5 mol%, greater than or equal to 2 mol% to less than or equal to 4 mol%, greater than or equal to 2 mol% to less than or equal to 3 mol%, greater than or equal to 3 mol% to less than or equal to 7 mol%, greater than or equal to 3 mol% to less than or equal to 6 mol%, greater than or equal to 3 mol% to less than or equal to 5 mol%, greater than or equal to 3 mol% to less than or equal to 4 mol%, greater than or equal to 4 mol% to less than or equal to 7 mol%, greater than or equal to 4 mol% to less than or equal to 6 mol%, greater than or equal to 4 mol% to less than or equal to 5 mol%, greater than or equal to 5 mol% to less than or equal to 7 mol%, greater than or equal to 5 mol% to less than or equal to 6 mol%, greater than or equal to 6 mol% to less than or equal to 7 mol%, or any and all subranges formed by any of these endpoints. In embodiments, the concentration of _ZrO2 in the precursor glass or glass-ceramic composition may be greater than 1.5 mol%, greater than or equal to 2 mol%, 3 mol%, or 4 mol%. In embodiments, the concentration of _ZrO2 may be less than or equal to 7 mol%, 6 mol%, or 5 mol%. In embodiments, the precursor glass or glass-ceramic composition may be substantially free of _ZrO2 .

In embodiments, the precursor glass or glass-ceramic composition may contain _HfO2 . Not wishing to be bound by theory, _HfO2 is believed to act as a nucleating agent, promoting the formation of the crystalline phase during heat treatment. In embodiments, _HfO2 may be used as a nucleating agent in addition to _ZrO2 , or _HfO2 may be used as a substitute for _ZrO2 . Additionally, _HfO2 can help lower the liquidus line of the precursor glass. In embodiments, the concentration of _HfO2 in the precursor glass or glass-ceramic composition may be greater than or equal to 0 mol% (if positive, such as greater than the amount of impurities (0.05 mol% or greater)) to less than or equal to 12 mol%. In embodiments, the HfO2 concentration in the precursor glass or glass-ceramic composition... The concentration of ₂ can be greater than or equal to 0 mol% to less than or equal to 12 mol%, greater than or equal to 0 mol% to less than or equal to 10 mol%, greater than or equal to 0 mol% to less than or equal to 7 mol%, greater than or equal to 0 mol% to less than or equal to 6 mol%, greater than or equal to 0 mol% to less than or equal to 5 mol%, greater than or equal to 0 mol% to less than or equal to 4 mol%, greater than or equal to 0 mol% to less than or equal to 3 mol%, greater than or equal to 0 mol% to less than or equal to 2 mol%, greater than or equal to 0 mol% to less than or equal to 1 mol%, greater than or equal to 1 mol% to less than or equal to 12 mol%, greater than or equal to 1 mol% to less than 1 mol%. 10 mol% or more, greater than or equal to 1 mol% to less than or equal to 7 mol%, greater than or equal to 1 mol% to less than or equal to 6 mol%, greater than or equal to 1 mol% to less than or equal to 5 mol%, greater than or equal to 1 mol% to less than or equal to 4 mol%, greater than or equal to 1 mol% to less than or equal to 3 mol%, greater than or equal to 1 mol% to less than or equal to 2 mol%, greater than or equal to 2 mol% to less than or equal to 12 mol%, greater than or equal to 2 mol% to less than or equal to 10 mol%, greater than or equal to 2 mol% to less than or equal to 7 mol%, greater than or equal to 2 mol% to less than or equal to 6 mol%, greater than or equal to 2 mol% % to less than or equal to 5 mol%, greater than or equal to 2 mol% to less than or equal to 4 mol%, greater than or equal to 2 mol% to less than or equal to 3 mol%, greater than or equal to 3 mol% to less than or equal to 12 mol%, greater than or equal to 3 mol% to less than or equal to 10 mol%, greater than or equal to 3 mol% to less than or equal to 7 mol%, greater than or equal to 3 mol% to less than or equal to 6 mol%, greater than or equal to 3 mol% to less than or equal to 5 mol%, greater than or equal to 3 mol% to less than or equal to 4 mol%, greater than or equal to 4 mol% to less than or equal to 12 mol%, greater than or equal to 4 mol% to less than or equal to 10 mol%, greater than or equal to 5 mol%, greater than or equal to 3 mol% to less than or equal to 4 ...%, greater than or equal to 4 mol%, greater than or equal to 10 mol%, greater than or equal to 5 mol%, greater than or equal to 3 mol%, greater than or equal to 4 mol%, greater than or equal to 10 mol%, greater than or equal to 5 mol%, greater than or equal to 3 mol%, greater than or equal to 4 mol%, greater than or equal to 5 mol%, greater than or equal to 3 mol%, greater than or equal to 4 mol%, greater than or equal to 10 mol%, greater than or equal to 5 mol%, greater than or equal to 3 mol%, greater than or equal to The concentration of HfO2 in the precursor glass or glass-ceramic composition may be greater than or equal to 1 mol%, 2 mol%, or 3 mol%. In embodiments, the concentration of HfO2 in the precursor glass or glass-ceramic composition may be less than or equal to 12 mol%, 10 mol%, 6 mol%, or 5 mol%. In embodiments, the concentration of _HfO2 in the precursor glass or glass-ceramic composition may be less than or equal to 12 mol%, 10 mol%, 7 mol%, 6 mol%, or 5 mol%. In embodiments, the precursor glass or glass-ceramic composition may be substantially free _{of HfO2} .

In embodiments, the precursor glass or glass-ceramic composition may contain _TiO2 . Without being bound by theory, _TiO2 is believed to act as a nucleating agent, promoting the formation of crystalline phases during heat treatment. Increasing the concentration of _TiO2 can also impart color to the precursor glass and the resulting glass-ceramic. In embodiments, TiO2 in the precursor glass or glass-ceramic composition... The concentration of ₂ can be greater than or equal to 0 mol% (if positive, greater than the amount of impurities (0.05 mol% or greater)) to less than or equal to 7 mol%, greater than or equal to 0 mol% to less than or equal to 6 mol%, greater than or equal to 0 mol% to less than or equal to 5 mol%, greater than or equal to 0 mol% to less than or equal to 4 mol%, greater than or equal to 0 mol% to less than or equal to 3 mol%, greater than or equal to 0 mol% to less than or equal to 2 mol%, greater than or equal to 0 mol% to less than or equal to 1 mol%, greater than or equal to 0.3 mol% to less than or equal to 7 mol%, greater than or equal to 0.3 mol% to less than 6 mol%, greater than or equal to 0.3 mol% to less than 5 mol% or more, greater than or equal to 0.3 mol% to less than or equal to 4 mol%, greater than or equal to 0.3 mol% to less than or equal to 3 mol%, greater than or equal to 0.3 mol% to less than or equal to 2 mol%, greater than or equal to 0.3 mol% to less than or equal to 1 mol%, greater than or equal to 0.5 mol% to less than or equal to 7 mol%, greater than or equal to 0.5 mol% to less than or equal to 6 mol%, greater than or equal to 0.5 mol% to less than or equal to 5 mol%, greater than or equal to 0.5 mol% to less than or equal to 4 mol%, greater than or equal to 0.5 mol% to less than or equal to 3 mol%, greater than or equal to 0.5 mol% to less than or equal to 2 mol%, greater than or equal to 0.5 mol% to less than or equal to 1 mol%, greater than or equal to 1 mol% to less than or equal to 7 mol%, greater than or equal to 1 mol% to less than or equal to 6 mol%, greater than or equal to 1 mol% to less than or equal to 5 mol%, greater than or equal to 1 mol% to less than or equal to 4 mol%, greater than or equal to 1 mol% to less than or equal to 3 mol%, greater than or equal to 1 mol% to less than or equal to 2 mol%, greater than or equal to 2 mol% to less than or equal to 7 mol%, greater than or equal to 2 mol% to less than or equal to 6 mol%, greater than or equal to 2 mol% to less than or equal to 5 mol%, greater than or equal to 2 mol% to less than or equal to 4 mol%, greater than or equal to 2 mol% to The concentration of TiO2 in the precursor glass or glass-ceramic composition may be less than or equal to 3 mol%, greater than or equal to 3 mol% to less than or equal to 7 mol%, greater than or equal to 3 mol% to less than or equal to 6 mol%, greater than or equal to 3 mol% to less than or equal to 5 mol%, greater than or equal to 3 mol% to less than or equal to 4 mol%, greater than or equal to 4 mol% to less than or equal to 7 mol%, greater than or equal to 4 mol% to less than or equal to 6 mol%, greater than or equal to 4 mol% to less than or equal to 5 mol%, greater than or equal to 5 mol% to less than or equal to 7 mol%, greater than or equal to 5 mol% to less than or equal to 6 mol%, greater than or equal to 6 mol% to less than or equal to 7 mol%, or any and all subranges formed by any of these endpoints. In embodiments, the concentration of _TiO2 in the precursor glass or glass-ceramic composition may be greater than or equal to 0 mol%, 1 mol%, or 2 mol%. In embodiments, the concentration of _TiO2 may be less than or equal to 7 mol%, 6 mol%, or 5 mol%. In embodiments, the precursor glass or glass-ceramic composition may be substantially free of _TiO2 .

In embodiments, the _ZrO₂ (mol%) + _TiO₂ (mol%) content in the precursor glass or glass-ceramic composition described herein can be greater than or equal to 2.0 mol%, greater than or equal to 3.0 mol%, or even greater than or equal to 4.0 mol%. In embodiments, the ratio of ZrO₂ (mol%)/( _ZrO₂ (mol%) + _TiO₂ (mol%)) in the precursor glass or glass-ceramic composition described herein can be greater than or equal to 0.3. Without being bound by theory, if the ratio of _ZrO₂ (mol%)/( _ZrO₂ (mol%) + _TiO₂ (mol%)) in the precursor glass or glass-ceramic composition is less than 0.3, the main crystalline phase in the glass-ceramic may be a forsterite crystalline phase rather than a crystalline phase with _a jeffbenite crystalline structure, which may be undesirable.

In embodiments, the precursor glass or glass-ceramic composition may contain _SnO2 . _SnO2 primarily functions as a clarifying agent in the precursor glass composition. However, the addition of _SnO2 can also aid nucleating the crystalline phase during heat treatment with nucleating agents (such as _TiO2 and _ZrO2 ). In embodiments, the concentration of _SnO2 in the precursor glass or glass-ceramic composition may be greater than or equal to 0 mol% to less than or equal to 0.2 mol%, greater than or equal to 0 mol% (if positive, such as greater than the amount of impurities (0.05 mol% or greater)) to less than or equal to 0.18 mol%, greater than or equal to 0 mol% to less than or equal to 0.16 mol%, greater than or equal to 0 mol% to less than or equal to 0.14 mol%, greater than or equal to 0.12 mol%, greater than or equal to 0 mol% to less than or equal to 0.11 mol%, greater than or equal to 0 mol% to less than 0.12 mol%, greater than or equal to 0 mol% to less than or equal to 0.11 mol%, greater than or equal to 0 mol% to less than 0.12 mol%, greater than or equal to 0 mol% to less than 0.12 mol%, greater than or equal to 0 mol% to less than or equal to ... The concentration of SnO2 in the precursor glass or glass-ceramic composition may be greater than or equal to 0.1 mol%, greater than or equal to 0.08 mol% to less than or equal to 0.2 mol%, greater than or equal to 0.09 mol% to less than or equal to 0.2 mol%, greater than or equal to 0.1 mol% to less than or equal to 0.2 mol%, greater than or equal to 0.12 mol% to less than or equal to 0.2 mol%, greater than or equal to 0.13 mol% to less than or equal to 0.2 mol%, greater than or equal to 0.14 mol% to less than or equal to 0.2 mol%, or any and all subranges formed by any of these endpoints. In embodiments, the concentration of _SnO2 in the precursor glass or glass-ceramic composition may be greater than or equal to 0 mol%, 0.08 mol%, or 0.09 mol%. In embodiments, the concentration of _SnO2 may be less than or equal to 0.2 mol%, 0.18 mol%, or 0.16 mol%. In embodiments, the precursor glass or glass-ceramic composition may be substantially free of _SnO2 .

In embodiments, the precursor glass or glass-ceramic composition may contain BaO. BaO can increase the refractive index of the residual glass in the glass-ceramic to better match the refractive index of the crystalline phase having a jeffbenite crystalline structure in the glass-ceramic. In embodiments, the concentration of BaO in the precursor glass or glass-ceramic composition may be greater than or equal to 0 mol% (if positive, such as greater than the amount of impurities (0.05 mol% or greater)) to less than or equal to 8 mol%, greater than or equal to 0 mol% to less than or equal to 7 mol%, greater than or equal to 0 mol% to less than or equal to 6 mol%, greater than or equal to 0 mol% to less than or equal to 5 mol%, greater than or equal to 0 mol% to less than or equal to 4 mol%, greater than or equal to 0 mol% to less than or equal to 3 mol%, greater than or equal to 0 mol% to less than or equal to 2 mol%, greater than or equal to 3 mol%, greater than or equal to 2 mol%, greater than or equal to 4 mol%, greater than or equal to 3 mol%, greater than or equal to 2 mol%, greater than or equal to 3 mol%, greater than or equal to 4 mol%, greater than or equal to 3 ... 0 mol% to less than or equal to 1 mol%, greater than or equal to 1 mol% to less than or equal to 8 mol%, greater than or equal to 1 mol% to less than or equal to 7 mol%, greater than or equal to 1 mol% to less than or equal to 6 mol%, greater than or equal to 1 mol% to less than or equal to 5 mol%, greater than or equal to 1 mol% to less than or equal to 4 mol%, greater than or equal to 1 mol% to less than or equal to 3 mol%, greater than or equal to 1 mol% to less than or equal to 2 mol%, greater than or equal to 2 mol% to less than or equal to 8 mol%, greater than or equal to 2 mol% to less than or equal to 7 mol%, greater than or equal to 2 mol% to less than or equal to 6 mol%; greater than or equal to 2 mol% to less than or equal to 5 mol%; greater than or equal to 2 mol% to less than or equal to 4 mol%; greater than or equal to 2 mol% to less than or equal to 3 mol%; greater than or equal to 3 mol% to less than or equal to 8 mol%; greater than or equal to 3 mol% to less than or equal to 7 mol%; greater than or equal to 3 mol% to less than or equal to 6 mol%; greater than or equal to 3 mol% to less than or equal to 5 mol%; greater than or equal to 3 mol% to less than or equal to 4 mol%; greater than or equal to 4 mol% to less than or equal to 8 mol% The range is greater than or equal to 4 mol% to less than or equal to 7 mol%, greater than or equal to 4 mol% to less than or equal to 6 mol%, greater than or equal to 4 mol% to less than or equal to 5 mol%, greater than or equal to 5 mol% to less than or equal to 8 mol%, greater than or equal to 5 mol% to less than or equal to 7 mol%, greater than or equal to 5 mol% to less than or equal to 6 mol%, greater than or equal to 6 mol% to less than or equal to 8 mol%, greater than or equal to 6 mol% to less than or equal to 7 mol%, greater than or equal to 7 mol% to less than or equal to 8 mol%, or any and all subranges formed by any of these endpoints. In embodiments, the precursor glass or glass-ceramic composition may be substantially free of BaO.

In embodiments, the precursor glass or glass-ceramic composition may contain ZnO. The addition of ZnO can increase the refractive index of the residual glass in the glass-ceramic to better match the refractive index of the crystalline phase with a Jeffbenite crystalline structure in the glass-ceramic. While not wishing to be bound by theory, it is believed that the addition of ZnO can lead to the substitution of at least a portion of Mg in the Jeffbenite crystalline structure with Zn. ZnO can also help stabilize the precursor glass, prevent devitrification, and reduce liquidus viscosity. However, too much ZnO may disrupt the formation of the crystalline phase with a Jeffbenite crystalline structure during ceramization. In embodiments, the concentration of ZnO in the precursor glass or glass-ceramic composition can be greater than or equal to 0 mol% (if positive, such as greater than the amount of impurities (0.05 mol% or greater)) to less than or equal to 15 mol%, greater than or equal to 0 mol% to less than or equal to 14 mol%, greater than or equal to 0 mol% to less than or equal to 13 mol%, greater than or equal to 0 mol% to less than or equal to 12 mol%, greater than or equal to 0 mol% to less than or equal to 11 mol%, greater than or equal to 0 mol% to less than or equal to 10 mol%, greater than or equal to 0 mol% to less than or equal to 9 mol%, greater than or equal to 0 mol% to less than or equal to 8 mol%, greater than or equal to 0 mol% to less than or equal to 9 mol%, greater than or equal to 0 mol% to less than or equal to 8 mol%, greater than or equal to 0 mol% to less than or equal to 9 mol%, and greater than or equal to 0 mol% to less than or equal to 9 mol%. 7 mol%, greater than or equal to 0 mol% to less than or equal to 6 mol%, greater than or equal to 0 mol% to less than or equal to 5 mol%, greater than or equal to 0 mol% to less than or equal to 4 mol%, greater than or equal to 0 mol% to less than or equal to 3 mol%, greater than or equal to 0 mol% to less than or equal to 2 mol%, greater than or equal to 0 mol% to less than or equal to 1 mol%, greater than or equal to 1 mol% to less than or equal to 15 mol%, greater than or equal to 1 mol% to less than or equal to 14 mol%, greater than or equal to 1 mol% to less than or equal to 13 mol%, greater than or equal to 1 mol% to less than or equal to 12 mol%, greater than or equal to 1 mol% to less than or equal to 11 mol%, greater than or equal to 7 mol%, greater than or equal to 1 mol%, less than or equal to 12 mol%, greater than or equal to 1 mol%, less than or equal to 11 mol%, greater than or equal to 12 mol%, less than or equal to 12 ... From 1 mol% to less than or equal to 10 mol%, greater than or equal to 1 mol% to less than or equal to 9 mol%, greater than or equal to 1 mol% to less than or equal to 8 mol%, greater than or equal to 1 mol% to less than or equal to 7 mol%, greater than or equal to 1 mol% to less than or equal to 6 mol%, greater than or equal to 1 mol% to less than or equal to 5 mol%, greater than or equal to 1 mol% to less than or equal to 4 mol%, greater than or equal to 1 mol% to less than or equal to 3 mol%, greater than or equal to 1 mol% to less than or equal to 2 mol%, greater than or equal to 2 mol% to less than or equal to 15 mol%, greater than or equal to 2 mol% to less than or equal to 14 mol%, greater than or equal to 2 mol% to less than or equal to 1 3 mol%, greater than or equal to 2 mol% to less than or equal to 12 mol%, greater than or equal to 2 mol% to less than or equal to 11 mol%, greater than or equal to 2 mol% to less than or equal to 10 mol%, greater than or equal to 2 mol% to less than or equal to 9 mol%, greater than or equal to 2 mol% to less than or equal to 8 mol%, greater than or equal to 2 mol% to less than or equal to 7 mol%, greater than or equal to 2 mol% to less than or equal to 6 mol%, greater than or equal to 2 mol% to less than or equal to 5 mol%, greater than or equal to 2 mol% to less than or equal to 4 mol%, greater than or equal to 2 mol% to less than or equal to 3 mol%, greater than or equal to 3 mol% to less than or equal to 15 mol%, greater than or equal to 3 mol% to less than or equal to 14 mol%, greater than or equal to 3 mol% to less than or equal to 13 mol%, greater than or equal to 3 mol% to less than or equal to 12 mol%, greater than or equal to 3 mol% to less than or equal to 11 mol%, greater than or equal to 3 mol% to less than or equal to 10 mol%, greater than or equal to 3 mol% to less than or equal to 9 mol%, greater than or equal to 3 mol% to less than or equal to 8 mol%, greater than or equal to 3 mol% to less than or equal to 7 mol%, greater than or equal to 3 mol% to less than or equal to 6 mol%, greater than or equal to 3 mol% to less than or equal to 5 mol%, greater than or equal to 3 mol% to less than or equal to 4 mol%, greater than or equal to 4 mol% to less than or equal to 1 5 mol%, greater than or equal to 4 mol% to less than or equal to 14 mol%, greater than or equal to 4 mol% to less than or equal to 13 mol%, greater than or equal to 4 mol% to less than or equal to 12 mol%, greater than or equal to 4 mol% to less than or equal to 11 mol%, greater than or equal to 4 mol% to less than or equal to 10 mol%, greater than or equal to 4 mol% to less than or equal to 9 mol%, greater than or equal to 4 mol% to less than or equal to 8 mol%, greater than or equal to 4 mol% to less than or equal to 7 mol%, greater than or equal to 4 mol% to less than or equal to 6 mol%, greater than or equal to 4 mol% to less than or equal to 5 mol%, greater than or equal to 5 mol% to less than or equal to 15 mol%, greater than or equal to 15 mol%, and so on. From 5 mol% to less than or equal to 14 mol%, greater than or equal to 5 mol% to less than or equal to 13 mol%, greater than or equal to 5 mol% to less than or equal to 12 mol%, greater than or equal to 5 mol% to less than or equal to 11 mol%, greater than or equal to 5 mol% to less than or equal to 10 mol%, greater than or equal to 5 mol% to less than or equal to 9 mol%, greater than or equal to 5 mol% to less than or equal to 8 mol%, greater than or equal to 5 mol% to less than or equal to 7 mol%, greater than or equal to 5 mol% to less than or equal to 6 mol%, greater than or equal to 6 mol% to less than or equal to 15 mol%, greater than or equal to 6 mol% to less than or equal to 14 mol%, greater than or equal to 6 mol% to less than The range may be 13 mol% or more, greater than or equal to 6 mol% to less than or equal to 12 mol%, greater than or equal to 6 mol% to less than or equal to 11 mol%, greater than or equal to 6 mol% to less than or equal to 10 mol%, greater than or equal to 6 mol% to less than or equal to 9 mol%, greater than or equal to 6 mol% to less than or equal to 8 mol%, greater than or equal to 6 mol% to less than or equal to 7 mol%, greater than or equal to 7 mol% to less than or equal to 15 mol%, greater than or equal to 7 mol% to less than or equal to 14 mol%, greater than or equal to 7 mol% to less than or equal to 13 mol%, greater than or equal to 7 mol% to less than or equal to 8 mol%, or any and all subranges formed by any of these endpoints. In embodiments, the precursor glass or glass-ceramic composition may be substantially free of ZnO.

In embodiments, the precursor glass or glass-ceramic composition may contain FeO. While not wishing to be bound by theory, it is believed that the addition of FeO can result in the substitution of at least a portion of Mg in the crystalline structure of jeffbenite with Fe. FeO can also impart color to the precursor glass and glass-ceramic. In embodiments, the concentration of FeO in the precursor glass or glass-ceramic composition may be greater than or equal to 0 mol% (if positive, such as greater than the amount of impurities (0.05 mol% or greater)) to less than or equal to 9 mol%, greater than or equal to 0 mol% to less than or equal to 8 mol%, greater than or equal to 0 mol% to less than or equal to 7 mol%, greater than or equal to 0 mol% to less than or equal to 6 mol%, greater than or equal to 0 mol% to less than or equal to 5 mol%, greater than or equal to 0 mol% to less than or equal to 4 mol%, greater than or equal to 0 mol% to less than or equal to 3 mol%, greater than or equal to 0 mol% to less than The range may be 2 mol% or more, greater than or equal to 0 mol% to less than or equal to 1 mol%, greater than or equal to 1 mol% to less than or equal to 9 mol%, greater than or equal to 2 mol% to less than or equal to 9 mol%, greater than or equal to 3 mol% to less than or equal to 9 mol%, greater than or equal to 4 mol% to less than or equal to 9 mol%, greater than or equal to 5 mol% to less than or equal to 9 mol%, greater than or equal to 6 mol% to less than or equal to 9 mol%, greater than or equal to 7 mol% to less than or equal to 9 mol%, greater than or equal to 8 mol% to less than or equal to 9 mol%, or any and all subranges formed by any of these endpoints. In embodiments, the precursor glass or glass-ceramic composition may be substantially free of FeO.

In embodiments, the precursor glass or glass-ceramic composition may contain CaO, SrO, or combinations thereof. The addition of CaO, SrO, and combinations thereof can increase the amount of residual glass in the glass-ceramic. While it is not desirable to be bound by theory, the inclusion of SrO in the glass-ceramic can increase the refractive index of the residual glass to better match the refractive index of the crystalline phase. In the implementation scheme, the concentration of CaO, SrO, or combinations thereof can be greater than or equal to 0 mol% (if positive, such as greater than the amount of impurities (0.05 mol% or greater)) to less than or equal to 2.0 mol%, greater than or equal to 0.2 mol% to less than or equal to 2.0 mol%, greater than or equal to 0.4 mol% to less than or equal to 2.0 mol%, greater than or equal to 0.6 mol% to less than or equal to 2.0 mol%, greater than or equal to 0.8 mol% to less than or equal to 2.0 mol%, greater than or equal to 1.0 mol% to less than or equal to 2.0 mol%, greater than or equal to 1.2 mol% to less than or equal to 2.0 mol%, greater than or equal to 1.4 mol% to less than or equal to 2.0 mol%, greater than or equal to 0 mol% to less than or equal to 1.7 mol%, greater than or equal to 0.2 mol% to less than or equal to 1.7 mol%, greater than or equal to 0.4 mol% to less than or equal to 2.0 mol%, and so on. The range is 1.7 mol%, greater than or equal to 0.6 mol% to less than or equal to 1.7 mol%, greater than or equal to 0.8 mol% to less than or equal to 1.7 mol%, greater than or equal to 1.0 mol% to less than or equal to 1.7 mol%, greater than or equal to 1.2 mol% to less than or equal to 1.7 mol%, greater than or equal to 1.4 mol% to less than or equal to 1.7 mol%, greater than or equal to 0 mol% to less than or equal to 1.4 mol%, greater than or equal to 0 mol% to less than or equal to 1.2 mol%, greater than or equal to 0 mol% to less than or equal to 1.0 mol%, greater than or equal to 0 mol% to less than or equal to 0.8 mol%, greater than or equal to 0 mol% to less than or equal to 0.6 mol%, greater than or equal to 0 mol% to less than or equal to 0.4 mol%, greater than or equal to 0 mol% to less than or equal to 0.2 mol%, or any and all subranges formed by any of these endpoints. In the implementation scheme, the concentration of CaO can be greater than or equal to 0 mol% and less than or equal to 10 mol%, greater than or equal to 1 mol% and less than or equal to 10 mol%, greater than or equal to 2 mol% and less than or equal to 10 mol%, greater than or equal to 3 mol% and less than or equal to 10 mol%, greater than or equal to 4 mol% and less than or equal to 10 mol%, greater than or equal to 5 mol% and less than or equal to 10 mol%, greater than or equal to 6 mol% and less than or equal to 10 mol%, greater than or equal to 7 mol% and less than or equal to 10 mol%, greater than or equal to 8 mol% and less than or equal to 10 mol%, greater than or equal to 9 mol%, and greater than or equal to 9 mol%. The range is defined as follows: % to less than or equal to 10 mol%, greater than or equal to 0 mol% to less than or equal to 9 mol%, greater than or equal to 0 mol% to less than or equal to 8 mol%, greater than or equal to 0 mol% to less than or equal to 7 mol%, greater than or equal to 0 mol% to less than or equal to 6 mol%, greater than or equal to 0 mol% to less than or equal to 5 mol%, greater than or equal to 0 mol% to less than or equal to 4 mol%, greater than or equal to 0 mol% to less than or equal to 3 mol%, greater than or equal to 0 mol% to less than or equal to 2 mol%, greater than or equal to 0 mol% to less than or equal to 1 mol%, or any and all subranges formed by any of these endpoints. In embodiments, the precursor glass or glass-ceramic composition may be substantially free of CaO. In embodiments, the precursor glass or glass-ceramic composition may be substantially free of SrO. In embodiments, the precursor glass or glass-ceramic composition may be substantially free of both CaO and SrO.

In embodiments, the precursor glass or glass-ceramic composition may contain _Cs₂O . It is not desirable to be bound by theory, but it is believed that the addition of _Cs₂O will remain in the residual glass after ceramization and serve to increase the refractive index of the residual glass without inducing crystallization. In embodiments, the concentration of _Cs₂O in the precursor glass or glass-ceramic composition may be greater than or equal to 0 mol% (if positive, such as greater than the amount of impurities (0.05 mol% or greater)) to less than or equal to 5 mol%, greater than or equal to 0 mol% to less than or equal to 4 mol%, greater than or equal to 0 mol% to less than or equal to 3 mol%, greater than or equal to 0 mol% to less than or equal to 2 mol%, greater than or equal to 0 mol% to less than or equal to 1 mol%, greater than or equal to 1 mol% to less than or equal to 5 mol%, greater than or equal to 2 mol% to less than or equal to 5 mol%, greater than or equal to 3 mol% to less than or equal to 5 mol%, greater than or equal to 4 mol% to less than or equal to 5 mol%, or any and all subranges formed by any of these endpoints. In an embodiment, the precursor glass or glass-ceramic composition may be substantially free of _Cs₂O .

In embodiments, the precursor glass or glass-ceramic composition may contain _Li₂O . For example, but not limited to, the precursor glass or glass-ceramic composition may contain less than or equal to 3 mol%, less than or equal to 2.5 mol%, less than or equal to 2 mol%, less than or equal to 1.5 mol%, less than or equal to 1 mol%, less than or equal to 0.7 mol%, less than or equal to 0.5 mol%, less than or equal to 0.3 mol%, or less than or equal to 0.1 mol% of _Li₂O , but in a positive amount, such as greater than the amount of impurities (0.05 mol% or more), or at most only the amount of impurities (i.e., less than 0.05 mol%). In embodiments, the precursor glass or glass-ceramic composition may be substantially free of _Li₂O . Without being bound by theory, when the precursor glass contains less than or equal to 3 mol% _Li₂O , the formation of β-quartz during heat treatment can be reduced.

In embodiments, the precursor glass or glass-ceramic composition may contain _Y₂O₃ . Not wishing to be bound by theory, _Y₂O₃ can stabilize _ZrO₂ contained in _the precursor glass or glass-ceramic composition. In embodiments, the concentration of _Y₂O₃ may be greater than or equal to 0 _mol % (if positive, such as greater than the amount of impurities (0.05 mol% or greater)) to less than or equal to 2.0 mol% _, greater than or equal to 0.2 mol% to less than or equal to 2.0 mol%, greater than or equal to 0.4 mol% to less than or equal to 2.0 mol%, greater than or equal to 0.6 mol% to less than or equal to 2.0 mol%, greater than or equal to 0.8 mol% to less than or equal to 2.0 mol%, greater than or equal to 1.0 mol% to less than or equal to 2.0 mol%, greater than or equal to 1.2 mol% to less than or equal to 2.0 mol%, greater than or equal to 1.4 mol% to less than or equal to 2.0 mol%, and greater than or equal to 1.6 mol% to less than or equal to 2.0 mol%. %, greater than or equal to 1.8 mol% to less than or equal to 2.0 mol%, greater than or equal to 0 mol% to less than or equal to 1.8 mol%, greater than or equal to 0 mol% to less than or equal to 1.6 mol%, greater than or equal to 0 mol% to less than or equal to 1.4 mol%, greater than or equal to 0 mol% to less than or equal to 1.2 mol%, greater than or equal to 0 mol% to less than or equal to 1.0 mol%, greater than or equal to 0 mol% to less than or equal to 0.8 mol%, greater than or equal to 0 mol% to less than or equal to 0.6 mol%, greater than or equal to 0 mol% to less than or equal to 0.4 mol%, greater than or equal to 0 mol% to less than or equal to 0.2 mol%, or any and all subranges formed by any of these endpoints. In embodiments, the precursor glass or glass-ceramic composition may be substantially free _{of Y₂O₃} .

In some embodiments, the precursor glass or glass-ceramic composition may be substantially free of _P₂O₅ . _However , it is not desirable to be bound by theory _; the presence _{of P₂O₅} in the precursor _glass or glass-ceramic composition may lead to the formation of magnesium phosphate and reduce the formation of crystalline phases with a jeffbenite crystalline structure.

In embodiments, the precursor glass or glass-ceramic composition may contain _P₂O₅ . While not wishing to be bound by theory, it is believed that the addition _{of P₂O₅} can improve the diffusivity of the glass-ceramic composition during the _ion exchange process. In embodiments, the concentration _{of P₂O₅ in} the precursor glass or glass-ceramic composition may be greater than or equal to 0 mol% (if positive, such as greater than the amount of impurities (0.05 mol% or greater)) to less than or equal to 4 mol%, greater than or equal to 0 mol% to less than or equal to 3.5 mol%, greater than or equal to 0 mol% to less than or equal to 3 mol%, greater than or equal to 0 mol% to less than or equal to 2.5 mol%, greater than or equal to 0 mol% to less than or equal to 2 mol%, greater than or equal to 0 mol% to less than or equal to 1.5 mol%, greater than or equal to 0 mol% to less than or equal to 1 mol%, greater than or equal to 0 mol%, and greater than or equal to 0 mol%. The range is defined as follows: mol% to less than or equal to 0.5 mol%, greater than or equal to 0.5 mol% to less than or equal to 4 mol%, greater than or equal to 1 mol% to less than or equal to 4 mol%, greater than or equal to 1.5 mol% to less than or equal to 4 mol%, greater than or equal to 2 mol% to less than or equal to 4 mol%, greater than or equal to 2.5 mol% to less than or equal to 4 mol%, greater than or equal to 3 mol% to less than or equal to 4 mol% _, greater than or equal to 3.5 mol% to less than or equal to 4 mol%, or any and all subranges formed by any of these endpoints. In embodiments, _P₂O₅ contained in the glass-ceramic composition may be retained in the residual glass phase of the glass-ceramic composition. In embodiments, the precursor glass or glass-ceramic composition may be substantially free _{of P₂O₅} .

In embodiments, the precursor glass or glass-ceramic composition may contain _MnO2 . While not wishing to be bound by theory, it is believed that the addition of _MnO2 can result in the substitution of at least a portion of Mg in the crystalline structure of jeffbenite with Mn. _MnO2 can also impart color to the precursor glass and glass-ceramic. For example, but not limited to, the addition of _MnO2 can impart a black color to the glass-ceramic. In embodiments, MnO The concentration of ₂ can be greater than or equal to 0 mol% (if positive, greater than the amount of impurities (0.05 mol% or greater)) to less than or equal to 10 mol%, greater than or equal to 0 mol% to less than or equal to 9 mol%, greater than or equal to 0 mol% to less than or equal to 8 mol%, greater than or equal to 0 mol% to less than or equal to 7 mol%, greater than or equal to 0 mol% to less than or equal to 6 mol%, greater than or equal to 0 mol% to less than or equal to 5 mol%, greater than or equal to 0 mol% to less than or equal to 4 mol%, greater than or equal to 0 mol% to less than or equal to 3 mol%, greater than or equal to 0 mol% to less than or equal to 2 mol%, greater than or equal to 0 mol% to less than or equal to 1.0 mol%, greater than or equal to 0.1 mol% to less than or equal to 1 mol%, greater than or equal to 0.2 mol% to less than or equal to 1.0 mol%, greater than or equal to 0.4 mol% to less than or equal to 1.0 mol%, and greater than or equal to 0.6 mol% to less than or equal to 1.0 mol%. mol%, greater than or equal to 0.8 mol% to less than or equal to 1.0 mol%, greater than or equal to 0 mol% to less than or equal to 0.8 mol%, greater than or equal to 0 mol% to less than or equal to 0.6 mol%, greater than or equal to 0 mol% to less than or equal to 0.4 mol%, greater than or equal to 0 mol% to less than or equal to 0.2 mol%, greater than or equal to 1 mol% to less than or equal to 10 mol%, greater than or equal to 2 mol% to less than or equal to 10 mol%, greater than or equal to 3 mol% to less than or equal to 10 mol%, greater than or equal to 4 mol% to less than or equal to 10 mol%, greater than or equal to 5 mol% to less than or equal to 10 mol%, greater than or equal to 6 mol% to less than or equal to 10 mol%, greater than or equal to 7 mol% to less than or equal to 10 mol%, greater than or equal to 8 mol% to less than or equal to 10 mol%, greater than or equal to 9 mol% to less than or equal to 10 mol%, or any and all subranges formed by any of these endpoints. In an embodiment, the precursor glass or glass-ceramic composition may be substantially free of _MnO2 .

In embodiments, the precursor glass or glass-ceramic composition may contain _{La₂O₃ .} While not wishing to be bound by theory, it is believed that the addition _{of La₂O₃} can increase the refractive index of the residual glass in the glass-ceramic composition, which can improve the transparency of the glass-ceramic composition. In embodiments, _La₂O₃ in the precursor glass or glass-ceramic composition The concentration of ₃ can be greater than or equal to 0 mol% to less than or equal to 7 mol%, greater than or equal to 0 mol% (if positive, such as greater than the amount of impurities (0.05 mol% or greater)) to less than or equal to 6 mol%, greater than or equal to 0 mol% to less than or equal to 5 mol%, greater than or equal to 0 mol% to less than or equal to 4 mol%, greater than or equal to 0 mol% to less than or equal to 3 mol%, greater than or equal to 0 mol% to less than or equal to 2 mol%, greater than or equal to 0 mol% to less than or equal to 1 mol%, greater than or equal to 1 mol% to less than or equal to 7 mol%, greater than or equal to 1 mol% to less than or equal to 6 mol%, greater than or equal to 1 mol% to less than or equal to 5 mol%, greater than or equal to 1 mol% to less than or equal to 4 mol%, greater than or equal to 1 mol% to less than or equal to 3 mol%, greater than or equal to 1 mol% to less than or equal to 2 mol%, greater than or equal to 2 ... The range is 7 mol%, greater than or equal to 2 mol% to less than or equal to 6 mol%, greater than or equal to 2 mol% to less than or equal to 5 mol%, greater than or equal to 2 mol% to less than or equal to 4 mol%, greater than or equal to 2 mol% to less than or equal to 3 mol%, greater than or equal to 3 mol% to less than or equal to 7 mol%, greater than or equal to 3 mol% to less than or equal to 6 mol%, greater than or equal to 3 mol% to less than or equal to 5 mol%, greater than or equal to 3 mol% to less than or equal to 4 mol%, greater than or equal to 4 mol% to less than or equal to 7 mol%, greater than or equal to 4 mol% to less than or equal to 6 mol%, greater than or equal to 4 mol% to less than or equal to 5 mol%, greater than or equal to 5 mol% to less than or equal to 7 mol%, greater than or equal to 5 mol% to less than or equal to 6 mol%, greater than or equal to 6 mol% to less than or equal to ₇ mol%, or any and all subranges formed by any of these endpoints. In embodiments, the precursor glass or glass-ceramic composition may be substantially free of _La₂O₃ .

Articles formed from precursor glass or glass-ceramic materials as described herein can have any suitable thickness, depending on the specific application of the glass-ceramic material. Glass-ceramic sheet embodiments can have a thickness T greater than or equal to 0.2 mm and less than or equal to 10 mm. In embodiments, glass-ceramic sheet embodiments can have a thickness T of 6 mm or less, 5 mm or less, 4 mm or less, 3 mm or less, 2 mm or less, 1.0 mm or less, 750 μm or less, 500 μm or less, or 250 μm or less. In embodiments, glass-ceramic sheet embodiments can have a thickness T greater than or equal to 200 μm and less than or equal to 5 mm, greater than or equal to 500 μm and less than or equal to 5 mm, greater than or equal to 200 μm and less than or equal to 4 mm, greater than or equal to 200 μm and less than or equal to 2 mm, greater than or equal to 400 μm and less than or equal to 5 mm, or greater than or equal to 400 μm and less than or equal to 2 mm. It should be understood that the thickness of the precursor glass or glass-ceramic article can be within a subrange formed by any and all of the aforementioned endpoints. Alternatively, the glass sheet can be thicker than 10 mm, for example, for use in certain armored windows or other applications. Or, for example, containers and tubes containing the glass or glass-ceramic disclosed herein can have such a thickness as their wall thickness, and rods, spheres, and other articles containing the glass or glass-ceramic disclosed herein can have similar thicknesses.

In embodiments, the precursor glass or glass-ceramic composition described herein is ion-exchangeable to facilitate the strengthening of the precursor glass or glass-ceramic. In a typical ion exchange process, smaller metal ions in the glass-ceramic are replaced or “exchanged” by larger metal ions of the same valence state within a layer near the outer surface of the glass-ceramic. Replacing smaller ions with larger ions generates compressive stress within the glass-ceramic layer. In embodiments, the metal ions are monovalent metal ions (e.g., Li ⁺ , Na ⁺ , K ^+, etc.), and the ion exchange is accomplished by immersing the glass-ceramic in a bath of a molten salt containing at least one larger metal ion of the smaller metal ion to be replaced in the glass-ceramic. One or more ion exchange processes for strengthening glass-ceramics may include, but are not limited to, immersion in a single bath or multiple baths of similar or different compositions with washing and/or annealing steps between immersions. In embodiments, the glass-ceramic can be ion-exchanged by exposure to molten _KNO3 salt, molten _NaNO3 salt, or a mixture of molten salts containing _KNO3 and _NaNO3 . If _Na₂O is present in the precursor glass or glass-ceramic, the ion exchange of ^Na⁺ to ^K⁺ can occur in a _KNO₃ salt bath or a salt bath containing a combination of _KNO₃ and _NaNO₃ . If _Li₂O is present in the precursor glass or glass-ceramic, the ion exchange of ^Li⁺ to ^Na⁺ can occur in a _NaNO₃ salt bath or a salt bath containing a combination of _NaNO₃ and _KNO₃ . In an embodiment, the glass-ceramic can undergo ion exchange in a molten salt bath at a bath temperature greater than or equal to 350°C and less than or equal to 500°C. For example, but not limited to, glass-ceramics can be used at temperatures greater than or equal to 350°C and less than or equal to 530°C, greater than or equal to 375°C and less than or equal to 530°C, greater than or equal to 400°C and less than or equal to 530°C, greater than or equal to 425°C and less than or equal to 530°C, greater than or equal to 450°C and less than or equal to 530°C, greater than or equal to 475°C and less than or equal to 530°C, greater than or equal to 500°C and less than or equal to 530°C, greater than or equal to 350°C and less than or equal to 500°C, greater than or equal to 375°C and less than or equal to 500°C, greater than or equal to 4... Ion exchange can be performed at bath temperatures ranging from 00°C to less than or equal to 500°C, greater than or equal to 425°C to less than or equal to 500°C, greater than or equal to 450°C to less than or equal to 500°C, greater than or equal to 475°C to less than or equal to 500°C, greater than or equal to 350°C to less than or equal to 475°C, greater than or equal to 350°C to less than or equal to 450°C, greater than or equal to 350°C to less than or equal to 425°C, greater than or equal to 350°C to less than or equal to 400°C, and greater than or equal to 350°C to less than or equal to 375°C, or any and all subranges formed by any of these endpoints. The ion exchange time can be greater than or equal to 1 hour to less than or equal to 48 hours. In embodiments, the ion exchange process can create a surface compression layer in the glass precursor or glass-ceramic composition. Compared to non-ion-exchanged materials, the formation of this surface compression layer is beneficial for achieving better crack resistance and higher flexural strength. The surface-compression layer has a higher concentration of ions exchanged into the glass-ceramic product compared to the concentration of ions exchanged into the glass-ceramic product in the main body (i.e., excluding the surface-compression region).

In the embodiments, the precursor glass and/or glass-ceramic can undergo ion exchange to achieve a compression depth of about 30 μm or greater, about 40 μm or greater, about 50 μm or greater, about 60 μm or greater, about 70 μm or greater, about 80 μm or greater, about 90 μm or greater, or about 100 μm or greater. In the embodiments, the compression depth can be greater than or equal to 3%, greater than or equal to 5%, greater than or equal to 10%, greater than or equal to 15%, greater than or equal to 20%, or even greater than or equal to 22% of the thickness of the article formed from the precursor glass and/or glass-ceramic. Compared to non-ion-exchanged materials, the formation of this surface compression layer is advantageous for achieving better crack resistance and higher flexural strength. The surface compression layer has a higher concentration of ions exchanged into the precursor glass and/or glass-ceramic article compared to the concentration of ions exchanged into the article in the bulk of the article (i.e., excluding the surface compression area).

In this embodiment, the precursor glass and/or glass-ceramic are ion-exchanged to achieve a center tension greater than or equal to 10 MPa. In this embodiment, the center tension can be greater than or equal to 10 MPa and less than or equal to 200 MPa, greater than or equal to 20 MPa and less than or equal to 200 MPa, greater than or equal to 30 MPa and less than or equal to 200 MPa, greater than or equal to 40 MPa and less than or equal to 200 MPa, greater than or equal to 50 MPa and less than or equal to 200 MPa, greater than or equal to 60 MPa and less than or equal to 200 MPa, greater than or equal to 70 MPa and less than or equal to 200 MPa, greater than or equal to 80 MPa and less than or equal to 200 MPa, greater than or equal to 90 MPa and less than or equal to 200 MPa, greater than or equal to 100 MPa and less than or equal to 200 MPa. MPa, greater than or equal to 110 MPa and less than or equal to 200 MPa, greater than or equal to 120 MPa and less than or equal to 200 MPa, greater than or equal to 130 MPa and less than or equal to 200 MPa, greater than or equal to 140 MPa and less than or equal to 200 MPa, greater than or equal to 150 MPa and less than or equal to 200 MPa, greater than or equal to 160 MPa and less than or equal to 200 MPa, greater than or equal to 170 MPa and less than or equal to 200 MPa, greater than or equal to 180 MPa and less than or equal to 200 MPa, greater than or equal to 190 MPa and less than or equal to 200 MPa, or any and all subranges formed by any of these endpoints.

In the implementation scheme, the precursor glass or glass-ceramic may have a pressure range of ≥100 MPa to ≤1 GPa, ≥100 MPa to ≤950 MPa, ≥100 MPa to ≤900 MPa, ≥100 MPa to ≤850 MPa, ≥100 MPa to ≤800 MPa, ≥100 MPa to ≤750 MPa, ≥100 MPa to ≤700 MPa, ≥100 MPa to ≤650 MPa, ≥100 MPa to ≤600 MPa, ≥100 MPa to ≤550 MPa, or ≥100 MPa to ≤500 MPa. Pa, greater than or equal to 100 MPa to less than or equal to 450 MPa, greater than or equal to 100 MPa to less than or equal to 400 MPa, greater than or equal to 100 MPa to less than or equal to 350 MPa, greater than or equal to 100 MPa to less than or equal to 300 MPa, greater than or equal to 100 MPa to less than or equal to 250 MPa, greater than or equal to 100 MPa to less than or equal to 200 MPa, greater than or equal to 100 MPa to less than or equal to 150 MPa, 150 MPa to less than or equal to 500 MPa, greater than or equal to 150 MPa to less than or equal to 450 MPa, greater than or equal to 150 MPa to less than or equal to 400 MPa, greater than or equal to 150 MPa to less than or equal to 350 MPa, greater than or equal to 150 MPa to less than or equal to 300 MPa. 0 MPa, greater than or equal to 150 MPa to less than or equal to 250 MPa, greater than or equal to 150 MPa to less than or equal to 200 MPa, 200 MPa to less than or equal to 500 MPa, greater than or equal to 200 MPa to less than or equal to 450 MPa, greater than or equal to 200 MPa to less than or equal to 400 MPa, greater than or equal to 200 MPa to less than or equal to 350 MPa, greater than or equal to 200 MPa to less than or equal to 300 MPa, greater than or equal to 200 MPa to less than or equal to 250 MPa, 250 MPa to less than or equal to 500 MPa, greater than or equal to 250 MPa to less than or equal to 450 MPa, greater than or equal to 250 MPa to less than or equal to 400 MPa, greater than or equal to 250 MPa to less than or equal to 350 MPa a. Surface compressive stress within the range of 250 MPa to 300 MPa, 300 MPa to 500 MPa, 300 MPa to 450 MPa, 300 MPa to 400 MPa, 300 MPa to 350 MPa, 350 MPa to 500 MPa, 350 MPa to 450 MPa, 350 MPa to 400 MPa, 400 MPa to 500 MPa, 400 MPa to 450 MPa, 450 MPa to 500 MPa, or any and all subranges formed by any of these endpoints. In the implementation, the precursor glass or glass-ceramic may have a surface compressive stress of about 100 MPa or greater, about 150 MPa or greater, about 200 MPa or greater, about 250 MPa or greater, about 300 MPa or greater, about 350 MPa or greater, about 400 MPa or greater, about 450 MPa or greater, or about 500 MPa or greater.

In one embodiment, the process of manufacturing the glass-ceramic includes melting a batch of constituent components to form a precursor glass. The molten precursor glass can be poured into a mold. In another embodiment, the mold may contain steel. The precursor glass can be annealed. The precursor glass can be sliced into discs and then heat-treated to form the glass-ceramic.

Alternatively, the precursor glass described herein may be manufactured from molten precursor glass and formed into a sheet by processes including but not limited to slot drawing, float glass, rolling and other sheet forming processes known in the art.

In the embodiments, the glass-ceramic manufacturing process includes heat-treating (also referred to herein as “ceramization”) the precursor glass at one or more preselected temperatures for one or more preselected times to induce glass homogenization and crystallization (i.e., nucleation and growth) of one or more crystalline phases (e.g., having one or more compositions, amounts, morphologies, sizes, or size distributions). Throughout the heat treatment process, the one or more preselected temperatures may be less than 1500 K. It should be noted that the temperature may refer to a range of temperatures and is not necessarily a static, singular temperature. Similarly, it should be noted that crystal nucleation and/or growth may occur in successive or multiple discrete heat treatments, which together achieve the desired crystal growth. Without wishing to be bound by theory, nucleating agents may act as or form nucleation sites for the nucleation and growth of grains of crystalline phases, including the nucleation and growth of grains of crystalline phases having a jeffbenite crystalline structure. The nucleation sites are positioned and oriented within the precursor glass such that the resulting crystalline phase grains (including grains of the crystalline phase with a jeffbenite crystalline structure) are uniformly distributed throughout the resulting glass-ceramic and grow in a random orientation, thereby producing a glass-ceramic with isotropic material properties. In an embodiment, heat treatment may include heating the precursor glass in a heat treatment furnace at a rate of 1-10°C/min until the furnace reaches a first temperature. The first furnace temperature may be greater than or equal to 700°C and less than or equal to 950°C. In the implementation plan, the first temperature of the furnace can be greater than or equal to 700°C and less than or equal to 950°C, greater than or equal to 710°C and less than or equal to 950°C, greater than or equal to 730°C and less than or equal to 950°C, greater than or equal to 750°C and less than or equal to 950°C, greater than or equal to 770°C and less than or equal to 950°C, greater than or equal to 790°C and less than or equal to 950°C, greater than or equal to 810°C and less than or equal to 950°C, greater than or equal to 830°C and less than or equal to 950°C, greater than or equal to 850°C and less than or equal to 950°C, greater than or equal to 870°C and less than or equal to 950°C, greater than or equal to 890°C and less than or equal to 950°C, greater than or equal to 910°C and less than or equal to 950°C, greater than or equal to 930°C and less than or equal to 950°C. Or equal to 950°C, greater than or equal to 700°C and less than or equal to 930°C, greater than or equal to 700°C and less than or equal to 910°C, greater than or equal to 700°C and less than or equal to 890°C, greater than or equal to 700°C and less than or equal to 870°C, greater than or equal to 700°C and less than or equal to 850°C, greater than or equal to 700°C and less than or equal to 830°C, greater than or equal to 700°C and less than or equal to 810°C, greater than or equal to 700°C and less than or equal to 790°C, greater than or equal to 700°C and less than or equal to 770°C, greater than or equal to 700°C and less than or equal to 750°C, greater than or equal to 700°C and less than or equal to 730°C, greater than or equal to 700°C and less than or equal to 710°C, or any and all subranges formed by any of these endpoints. Unless otherwise specified, the temperature of heat treatment or ion exchange treatment refers to the temperature of the environment in which the article is exposed (such as the furnace used for heat treatment or the molten salt bath used for ion exchange treatment). In embodiments, the process of manufacturing glass-ceramics includes holding the precursor glass at a first temperature for a first time in the range of 0.25 hours to 6 hours. For example, but not limited to, the precursor glass may be held at the first temperature for greater than or equal to 0.25 hours to less than or equal to 6 hours, greater than or equal to 0.5 hours to less than or equal to 6 hours, greater than or equal to 0.75 hours to less than or equal to 6 hours, greater than or equal to 1 hour to less than or equal to 6 hours, greater than or equal to 1.25 hours to less than or equal to 6 hours, greater than or equal to 1.5 hours to less than or equal to 6 hours, greater than or equal to 1.75 hours to less than or equal to 6 hours, greater than or equal to 2 hours to less than or equal to 6 hours, greater than or equal to 2.25 hours to less than or equal to 6 hours, greater than or equal to 2.5 hours to less than or equal to 6 hours, greater than or equal to 2. 75 hours to less than or equal to 6 hours, greater than or equal to 3 hours to less than or equal to 6 hours, greater than or equal to 3.25 hours to less than or equal to 6 hours, greater than or equal to 3.5 hours to less than or equal to 6 hours, greater than or equal to 3.75 hours to less than or equal to 6 hours, greater than or equal to 4 hours to less than or equal to 6 hours, greater than or equal to 4.25 hours to less than or equal to 6 hours, greater than or equal to 4.5 hours to less than or equal to 6 hours, greater than or equal to 4.75 hours to less than or equal to 6 hours, greater than or equal to 5 hours to less than or equal to 6 hours, greater than or equal to 5.25 hours to less than or equal to 6 hours, greater than or equal to 5.5 hours to less than or equal to 6 hours, and more. The following are ranges: 5.75 hours or less than or equal to 6 hours; 0.25 hours or less than or equal to 5.75 hours; 0.25 hours or less than or equal to 5.5 hours; 0.25 hours or less than or equal to 5.25 hours; 0.25 hours or less than or equal to 5 hours; 0.25 hours or less than or equal to 4.75 hours; 0.25 hours or less than or equal to 4.5 hours; 0.25 hours or less than or equal to 4.25 hours; 0.25 hours or less than or equal to 4 hours; 0.25 hours or less than or equal to 3.75 hours; and so on. The first time period can be any and all sub-ranges formed by any of these endpoints, within the ranges of 0.25 hours to less than or equal to 3.5 hours, greater than or equal to 0.25 hours to less than or equal to 3.25 hours, greater than or equal to 0.25 hours to less than or equal to 3 hours, greater than or equal to 0.25 hours to less than or equal to 2.75 hours, greater than or equal to 0.25 hours to less than or equal to 2.5 hours, greater than or equal to 0.25 hours to less than or equal to 2.25 hours, greater than or equal to 0.25 hours to less than or equal to 1 hour, greater than or equal to 0.25 hours to less than or equal to 0.75 hours, and greater than or equal to 0.25 hours to less than or equal to 0.5 hours. In an embodiment, heat-treating the precursor glass in a heat treatment furnace at a first temperature for a first time can promote the nucleation and growth of the desired crystalline phase in the precursor glass to form a glass-ceramic. In other embodiments, heat-treating the precursor glass in a heat treatment furnace at a first temperature for a first time can promote the nucleation of the desired crystalline phase in the precursor glass, and performing a second heat treatment step to allow the nucleated crystalline phase in the precursor glass to grow to form a glass-ceramic.

For example, in one embodiment, the heat treatment may include a second step of heating the precursor glass in a heat treatment furnace at a rate of 1-10°C/min until the furnace reaches a second temperature. The second temperature may differ from the first temperature. The second temperature of the furnace may be greater than or equal to 750°C and less than or equal to 950°C. In another embodiment, the second temperature may be greater than or equal to 750°C and less than or equal to 950°C, greater than or equal to 770°C and less than or equal to 950°C, greater than or equal to 790°C and less than or equal to 950°C, greater than or equal to 810°C and less than or equal to 950°C, greater than or equal to 830°C and less than or equal to 950°C, greater than or equal to 850°C and less than or equal to 950°C, greater than or equal to 870°C and less than or equal to 950°C, greater than or equal to 890°C and less than or equal to 950°C, greater than or equal to 910°C and less than or equal to 950°C, greater than or equal to 930°C and less than or equal to 950°C, or greater than or equal to 930°C and less than or equal to 950°C. The temperature range is equal to 950°C, greater than or equal to 750°C but less than or equal to 930°C, greater than or equal to 750°C but less than or equal to 910°C, greater than or equal to 750°C but less than or equal to 890°C, greater than or equal to 750°C but less than or equal to 870°C, greater than or equal to 750°C but less than or equal to 850°C, greater than or equal to 750°C but less than or equal to 830°C, greater than or equal to 750°C but less than or equal to 810°C, greater than or equal to 750°C but less than or equal to 790°C, greater than or equal to 750°C but less than or equal to 770°C, or any and all subranges formed by any of these endpoints. In an embodiment, the process of manufacturing the glass-ceramic includes holding the precursor glass at the second temperature for a second time in the range of greater than or equal to 0.25 hours but less than or equal to 6 hours. For example, but not limited to, the precursor glass can be maintained at a second temperature for ≥0.25 hours to ≤6 hours, ≥0.5 hours to ≤6 hours, ≥0.75 hours to ≤6 hours, ≥1 hour to ≤6 hours, ≥1.25 hours to ≤6 hours, ≥1.5 hours to ≤6 hours, ≥1.75 hours to ≤6 hours, ≥2 hours to ≤6 hours, ≥2.25 hours to ≤6 hours, ≥2.5 hours to ≤6 hours, and ≥2... 75 hours to less than or equal to 6 hours, greater than or equal to 3 hours to less than or equal to 6 hours, greater than or equal to 3.25 hours to less than or equal to 6 hours, greater than or equal to 3.5 hours to less than or equal to 6 hours, greater than or equal to 3.75 hours to less than or equal to 6 hours, greater than or equal to 4 hours to less than or equal to 6 hours, greater than or equal to 4.25 hours to less than or equal to 6 hours, greater than or equal to 4.5 hours to less than or equal to 6 hours, greater than or equal to 4.75 hours to less than or equal to 6 hours, greater than or equal to 5 hours to less than or equal to 6 hours, greater than or equal to 5.25 hours to less than or equal to 6 hours, greater than or equal to 5.5 hours to less than or equal to 6 hours, and more. The following are ranges: 5.75 hours or less than or equal to 6 hours; 0.25 hours or less than or equal to 5.75 hours; 0.25 hours or less than or equal to 5.5 hours; 0.25 hours or less than or equal to 5.25 hours; 0.25 hours or less than or equal to 5 hours; 0.25 hours or less than or equal to 4.75 hours; 0.25 hours or less than or equal to 4.5 hours; 0.25 hours or less than or equal to 4.25 hours; 0.25 hours or less than or equal to 4 hours; 0.25 hours or less than or equal to 3.75 hours; and so on. A second time within the range of 0.25 hours to less than or equal to 3.5 hours, greater than or equal to 0.25 hours to less than or equal to 3.25 hours, greater than or equal to 0.25 hours to less than or equal to 3 hours, greater than or equal to 0.25 hours to less than or equal to 2.75 hours, greater than or equal to 0.25 hours to less than or equal to 2.5 hours, greater than or equal to 0.25 hours to less than or equal to 2.25 hours, greater than or equal to 0.25 hours to less than or equal to 1 hour, greater than or equal to 0.25 hours to less than or equal to 0.75 hours, greater than or equal to 0.25 hours to less than or equal to 0.5 hours, or any and all subranges formed by any of these endpoints. Heat treatment of a precursor glass having a nucleating crystalline phase at a second temperature in a heat treatment furnace for a second time will promote the growth of the desired crystalline phase in the precursor glass to form a glass-ceramic.

In the implementation scheme, heat treatment of the precursor glass may further include heating the precursor glass in a heat treatment furnace to one or more subsequent furnace temperatures, such as greater than or equal to 750°C to less than or equal to 950°C, and holding the precursor glass at each subsequent furnace temperature for a period of time, such as greater than or equal to 0.25 hours to less than or equal to 6 hours.

In one embodiment, the heat treatment of the precursor glass can be performed at ambient pressure. In another embodiment, the heat treatment of the precursor glass can be performed at ambient atmospheric pressure (e.g., 101.325 kPa). In yet another embodiment, the heat treatment of the precursor glass can be performed at approximately 100 kPa. In one or more embodiments, the heat treatment of the precursor glass can be performed at a pressure less than or equal to 15 GPa. For example, but not limited to, the heat treatment of the precursor glass can be performed at pressures less than or equal to 15 GPa, less than or equal to 10 GPa, less than or equal to 5 GPa, or less than or equal to 1 GPa. According to the method described herein, jeffbenite can be formed in glass-ceramic articles without requiring such pressure.

Following heat treatment (i.e., after nucleation and growth of the crystalline phase in the precursor glass), at least some grains of the crystalline phase having a Jeffbenite crystalline structure will overlap and interlock with each other within the residual glassy phase. The grains of the crystalline phase having a Jeffbenite crystalline structure may overlap and interlock with each other within the host glass-ceramic to the extent that the glass-ceramic has a fracture toughness as disclosed herein, such as about 0.75 MPa·m ^{^1/2} or other such values as disclosed herein. In other aspects of this disclosure, overlap and interlocking of the Jeffbenite crystalline structure occur within the host glass-ceramic, but not to the extent that such fracture toughness is provided. In yet another aspect, crystals with a Jeffbenite crystalline structure may be present, but so sparsely that they do not overlap or interlock with each other to any extent within the host glass-ceramic.

In the embodiments, the resulting glass-ceramic can be transparent, translucent, or opaque. In the embodiments, the glass-ceramic, with an article thickness of 0.85 mm, has an average transmittance of ≥85% for light in the wavelength range of about 400 nm to about 1,000 nm. In the embodiments, the glass-ceramic, with an article thickness of 0.85 mm, has an average transmittance of 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, or about 93% or greater for light in the wavelength range of about 400 nm to about 1,000 nm.

In this embodiment, the resulting glass-ceramic can be colored. Colored glass-ceramic articles may contain at least one colorant in a colorant package, the function of which is to impart the desired color to the glass-ceramic. The colorant package may contain at least one and _{/ or} a combination of Au, Ag, _Cr₂O₃ , transition metal oxides (e.g., CuO, _NiO , _Co₃O₄ , _TiO₂ , _Cr₂O₃ ), rare earth metal oxides (e.g., _CeO₂ ) as colorants in the colorant package, and the precursor glass or glass-ceramic may contain more than or equal to 1 x ^10⁻⁶ mol%, such as more than 0.0005 mol%, such as more than 0.001 mol%, such as more than or equal to 0.01 mol%, such as more than or equal to 0.1 mol%, such as more than or equal to 0.2 mol%, such as more than or equal to 0.01 mol%, and/or less than or equal to 10 mol% of colorant (i.e., the sum of all colorants in the colorant package), and in some cases less than 5 mol%, such as less than 2 mol%, such as less than 1 mol%, such as less than 0.5 mol%, such as less than 0.25 mol%. For example, yellow glass or glass-ceramics may contain rare earth metal oxides, such as greater than about 0.2 mol% and less than 1 mol _% ; black or gray glass may contain NiO and _Co3O4 in such amounts; green glass or glass-ceramics may similarly contain _{Cr2O3 ;} and pink, red, or orange glass or glass-ceramics may contain small amounts of gold, such as greater than 1 x ^10⁻⁶ mol% and less than 0.5 mol%, consistent with the disclosure of U.S. Application No. 17/691,813. Other colorants may also be used in such amounts, such as iron oxides for, for example, green or brown glass or glass-ceramics, manganese oxides for amber or purple, selenium for red, antimony for white, uranium for luminescent colors, copper for red, tin for white, lead for yellow, and other colorants. However, some such colorants, such as lead, antimony, and selenium, may not be as desirable as, for example, other colorants. Further oxidation-reduction of colorants, UV light treatment, and particulate matter can all contribute to the color of glass, and the applicant hereby incorporates in their entirety U.S. Application Nos. 63/433,060, 63/433,065, and 63/433,119, all filed December 16, 2022.

In the embodiments, the colored glass-ceramic can be formed into glass-ceramic sheets. The colored glass-ceramic can be semi-transparent (e.g., >1%, >5 ^% , >10% and/or <95%, <92%, <90%, <85%, <80%, <70%) at some, most and/or all frequencies in the visible spectrum (e.g., 4 × 10¹⁴ to 8 × ^10¹⁴ Hz; 380 to 750 nm wavelength) at the thicknesses disclosed herein. Furthermore, the total transmittance of the glass in at least one 10nm broadband (e.g., 380 to 390nm; 390 to 400nm; 385 to 395nm; and/or 740 to 750nm) of a sheet at a major thickness (e.g., about 1mm, about 0.6mm, about 0.8mm, about 1.2mm, about 1.6mm, about 2mm, where about means within 0.2mm in this context) is less than 90%, such as less than 85%, less than 80%, less than 70%, less than 60%, and/or less than 50%.

In the embodiments, the colored glass-ceramic can be opaque, such as a pure color that is substantially nontransmissive to visible light (e.g., white, black, forest green) (e.g., with a total transmittance of less than 1% between 380 and 750 nm wavelengths). The colored glass-ceramic can also be translucent at some, most, and/or all frequencies in the visible spectrum (e.g., 4 × ^10¹⁴ to 8 × ^10¹⁴ Hz; 380 to 750 nm wavelengths) at the thicknesses disclosed herein, such as having transmittance of >95%, >96%, and/or <100%.

In this implementation, the color of the glass-ceramic can be described using CIELAB color space coordinates L*, a*, and b*. In this implementation, the value of L* can be 0 to 100, 10 to 100, 20 to 100, 30 to 100, 40 to 100, 50 to 100, 60 to 100, 70 to 100, 80 to 100, 90 to 100, 0 to 90, 0 to 80, 0 to 70, 0 to 60, 0 to 50, 0 to 40, 0 to 30, 0 to 20, 0 to 10, or any and all subranges formed by these endpoints. In this implementation, the L* coordinate can be greater than or equal to 50, greater than or equal to 60, greater than or equal to 70, greater than or equal to 80, and less than or equal to 100. In the implementation scheme, the value of a* can be -128 to 128, -120 to 128, -110 to 128, -100 to 128, -90 to 128, -80 to 128, -70 to 128, -60 to 128, -50 to 128, -40 to 128, -30 to 128, -20 to 128, -10 to 128, 0 to 128, 10 to 128, 20 to 128, 30 to 128, 40 to 128, 50 to 128, 60 to 128, 70 to 128, 80 to 128, 90 to 128, 100 to 128, 110 to 128, 120 to 128, or any and all subranges formed by these endpoints. In the implementation scheme, the a* coordinate can be greater than or equal to -100, greater than or equal to -90, greater than or equal to -80, greater than or equal to -70, greater than or equal to -60, greater than or equal to -50, greater than or equal to -40, greater than or equal to -30, or greater than or equal to -20. In the implementation scheme, the a* coordinate can be less than or equal to 100, less than or equal to 90, less than or equal to 80, less than or equal to 70, less than or equal to 60, less than or equal to 50, less than or equal to 40, less than or equal to 30, or less than or equal to 20. In the implementation, the value of b* can be -128 to 128, -120 to 128, -110 to 128, -100 to 128, -90 to 128, -80 to 128, -70 to 128, -60 to 128, -50 to 128, -40 to 128, -30 to 128, -20 to 128, -10 to 128, 0 to 128, 10 to 128, 20 to 128, 30 to 128, 40 to 128, 50 to 128, 60 to 128, 70 to 128, 80 to 128, 90 to 128, 100 to 128, 110 to 128, 120 to 128, or any and all subranges formed by these endpoints. In the implementation scheme, the b* coordinate can be greater than or equal to -100, greater than or equal to -90, greater than or equal to -80, greater than or equal to -70, greater than or equal to -60, greater than or equal to -50, greater than or equal to -40, greater than or equal to -30, or greater than or equal to -20. In the implementation scheme, the b* coordinate can be less than or equal to 100, less than or equal to 90, less than or equal to 80, less than or equal to 70, less than or equal to 60, less than or equal to 50, less than or equal to 40, less than or equal to 30, or less than or equal to 20.

In one embodiment, the resulting glass-ceramic can have a density greater than or equal to 2.65 g/ ^cm³ to less than or equal to 2.95 g/ ^cm³ . In another embodiment, the resulting glass-ceramic can have a density greater than or equal to 2.50 g/ ^cm³ to less than or equal to 3.70 g/ ^cm³ . For example, but not limited to, glass-ceramics can have a molecular weight distribution of ≥2.50 g/ ^cm³ to ≤3.70 g/ ^cm³ , ≥2.55 g/ ^cm³ to ≤3.70 g/ ^cm³ , ≥2.60 g/ ^cm³ to ≤3.70 g/ ^cm³ , ≥2.65 g/ ^cm³ to ≤3.70 ^g / ^cm³ , ≥2.70 g/ ^cm³ to ≤3.70 g/cm³, ≥2.75 g/ ^cm³ to ≤3.70 g/ ^cm³ , ≥2.80 g/cm³ to ≤3.70, ≥2.85 ^{g/cm³ to} ≤3.70, and ≥2.90 g/cm³ to ≤3.70 g/ ^{cm³ .} 1. ≥3.00 g/ ^cm³ to ≤3.70 g/cm³; ^2. ≥3.10 g/cm³ to ≤3.70 g/cm³ ^{; 3. ≥3.20} g/cm³ to ≤3.70 g/ ^cm³ ; 3. ≥3.30 g/ ^cm³ to ≤3.70 g/cm³; ^3. ≥3.40 g/cm³ to ≤3.70 g/ ^{cm³; 3. ≥2.50} g/ ^cm³ to ≤3.60 g/cm³; ^3. ≥2.55 g/ ^cm³ to ≤3.60 g/cm³ ^{; 3. ≥2.60} g/ ^cm³ to ≤3.60 g/ ^cm³ ; 4. ≥2.65 g/ ^cm³ to ≤3.60 g/ ^cm³. 1. ≥2.70 g/ ^cm³ to ≤3.60 g/cm³; ^2. ≥2.75 g/cm³ to ≤3.60 g/cm³ ^{; 2.} ≥2.80 g/cm³ to ≤3.60 g/ ^cm³ ; 2. ≥2.85 ^g /cm³ to ≤3.60 g/cm³; 2. ≥2.90 g/cm³ to ≤3.60 g/cm³; ^{3. ≥3.00} g/cm³ to ≤3.60 g/ ^cm³ ; ^3. ≥3.10 g/ ^cm³ to ≤3.60 g/cm³; ^3. ≥3.20 g/cm³ to ≤3.60 g/cm³ ^{; 3. ≥3.30} g/cm³ to ≤3.60 g/cm³ ^{; 3.} ≥3.40 g/cm³ ³ to less than or equal to 3.60 g/ ^cm³ , ³ to greater than or equal to 2.65 g/cm³, ³ to less than or equal to 2.95 g/cm³, ³ to greater than or equal to 2.70 g/cm³, ³ to less than or equal to 2.95 g/ ^cm³ , ³ to greater than or equal to 2.75 g/cm³, ³ to less than or equal to 2.95 g/cm³, ³ to greater than or equal to 2.80 g/cm³, ³ to less than or equal to 2.95 g/cm³, ³ to greater than or equal to 2.85 g/cm³, ³ to less than or equal to 2.95 g/cm³, ³ to greater than or equal to 2.75 g/cm³, ³ to less than or equal to 2.90 g/cm³, ³ to greater than or equal to 2.75 g/cm³, ³ to less than or equal to 2.85 g/cm³, ³ to greater than or equal to 2.75 g/cm³. A density of ³ to less than or equal to 2.80 g/ ^cm³ , or any and all subranges formed by any of these endpoints. Without intending to be bound by theory, the presence of a crystalline phase with a jeffbenite crystalline structure in glass-ceramic articles may result in glass-ceramics with relatively high densities, taking into account the relatively light components of the glass-ceramic precursor.

In an embodiment, the resulting glass-ceramic may comprise a crystalline phase having a Jeffbenite crystalline structure. In an embodiment, at least some, or even most, grains of the crystalline phase having a Jeffbenite crystalline structure in the glass-ceramic may have dimensions smaller than the wavelength of visible light (e.g., measured from a slice/polished cut of the glass-ceramic, where "dimension" refers to a linear cross-sectional dimension measured from the outermost surface of the opposing faces of the grain along the surface of the slice/polished cut of the glass-ceramic through the geometric centroid of the grain, such as the longest cross-sectional dimension, the shortest cross-sectional dimension, the average cross-sectional dimension; unless otherwise stated, "dimension" in this context refers to the longest such cross-sectional dimension of a given grain; see grains shown in Figures 3-4, 6A-6F, and in general map 9). For example, but not limited to, at least some, or even most, grains of the crystalline phase having a Jeffbenite crystalline structure may have dimensions less than or equal to 500 nm, 400 nm, 350 nm, 300 nm, 250 nm, 200 nm, 150 nm, or even less than or equal to 100 nm. In the implementation scheme, at least some, or even most, grains of the crystalline phase having a Jeffbenite crystalline structure in the glass-ceramic may have a size greater than or equal to 20 nm or even greater than or equal to 30 nm. For example, but not limited to, at least some, or even most, grains of the crystalline phase having a Jeffbenite crystalline structure in the glass-ceramic may have a size greater than or equal to 20 nm and less than or equal to 100 nm, greater than or equal to 30 nm and less than or equal to 100 nm, greater than or equal to 40 nm and less than or equal to 100 nm, greater than or equal to 50 nm and less than or equal to 100 nm, greater than or equal to 60 nm and less than or equal to 100 nm, greater than or equal to 70 nm and less than or equal to 100 nm, greater than or equal to 80 nm and less than or equal to 100 nm, greater than or equal to 90 nm and less than or equal to 100 nm, greater than or equal to 20 nm and less than or equal to 90 nm, etc. The dimensions are 30 nm or equal to 90 nm, 20 nm or equal to 80 nm, 30 nm or equal to 80 nm, 20 nm or equal to 70 nm, 30 nm or equal to 70 nm, 20 nm or equal to 60 nm, 30 nm or equal to 60 nm, 20 nm or equal to 50 nm, 30 nm or equal to 50 nm, 20 nm or equal to 40 nm, or 30 nm or equal to 40 nm, or any and all subranges formed by any of these endpoints. In embodiments, at least some grains of the crystalline phase having a jeffbenite crystalline structure may be elongated. In embodiments, at least some grains of the crystalline phase having a jeffbenite crystalline structure may include needle-like or plate-like shapes. In embodiments, grains of the crystalline phase having a jeffbenite crystalline structure may include a bulk modulus of about 170 GPa. In an embodiment, the grains of the crystalline phase having a jeffbenite crystalline structure may include a hardness of about 1350 VHn.

In an embodiment, the resulting glass-ceramic may comprise a phase set, wherein at least some, or even most, grains of the crystalline phase in the phase set have a size smaller than the wavelength of visible light. For example, but not limited to, at least some, or even most, grains of the crystalline phase in the phase set may have a size less than or equal to 500 nm, 400 nm, 350 nm, 300 nm, 250 nm, 200 nm, 150 nm, or even less than or equal to 100 nm. In an embodiment, at least some, or even most, grains of the crystalline phase in the phase set may have a size greater than or equal to 20 nm or even greater than or equal to 30 nm. For example, but not limited to, at least some, or even most, grains of the crystalline phase in glass-ceramics may have a grain size greater than or equal to 20 nm and less than or equal to 100 nm, greater than or equal to 30 nm and less than or equal to 100 nm, greater than or equal to 40 nm and less than or equal to 100 nm, greater than or equal to 50 nm and less than or equal to 100 nm, greater than or equal to 60 nm and less than or equal to 100 nm, greater than or equal to 70 nm and less than or equal to 100 nm, greater than or equal to 80 nm and less than or equal to 100 nm, greater than or equal to 90 nm and less than or equal to 100 nm, greater than or equal to 20 nm and less than or equal to 90 nm, greater than or equal to 30 nm and less than or equal to 100 nm, or greater than or equal to 30 nm and less than or equal to 100 nm. Grain sizes less than or equal to 90 nm, greater than or equal to 20 nm to less than or equal to 80 nm, greater than or equal to 30 nm to less than or equal to 80 nm, greater than or equal to 20 nm to less than or equal to 70 nm, greater than or equal to 30 nm to less than or equal to 70 nm, greater than or equal to 20 nm to less than or equal to 60 nm, greater than or equal to 30 nm to less than or equal to 60 nm, greater than or equal to 20 nm to less than or equal to 50 nm, greater than or equal to 30 nm to less than or equal to 50 nm, greater than or equal to 20 nm to less than or equal to 40 nm, greater than or equal to 30 nm to less than or equal to 40 nm, or any and all subranges formed by any of these endpoints.

In one embodiment, the glass-ceramic can have an elastic modulus greater than or equal to 50 GPa and less than or equal to 200 GPa. In another embodiment, the glass-ceramic can have an elastic modulus greater than or equal to 50 GPa, greater than or equal to 80 GPa, greater than or equal to 90 GPa, or even greater than or equal to 100 GPa. In yet another embodiment, the glass-ceramic can have an elastic modulus less than or equal to 200 GPa or even less than or equal to 150 GPa. In the implementation, the glass-ceramic may have an elastic modulus greater than or equal to 50 GPa and less than or equal to 200 GPa, greater than or equal to 50 GPa and less than or equal to 175 GPa, greater than or equal to 60 GPa and less than or equal to 175 GPa, greater than or equal to 60 GPa and less than or equal to 150 GPa, greater than or equal to 70 GPa and less than or equal to 175 GPa, greater than or equal to 70 GPa and less than or equal to 150 GPa, greater than or equal to 80 GPa and less than or equal to 175 GPa, or even greater than or equal to 80 GPa and less than or equal to 150 GPa, or any and all subranges formed by any of these endpoints.

In the implementation scheme, the glass-ceramic exhibits fracture toughness of about 0.75 MPa·m ^1/2 or greater, about 0.85 MPa·m ^1/2 or greater, about 1.0 MPa·m ^1/2 or greater, about 1.1 ^MPa ·m ^1/2 or greater, 1.2 MPa·m ^1/2 or greater, 1.3 MPa·m ^1/2 or greater, 1.4 MPa·m ^1/2 or greater, 1.5 MPa·m ^1/2 or greater, 1.6 MPa·m ^1/2 or greater, 1.7 MPa·m 1/2 or greater, 1.8 MPa·m ^1/2 or greater, 1.9 MPa·m ^1/2 or greater, or about 2.0 MPa·m ^1/2 . In the implementation, the fracture toughness is in the range of greater than or equal to 0.75 MPa·m ^1/2 to less than or equal to 2 MPa·m ^1/2 , or any and all subranges formed by any of these endpoints.

In one or more embodiments, the glass-ceramic exhibits high crack resistance and scratch resistance by developing Vickers hardness. In some implementations, non-ion-exchanged glass-ceramics exhibit strengths of ≥600 kgf/ ^mm² to ≤1400 kgf/ ^mm² , ≥600 kgf/ ^mm² to ≤1300 kgf/ ^mm² , ≥600 kgf/ ^mm² to ≤1200 kgf/ ^mm² , ≥600 kgf/ ^mm² to ≤1100 kgf/ ^mm² , ≥600 kgf/ ^mm² to ≤1000 kgf/ ^mm² , ≥600 kgf/ ^mm² to ≤900 kgf/mm², ≥600 kgf/ ^mm² to ≤875 kgf/ ^mm² , ≥600 kgf/ ^mm² to ≤850 kgf/ ^mm² , and ≥600 kgf/mm² ^{. 2} to less than or equal to 825 kgf/ ^mm² , ² to less than or equal to 600 kgf/mm², ² to less than or equal to 800 kgf/mm², ² to less than or equal to 775 kgf/mm², ² to less than or equal to 600 kgf/ ^{mm², 2 to} less than or equal to 750 kgf/mm² ^{, 2} to less than or equal to 725 kgf/ ^mm² , ² to less than or equal to 600 kgf/mm², ² to less than or equal to 700 kgf/mm², ² to less than or equal to 900 kgf/mm², ² to less than or equal to 700 kgf/mm², ² to less than or equal to 875 kgf/ ^mm² , ² to less than or equal to 850 kgf/mm², ² to less than or equal to 700 kgf/mm² Vickers hardness is in the range of ² to less than or equal to 825 kgf/ ^mm² , or greater than or equal to 700 kgf/ ^mm² to less than or equal to 800 kgf/ ^mm² . In some embodiments, the Vickers hardness is 600 kgf/ ^mm² or higher, 625 kgf/ ^mm² or higher, 650 kgf/ ^mm² or higher, 675 kgf/ ^mm² or higher, 700 kgf/ ^mm² or higher, 725 kgf/ ^mm² or higher, 750 kgf/ ^mm² or higher, 775 kgf/ ^mm² or higher, 800 kgf/ ^mm² or higher, 825 kgf/ ^mm² or higher, 850 kgf/ ^mm² or higher, 875 kgf/ ^mm² or higher, or 900 kgf/ ^mm² or higher, or any and all subranges formed by any of these endpoints.

The resulting glass-ceramic can be supplied in sheet form and then reshaped or reformed into a bent or folded part of uniform thickness by pressing, blowing, bending, debossing, vacuum forming, or other means. Reshaping can be performed before heat treatment, or the forming step can also serve as a heat treatment step, with forming and heat treatment occurring substantially simultaneously.

The glass-ceramics and glass-ceramic articles described herein can be used in a variety of applications, including, for example, cover glass or glass backplate applications in consumer or commercial electronic devices (including, for example, LCD and LED displays, computer monitors, and ATMs); touchscreen or touch sensor applications; portable electronic devices, including, for example, mobile phones, personal media players, and tablet computers; integrated circuit applications, including, for example, semiconductor wafers; photovoltaic applications; architectural glass applications; automotive or vehicle glass applications; or commercial or household appliance applications. In embodiments, consumer electronic devices (e.g., smartphones, tablet computers, personal computers, ultrabooks, televisions, and cameras), architectural glass, and/or automotive glass may include glass articles as described herein.

Figures 1 and 2 illustrate an exemplary electronic device incorporating any glass-ceramic article disclosed herein. Specifically, Figures 1 and 2 illustrate a consumer electronic device 100 comprising a housing 102 having a front surface 104, a rear surface 106, and a side surface 108; electrical components (not shown) at least partially or completely within the housing and including at least a controller, memory, and a display 110 located at or adjacent to the front surface of the housing; and a cover substrate 112 located at or above the front surface of the housing such that it is above the display. In embodiments, at least a portion of at least one of the cover substrate 112 and the housing 102 may comprise any glass-ceramic article disclosed herein.

Referring now to Figures 8A and 8B, one embodiment of a glass-ceramic article 200 formed by glass-ceramic as described herein is illustrated. In this embodiment, the glass-ceramic article is in the form of a glass sheet and may include a body 201 disposed between opposing first surfaces 202 and second surfaces 204. The body 201 comprises or is substantially composed of glass-ceramic as described herein. The first surface 202 and the second surface 204 may be the main surfaces of the glass sheet facing away from each other. In this embodiment, the first surface 202 and the second surface 204 may be generally planar and spaced apart from each other by a thickness T defined between the first surface 202 and the second surface 204. The first surface 202 and the second surface 204 are defined by at least one edge surface 206, which forms a periphery that generally defines the shape of the glass-ceramic article 200. In the embodiment illustrated in Figures 8A and 8B, the glass-ceramic article is rectangular in shape and includes a length L and a width W. In this embodiment, the width W of the glass sheet is defined as the distance along the first surface 202 orthogonal to the thickness T and between opposing edges. The length L is defined as the distance along the first surface 202 orthogonal to the thickness T and the width W, and between opposing edges. In embodiments, the width W may be greater than or equal to the thickness T and the length L may be greater than or equal to the width W. However, it should be understood that other shapes of glass-ceramic articles are also contemplated and possible, including but not limited to squares, circles, and other regular or irregular geometries. For example, glass-ceramic articles may also include rods, fibers, spherical or near-spherical shapes, curved sheets, tubes, bowls, lenses, vials, bottles, or other containers.

In the embodiments, the thickness T of the glass-ceramic article 200 can be as described herein. The length L and width W of the glass-ceramic article can be selected according to the specific application using the glass-ceramic article 200. In the embodiments, the length L and width W of the glass-ceramic article can be greater than or equal to 5 mm, such as greater than or equal to 10 mm, greater than or equal to 15 mm, greater than or equal to 20 mm, greater than or equal to 25 mm, and greater than or equal to 30 mm. For example, but not limited to, the length L of the glass-ceramic article can be greater than or equal to 30 mm and less than or equal to 1 m, greater than or equal to 30 mm and less than or equal to 75 cm, greater than or equal to 30 mm and less than or equal to 50 cm, greater than or equal to 30 mm and less than or equal to 25 cm, greater than or equal to 30 mm and less than or equal to 20 cm, greater than or equal to 30 mm and less than or equal to 15 cm, greater than or equal to 30 mm and less than or equal to 10 cm, greater than or equal to 30 mm and less than or equal to 5 cm, or any and all subranges formed by any of these endpoints. The width W of the glass-ceramic article can be greater than or equal to 30 mm and less than or equal to 1 m, greater than or equal to 30 mm and less than or equal to 75 cm, greater than or equal to 30 mm and less than or equal to 50 cm, greater than or equal to 30 mm and less than or equal to 25 cm, greater than or equal to 30 mm and less than or equal to 20 cm, greater than or equal to 30 mm and less than or equal to 15 cm, greater than or equal to 30 mm and less than or equal to 10 cm, greater than or equal to 30 mm and less than or equal to 5 cm, or any and all sub-ranges formed by any of these endpoints. In embodiments where the glass-ceramic article is a glass sheet, as illustrated in Figures 8A and 8B, the surface of the glass sheet can have an area greater than or equal to 25 ^mm² . In embodiments where the glass-ceramic article is a glass sheet, the glass-ceramic in the body 201 of the glass sheet can have a volume greater than or equal to 25 ^mm³ .

In one embodiment, the body 201 of the glass-ceramic article 200, with an article thickness of 0.85 mm, has an average transmittance of at least 75% for light in the wavelength range of 400 nm to 800 nm (inclusive), making the glass-ceramic article transparent. In another embodiment, the body 201 of the glass-ceramic article 200, with an article thickness of 0.85 mm, has an average transmittance of greater than or equal to 20% and less than 75% for light in the wavelength range of 400 nm to 800 nm (inclusive), making the glass-ceramic article translucent. In yet another embodiment, when measured under normal incidence, the body of the glass-ceramic article has an average transmittance of less than 20% for light in the wavelength range of 400 nm to 800 nm (inclusive), with an article thickness of 0.85 mm, making the glass-ceramic article opaque. In one embodiment, the body 201 of the glass-ceramic article 200 is at least partially translucent, such that at least 20% of light with wavelengths of 400 nm to 800 nm directed into the article thickness is transmitted through the body.

Jeffbenite characterization method

In this implementation, glass-ceramic articles can be tested by X-ray diffraction to determine whether they contain the crystalline phase of jeffbenite, as described in detail herein. The following apparatus and software were used for the test: an X-ray diffractometer – a Bruker-AXSD8 Endeavor equipped with Cu radiation and a Lynx Eye detector, a Rocklabs Whisper series ring mill, backfill sample holders (Malvern Panalytical PW1770/10 powder sample preparation kit and PW18XX sample holder), 6”×6” weighing paper, glass slides, a spatula, and data analysis software (MDI Jade, Bruker Topas, and the Powder Diffraction File Database PDF-4).

The glass-ceramic sample is received as a small piece. The glass-ceramic block is crushed in a ring mill to obtain approximately 3 grams of glass-ceramic. The 3-gram glass-ceramic sample is then ground into a fine powder using a Rocklabs ring mill for approximately 30 seconds.

The PW18XX sample holder is filled with the fine powder as described herein. Clamp the sample holder ring onto the preparation stage. Spread the fine powder in the sample holder ring so that it accumulates in a conical shape within the ring. Use a glass slide to firmly press the powder into the holder ring. Use the slide to scrape any excess powder back into the holder ring. Additional fine powder may be added to fill the sample holder as needed. Repeat this process until a densely packed powder sample is obtained. Use the edge of a glass slide to remove any excess powder above the edge of the holder ring. Place the base plate onto the holder ring and clamp it in place. Remove the complete sample holder from the preparation stage and load it into the X-ray diffractometer.

Create a job file for the sample in the XRD Commander. This job file includes the sample's location in the X-ray diffractometer and the sample's identification information. After creating the job file, the X-ray diffractometer scans the sample.

After scanning the sample with an X-ray diffractometer, the data obtained from the X-ray diffractometer were analyzed using MDI Jade software. The file containing the data from the X-ray diffractometer was opened in MDI Jade. The "Phases" window was used to identify index peaks in the data. Table 1 lists the index peaks of at least some phases that may be present in glass-ceramics containing jeffbenite. The PDF number for each phase was entered into the "PDF Recall" field. Figure 14 illustrates the location of the PDF Recall field in the phase window of MDI Jade.

Table 1

Peak (Egypt) Mutually card number 6.2, 3.2, 2.7 Jeffbenite 69-138 2.95, 2.54, 1.81 <![CDATA[Sifang ZrO₂]]> 50-1089 3.87, 2.45 Magnesium olivine 34-189

For some phases, large solid solutions are possible. Lattice parameters can be scaled to match card data to sample data. To scale lattice parameters, select the phase name in the Phase tab, and then select the ascending size arrow on the right side of the main display. The arrow's position is shown in Figure 15. The lattice constraint can be increased and decreased using the left and right mouse buttons respectively.

The phases listed in Table 1 can be found in glass-ceramic samples containing jeffbenite. If unidentified peaks are present in the data, the PDF-4 database can be searched using the glass-ceramic composition and peak positions. After identifying all phases and adjusting the lattice to match the sample data, use the "Assign Phases" function on the "Peaks" tab. The software lists the peaks and finds the assigned phase for each peak. Some peaks may not have an assigned phase. This is illustrated by peak number 1 in the peak list shown in Figure 16. If a peak does not include an assigned phase, it is evaluated by instrumentation or a peak search algorithm to determine whether it is a true peak or an artifact. If the peak is a true peak, the PDF-4 database is searched manually to match the missing peak with the sample's chemical composition. While the automated search and matching program is powerful, high solid solutions in some glass-ceramic products can cause problems for the automated matching program. Therefore, the operator may have to perform the steps described above.

Rietveld analysis was performed using Topas to determine the lattice constant and cell volume. The file “Jeffbenite with hkl phase and ZrO2.pro” was opened in Topas. An initial refinement was run by clicking the red run arrow, as shown in Figure 17. The parameters were saved when the refinement converged. Then, the X-ray diffractometer scan data was loaded into Topas by clicking the filename at the top of the file tree in the left-hand window, selecting “Replace Scan Data”, navigating to the folder containing the data, and double-clicking the file containing the data. Figure 18 shows the location of “Replace Scan Data” in Topas. The file tree under the scan can be expanded so that all phases are visible. The model was set to represent the phase present in the current sample. This was done by clicking the phase in the file tree and then selecting or deselecting the “Use Phase” box in the structure window. The box was selected if the phase exists and deselected if the phase does not exist. The location of the “Use Phase” box is illustrated in Figure 19. If no matching structure for experimental Jeffbenite is found in the database, the Jeffbenite HKL phase is used in this step. The lattice parameters and cell volume of the Jeffbenite HKL phase are optimally matched and can be used to characterize Jeffbenite in the sample.

Once all structures and phases of the sample have been correctly identified, click the red run arrow, and Topas refines the analysis until it converges to a solution. After convergence, analyze the RwP values, difference plots, and modeled phase data. Figure 20 illustrates the RwP values, difference plots, and modeled phase data. The RwP value in the upper right window should be less than 5. The difference plot shows the curves between the experimental data and the modeled data (within the ellipse), as well as the bar charts for each phase. If peaks are present in the difference curves, a phase may be missing. If a phase is missing, repeat the phase identification steps of the analysis. Examine the modeled phase data to determine if each phase appears reasonable. Reasonable phases remain in the background, have no negative data points, and have peak widths that match the experimental data. If the modeled phase data appears unreasonable, the model may be trapped in a local minimum. If the model is trapped in a local minimum, restart the Rietveld analysis in Topas. If the RwP value, difference map, and modeled phase data are acceptable, then the lattice constraint and cell volume of the Jeffbenite are correct, and the lattice constraint and cell volume of the sample are recorded.

In embodiments, the glass-ceramic article may have lattice parameters corresponding to jeffbenite and indicating the presence of the jeffbenite crystalline phase in the glass-ceramic article. For example, in embodiments, the glass-ceramic article may have an "a" lattice parameter greater than or equal to and less than or equal to or even greater than or equal to and less than or equal to. In embodiments, the glass-ceramic article may have a "c" lattice parameter greater than or equal to and less than or equal to and less than or equal to and greater than or equal to and less than or equal to or even greater than or equal to 18.2 and less than or equal to. In embodiments, the glass-ceramic article may have lattice volumes greater than or equal to 775 ^ų and less than or equal to 825 ^ų , greater than or equal to 775 ^ų and less than or equal to 810 ^ų , greater than or equal to 790 ^ų and less than or equal to 825 ^ų , or even greater than or equal to 790 ^ų and less than or equal to 810 ^ų . In the implementation, the glass-ceramic article may have a peak position that is greater than or equal to and less than or equal to, greater than or equal to and less than or equal to, greater than or equal to and less than or equal to, or even greater than or equal to and less than or equal to.

In an embodiment, the glass-ceramic article may have an X-ray diffraction (XRD) spectrum corresponding to Jeffbenite and indicating the presence of a Jeffbenite crystalline phase in the glass-ceramic article. For example, in an embodiment, the glass-ceramic article may have an XRD spectrum including a first peak with a 2θ angle between 30° and 32°, a second peak with a 2θ angle between 33° and 35°, a third peak with a 2θ angle between 40° and 42°, and a fourth and fifth peak with a 2θ angle between 55° and 58°, wherein the first, second, third, fourth, and fifth peaks correspond to Jeffbenite.

Example

To make the various implementation schemes easier to understand, refer to the following examples, which are intended to illustrate the various glass-ceramic implementation schemes described herein.

Table 2 shows example precursor glass compositions AA-DH (in mol%).

Table 2

Table 2 (continued)

Table 2 (continued)

Table 2 (continued)

Table 2 (continued)

Table 2 (continued)

Table 2 (continued)

Table 2 (continued)

Table 2 (continued)

Table 2 (continued)

Table 2 (continued)

Table 2 (continued)

Table 2 (continued)

Individual samples are formed by melting a batch of constituent components to form a precursor glass with a specified composition. The molten precursor glass is then poured into a steel mold and cooled to form a disk. The disk of precursor glass is sliced and then heat-treated to form a glass-ceramic. The glass-ceramic sample is approximately 1 cm thick (unless otherwise specified).

The properties of the glass-ceramics were determined, including the crystalline phase, sample appearance, volume reduction (i.e., shrinkage) during crystallization, precursor glass density, glass-ceramic (GC) density, density increase (%), elastic modulus, shear modulus, Poisson's ratio, fracture toughness, and Vickers hardness. The crystalline phase of the glass-ceramics was determined using the "Jeffbenite characterization method" described above. Table 3-6 shows the ceramization schemes for achieving glass-ceramics GC1-GC97 and their respective properties.

When describing the appearance of the samples, the term "white" refers to white and opaque glass-ceramics. The term "opal" refers to white and slightly translucent glass-ceramics. The term "transparent opal" refers to white but more translucent glass-ceramics. Additionally, some samples listed in Tables 3-6 are transparent, such as glass-ceramics GC22 and GC23 formed from formulations CX and CY, as shown in Figure 30.

Table 3-6 includes several glass-ceramic samples containing Jeffbenite. Table 3-6 also includes comparative examples where the crystalline phase does not contain Jeffbenite. For example, some compositions in Table 3-6 (i.e., formulations AE, BI, BN, etc.) contain _ZrO2 as the crystalline phase and do not contain Jeffbenite.

Table 3

Table 3 (continued)

Table 3 (continued)

Table 3 (continued)

Table 3 (continued)

Table 4

Table 4 (continued)

Table 5

Table 5 (continued)

Table 5 (continued)

Table 6

Table 6 (continued)

Table 6 (continued)

Table 6 (continued)

Table 6 (continued)

Table 6 (continued)

Table 6 (continued)

Table 6 (continued)

The lattice parameters of the glass-ceramic formed from the precursor glass composition were determined according to the "Jeffbenite characterization method" described above. Table 7 shows the batch composition, ceramization scheme, corresponding glass-ceramic composition, and lattice parameters.

Table 7

XRD spectra of glass-ceramics were obtained according to the "Jeffbenite characterization method" described above. The figures contain XRD spectra of several glass-ceramic products. Figure 21 shows the XRD spectrum of glass-ceramic GC19 from Table 7. Figure 22 shows the XRD spectrum of glass-ceramic GC2 from Table 7. Figure 23 shows the XRD spectrum of glass-ceramics formed from the heat-treated composition AB as shown in Table 7. Figure 24 shows the XRD spectrum of glass-ceramic GC71 from Table 7. Figure 25 shows the XRD spectrum of glass-ceramic GC20 from Table 7. Figure 26 shows the XRD spectrum of glass-ceramic GC21 from Table 7. Figure 27 shows the XRD spectrum of glass-ceramic GC24 from Table 7.

Figure 28 shows the XRD pattern of glass-ceramic GC25 from Table 3. Figure 29 shows the XRD pattern of glass-ceramic GC26 from Table 3. Both glass-ceramic GC25 and GC26 in Table 3 contain _P₂O₅ , _which can improve the diffusion rate during the ion exchange process. The XRD patterns of glass-ceramic GC25 and GC26 in Table 3 illustrate that jeffbenite can be formed in glass- _ceramic articles containing _P₂O₅ .

Figure 3 illustrates the microstructure of glass-ceramic GC53. Figure 4 illustrates the microstructure of glass-ceramic GC4. Figure 3 also shows the _ZrO2 crystals (lighter colored area) in the glass-ceramic microstructure.

Samples of the glass-ceramic composition with ingredient composition AB were analyzed by high-temperature X-ray diffraction (XRD). Samples were held for one hour at each of the following temperatures: 800°C, 825°C, 850°C, 875°C, 900°C, 925°C, 950°C, 975°C, and 1000°C. XRD spectra of the samples were obtained during the last fifteen minutes of holding the samples at each specific temperature. The XRD spectra are plotted in Figure 5. The high-temperature XRD analysis indicated the stability range of various crystalline phases in the samples. As shown in Figure 5, the samples contained a crystalline phase with a jeffbenite crystalline structure and a tetragonal _ZrO₂ crystalline phase.

The surface of the glass-ceramic GC53 was observed using scanning electron microscopy (SEM). The sample appeared translucent. To enable SEM imaging, the sample surface was etched in 0.5% HF for 10 seconds. Then, a conductive carbon coating on the sample was evaporated to reduce its charge. SEM images of the sample surface were taken using a Hitachi SU70, 5kV scanning electron microscope. SEM images were obtained at magnifications ranging from 5K to 150K. Figures 6A-6F illustrate the sample surface. The magnification of the SEM micrographs increases from Figure 6A to Figure 6F. The grain size of the crystals in the sample was measured to be approximately 30 nm.

Referring now to Figure 7, a sample of the precursor glass composition of AP was heat-treated at 780°C for 4 hours and then at 850°C for 4 hours to form a glass-ceramic. The resulting glass-ceramic was then analyzed by X-ray diffraction, yielding the diffraction pattern shown in Figure 7. The X-ray diffraction pattern in Figure 7 shows that the composition in which a portion of MgO is replaced by ZnO (in this case, 21.5% of MgO is replaced by ZnO) can still result in the formation of a crystalline phase with a jeffbenite crystal structure without the formation of other crystalline phases during heat treatment.

Samples formed from an AA-based composition with a thickness of 0.6 mm were heat-treated at 725°C for 4 hours and then at 850°C for 4 hours to form a glass-ceramic. Samples formed from an AA-based composition with a thickness of 0.6 mm were heat-treated at 775°C for 4 hours and then at 850°C for 4 hours to form a glass-ceramic. The glass-ceramic samples were then ion-exchanged in a 100 wt% _KNO3 bath for 1 hour, 2 hours, 4 hours, 8 hours, 16 hours, and 32 hours. The samples were then analyzed to determine the changes in maximum surface compressive stress and maximum central tension with ion-exchange time. The results are reported in Table 8.

Table 8

As shown in Table 8, a maximum central tension of 187.08 MPa and a maximum surface compressive stress of 690.57 MPa were achieved with different ion exchange times, demonstrating that the stress distribution in glass-ceramics can be tailored to meet different performance criteria.

The transmittance of a glass-ceramic composition of AA, ceramized at 725°C for 4 hours and then at 850°C for 4 hours, was measured using the following procedure. Transmittance measurements were performed on a Lambda 950UV-Vis-NIR spectrophotometer manufactured by PerkinElmer Inc. (Waltham, Massachusetts, USA). In this embodiment, the spectrophotometer was configured with the following instrumentation: 150 mm integrating sphere; 2 nm data interval; detector switching at 860 nm (InGaAs to PMT); lamp switching at 340 nm; tungsten-halogen source; servo-controlled InGaAs spectral bandwidth; InGaAs gain 15; InGaAs averaging time 0.4 sec; PMT spectral bandwidth 3.5 nm; PMT averaging time 0.2 sec; dual-beam mode. For total transmittance (total Tx), the sample was fixed at the entrance point of the integrating sphere. For diffuse transmittance (diffuse Tx), the reference reflector above the sphere exit port was removed to allow coaxial light to exit the sphere and enter the optical trap. Zero-offset measurements of the diffuse portion were performed in the absence of a sample to determine the efficiency of the optical trap. To correct for the diffuse transmittance measurement, the zero-offset contribution was subtracted from the sample measurement using the following formula: Diffuse Tx = Diffuse Reflectance _Measurement - (Zero Offset * (Total Tx/100)). For all wavelengths, the scattering ratio was measured as follows: (%Diffuse Tx/%Total Tx). Axial transmittance was also measured. Axial transmittance was measured using coaxial light exiting the integrating sphere through the exit port. Figure 10 illustrates the total transmittance of the glass-ceramic of Example A. Figure 11 illustrates the diffuse transmittance of the glass-ceramic. Figure 12 illustrates the axial transmittance of the glass-ceramic, and Figure 13 illustrates the scattering ratio of the glass-ceramic.

The transmittance of five glass-ceramic products was measured using the procedure described above. Table 9 lists the ingredient composition, ceramization scheme, corresponding glass-ceramic composition, and thickness.

Table 9.

Figure 31 shows the total transmittance of each glass-ceramic in Table 9. Figure 32 shows the diffuse transmittance of each glass-ceramic in Table 9. Figure 33 shows the scattering ratio of each glass-ceramic in Table 9. The scattering ratio given in Figure 33 is calculated using the following formula: %scattering ratio = (%diffuse Tx / %total Tx) * 100.

The color coordinates of each glass-ceramic item listed in Table 9 were determined using the following procedure. Color measurements were performed on a Lambda 950UV-Vis-NIR spectrophotometer manufactured by PerkinElmer Inc. (Waltham, MA, USA), as previously described. Color coordinates are typically calculated using a weighted sum of the object's spectral transmittance, the human eye's "standard observer" spectral function, and the irradiator's power spectral distribution. The color coordinates of each sample were calculated based on transmittance data obtained using three irradiators (irradiator CIE D65, irradiator CIE A, and irradiator CIE F2). Measurements were performed using 2° and 10° observer angles and a wavelength range of 770 nm to 380 nm (intervals of 2 nm). The first set of color coordinates was calculated using the total transmittance data, and the second set was calculated using the diffuse transmittance data from each glass-ceramic item listed in Table 9. Color measurements using total transmittance are included in Table 10 below. Color measurements using diffuse transmittance are included in Table 11 below. Tables 10 and 11 include CIE L*A*B* color space data and CIE Yxy color space data.

Table 10. Colors calculated from total transmittance data

Table 11. Colors calculated from self-diffuse transmittance data

In addition to the foregoing embodiments and disclosures relating to glass-ceramics containing jeffbenite, as part of exploring the techniques for the currently disclosed precursor glass compositions and glass-ceramics formed therefrom, the following table provides additional compositions melted by the applicant as described herein, corresponding to the information disclosed herein and other samples disclosed and further described herein. These additional compositions are presented in mol% based on oxides and are listed in Table 12.

Table 12:

Table 12 (continued)

Table 12 (continued)

Table 12 (continued)

Table 12 (continued)

Table 12 (continued)

Table 12 (continued)

Table 12 (continued)

Table 12 (continued)

Table 12 (continued)

Table 12 (continued)

Table 12 (continued)

Table 12 (continued)

Table 12 (continued)

Table 12 (continued)

Table 12 (continued)

Table 12 (continued)

Table 12 (continued)

Table 12 (continued)

Table 12 (continued)

Table 12 (continued)

Table 12 (continued)

Table 12 (continued)

Table 12 (continued)

Table 12 (continued)

Table 12 (continued)

Table 12 (continued)

Table 12 (continued)

Table 12 (continued)

Table 12 (continued)

Table 12 (continued)

Table 12 (continued)

Table 12 (continued)

Table 12 (continued)

Table 12 (continued)

Table 12 (continued)

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Table 12 (continued)

Table 12 (continued)

Table 12 (continued)

Table 12 (continued)

Table 12 (continued)

Table 12 (continued)

Table 12 (continued)

It will be apparent to those skilled in the art that various modifications and variations can be made to the embodiments described herein without departing from the spirit and scope of the claimed subject matter. Therefore, this specification is intended to cover modifications and variations to the various embodiments described herein, provided that such modifications and variations fall within the scope of the appended claims and their equivalents.

The embodiments of the present invention also include:

Project 1. Glass-ceramics containing Jeffbenite.

Project 2. An article comprising:

Surface; and

The main body inside the surface,

The body comprises the glass-ceramic according to claim 1.

Item 3. The article of claim 2, wherein the surface is a first surface, the article further comprising a second surface facing away from the first surface, wherein the body is located between the first and second surfaces such that the article is a sheet.

Project 4. A method for manufacturing a material, the method comprising growing jeffbenite under pressure below 10 GPa.

Project 5. The method according to Project 4, wherein the growth is carried out at a temperature below 1400K.

Project 6. The method according to Project 4, wherein the jeffbenite is grown as a crystalline phase within the glass to form a glass-ceramic.

Item 7. A glass-ceramic article, said glass-ceramic article comprising:

First surface;

The second surface opposite to the first surface;

The periphery defining the shape of the glass-ceramic article; and

A phase set comprising one or more crystalline phases and a glassy phase, wherein the one or more crystalline phases include crystalline phases comprising a jeffbenite crystalline structure.

Item 8. The glass-ceramic article according to Item 7, wherein the crystalline phase comprising the crystalline structure of the jeffbenite is the main crystalline phase.

Item 9. A glass-ceramic article according to any one of Items 7 to 8, wherein the phase set comprises more than or equal to 25% by weight of the one or more crystalline phases and less than or equal to 75% by weight of the glass phase.

Item 10. A glass-ceramic article according to any one of Items 7 to 9, wherein at least some of the grains of the crystalline phase comprising the jeffbenite crystalline structure have a maximum size greater than or equal to 20 nm and less than or equal to 100 nm.

Item 11. A glass-ceramic article according to any one of Items 7 to 10, wherein the glass-ceramic article is substantially free of lithium.

Item 12. A glass-ceramic article according to any one of Items 7 to 11, wherein the crystalline phase comprising the jeffbenite crystalline structure has a composition according to the following formula:

(Mg,R ²⁺ ) _3+x (Zr,R ⁴⁺ ) _x Al _2-2x Si ₃ O ₁₂ ,

Where ^R²⁺ is a divalent metal cation, ^R⁴⁺ is a tetravalent metal cation, and x is greater than or equal to 0 and less than or equal to 1.

Item 13. The glass-ceramic article according to Item 12, wherein R2 ⁺ is one or more divalent metal cations selected from Ca2 ⁺ , Mn2 ⁺ , Fe2 ⁺ , and wherein R4 ⁺ is one or more tetravalent metal cations selected from Ti4 ⁺ , Sn4 ⁺ , Hf4 ⁺ .

Item 14. A glass-ceramic article according to any one of Items 7 to 13, wherein the glass-ceramic article has an average transmittance of at least 75% for light in the wavelength range of 400 nm to 800 nm at an article thickness of 0.6 mm.

Item 15. A glass-ceramic article, comprising, based on a mole percentage (mol%) of oxides, the glass-ceramic article:

_SiO2 with a content greater than or equal to 35 mol% and less than or equal to 65 mol%;

_Al₂O₃ with a content greater than or equal to 5 mol% and less than or equal to 20 mol% _;

MgO greater than or equal to 7 mol% and less than or equal to 65 mol%;

_ZrO2 with a content greater than or equal to 0 mol% and less than or equal to 7 mol%;

Greater than or equal to 0 mol% to less than or equal to 15 mol% _Na₂O ;

_K₂O with a concentration greater than or equal to 0 mol% and less than or equal to 15 mol%;

FeO greater than or equal to 0 mol% to less than or equal to 9 mol%;

_MnO₂ greater than or equal to 0 mol% and less than or equal to 10 mol%; and

ZnO with a content greater than or equal to 0 mol% and less than or equal to 15 mol%;

The glass-ceramic comprises a set of phases, the set of phases comprising one or more crystalline phases and a glassy phase, the one or more crystalline phases including a crystalline phase comprising a jeffbenite crystalline structure.

Item 16. The glass-ceramic article according to Item 15, wherein the glass-ceramic article further comprises less than or equal to 3 mol% _Li₂O .

Item 17. The glass-ceramic article according to Item 15, wherein the glass-ceramic article is substantially free of _Li₂O .

Item 18. A glass-ceramic article according to any one of items 15 to 17, wherein the glass-ceramic article contains more than or equal to 1.5 mol% to less than or equal to 3 mol% of _ZrO2 .

Item 19. A glass-ceramic article according to any one of Items 15 to 18, wherein the glass-ceramic article comprises more than 0 mol% to less than or equal to 12 mol% of _HfO2 , wherein the sum of _ZrO2 and _HfO2 is greater than 1 mol.

Item 20. A glass-ceramic article according to any one of items 15 to 19, wherein the glass-ceramic article contains more than 0 mol% to less than or equal to 15 mol% CaO.

Item 21. A glass-ceramic article according to any one of items 15 to 20, wherein the glass-ceramic article contains more than 0 mol% to less than or equal to 4 mol% _{of P₂O₅} .

Item 22. A glass-ceramic article according to any one of items 15 to 21, wherein the glass-ceramic article contains more than 0 mol% to less than or equal to 7 mol% _{of La₂O₃} .

Item 23. A glass-ceramic article according to any one of Items 15 to 22, wherein the concentration of _Na₂O (mol%) + _K₂O (mol%) is greater than or equal to 2 mol% and less than or equal to 15 mol%.

Item 24. A glass-ceramic article according to any one of Items 15 to 23, wherein the ratio of _Na₂O (mol%)/( _Na₂O (mol%) + _K₂O (mol%)) is greater than or equal to 0.2.

Item 25. A glass-ceramic article according to any one of items 15 to 24, wherein the glass-ceramic article further comprises 0.3 mol% to 7 mol% _TiO2 .

Item 26. A glass-ceramic article according to any one of Items 15 to 25, wherein the total amount of _ZrO₂ (mol%) + _TiO₂ (mol%) is greater than or equal to 2 mol%.

Item 27. A glass-ceramic article according to any one of Items 15 to 26, wherein _ZrO2 (mol%)/( _ZrO2 (mol%) + _TiO2 (mol%)) is greater than or equal to 0.3.

Item 28. A glass-ceramic article according to any one of items 15 to 27, wherein the glass-ceramic article contains more than or equal to 1 mol% to less than or equal to 12 mol% of ZnO.

Item 29. A glass-ceramic article according to any one of items 15 to 28, wherein the glass-ceramic article further comprises greater than or equal to 1 mol% to less than or equal to 8 mol% of BaO.

Item 30. A glass-ceramic article according to any one of items 15 to 29, wherein the glass-ceramic article further comprises at least one of CaO and SrO in an amount greater than or equal to 0.2 mol% to less than or equal to 1.7 mol%.

Item 31. A method for manufacturing glass-ceramic articles, the method comprising:

Heat treatment of a precursor glass comprising _SiO₂ , _Al₂O₃ , and _MgO to nucleate one or more crystalline phases in the precursor glass, wherein the one or more crystalline phases include crystalline phases comprising a jeffbenite crystalline structure; and

One or more crystalline phases are grown in a glassy phase.

Item 32. The method of manufacturing glass-ceramic articles according to Item 31, wherein the heat treatment comprises:

The precursor glass is heated in an environment of 700°C or higher to 950°C or lower; and

The precursor glass is held in the environment for a first period of time greater than or equal to 0.25 hours to less than or equal to 6 hours.

Item 33. The method for manufacturing glass-ceramic articles according to Item 32, wherein the heat treatment further comprises:

The precursor glass is heated in an environment of 750°C or higher to 950°C or lower; and

The precursor glass is held in the environment for a second time, from 0.25 hours to 6 hours.

Item 34. A glass-ceramic sheet, said glass-ceramic sheet comprising:

A first main surface and a second main surface opposite to the first main surface form the periphery of the first and second main surfaces and extend between the first and second main surfaces; wherein the thickness of the article is defined as the distance between the first and second main surfaces, the width of the article is defined as the distance orthogonal to the thickness and along the first main surface between the edges, and the length of the article is defined as the distance orthogonal to both the width and the thickness and along the first main surface between the edges;

The width is greater than or equal to the thickness;

Wherein the length is greater than or equal to the width; and

The body between the first main surface, the second main surface, and the edge, wherein the body comprises a glass-ceramic, and wherein the glass-ceramic comprises a crystalline phase having a jeffbenite crystalline structure.

Item 35. The glass-ceramic sheet according to Item 34, wherein the grains of the crystalline phase having the jeffbenite crystalline structure are uniformly distributed throughout the glass-ceramic body.

Item 36. The glass-ceramic sheet according to Item 34 or Item 35, wherein the grains of the crystalline phase having the jeffbenite crystalline structure are randomly oriented within the glass-ceramic body.

Item 37. A glass-ceramic sheet according to any one of Items 34 to 36, wherein the grains of the crystalline phase having the jeffbenite crystalline structure overlap and interlock with each other within the glass-ceramic body to such that its fracture toughness is 0.75 MPa·m ^1/2 or higher.

Item 38. A glass-ceramic sheet according to any one of Items 34 to 37, wherein the glass-ceramic has isotropic material properties.

Item 39. A glass-ceramic sheet according to any one of Items 34 to 38, wherein the thickness is greater than or equal to 200 μm and less than or equal to 5 mm, and wherein both the length and the width are greater than 5 mm.

Item 40. A method for manufacturing glass-ceramics, the method comprising:

Heat treatment involves a precursor glass containing nucleation sites to grow grains of a crystalline phase having a Jeffbenite crystal structure from the nucleation sites within the precursor glass, thereby forming a glass-ceramic comprising the crystalline phase having the Jeffbenite crystal structure and residual glass; and

During the heat treatment, grains of the crystalline phase having the jeffbenite crystalline structure are grown such that at least some grains of the crystalline phase having the jeffbenite crystalline structure have a size greater than or equal to 20 nm.

Item 41. The method according to Item 40, wherein the growth is carried out under atmospheric pressure.

Item 42. The method according to Item 40 or Item 41, wherein, after the growth, at least some grains of the crystalline phase having the jeffbenite crystalline structure have a size of less than or equal to 5 μm.

Item 43. A glass-ceramic article, said glass-ceramic article comprising:

A tetragonal stoichiometric crystal of pyrope-almandine garnet; and

An amorphous glass surrounds and encapsulates the crystal, such that the crystal and the glass together form the glass-ceramic of the glass-ceramic article.

Item 44. The glass-ceramic article according to Item 43, wherein the tetragonal structure falls within the I-42d space group.

Item 45. A glass-ceramic article, said glass-ceramic article comprising:

A lattice parameter of “a” that is greater than or equal to and less than or equal to.

The lattice parameter “c” that is greater than or equal to and less than or equal to; and

Includes the following X-ray diffraction patterns:

The first peak with an angle of 2θ between 30° and 32°;

The second peak at 2θ angle between 33° and 35°;

The third peak with a 2θ angle between 40° and 42°; and

The fourth and fifth peaks have a 2θ angle between 55° and 58°.

The first, second, third, fourth, and fifth peaks correspond to jeffbenite.

Claims (13)

1. A glass-ceramic material, comprising: Glass phase; and This includes crystalline phases containing the crystalline structure of jeffbenite. 2. The glass-ceramic according to claim 1, wherein at least some of the crystals comprising the jeffbenite crystalline structure have a composition according to the following formula: (Mg,R ²⁺ ) _3+x (Zr,R ⁴⁺ ) _x Al _2-2x Si ₃ O ₁₂ , Wherein, R2 ⁺ is a divalent metal cation, R4 ⁺ is a tetravalent metal cation, and x is greater than 0 and less than 1. 3. The glass-ceramic according to claim 2, wherein R2 ⁺ is selected from Ca2 ⁺ , Mn2 ⁺ and Fe2 ⁺ . 4. The glass-ceramic according to claim 3, wherein ^R⁴⁺ is selected from ^Ti⁴⁺ , ^Sn⁴⁺ and ^Hf⁴⁺ . 5. The glass-ceramic according to claim 1, wherein the crystal containing the jeffbenite crystal structure is the main crystalline phase of the glass-ceramic. 6. The glass-ceramic according to claim 1, wherein the glass-ceramic has a crystallinity of greater than or equal to 25% by weight and less than or equal to 75% by weight. 7. The glass-ceramic according to claim 1, wherein the glass-ceramic has an average transmittance of at least 75% for light in the wavelength range of 400 nm to 800 nm through a thickness of 0.6 mm. 8. The glass-ceramic article of claim 1, wherein the glass-ceramic article comprises, based on the mole percentage (mol%) of oxides: _SiO2 with a content greater than or equal to 35 mol% and less than or equal to 65 mol%; _Al₂O₃ with a content greater than or equal to 5 mol% and less than or equal to 20 mol% _; MgO greater than or equal to 7 mol% and less than or equal to 65 mol%; _ZrO₂ greater than 0 mol% to less than or equal to 7 mol%; Greater than or equal to 0 mol% to less than or equal to 15 mol% _Na₂O ; _K₂O with a concentration greater than or equal to 0 mol% and less than or equal to 15 mol%; FeO greater than or equal to 0 mol% to less than or equal to 9 mol%; _MnO₂ greater than or equal to 0 mol% and less than or equal to 10 mol%; and ZnO with a content greater than or equal to 0 mol% to less than or equal to 15 mol%. 9. The glass-ceramic according to claim 8, wherein the glass-ceramic further comprises less than or equal to 3 mol% _Li₂O . 10. The glass-ceramic of claim 9, wherein the glass-ceramic contains less than 0.05 mol% _Li₂O . 11. The glass-ceramic article of claim 8, wherein the glass-ceramic article contains greater than or equal to 1.5 mol% _ZrO2 . 12. A sheet comprising the glass-ceramic material of claim 1, said sheet comprising: A first main surface and a second main surface opposite to the first main surface form the periphery of the first and second main surfaces and extend between the first and second main surfaces; wherein the thickness of the article is defined as the distance between the first and second main surfaces, the width of the article is defined as the distance orthogonal to the thickness and along the first main surface between the edges, and the length of the article is defined as the distance orthogonal to both the width and the thickness and along the first main surface between the edges; The width is greater than or equal to the thickness; Wherein the length is greater than or equal to the width; and The body between the first main surface, the second main surface, and the edge. 13. The sheet according to claim 12, wherein the thickness is greater than or equal to 200 μm and less than or equal to 5 mm, and wherein both the length and width are greater than 5 mm.