Glass-based article having a bendable amorphous region

Abstract

A glass-based article having a first crystal-containing region, a second crystal-containing region, and a bendable amorphous region positioned between the first crystal-containing region and the second crystal-containing region. The glass-based article is a continuous glass-based article, and the bendable amorphous region is configured so that the glass-based article bends about the bendable amorphous region.

Description

Attorney Docket No.: SP23-216 GLASS-BASED ARTICLE HAVING A BENDABLE AMORPHOUS REGION BACKGROUND Cross-Reference To Related Applications

[0001] This application claims the benefit of priority under 35 U.S.C. § 119 of U.S. Provisional Application Serial No.63 / 530542 filed on August 3, 2023, the content of which is relied upon and incorporated herein by reference in its entirety. Field

[0002] The present specification generally relates to glass-based articles and, more specifically, to glass-based articles having two regions comprising an amorphous phase and a crystalline phase, and a bendable amorphous region positioned between the two regions comprising an amorphous phase and a crystalline phase. Technical Background

[0003] Consumer electronics devices, including handheld devices such as smart phones, tablets, electronic-book readers, and laptops often incorporate chemically strengthened glass articles for use as cover glass. Recently, it has been found that glass-ceramic articles may be desirable to use as cover glasses because of their improved mechanical properties, such as scratch and crack resistance, when compared to amorphous glass articles. However, these improved mechanical properties come at a cost of flexibility. Therefore, glass-ceramic articles are generally not usable as cover glass for bendable glasses, such as those used in foldable handheld devices.

[0004] Accordingly, a need exists for glass-based articles having an amorphous phase and a crystalline phase that are also bendable. SUMMARY

[0005] Aspect 1: A glass-based article comprising: a first crystal-containing region; a second crystal-containing region; and a bendable amorphous region positioned between the first crystal-containing region and the second crystal-containing region, wherein the glass-basedarticle is a continuous glass-based article, and the bendable amorphous region is configured so that the glass-based article bends about the bendable amorphous region.

[0006] Aspect 2: The glass-based article of aspect 1, wherein the bendable amorphous region is configured so that when a bending force is applied to one or more of the first crystal- containing region and the second crystal-containing region, the bendable amorphous region is in a bent position; and the first crystal-containing region and the second crystal-containing region are not bent.

[0007] Aspect 3: The glass-based article of any of the preceding aspects, wherein the bendable amorphous region comprises a first edge adjacent to the first crystal-containing region and a second edge adjacent to the second crystal-containing region, wherein the bendable amorphous region is configured so that: the first edge, the second edge, the first crystal-containing region, and the second crystal-containing region are planar to one another when the glass-based article is not bent, and the first crystal-containing layer and the second crystal-containing layer are not planar when the glass-based article is in a bent position.

[0008] Aspect 4: The glass-based article of aspect 3, wherein the bendable amorphous region is configured so that the first edge is planar to the first crystal-containing region and the second edge is planar to the second crystal-containing region when the glass-based article is in a bent position.

[0009] Aspect 5: The glass-based article of any one of aspects 3 or 4, wherein the bendable amorphous region is configured so that the first edge is adjacent to the second edge when the glass-based article is in a bent position.

[0010] Aspect 6: The glass-based article of any of the preceding aspects, wherein the glass- based article comprises more than one bendable amorphous region and more than two crystal- containing regions.

[0011] Aspect 7: The glass-based article of aspect 6, wherein a number of crystal-containing regions is n+1, where n is the number of amorphous bendable regions.

[0012] Aspect 8: The glass-based article of any of the preceding aspects, wherein the first crystal-containing region and the second crystal-containing region individually comprise greater than or equal to 75 wt.% and less than or equal to 95 wt.% crystalline phase.

[0013] Aspect 9: The glass-based article of any one of the preceding aspects, wherein the bendable amorphous region comprises up to 10 wt.% crystalline phase.

[0014] Aspect 10: The glass-based article of any one of the preceding aspects, wherein the bendable amorphous region comprises less than 1 wt.% crystalline phase.

[0015] Aspect 11: The glass-based article of any one of the preceding aspects, wherein the bendable amorphous region comprises 100 wt.% amorphous glass.

[0016] Aspect 12: The glass-based article of any one of aspects 1 to 10 wherein the bendable amorphous region comprises a crystal-containing layer on a surface of the bendable amorphous region.

[0017] Aspect 13: The glass-based article of any one of the preceding aspects, wherein the first crystal-containing region, the second crystal-containing region, and the bendable amorphous region have a uniform thickness.

[0018] Aspect 14: The glass-based article of any one of aspects 1 to 12, wherein a thickness of the bendable amorphous region is less than a thickness of at least one of the first crystal- containing region and the second crystal-containing region.

[0019] Aspect 15: The glass-based article of any one of the preceding aspects, wherein the bendable amorphous region has a ratio of compressive stress to Young’s modulus (CS / E) that is less than a CS / E of the first crystal-containing region and the second crystal-containing region.

[0020] Aspect 16: The glass-based article of any one of the preceding aspects, wherein the glass-based article comprises: greater than or equal to 65.00 wt.% and less than or equal to 80.00 wt.% SiO2; greater than 4.00 wt.% and less than or equal to 12.00 wt.% Al2O3; greater than or equal to 8.00 wt.% and less than or equal to 17.00 wt.% Li2O; greater than or equal to 4.00 wt.% and less than or equal to 15.00 wt.% ZrO2; and greater than or equal to 0.05 wt.% and less than or equal to 4.00 wt.% CaO.

[0021] Aspect 17: The glass-based article of any one of the preceding aspects, wherein the glass-based article comprises greater than or equal to 0.10 wt.% and less than or equal to 3.5 wt.% P2O5.

[0022] Aspect 18: The glass-based article of any one of the preceding aspects, wherein the glass-based article comprises metallic nucleating agents.

[0023] Aspect 19: The glass-based article of aspect 18, wherein the metallic nucleating agents are selected from the group consisting of cerium, antimony, silver, copper, gold, oxides thereof, and combinations thereof.

[0024] Aspect 20: The glass-based article of any one of the preceding aspects, wherein the glass-based article has a thickness that is greater than or equal to 0.1 mm and less than or equal to 2.0 mm.

[0025] Aspect 21: The glass-based article of any one of the preceding aspects, wherein the glass-based article has a thickness that is greater than or equal to 0.1 mm and less than or equal to 1.0 mm.

[0026] Aspect 22: The glass article of any one of the preceding aspects, comprising greater than or equal to 68.00 wt.% and less than or equal to 74.00 wt.% SiO2.

[0027] Aspect 23: The glass-based article of any one of the preceding aspects, comprising greater than 5.00 wt.% and less than or equal to 9.00 wt.% Al2O3.

[0028] Aspect 24: The glass-based article of any one of the preceding aspects, comprising greater than or equal to 1.00 wt.% and less than or equal to 3.00 wt.% P2O5.

[0029] Aspect 25: The glass-based article of any one of the preceding aspects, comprising greater than or equal to 9.00 wt.% and less than or equal to 14.00 wt.% Li2O.

[0030] Aspect 26: The glass-based article of any one of the preceding aspects, comprising greater than or equal to 4.50 wt.% and less than or equal to 8.00 wt.% ZrO2.

[0031] Aspect 27: The glass-based article of any one of the preceding aspects, comprising greater than or equal to 0.10 wt.% and less than or equal to 1.00 wt.% CaO.

[0032] Aspect 28: The glass-based article of any one of the preceding aspects, comprising greater than or equal to 0.01 wt.% and less than or equal to 0.5 wt.% SnO2.

[0033] Aspect 29: A strengthened glass-based article of any one of the preceding aspects, wherein the strengthened glass-based article has a compressive stress that is greater than or equal to 250 MPa and less than or equal to 400 MPa.

[0034] Aspect 30: A strengthened glass-based article of any one of preceding aspects, wherein the strengthened glass-based article has a compressive stress that is greater than or equal to 300 MPa and less than or equal to 400 MPa.

[0035] Aspect 31: A strengthened glass-based article of any one of preceding aspects, wherein the strengthened glass-based article has a central tension that is greater than or equal to 100 MPa and less than or equal to 170 MPa.

[0036] Aspect 32: A strengthened glass-based article of any one of preceding aspects, wherein the strengthened glass-based article has a central tension that is greater than or equal to 140 MPa and less than or equal to 170 MPa.

[0037] Aspect 33: A strengthened glass-based article of any one of the preceding aspects, wherein the strengthened glass-based article has a stored strain energy that is greater than or equal to 22 J / m2and less than or equal to 60 J / m2.

[0038] Aspect 34: A the strengthened glass-based article of any one of the preceding aspects, wherein the strengthened glass-based article has a fracture toughness that is greater than or equal to 1.0 MPa√m and less than or equal to 2.0 MPa√m.

[0039] Aspect 35: A strengthened glass-based article of any one of the preceding aspects, wherein the strengthened glass-based article has a haze less than 0.15 measured on a 0.6 mm thick glass-based article using a BYK Hazegard I Pro Setup.

[0040] Aspect 36: A strengthened glass-based article of any one of the preceding aspects, wherein the strengthened glass-based article has a density that is greater than or equal to 2.40 g / cm3and less than or equal to 2.60 g / cm3.

[0041] Aspect 37: A strengthened glass-based article of any one of the preceding aspects, wherein the strengthened glass-based article has a fracture strength measured on a glass-based article having a thickness of 0.6 mm using 80 grit sandpaper is greater than or equal to 350 MPa and less than or equal to 450 MPa.

[0042] Aspect 38: A strengthened glass-based article of any one of the preceding aspects, wherein the strengthened glass-based article has a fracture strength measured on a glass-based article having a thickness of 0.6 mm using 80 grit sandpaper is greater than or equal to 400 MPa and less than or equal to 450 MPa.

[0043] Aspect 39: A strengthened glass-based article of any one of the preceding aspects, wherein the strengthened glass-based article has: a maximum compressive stress greater than or equal to 300 MPa and less than or equal to 400 MPa; a maximum central tension from greater than or equal to 120 MPa and less than or equal to 170 MPa, and a fracture stress of greater than or equal to 450 MPa and less than or equal to 550 MPa measured on a strengthened glass-based article have a thickness of 0.6 mm.

[0044] Aspect 40: A method for forming a glass-based article comprising a first crystal- containing region, a second crystal-containing region, and a bendable amorphous region positioned between the first crystal-containing region and the second crystal-containing region, the method comprising: doping a glass composition with metallic dopants; applying a mask to a region of the glass-based article where the bendable amorphous region is to be formed; applying ultraviolet light to the masked glass-based article to form metal droplets in unmasked regions of the glass-based article; removing the mask; and ceramming the glass-based article to form crystal-containing regions where the metal droplets were formed.

[0045] Aspect 41: The method of aspect 40, wherein the metal dopants are selected from the group consisting of cerium, antimony, silver, copper, gold, oxides thereof, and combinations thereof.

[0046] Aspect 42: A method for forming a glass-based article comprising a first crystal- containing region, a second crystal-containing region, and a bendable amorphous region positioned between the first crystal-containing region and the second crystal-containing region, the method comprising: ceramming a glass-based article; and applying a focused energy source to a portion of the glass-based article where the bendable amorphous region is to be formed.

[0047] Aspect 43: A method for forming a glass-based article comprising a first crystal- containing region, a second crystal-containing region, and a bendable amorphous region positioned between the first crystal-containing region and the second crystal-containing region, the method comprising: applying a focused energy source to a glass-based article where the bendable amorphous region is to be formed; and ceramming the glass-based article.

[0048] Aspect 44: The method of any one of aspects 42 and 43, wherein the focused energy source is laser.

[0049] Aspect 45: The method of any one of aspects 42 to 44, wherein the focused energy source is a CW / QCW or diode laser.

[0050] Aspect 46: A method for forming a glass-based article comprising a first crystal- containing region, a second crystal-containing region, and a bendable amorphous region positioned between the first crystal-containing region and the second crystal-containing region, the method comprising: applying a mask to a portion of the glass-based article where the bendable amorphous region is to be formed; ion-exchanging the masked glass-based article; removing the mask; and creaming the ion-exchanged glass-based article.

[0051] Aspect 47: The method of aspect 46, wherein the glass-based article does not comprise lithium prior to the ion exchanging, and the glass-based article is ion-exchanged in a lithium- containing ion exchange bath.

[0052] Aspect 48: A method for forming a glass-based article comprising: heating a precursor glass composition to a nucleation temperature, wherein the nucleation temperature is greater than or equal to 550 °C and less than or equal to 650 °C; holding the precursor glass composition for a first duration in a temperature range that is greater than or equal to the nucleation temperature and less than or equal to 650 °C to form a nucleated precursor glass composition; heating the nucleated precursor glass composition to a growth temperature, wherein the growth temperature is greater than or equal to 680 °C and less than or equal to 800 °C; and holding the nucleated precursor glass composition for a second duration in a temperature range that is greater than or equal to the growth temperature and less than or equal to 800 °C to form the glass-based article.

[0053] Aspect 49: The method of aspect 48, wherein the first duration and the second duration are each greater than or equal to 1 minute to less than or equal to 240 minutes.

[0054] Aspect 50: The method of any one of aspects 48 or 49, wherein holding the precursor glass composition for a first duration in a temperature range that is greater than or equal to the nucleation temperature and less than or equal to 650 °C is an isothermal hold at the nucleation temperature for the first duration.

[0055] Aspect 51: The method of any one of aspects 48 to 50, wherein holding the nucleated precursor glass composition for a second duration in a temperature range that is greater than or equal to the growth temperature and less than or equal to 800 °C comprises an isothermal hold at the growth temperature for the second duration.

[0056] Aspect 52: The method of any one of aspects 48 to 51, wherein holding the precursor glass composition for a first duration in a temperature range that is greater than or equal to the nucleation temperature and less than or equal to 650 °C comprises heating the precursor glass composition from the nucleation temperature to a temperature that is less than or equal to 650 °C for the first duration.

[0057] Aspect 53: The method of any one of aspects 48 to 52, wherein holding the nucleated precursor glass composition for a second duration in a temperature range that is greater than or equal to the growth temperature and less than or equal to 800 °C comprises heating the nucleated precursor glass composition from the growth temperature to a temperature that is less than or equal to 800 °C for the second duration.

[0058] Aspect 54: The method of any one of aspects 48 to 53, wherein heating a precursor glass composition to a nucleation temperature, wherein the nucleation temperature is greater than or equal to 550 °C and less than or equal to 650 °C and heating the nucleated precursor glass composition to a growth temperature, wherein the growth temperature is greater than or equal to 680 °C and less than or equal to 800 °C comprises heating the precursor glass composition and the nucleated precursor glass composition is conducted at a heating rate that is greater than or equal to 0.1 °C / min and less than or equal to 50 °C / min.

[0059] Aspect 55: The method of any one of aspects 48 to 54, further comprising: exposing the glass-based article to an ion exchange medium comprising a molten potassium salt, a molten sodium salt, and a molten lithium salt to form a strengthened glass-based.

[0060] Aspect 56: The method of aspect 55, wherein the ion exchange medium comprises: greater than or equal to 50 wt.% and less than or equal to 70 wt.% KNO3; greater than or equal to 30 wt.% and less than or equal to 50 wt.% NaNO3; and greater than or equal to 0.05 wt.% and less than or equal to 0.15 wt.% LiNO3.

[0061] Aspect 57: The method of any one of aspects 55 or 56, wherein the ion exchange medium comprises greater than or equal to 0.08 wt.% and less than or equal to 0.12 wt.% LiNO3.

[0062] Aspect 58: The method of any one of aspects 55 to 57, wherein the ion exchange medium further comprises NaNO2 and silicic acid.

[0063] Aspect 59: The method of any one of aspects 55 to 58, wherein a temperature of the ion exchange medium during exposure to the glass-based is greater than or equal to 450 °C and less than or equal to 550 °C, and the glass-based is exposed to the ion exchange medium for a duration hat is greater than or equal to 1 hour and less than or equal to 16 hours.

[0064] Aspect 60: A method for forming a glass-based article comprising a first crystal- containing region, a second crystal-containing region, and a bendable amorphous region positioned between the first crystal-containing region and the second crystal-containing region, the method comprising: applying one or more masks to a portion of the glass-based article where the first crystal-containing region and the second crystal-containing region are to be formed; ion-exchanging the masked glass-based article; removing the one or more masks; and creaming the ion-exchanged glass-based article.

[0065] Aspect 61: The method of aspect 60, wherein the glass-based article comprises lithium prior to the ion exchanging, and the glass-based article is ion-exchanged in a potassium- containing ion exchange bath.

[0066] Additional features and advantages will be set forth in the detailed description, which follows, and in part will be readily apparent to those skilled in the art from that description or recognized by practicing the embodiments described herein, including the detailed description, which follows, the claims, as well as the appended drawings.

[0067] It is to be understood that both the foregoing general description and the following detailed description describe various embodiments and are intended to provide an overview or framework for understanding the nature and character of the claimed subject matter. The accompanying drawings are included to provide a further understanding of the various embodiments, and are incorporated into and constitute a part of this specification. The drawings illustrate the various embodiments described herein, and together with the description serve to explain the principles and operations of the claimed subject matter.BRIEF DESCRIPTION OF THE DRAWINGS

[0068] FIG.1A schematically depicts a top view of an unbent glass-based article according to embodiments disclosed and described herein;

[0069] FIG.1B schematically depicts a side view of an unbent glass-based article according to embodiments disclosed and described herein;

[0070] FIG. 1C schematically depicts a side view of a bent glass-based article according to embodiments disclosed and described herein;

[0071] FIG.2 is a flow chart of a ceramming process according to embodiments disclosed and described herein;

[0072] FIG.3 schematically depicts a cross-section of a chemically strengthened glass-based article according to embodiments disclosed and described herein;

[0073] FIG. 4 depicts a method for forming a glass-based article according to embodiments disclosed and described herein using metallic dopants;

[0074] FIG. 5A is a cross-section SEM image of a glass-based article that has been ion exchanged for 1 hour;

[0075] FIG. 5B is a cross-section SEM image of a glass-based article that has been ion exchanged for 2 hours;

[0076] FIG. 5C is a cross section SEM image of a glass-based article that has been ion exchanged for 6 hours;

[0077] FIG.6 is an image of a glass-based article with amorphous regions;

[0078] FIG.7 is an image showing a glass-based article with amorphous regions formed by a focused energy source;

[0079] FIG.8 is a schematic illustration of the retained strength model;

[0080] FIG. 9 is a residual stress profile showing compressive stress in MPa versus depth in microns;

[0081] FIG.10 is a graph showing retained strength for glass and glass-ceramics with strength in MPa versus depth in microns;

[0082] FIG.11 is a graph showing stress intensity factor as a function of flaw depth for glass and glass ceramics with a ratio of stress intensity factor / material toughness versus flaw depth in microns;

[0083] FIG. 12 is an image depicting Knoop Scratch Threshold results for a glass and glass ceramic;

[0084] FIG. 13A schematically depicts a front view of an electronic device incorporating a glass-based article according to embodiments disclosed and described herein; and

[0085] FIG.13B schematically depicts a perspective view of an electronic device incorporating a glass-based article according to embodiments disclosed and described herein. DETAILED DESCRIPTION

[0086] Beyond simply manipulating the strength of the material, this concept of a highly controlled and localized crystallization is very applicable to the nascent bendable glass industry. While the excellent retained strength of glass-ceramics would be very beneficial in this industry, the cerammed glass ceramic has several issues making it a challenge for the bendable glass industry. For example, to be bent to the tight radii required in today’s devices (bend radius in the range of 1 – 5 mm), the glass or glass ceramic article must be very thin to avoid failure due to biaxial flexure on bending (the tensile stress on bending drastically increases as the thickness of the article increases). Simply making a glass ceramic at that thickness is quite a challenge. If a part is thinned to the desired thickness and then cerammed, it will likely deform and have thickness variations that will act as stress concentrators on bending. If the part is cerammed first and then chemically thinned, differential etching rates between the glass matrix and the crystal phases will also make a uniform thickness challenging to achieve. Yet another aspect making this even more challenging is the fact that the required thickness for a given radius is set by the metric “CS / E” where CS is the compressive stress at the tensile surface and E is the Young’s Modulus of the material. Since glass-ceramics will generally have a lower CS / E vs. typical glasses, the final glass ceramic part would likely have to be even thinner than a comparable glass part for bending at a given radius. This thinner final article may sacrifice the benefit of using the glass ceramic in the first place. And, in additionto all these challenges, bending to these tight radii activates exceptionally small flaws as the source of failure (on the order of 100-200 nm). Therefore, any processing of the glass ceramics must not introduce these flaws in the bending region.

[0087] Description of a bendable glass-based article

[0088] With reference now to FIG. 1A - FIG. 1C, a glass-based article 100 according to embodiments disclosed and described herein will be described. FIG. 1A is a top view of an unfolded glass-based article 100 according to embodiments disclosed and described herein and includes a first crystal-containing region 110 and a second crystal-containing region 120 separated by a bendable amorphous region 130. In embodiments, the glass-based article 100 is a continuous article meaning that it does not included a laminated layers of glass and / or glass- based materials and the glass-based article 100 is not multiple articles adhered to one another. The first crystal-containing region 110 and the second crystal-containing region 120 comprise the majority of the glass-based article’s 100 surface. Accordingly, the majority of the glass- based article’s 100 surface area is a glass-ceramic material that has the improved mechanical properties of glass-ceramics, compared to amorphous glass.

[0089] FIG. 1B is a side view of an unbent class-based article according to embodiments disclosed and described herein. As seen in FIG.1B the first crystal-containing region 110 and the second crystal-containing region 120 are separated by the bendable amorphous region 130, such that a first edge 131 of the bendable amorphous region 130 is adjacent to the first crystal- containing region 110 and a second edge 132 of the bendable amorphous region 130 is adjacent to the second crystal-containing region. The first edge 131 of the bendable amorphous region 130 is opposite the second edge 132 of the bendable amorphous region 130 and are separated by the width w of the bendable amorphous region 130. As shown in FIG. 1B, the bendable amorphous regions extends through the thickness t of the glass-based article 100.

[0090] As shown in FIG.1C, which is a side view of a bent glass-based article (a glass-based article in a bent position) according to embodiments disclosed and described herein, the width w and the placement of the bendable amorphous region 130 between the first crystal-containing region 110 and the second crystal-containing region 120 are configured so that the glass-based article 100 can be bent along the bendable amorphous region 130 when a bending force is applied to the glass-based article, such that the first crystal-containing region 110 is opposite the second crystal-containing region 120. More particularly, as shown in the embodimentdepicted in FIG.1C, the bendable amorphous region 130 is bent such that the first edge 131 of the bendable amorphous region 130 is bent toward the second edge 132 of the bendable amorphous region 130 so that the first edge 131 of the bendable amorphous region 130 is adjacent to the second edge 132 of the bendable amorphous region 130 and the first crystal- containing region 110 and the second crystal-containing region 120 remain straight. Accordingly, the bendable amorphous region 130 is configured so that the first edge 131, the second edge 132, the first crystal-containing region 110, and the second crystal-containing region 120 are planar to one another when the glass-based article 100 is not bent, and the first crystal-containing layer 110 and the second crystal-containing layer 120 are not planar when the glass-based article 100 is in a bent position. However, the bendable amorphous region 130 is also configured so that the first edge 131 is planar to the first crystal-containing region 110 and the second edge 132 is planar to the second crystal-containing region 120 when the glass- based article 100 is in a bent position .It should be understood that the configuration shown in FIG.1B is for illustrative purposes only and other configurations are included in embodiments disclosed and described herein.

[0091] Having a combination of crystal-containing regions and a bendable amorphous regions allows for a glass-based article 100 to have a majority of its surface comprise the mechanical properties of a glass-ceramic while taking advantage of the improved bendability of amorphous glass by having the amorphous glass only in a region where bending is required. The width w of the bendable amorphous region 130 is not particularly limited so long as it is sufficient to allow the glass-based article 100 to bend to the desired degree without requiring either of the first crystal-containing region 110 or the second crystal-containing region 120 to bend.

[0092] In one or more embodiments, the glass-based article may comprise more than one bendable amorphous regions and more than two crystal-containing regions. In such embodiments the number of crystal-containing regions is n+1, where n is the number of amorphous bendable regions.

[0093] In one or more embodiments, the crystal-containing regions (used herein to refer to both the first crystal-containing region 110 and the second crystal-containing region 120) individually comprise greater than or equal to 75 wt.% and less than or equal to 95 wt.% crystalline phase, such as greater than or equal to 80 wt.% and less than or equal to 95 wt.% crystalline phase, greater than or equal to 85 wt.% and less than or equal to 95 wt.% crystalline phase, greater than or equal to 90 wt.% and less than or equal to 95 wt.% crystalline phase,greater than or equal to 80 wt.% and less than or equal to 90 wt.% crystalline phase, or greater than or equal to 80 wt.% and less than or equal to 85 wt.% crystalline phase.

[0094] The bendable amorphous region 130 may be 100 wt.% amorphous phase. However, in one or more embodiments, the bendable amorphous region 100 may include up to 10 wt.% crystalline phase, such as up to 8 wt.% crystalline phase, up to 6 wt.% crystalline phase, up to 4 wt.% crystalline phase, up to 2 wt.% crystalline phase, up to 1 wt.% crystalline phase, or less than 1 wt.% crystalline phase.

[0095] In embodiments, the glass-based article, including the first crystal-containing region, the second crystal-containing region, and the bendable amorphous region has a uniform thickness, such that the thickness of the first crystal-containing region and the second crystal- containing region are essentially the same as the thickness of the bendable amorphous region. It should be understood that “uniform thickness” does not take into account micro-scale surface undulations traditionally measure by BET as surface roughness. In addition, “uniform thickness” includes small variations in thickness that cannot be controlled despite best manufacturing practices, but does not include designed variations in thickness. In one or more embodiments, the bendable amorphous region has a thickness that is less than the thickness of one or both of the first crystal-containing region and the second crystal-containing region, which can provide improved bendability according to embodiments. However, having the thickness of the bendable amorphous region too small can result in failure of the glass-based article.

[0096] Composition of the glass-based article

[0097] The composition of glass-based articles according to embodiments disclosed and described herein will now be provided.

[0098] By way of example and not limitation, in various embodiments, the glass sheets may be formed from a glass composition including greater than or equal to 65 wt.% and less than or equal to 80 wt.% SiO2, greater than or equal to 4 wt.% and less than or equal to 12 wt.% Al2O3, greater than or equal to 0.10 wt.% and less than or equal to 3.5 wt.% P2O5, greater than or equal to 8 wt.% and less than or equal to 17 wt.% Li2O, greater than or equal to 4 and less than or equal to 15 wt.% ZrO2, and greater than or equal to 0.05 wt.% and less than or equal to 4 wt.% CaO. In embodiments, the glass composition may further include greater than 0 wt.%and less than or equal to 2 wt.% Na2O, greater than 0 wt.% and less than or equal to 2 wt.% K2O, greater than 0 wt.% and less than or equal to 1.5 wt.% Fe2O3, and combinations thereof.

[0099] SiO2, an oxide involved in the formation of glass, can function to stabilize the networking structure of glasses and glass-ceramics. In various glass compositions, the concentration of SiO2 should be sufficiently high in order to form petalite crystal phase when the glass sheet is heat treated to convert to a glass-ceramic. The amount of SiO2 may be limited to control the melting temperature of the glass, as the melting temperature of pure SiO2or high- SiO2 glasses is undesirably high. In embodiments, the glass-based articles composition comprises greater than or equal to 65 wt.% and less than or equal to 80 wt.% SiO2, greater than or equal to 70 wt.% and less than or equal to 80 wt.% SiO2, greater than or equal to 75 wt.% and less than or equal to 80 wt.% SiO2, greater than or equal to 65 wt.% and less than or equal to 75 wt.% SiO2, greater than or equal to 70 wt.% and less than or equal to 75 wt.% SiO2, or greater than or equal to 65 wt.% and less than or equal to 70 wt.% SiO2. It should be understood that the above ranges include all subranges within the explicitly disclosed ranges.

[0100] Al2O3 may also provide stabilization to the network and also provides improved mechanical properties and chemical durability. If the amount of Al2O3 is too high, however, the fraction of lithium silicate crystals may be decreased, possibly to the extent that an interlocking structure cannot be formed. The amount of Al2O3 can be tailored to control viscosity. Further, if the amount of Al2O3 is too high, the viscosity of the melt is also generally increased. In embodiments, the glass-based composition comprises greater than or equal to 4 wt.% and less than or equal to 12 wt.% Al2O3, greater than or equal to 6 wt.% and less than or equal to 12 wt.% Al2O3, greater than or equal to 8 wt.% and less than or equal to 12 wt.% Al2O3, greater than or equal to 10 wt.% and less than or equal to 12 wt.% Al2O3, greater than or equal to 4 wt.% and less than or equal to 10 wt.% Al2O3, greater than or equal to 6 wt.% and less than or equal to 10 wt.% Al2O3, greater than or equal to 8 wt.% and less than or equal to 10 wt.% Al2O3, greater than or equal to 4 wt.% and less than or equal to 8 wt.% Al2O3, greater than or equal to 6 wt.% and less than or equal to 8 wt.% Al2O3, or greater than or equal to 4 wt.% and less than or equal to 6 wt.% Al2O3. It should be understood that the above ranges include all subranges within the explicitly disclosed ranges.

[0101] In the glass-based herein, Li2O aids in forming both petalite and lithium silicate crystal phases. In fact, to obtain petalite and lithium silicate as the predominant crystal phases, it is desirable to have at least about 8 wt.% Li2O in the composition. Additionally, it has beenfound that once Li2O approaches about 17 wt.%), the composition becomes very fluid. Accordingly, in embodiments, the glass-based composition can comprise greater than or equal to 8 wt.% and less than or equal to 17 wt.% Li2O, greater than or equal to 10 wt.% and less than or equal to 17 wt.% Li2O, greater than or equal to 12 wt.% and less than or equal to 17 wt.% Li2O, greater than or equal to 14 wt.% and less than or equal to 17 wt.% Li2O, greater than or equal to 16 wt.% and less than or equal to 17 wt.% Li2O, greater than or equal to 8 wt.% and less than or equal to 16 wt.% Li2O, greater than or equal to 10 wt.% and less than or equal to 16 wt.% Li2O, greater than or equal to 12 wt.% and less than or equal to 16 wt.% Li2O, greater than or equal to 14 wt.% and less than or equal to 16 wt.% Li2O, greater than or equal to 8 wt.% and less than or equal to 14 wt.% Li2O, greater than or equal to 10 wt.% and less than or equal to 14 wt.% Li2O, greater than or equal to 12 wt.% and less than or equal to 14 wt.% Li2O, greater than or equal to 8 wt.% and less than or equal to 12 wt.% Li2O, greater than or equal to 10 wt.% and less than or equal to 12 wt.% Li2O, or greater than or equal to 8 wt.% and less than or equal to 10 wt.% Li2O. It should be understood that the above ranges include all subranges within the explicitly disclosed ranges.

[0102] As noted above, Li2O is generally useful for forming various glass-ceramics, but other alkali metal oxides tend to decrease glass-ceramic formation and form an aluminosilicate residual glass in the glass-ceramic. It has been found that more than about 5 wt.% Na2O or K2O, or combinations thereof, leads to an undesirable amount of residual glass, which can lead to deformation during crystallization and undesirable microstructures from a mechanical property perspective. The composition of the residual glass may be tailored to control viscosity during crystallization, minimizing deformation or undesirable thermal expansion, or control microstructure properties. Therefore, in general, the glass sheets may be made from glass compositions having low amounts of non-lithium alkali metal oxides. In embodiments, the glass-based composition can comprise from about 0 wt.% to about 5 wt.% R2O, wherein R is one or more of the alkali cations Na and K. In embodiments, the glass-based composition can comprise from about 1 wt.% to about 3 wt.% R2O, wherein R is one or more of the alkali cations Na and K. It should be understood that, in embodiments, the glass-based composition does not comprise R2O.

[0103] In embodiments, the glass-based composition comprise greater than 0 wt.% and less than or equal to 2 wt.% Na2O, greater than or equal to 1 wt.% and less than or equal to 2 wt.% Na2O, greater than 0 wt.% and less than or equal to 1 wt.% Na2O. In embodiments, the glass-based composition comprise greater than 0 wt.% and less than or equal to 2 wt.% K2O, greater than or equal to 1 wt.% and less than or equal to 2 wt.% K2O, greater than 0 wt.% and less than or equal to 1 wt.% K2O. It should be understood that the above ranges include all subranges within the explicitly disclosed ranges.

[0104] The glass-based compositions of embodiments may include P2O5. P2O5 can function as a nucleating agent to produce bulk nucleation. If the concentration of P2O5 is too low, the precursor glass does crystallize, but only at higher temperatures (due to a lower viscosity) and from the surface inward, yielding a weak and often deformed body. However, if the concentration of P2O5 is too high, the devitrification, upon cooling during the formation of the glass sheets, can be difficult to control. Embodiments of glass-based compositions comprise greater than or equal to 0.1 wt.% and less than or equal to 3.5 wt.% P2O5, greater than or equal to 0.5 wt.% and less than or equal to 3.5 wt.% P2O5, greater than or equal to 1.0 wt.% and less than or equal to 3.5 wt.% P2O5, greater than or equal to 1.5 wt.% and less than or equal to 3.5 wt.% P2O5, greater than or equal to 2.0 wt.% and less than or equal to 3.5 wt.% P2O5, greater than or equal to 2.5 wt.% and less than or equal to 3.5 wt.% P2O5, greater than or equal to 3.0 wt.% and less than or equal to 3.5 wt.% P2O5, greater than or equal to 0.1 wt.% and less than or equal to 3.0 wt.% P2O5, greater than or equal to 0.5 wt.% and less than or equal to 3.0 wt.% P2O5, greater than or equal to 1.0 wt.% and less than or equal to 3.0 wt.% P2O5, greater than or equal to 1.5 wt.% and less than or equal to 3.0 wt.% P2O5, greater than or equal to 2.0 wt.% and less than or equal to 3.0 wt.% P2O5, greater than or equal to 2.5 wt.% and less than or equal to 3.0 wt.% P2O5, greater than or equal to 0.1 wt.% and less than or equal to 2.5 wt.% P2O5, greater than or equal to 0.5 wt.% and less than or equal to 2.5 wt.% P2O5, greater than or equal to 1.0 wt.% and less than or equal to 2.5 wt.% P2O5, greater than or equal to 1.5 wt.% and less than or equal to 2.5 wt.% P2O5, greater than or equal to 2.0 wt.% and less than or equal to 2.5 wt.% P2O5, greater than or equal to 0.1 wt.% and less than or equal to 2.0 wt.% P2O5, greater than or equal to 0.5 wt.% and less than or equal to 2.0 wt.% P2O5, greater than or equal to 1.0 wt.% and less than or equal to 2.0 wt.% P2O5, greater than or equal to 1.5 wt.% and less than or equal to 2.0 wt.% P2O5, greater than or equal to 0.1 wt.% and less than or equal to 1.5 wt.% P2O5, greater than or equal to 0.5 wt.% and less than or equal to 1.5 wt.% P2O5, greater than or equal to 1.0 wt.% and less than or equal to 1.5 wt.% P2O5, greater than or equal to 0.1 wt.% and less than or equal to 1.0 wt.% P2O5, greater than or equal to 0.5 wt.% and less than or equal to 1.0 wt.% P2O5, or greater than or equal to 0.1 wt.% and less than or equal to 0.5 wt.% P2O5.It should be understood that the above ranges include all subranges within the explicitly disclosed ranges.

[0105] However, in embodiments, the glass-based composition may not include P2O5 and instead includes other, metallic nucleating agents in the place of P2O5. Such metallic nucleating agents include cerium, antimony, silver, copper, gold, oxides thereof, and combinations thereof. Embodiments of glass-based compositions comprise greater than or equal to 0.1 wt.% and less than or equal to 3.5 wt.% nucleating agents, greater than or equal to 0.5 wt.% and less than or equal to 3.5 wt.% nucleating agents, greater than or equal to 1.0 wt.% and less than or equal to 3.5 wt.% nucleating agents, greater than or equal to 1.5 wt.% and less than or equal to 3.5 wt.% nucleating agents, greater than or equal to 2.0 wt.% and less than or equal to 3.5 wt.% nucleating agents, greater than or equal to 2.5 wt.% and less than or equal to 3.5 wt.% nucleating agents, greater than or equal to 3.0 wt.% and less than or equal to 3.5 wt.% nucleating agents, greater than or equal to 0.1 wt.% and less than or equal to 3.0 wt.% nucleating agents, greater than or equal to 0.5 wt.% and less than or equal to 3.0 wt.% nucleating agents, greater than or equal to 1.0 wt.% and less than or equal to 3.0 wt.% nucleating agents, greater than or equal to 1.5 wt.% and less than or equal to 3.0 wt.% nucleating agents, greater than or equal to 2.0 wt.% and less than or equal to 3.0 wt.% nucleating agents, greater than or equal to 2.5 wt.% and less than or equal to 3.0 wt.% nucleating agents, greater than or equal to 0.1 wt.% and less than or equal to 2.5 wt.% nucleating agents, greater than or equal to 0.5 wt.% and less than or equal to 2.5 wt.% nucleating agents, greater than or equal to 1.0 wt.% and less than or equal to 2.5 wt.% nucleating agents, greater than or equal to 1.5 wt.% and less than or equal to 2.5 wt.% nucleating agents, greater than or equal to 2.0 wt.% and less than or equal to 2.5 wt.% nucleating agents, greater than or equal to 0.1 wt.% and less than or equal to 2.0 wt.% nucleating agents, greater than or equal to 0.5 wt.% and less than or equal to 2.0 wt.% nucleating agents, greater than or equal to 1.0 wt.% and less than or equal to 2.0 wt.% nucleating agents, greater than or equal to 1.5 wt.% and less than or equal to 2.0 wt.% nucleating agents, greater than or equal to 0.1 wt.% and less than or equal to 1.5 wt.% nucleating agents, greater than or equal to 0.5 wt.% and less than or equal to 1.5 wt.% nucleating agents, greater than or equal to 1.0 wt.% and less than or equal to 1.5 wt.% nucleating agents, greater than or equal to 0.1 wt.% and less than or equal to 1.0 wt.% nucleating agents, greater than or equal to 0.5 wt.% and less than or equal to 1.0 wt.% nucleating agents, or greater than or equal to 0.1 wt.% and less than or equal to 0.5 wt.%nucleating agents. It should be understood that the above ranges include all subranges within the explicitly disclosed ranges.

[0106] In various glass-based compositions, it is generally found that ZrO2 can improve the stability of Li2O—Al2O3—SiO2—P2O5glass by significantly reducing glass devitrification during forming and lowering liquidus temperature. At concentrations above 8 wt.%, ZrSiO4 can form a primary liquidus phase at a high temperature, which significantly lowers liquidus viscosity. Transparent glasses can be formed when the glass contains over 2 wt.% ZrO2. The addition of ZrO2 can also help decrease the petalite grain size, which aids in the formation of a transparent glass-ceramic. In embodiments, the glass-based composition comprises greater than or equal to 4 wt.% and less than or equal to 15 wt.% ZrO2, greater than or equal to 6 wt.% and less than or equal to 15 wt.% ZrO2, greater than or equal to 8 wt.% and less than or equal to 15 wt.% ZrO2, greater than or equal to 10 wt.% and less than or equal to 15 wt.% ZrO2, greater than or equal to 12 wt.% and less than or equal to 15 wt.% ZrO2, greater than or equal to 14 wt.% and less than or equal to 15 wt.% ZrO2, greater than or equal to 4 wt.% and less than or equal to 14 wt.% ZrO2, greater than or equal to 6 wt.% and less than or equal to 14 wt.% ZrO2, greater than or equal to 8 wt.% and less than or equal to 14 wt.% ZrO2, greater than or equal to 10 wt.% and less than or equal to 14 wt.% ZrO2, greater than or equal to 12 wt.% and less than or equal to 14 wt.% ZrO2, greater than or equal to 4 wt.% and less than or equal to 12 wt.% ZrO2, greater than or equal to 6 wt.% and less than or equal to 12 wt.% ZrO2, greater than or equal to 8 wt.% and less than or equal to 12 wt.% ZrO2, greater than or equal to 10 wt.% and less than or equal to 12 wt.% ZrO2, greater than or equal to 4 wt.% and less than or equal to 10 wt.% ZrO2, greater than or equal to 6 wt.% and less than or equal to 10 wt.% ZrO2, greater than or equal to 8 wt.% and less than or equal to 10 wt.% ZrO2, greater than or equal to 4 wt.% and less than or equal to 8 wt.% ZrO2, greater than or equal to 6 wt.% and less than or equal to 8 wt.% ZrO2, or greater than or equal to 4 wt.% and less than or equal to 6 wt.% ZrO2. It should be understood that the above ranges include all subranges within the explicitly disclosed ranges.

[0107] CaO can enter petalite crystals in a partial solid solution. In embodiments, the glass- based composition comprises greater than or equal to 0.05 wt.% and less than or equal to 4.0 wt.%, greater than or equal to 0.1 wt.% and less than or equal to 4.0 wt.%, greater than or equal to 0.5 wt.% and less than or equal to 4.0 wt.%, greater than or equal to 1.0 wt.% and less than or equal to 4.0 wt.%, greater than or equal to 1.5 wt.% and less than or equal to 4.0 wt.%,greater than or equal to 2.0 wt.% and less than or equal to 4.0 wt.%, greater than or equal to 2.5 wt.% and less than or equal to 4.0 wt.%, greater than or equal to 3.0 wt.% and less than or equal to 4.0 wt.%, greater than or equal to 3.5 wt.% and less than or equal to 4.0 wt.%, greater than or equal to 0.05 wt.% and less than or equal to 3.5 wt.%, greater than or equal to 0.1 wt.% and less than or equal to 3.5 wt.%, greater than or equal to 0.5 wt.% and less than or equal to 3.5 wt.%, greater than or equal to 1.0 wt.% and less than or equal to 3.5 wt.%, greater than or equal to 1.5 wt.% and less than or equal to 3.5 wt.%, greater than or equal to 2.0 wt.% and less than or equal to 3.5 wt.%, greater than or equal to 2.5 wt.% and less than or equal to 3.5 wt.%, greater than or equal to 3.0 wt.% and less than or equal to 3.5 wt.%, greater than or equal to 0.05 wt.% and less than or equal to 3.0 wt.%, greater than or equal to 0.1 wt.% and less than or equal to 3.0 wt.%, greater than or equal to 0.5 wt.% and less than or equal to 3.0 wt.%, greater than or equal to 1.0 wt.% and less than or equal to 3.0 wt.%, greater than or equal to 1.5 wt.% and less than or equal to 3.0 wt.%, greater than or equal to 2.0 wt.% and less than or equal to 3.0 wt.%, greater than or equal to 2.5 wt.% and less than or equal to 3.0 wt.%, greater than or equal to 0.05 wt.% and less than or equal to 2.5 wt.%, greater than or equal to 0.1 wt.% and less than or equal to 2.5 wt.%, greater than or equal to 0.5 wt.% and less than or equal to 2.5 wt.%, greater than or equal to 1.0 wt.% and less than or equal to 2.5 wt.%, greater than or equal to 1.5 wt.% and less than or equal to 2.5 wt.%, greater than or equal to 2.0 wt.% and less than or equal to 2.5 wt.%, greater than or equal to 0.05 wt.% and less than or equal to 2.0 wt.%, greater than or equal to 0.1 wt.% and less than or equal to 2.0 wt.%, greater than or equal to 0.5 wt.% and less than or equal to 2.0 wt.%, greater than or equal to 1.0 wt.% and less than or equal to 2.0 wt.%, greater than or equal to 1.5 wt.% and less than or equal to 2.0 wt.%, greater than or equal to 0.05 wt.% and less than or equal to 1.5 wt.%, greater than or equal to 0.1 wt.% and less than or equal to 1.5 wt.%, greater than or equal to 0.5 wt.% and less than or equal to 1.5 wt.%, greater than or equal to 1.0 wt.% and less than or equal to 1.5 wt.%, greater than or equal to 0.05 wt.% and less than or equal to 1.0 wt.%, greater than or equal to 0.1 wt.% and less than or equal to 1.0 wt.%, greater than or equal to 0.5 wt.% and less than or equal to 1.0 wt.%, greater than or equal to 0.05 wt.% and less than or equal to 0.5 wt.%, greater than or equal to 0.1 wt.% and less than or equal to 0.5 wt.%, or greater than or equal to 0.05 wt.% and less than or equal to 0.1 wt.%. It should be understood that the above ranges include all subranges within the explicitly disclosed ranges.

[0108] Fe2O3 can lower the melting point of the glass-based composition. However, adding too much Fe2O3 can alter the color of the glass-based composition. In embodiments, the glass-based composition does not comprise Fe2O3. In embodiments, the glass-based comprises greater than 0.0 wt.% and less than or equal to 1.5 wt.% Fe2O3, greater than or equal to 0.5 wt.% and less than or equal to 1.5 wt.% Fe2O3, greater than or equal to 1.0 wt.% and less than or equal to 1.5 wt.% Fe2O3, greater than 0.0 wt.% and less than or equal to 1.0 wt.% Fe2O3, greater than or equal to 0.5 wt.% and less than or equal to 1.0 wt.% Fe2O3, or greater than 0.0 wt.% and less than or equal to 0.5 wt.% Fe2O3. It should be understood that the above ranges include all subranges within the explicitly disclosed ranges.

[0109] In various embodiments, the glass-based composition may further include one or more constituents, such as, by way of example and not limitation, TiO2, CeO2, and SnO2. Additionally or alternatively, antimicrobial components may be added to the glass-based composition. Antimicrobial components that may be added to the glass-based composition may include, but are not limited to, Ag, AgO, Cu, CuO, Cu2O, and the like. In embodiments, the glass-based composition may further include a chemical fining agent. Such fining agents include, but are not limited to, SnO2, As2O3, Sb2O3, F, Cl, and Br. In embodiments, the glass- based articles includes greater than or equal to 0.01 wt.% and less than or equal to 0.5 wt.% SnO2. Additional details on glass-based compositions suitable for use in various embodiments may be found in, for example, U.S. Patent Application Publication No.2016 / 0102010 entitled “High Strength Glass-Ceramics Having Petalite and Lithium Silicate Structures,” filed October 8, 2015, which is incorporated by reference herein in its entirety.

[0110] Heat treatment for ceramming

[0111] The glass-based compositions may be cerammed to form portions in the glass-based article that have a crystalline phase and an amorphous phase (also referred to herein as “crystal- containing regions”). In embodiments, and as will be discussed in more detail below, the entire glass-based article may be cerammed so that the entire glass-based article comprises a combination of amorphous phases and crystalline phases. Subsequently, the bendable amorphous region may be formed by converting a portion of the glass based article comprising amorphous phases and crystalline phases to be almost entirely an amorphous phase. In other embodiments, and as will be described in more detail below, the bendable amorphous region is formed by not ceramming a portion of the glass-based article. Regardless of whether the entire glass-based article is cerammed and then a bendable amorphous region is produced or if a portion of the glass-based article is not cerammed to make the bendable amorphous region,the ceramming cycles described below can be used to ceram at least a portion of the glass- based article.

[0112] The processes for making glass-based articles according to embodiments includes heat treating the precursor glasses at two 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, etc.). These two temperatures may be referred to as the nucleation temperature and the growth temperature, respectively.

[0113] With reference now to FIG. 2, embodiments of methods for making glass ceramics 200 will generally be described. Initially, a precursor glass composition at 201 is heated to a nucleation temperature that is greater than or equal to 535 °C and less than or equal to 650 °C. The precursor glass at 202 is held for a first duration in a temperature range that is greater than or equal to the nucleation temperature and less than or equal to 650 °C to form a nucleated precursor glass composition. The nucleated precursor glass composition at 203 is heated to a growth temperature that is greater than or equal to 680 °C and less than or equal to 800 °C. The nucleated precursor glass composition at 204 is held for a second duration in a temperature range that is greater than or equal to the growth temperature and less than or equal to 800 °C to form the glass-based articles. In embodiments, the glass-based articles at 205 is exposed to an ion exchange medium comprising a molten potassium salt, a molten sodium salt, and a molten lithium salt to form a strengthened glass-based articles. Each of these steps will be described in more detail below.

[0114] In embodiments, the nucleation stage takes place when a precursor glass is held at the predetermined nucleation temperature for a predetermined duration. In embodiments, the nucleation temperature is greater than or equal to 550 °C and less than or equal to 650 °C, greater than or equal to 560 °C and less than or equal to 650 °C, greater than or equal to 570 °C and less than or equal to 650 °C, greater than or equal to 580 °C and less than or equal to 650 °C, greater than or equal to 590 °C and less than or equal to 650 °C, greater than or equal to 600 °C and less than or equal to 650 °C, greater than or equal to 610 °C and less than or equal to 650 °C, greater than or equal to 620 °C and less than or equal to 650 °C, greater than or equal to 630 °C and less than or equal to 650 °C, greater than or equal to 640 °C and less than or equal to 650 °C, greater than or equal to 550 °C and less than or equal to 640 °C, greater than or equal to 560 °C and less than or equal to 640 °C, greater than or equal to 570 °C andless than or equal to 640 °C, greater than or equal to 580 °C and less than or equal to 640 °C, greater than or equal to 590 °C and less than or equal to 640 °C, greater than or equal to 600 °C and less than or equal to 640 °C, greater than or equal to 610 °C and less than or equal to 640 °C, greater than or equal to 620 °C and less than or equal to 640 °C, greater than or equal to 630 °C and less than or equal to 640 °C, greater than or equal to 550 °C and less than or equal to 630 °C, greater than or equal to 560 °C and less than or equal to 630 °C, greater than or equal to 570 °C and less than or equal to 630 °C, greater than or equal to 580 °C and less than or equal to 630 °C, greater than or equal to 590 °C and less than or equal to 630 °C, greater than or equal to 600 °C and less than or equal to 630 °C, greater than or equal to 610 °C and less than or equal to 630 °C, greater than or equal to 620 °C and less than or equal to 630 °C, greater than or equal to 550 °C and less than or equal to 620 °C, greater than or equal to 560 °C and less than or equal to 620 °C, greater than or equal to 570 °C and less than or equal to 620 °C, greater than or equal to 580 °C and less than or equal to 620 °C, greater than or equal to 590 °C and less than or equal to 620 °C, greater than or equal to 600 °C and less than or equal to 620 °C, greater than or equal to 610 °C and less than or equal to 620 °C, greater than or equal to 550 °C and less than or equal to 610 °C, greater than or equal to 560 °C and less than or equal to 610 °C, greater than or equal to 570 °C and less than or equal to 610 °C, greater than or equal to 580 °C and less than or equal to 610 °C, greater than or equal to 590 °C and less than or equal to 610 °C, greater than or equal to 600 °C and less than or equal to 610 °C, greater than or equal to 550 °C and less than or equal to 600 °C, greater than or equal to 560 °C and less than or equal to 600 °C, greater than or equal to 570 °C and less than or equal to 600 °C, greater than or equal to 580 °C and less than or equal to 600 °C, greater than or equal to 590 °C and less than or equal to 600 °C, greater than or equal to 550 °C and less than or equal to 590 °C, greater than or equal to 560 °C and less than or equal to 590 °C, greater than or equal to 570 °C and less than or equal to 590 °C, greater than or equal to 580 °C and less than or equal to 590 °C, greater than or equal to 550 °C and less than or equal to 580 °C, greater than or equal to 560 °C and less than or equal to 580 °C, greater than or equal to 570 °C and less than or equal to 580 °C, greater than or equal to 550 °C and less than or equal to 570 °C, greater than or equal to 560 °C and less than or equal to 570 °C, or greater than or equal to 550 °C and less than or equal to 560 °C. It should be understood that the above ranges include all subranges within the explicitly disclosed ranges.

[0115] In embodiments, the glass is held at the nucleation temperature for a duration that is greater than or equal to 1 minute to less than or equal to 240 minutes, greater than or equal to30 minutes to less than or equal to 240 minutes, greater than or equal to 60 minutes to less than or equal to 240 minutes, greater than or equal to 90 minutes to less than or equal to 240 minutes, greater than or equal to 120 minutes to less than or equal to 240 minutes, greater than or equal to 150 minutes to less than or equal to 240 minutes, greater than or equal to 180 minutes to less than or equal to 240 minutes, greater than or equal to 210 minutes to less than or equal to 240 minutes, greater than or equal to 1 minute to less than or equal to 210 minutes, greater than or equal to 30 minutes to less than or equal to 210 minutes, greater than or equal to 60 minutes to less than or equal to 210 minutes, greater than or equal to 90 minutes to less than or equal to 210 minutes, greater than or equal to 120 minutes to less than or equal to 210 minutes, greater than or equal to 150 minutes to less than or equal to 210 minutes, greater than or equal to 180 minutes to less than or equal to 210 minutes, greater than or equal to 1 minute to less than or equal to 180 minutes, greater than or equal to 30 minutes to less than or equal to 180 minutes, greater than or equal to 60 minutes to less than or equal to 180 minutes, greater than or equal to 90 minutes to less than or equal to 180 minutes, greater than or equal to 120 minutes to less than or equal to 180 minutes, greater than or equal to 150 minutes to less than or equal to 180 minutes, greater than or equal to 1 minute to less than or equal to 150 minutes, greater than or equal to 30 minutes to less than or equal to 150 minutes, greater than or equal to 60 minutes to less than or equal to 150 minutes, greater than or equal to 90 minutes to less than or equal to 150 minutes, greater than or equal to 120 minutes to less than or equal to 150 minutes, greater than or equal to 1 minute to less than or equal to 120 minutes, greater than or equal to 30 minutes to less than or equal to 120 minutes, greater than or equal to 60 minutes to less than or equal to 120 minutes, greater than or equal to 90 minutes to less than or equal to 120 minutes, greater than or equal to 1 minute to less than or equal to 90 minutes, greater than or equal to 30 minutes to less than or equal to 90 minutes, greater than or equal to 60 minutes to less than or equal to 90 minutes, greater than or equal to 1 minute to less than or equal to 60 minutes, greater than or equal to 30 minutes to less than or equal to 60 minutes, or greater than or equal to 1 minute to less than or equal to 30 minutes. It should be understood that the above ranges include all subranges within the explicitly disclosed ranges. After the nucleation stage, the precursor glass is referred to as a nucleated precursor glass.

[0116] The growth stage takes place when a nucleated precursor glass is held at the predetermined growth temperature for a predetermined duration. The growth temperature is, in embodiments, greater than the nucleation temperature. In embodiments, the growth temperature is greater than or equal to 680 °C and less than or equal to 800 °C, greater than orequal to 690 °C and less than or equal to 800 °C, greater than or equal to 700 °C and less than or equal to 800 °C, greater than or equal to 710 °C and less than or equal to 800 °C, greater than or equal to 720 °C and less than or equal to 800 °C, greater than or equal to 730 °C and less than or equal to 800 °C, greater than or equal to 740 °C and less than or equal to 800 °C, greater than or equal to 750 °C and less than or equal to 800 °C, greater than or equal to 760 °C and less than or equal to 800 °C, greater than or equal to 770 °C and less than or equal to 800 °C, greater than or equal to 780 °C and less than or equal to 800 °C, greater than or equal to 790 °C and less than or equal to 800 °C, greater than or equal to 680 °C and less than or equal to 790 °C, greater than or equal to 690 °C and less than or equal to 790 °C, greater than or equal to 700 °C and less than or equal to 790 °C, greater than or equal to 710 °C and less than or equal to 790 °C, greater than or equal to 720 °C and less than or equal to 790 °C, greater than or equal to 730 °C and less than or equal to 790 °C, greater than or equal to 740 °C and less than or equal to 790 °C, greater than or equal to 750 °C and less than or equal to 790 °C, greater than or equal to 760 °C and less than or equal to 790 °C, greater than or equal to 770 °C and less than or equal to 790 °C, greater than or equal to 780 °C and less than or equal to 790 °C, greater than or equal to 680 °C and less than or equal to 780 °C, greater than or equal to 690 °C and less than or equal to 780 °C, greater than or equal to 700 °C and less than or equal to 780 °C, greater than or equal to 710 °C and less than or equal to 780 °C, greater than or equal to 720 °C and less than or equal to 780 °C, greater than or equal to 730 °C and less than or equal to 780 °C, greater than or equal to 740 °C and less than or equal to 780 °C, greater than or equal to 750 °C and less than or equal to 780 °C, greater than or equal to 760 °C and less than or equal to 780 °C, greater than or equal to 770 °C and less than or equal to 780 °C, greater than or equal to 680 °C and less than or equal to 770 °C, greater than or equal to 690 °C and less than or equal to 770 °C, greater than or equal to 700 °C and less than or equal to 770 °C, greater than or equal to 710 °C and less than or equal to 770 °C, greater than or equal to 720 °C and less than or equal to 770 °C, greater than or equal to 730 °C and less than or equal to 770 °C, greater than or equal to 740 °C and less than or equal to 770 °C, greater than or equal to 750 °C and less than or equal to 770 °C, greater than or equal to 760 °C and less than or equal to 770 °C, greater than or equal to 680 °C and less than or equal to 760 °C, greater than or equal to 690 °C and less than or equal to 760 °C, greater than or equal to 700 °C and less than or equal to 760 °C, greater than or equal to 710 °C and less than or equal to 760 °C, greater than or equal to 720 °C and less than or equal to 760 °C, greater than or equal to 730 °C and less than or equal to 760 °C, greater than or equal to 740 °C and less than or equal to 760 °C, greater than or equal to 750 °C and less than or equal to 760 °C, greater than or equalto 680 °C and less than or equal to 750 °C, greater than or equal to 690 °C and less than or equal to 750 °C, greater than or equal to 700 °C and less than or equal to 750 °C, greater than or equal to 710 °C and less than or equal to 750 °C, greater than or equal to 720 °C and less than or equal to 750 °C, greater than or equal to 730 °C and less than or equal to 750 °C, greater than or equal to 740 °C and less than or equal to 750 °C, greater than or equal to 680 °C and less than or equal to 740 °C, greater than or equal to 690 °C and less than or equal to 740 °C, greater than or equal to 700 °C and less than or equal to 740 °C, greater than or equal to 710 °C and less than or equal to 740 °C, greater than or equal to 720 °C and less than or equal to 740 °C, greater than or equal to 730 °C and less than or equal to 740 °C, greater than or equal to 680 °C and less than or equal to 730 °C, greater than or equal to 690 °C and less than or equal to 730 °C, greater than or equal to 700 °C and less than or equal to 730 °C, greater than or equal to 710 °C and less than or equal to 730 °C, greater than or equal to 720 °C and less than or equal to 730 °C, greater than or equal to 680 °C and less than or equal to 720 °C, greater than or equal to 690 °C and less than or equal to 720 °C, greater than or equal to 700 °C and less than or equal to 720 °C, greater than or equal to 710 °C and less than or equal to 720 °C, greater than or equal to 680 °C and less than or equal to 710 °C, greater than or equal to 690 °C and less than or equal to 710 °C, greater than or equal to 700 °C and less than or equal to 710 °C, greater than or equal to 680 °C and less than or equal to 700 °C, greater than or equal to 690 °C and less than or equal to 700 °C, or greater than or equal to 680 °C and less than or equal to 690 °C. It should be understood that the above ranges include all subranges within the explicitly disclosed ranges.

[0117] In embodiments, the glass is held at the growth temperature for a duration that is greater than or equal to 1 minute to less than or equal to 240 minutes, greater than or equal to 30 minutes to less than or equal to 240 minutes, greater than or equal to 60 minutes to less than or equal to 240 minutes, greater than or equal to 90 minutes to less than or equal to 240 minutes, greater than or equal to 120 minutes to less than or equal to 240 minutes, greater than or equal to 150 minutes to less than or equal to 240 minutes, greater than or equal to 180 minutes to less than or equal to 240 minutes, greater than or equal to 210 minutes to less than or equal to 240 minutes, greater than or equal to 1 minute to less than or equal to 210 minutes, greater than or equal to 30 minutes to less than or equal to 210 minutes, greater than or equal to 60 minutes to less than or equal to 210 minutes, greater than or equal to 90 minutes to less than or equal to 210 minutes, greater than or equal to 120 minutes to less than or equal to 210 minutes, greater than or equal to 150 minutes to less than or equal to 210 minutes, greater than or equal to 180minutes to less than or equal to 210 minutes, greater than or equal to 1 minute to less than or equal to 180 minutes, greater than or equal to 30 minutes to less than or equal to 180 minutes, greater than or equal to 60 minutes to less than or equal to 180 minutes, greater than or equal to 90 minutes to less than or equal to 180 minutes, greater than or equal to 120 minutes to less than or equal to 180 minutes, greater than or equal to 150 minutes to less than or equal to 180 minutes, greater than or equal to 1 minute to less than or equal to 150 minutes, greater than or equal to 30 minutes to less than or equal to 150 minutes, greater than or equal to 60 minutes to less than or equal to 150 minutes, greater than or equal to 90 minutes to less than or equal to 150 minutes, greater than or equal to 120 minutes to less than or equal to 150 minutes, greater than or equal to 1 minute to less than or equal to 120 minutes, greater than or equal to 30 minutes to less than or equal to 120 minutes, greater than or equal to 60 minutes to less than or equal to 120 minutes, greater than or equal to 90 minutes to less than or equal to 120 minutes, greater than or equal to 1 minute to less than or equal to 90 minutes, greater than or equal to 30 minutes to less than or equal to 90 minutes, greater than or equal to 60 minutes to less than or equal to 90 minutes, greater than or equal to 1 minute to less than or equal to 60 minutes, greater than or equal to 30 minutes to less than or equal to 60 minutes, or greater than or equal to 1 minute to less than or equal to 30 minutes. It should be understood that the above ranges include all subranges within the explicitly disclosed ranges. The growth stage transitions the nucleated precursor glass into a glass-ceramic material.

[0118] A precursor glass article as disclosed and described herein held at the nucleation temperature and growth temperature for the durations disclosed and described herein will form a glass-based articles having a phase assemblage that is high in an amorphous glassy phase, petalite (LiAlSi4O10), and lithium disilicate (Li2Si2O5). The glass-based articles comprises less than 5 wt.%, such as less than 3 wt.%, of the sum of other crystalline phases (such as, but not limited to lithium metasilicate (Li2SiO3), virgilite (LixAlxSi3-xO6), cristabolite (SiO2), Quartz (SiO2), zirconia (ZrO2), baddeleyite (ZrO2), spodumene (LiAlSi2O6), and lithium phosphate (Li3PO4)). This phase assemblage provides a glass-based articles that has low haze (high clarity) and improved mechanical properties compared to glass-based articles previously available.

[0119] It is believed that the nucleation and growth temperatures and durations disclosed and described herein are the heat treatments that primarily result in the desired phase assemblage in the glass-ceramic material. Therefore, additional heat treatments may beincluded before the nucleation stage, between the nucleation stage and the growth stage, and after the growth stage without causing significant deviation in the phase assemblage of the glass-ceramic material. These additional heat treatments include isothermal holds, heating at specific heating schedules including a number of differing heating rates, and combinations thereof.

[0120] Accordingly, in embodiments, there may be one of more additional temperature holds between the nucleation temperature and the growth temperature. Thus, in embodiments, after maintaining the precursor glass at the nucleation temperature, the article may be heated to one or more intermediate temperatures (wherein the intermediate temperatures are in a range between the nucleation temperature and the growth temperature) and held at the one or more intermediate temperatures for a predetermined time (for example, between 1 minute and 240 minutes and all ranges and subranges there between) and then heated to the growth temperature.

[0121] In embodiments, the nucleation stage comprises an isothermal hold at a single nucleation temperature for a duration. However, in other embodiments, the nucleation stage includes heating the precursor glass at one or more heating rates through the nucleation temperature range described herein (i.e., from greater than or equal to 550 °C to less than or equal to 650 °C). Likewise, in embodiments, the growth stage comprises an isothermal hold at a single growth temperature for a duration. However, in other embodiments, the growth stage includes heating or cooling the nucleated precursor glass at one or more heating rates within the growth temperature range described herein (i.e., from greater than or equal to 680 °C to less than or equal to 800 °C).

[0122] According to embodiments, heating rates used to heat from room temperature to the nucleation temperature, within the nucleation stage, between the nucleation stage and the growth stage, within the growth stage, and after the growth stage is greater than or equal to 0.1 °C / min and less than or equal to 50 °C / min, greater than or equal to 5 °C / min and less than or equal to 50 °C / min, greater than or equal to 10 °C / min and less than or equal to 50 °C / min, greater than or equal to 15 °C / min and less than or equal to 50 °C / min, greater than or equal to 20 °C / min and less than or equal to 50 °C / min, greater than or equal to 25 °C / min and less than or equal to 50 °C / min, greater than or equal to 30 °C / min and less than or equal to 50 °C / min, greater than or equal to 35 °C / min and less than or equal to 50 °C / min, greater than or equal to 40 °C / min and less than or equal to 50 °C / min, greater than or equal to 45 °C / min and less than or equal to 50 °C / min, greater than or equal to 0.1 °C / min and less than or equal to 45 °C / min,greater than or equal to 5 °C / min and less than or equal to 45 °C / min, greater than or equal to 10 °C / min and less than or equal to 45 °C / min, greater than or equal to 15 °C / min and less than or equal to 45 °C / min, greater than or equal to 20 °C / min and less than or equal to 45 °C / min, greater than or equal to 25 °C / min and less than or equal to 45 °C / min, greater than or equal to 30 °C / min and less than or equal to 45 °C / min, greater than or equal to 35 °C / min and less than or equal to 45 °C / min, greater than or equal to 40 °C / min and less than or equal to 45 °C / min, greater than or equal to 0.1 °C / min and less than or equal to 40 °C / min, greater than or equal to 5 °C / min and less than or equal to 40 °C / min, greater than or equal to 10 °C / min and less than or equal to 40 °C / min, greater than or equal to 15 °C / min and less than or equal to 40 °C / min, greater than or equal to 20 °C / min and less than or equal to 40 °C / min, greater than or equal to 25 °C / min and less than or equal to 40 °C / min, greater than or equal to 30 °C / min and less than or equal to 40 °C / min, greater than or equal to 35 °C / min and less than or equal to 40 °C / min, greater than or equal to 0.1 °C / min and less than or equal to 35 °C / min, greater than or equal to 5 °C / min and less than or equal to 35 °C / min, greater than or equal to 10 °C / min and less than or equal to 35 °C / min, greater than or equal to 15 °C / min and less than or equal to 35 °C / min, greater than or equal to 20 °C / min and less than or equal to 35 °C / min, greater than or equal to 25 °C / min and less than or equal to 35 °C / min, greater than or equal to 30 °C / min and less than or equal to 35 °C / min, greater than or equal to 0.1 °C / min and less than or equal to 30 °C / min, greater than or equal to 5 °C / min and less than or equal to 30 °C / min, greater than or equal to 10 °C / min and less than or equal to 30 °C / min, greater than or equal to 15 °C / min and less than or equal to 30 °C / min, greater than or equal to 20 °C / min and less than or equal to 30 °C / min, greater than or equal to 25 °C / min and less than or equal to 30 °C / min, greater than or equal to 0.1 °C / min and less than or equal to 25 °C / min, greater than or equal to 5 °C / min and less than or equal to 25 °C / min, greater than or equal to 10 °C / min and less than or equal to 25 °C / min, greater than or equal to 15 °C / min and less than or equal to 25 °C / min, greater than or equal to 20 °C / min and less than or equal to 25 °C / min, greater than or equal to 0.1 °C / min and less than or equal to 20 °C / min, greater than or equal to 5 °C / min and less than or equal to 20 °C / min, greater than or equal to 10 °C / min and less than or equal to 20 °C / min, greater than or equal to 15 °C / min and less than or equal to 20 °C / min, greater than or equal to 0.1 °C / min and less than or equal to 15 °C / min, greater than or equal to 5 °C / min and less than or equal to 15 °C / min, greater than or equal to 10 °C / min and less than or equal to 15 °C / min, greater than or equal to 0.1 °C / min and less than or equal to 10 °C / min, greater than or equal to 5 °C / min and less than or equal to 10 °C / min, or greater than or equal to 0.1 °C / min and less than or equal to 5 °C / min. It should be understood that theabove ranges include all subranges within the explicitly disclosed ranges. Such heating rates allow the proper amount of nucleation and crystal growth without damaging the glass-based article. If heating is done to quickly, the material may be damaged. However, if heating is done too slowly, proper nucleation and growth may not occur.

[0123] In embodiments, the glass-based article is cooled after being held at the growth temperature. In embodiments, the glass-based article may be cooled to room temperature in a single stage at a constant cooling rate, in two stages each with a different cooling rate, or in three or more stages each with a different cooling rate. In embodiments, the glass-based articles are cooled at a controlled rate from the growth temperature in order to minimize temperature gradients across the articles as well as minimize residual stress across the articles. Temperature gradients and differences in residual stress may lead to the articles warping during cooling. Thus, controlling the cooling to control the temperature gradients and residuals stresses may also minimize warpage of the glass-based articles.

[0124] Chemical strengthening

[0125] In embodiments, glass-based articles may be strengthened to have a compressive stress layer on one or more surface thereof. With reference now to FIG.3, an exemplary cross- sectional side view of a strengthened glass-based article 300 is depicted having a first surface 302 and an opposing second surface 304 separated by a thickness (t). In embodiments, strengthened glass-based articles 300 has been ion exchanged and has a compressive stress (CS) layer 306 (or first region) extending from first surface 302 to a depth of compression (DOC). In embodiments, as shown in FIG. 3, the glass-based articles 300 also has a compressive stress (CS) layer 308 extending from second surface 304 to a depth of compression DOC’.

[0126] In embodiments, the glass-based articles is capable of being chemically strengthened using one or more ion exchange techniques. In these embodiments, ion exchange can occur by subjecting one or more surfaces of such glass-based articles to one or more ion exchange mediums (for example molten salt baths), having a specific composition and temperature, for a specified time period to impart to the one or more surfaces with compressive stress layer(s). In embodiments, the ion exchange medium is a molten salt bath containing an ion (for example an alkali metal ion) that is larger than an ion (for example an alkali metal ion) present in the glass-based articles wherein the larger ion from the molten bath is exchanged with the smallerion in the glass-based articles to impart a compressive stress in the glass-based articles, and thereby increases the strength of the glass-based articles.

[0127] In embodiments, a one-step ion exchange process can be used and in other embodiments, a multi-step ion exchange process can be used. In embodiments, for both one- step and multi-step ion exchange processes the ion exchange mediums (for example, molten baths) can include potassium nitrate (KNO3) and sodium nitrate (NaNO3) as primary components. The ion exchange mediums can, in embodiments, further comprise lithium nitrate (LiNO3), sodium nitrite (NaNO2), and silicic acid.

[0128] In embodiments, the ion exchange medium comprises greater than or equal to 50 wt.% and less than or equal to 70 wt.% KNO3, greater than or equal to 55 wt.% and less than or equal to 70 wt.% KNO3, greater than or equal to 60 wt.% and less than or equal to 70 wt.% KNO3, greater than or equal to 65 wt.% and less than or equal to 70 wt.% KNO3, greater than or equal to 50 wt.% and less than or equal to 65 wt.% KNO3, greater than or equal to 55 wt.% and less than or equal to 65 wt.% KNO3, greater than or equal to 60 wt.% and less than or equal to 65 wt.% KNO3, greater than or equal to 50 wt.% and less than or equal to 60 wt.% KNO3, greater than or equal to 55 wt.% and less than or equal to 60 wt.% KNO3, or greater than or equal to 50 wt.% and less than or equal to 55 wt.% KNO3. It should be understood that the above ranges include all subranges within the explicitly disclosed ranges.

[0129] In embodiments, the ion exchange medium comprises greater than or equal to 30 wt.% and less than or equal to 50 wt.% NaNO3, greater than or equal to 35 wt.% and less than or equal to 50 wt.% NaNO3, greater than or equal to 40 wt.% and less than or equal to 50 wt.% NaNO3, greater than or equal to 45 wt.% and less than or equal to 50 wt.% NaNO3, greater than or equal to 30 wt.% and less than or equal to 45 wt.% NaNO3, greater than or equal to 35 wt.% and less than or equal to 45 wt.% NaNO3, greater than or equal to 40 wt.% and less than or equal to 45 wt.% NaNO3, greater than or equal to 30 wt.% and less than or equal to 40 wt.% NaNO3, greater than or equal to 35 wt.% and less than or equal to 40 wt.% NaNO3, or greater than or equal to 30 wt.% and less than or equal to 35 wt.% NaNO3. It should be understood that the above ranges include all subranges within the explicitly disclosed ranges.

[0130] In embodiments, the ion exchange medium comprises greater than or equal to 0.05 wt.% and less than or equal to 0.15 wt.% LiNO3, greater than or equal to 0.08 wt.% and less than or equal to 0.15 wt.% LiNO3, greater than or equal to 0.10 wt.% and less than or equal to0.15 wt.% LiNO3, greater than or equal to 0.12 wt.% and less than or equal to 0.15 wt.% LiNO3, greater than or equal to 0.05 wt.% and less than or equal to 0.12 wt.% LiNO3, greater than or equal to 0.08 wt.% and less than or equal to 0.12 wt.% LiNO3, greater than or equal to 0.10 wt.% and less than or equal to 0.12 wt.% LiNO3, greater than or equal to 0.05 wt.% and less than or equal to 0.10 wt.% LiNO3, greater than or equal to 0.08 wt.% and less than or equal to 0.10 wt.% LiNO3, or greater than or equal to 0.05 wt.% and less than or equal to 0.08 wt.% LiNO3. It should be understood that the above ranges include all subranges within the explicitly disclosed ranges.

[0131] Including lithium in the ion exchange medium—by the addition of LiNO3—may improve the corrosion resistance of glass-ceramics according to embodiments disclosed and described herein.

[0132] In embodiments, the ion exchange medium comprises greater than or equal to 0.40 wt.% and less than or equal to 0.60 wt.% NaNO2, greater than or equal to 0.45 wt.% and less than or equal to 0.60 wt.% NaNO2, greater than or equal to 0.50 wt.% and less than or equal to 0.60 wt.% NaNO2, greater than or equal to 0.55 wt.% and less than or equal to 0.60 wt.% NaNO2, greater than or equal to 0.40 wt.% and less than or equal to 0.55 wt.% NaNO2, greater than or equal to 0.45 wt.% and less than or equal to 0.55 wt.% NaNO2, greater than or equal to 0.50 wt.% and less than or equal to 0.55 wt.% NaNO2, greater than or equal to 0.40 wt.% and less than or equal to 0.50 wt.% NaNO2, greater than or equal to 0.45 wt.% and less than or equal to 0.50 wt.% NaNO2, or greater than or equal to 0.40 wt.% and less than or equal to 0.45 wt.%. It should be understood that the above ranges include all subranges within the explicitly disclosed ranges.

[0133] In embodiments, the ion exchange medium comprises greater than or equal to 0.40 wt.% and less than or equal to 0.60 wt.% silicic acid, greater than or equal to 0.45 wt.% and less than or equal to 0.60 wt.% silicic acid, greater than or equal to 0.50 wt.% and less than or equal to 0.60 wt.% silicic acid, greater than or equal to 0.55 wt.% and less than or equal to 0.60 wt.% silicic acid, greater than or equal to 0.40 wt.% and less than or equal to 0.55 wt.% silicic acid, greater than or equal to 0.45 wt.% and less than or equal to 0.55 wt.% silicic acid, greater than or equal to 0.50 wt.% and less than or equal to 0.55 wt.% silicic acid, greater than or equal to 0.40 wt.% and less than or equal to 0.50 wt.% silicic acid, greater than or equal to 0.45 wt.% and less than or equal to 0.50 wt.% silicic acid, or greater than or equal to 0.40 wt.% and lessthan or equal to 0.45 wt.%. It should be understood that the above ranges include all subranges within the explicitly disclosed ranges.

[0134] The temperature of the ion exchange medium is, in embodiments, greater than or equal to 450 °C and less than or equal to 550 °C, greater than or equal to 475 °C and less than or equal to 550 °C, greater than or equal to 500 °C and less than or equal to 550 °C, greater than or equal to 525 °C and less than or equal to 550 °C, greater than or equal to 530 °C and less than or equal to 550 °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 525 °C and less than or equal to 530 °C, greater than or equal to 450 °C and less than or equal to 525 °C, greater than or equal to 475 °C and less than or equal to 525 °C, greater than or equal to 500 °C and less than or equal to 525 °C, greater than or equal to 450 °C and less than or equal to 500 °C, greater than or equal to 475 °C and less than or equal to 500 °C, or greater than or equal to 450 °C and less than or equal to 475 °C. It should be understood that the above ranges include all subranges within the explicitly disclosed ranges.

[0135] According to embodiments, the glass-based articles is contacted with the ion exchange medium for a duration that is greater than or equal to 1 hour and less than or equal to 16 hours, greater than or equal to 2 hour and less than or equal to 16 hours, greater than or equal to 4 hour and less than or equal to 16 hours, greater than or equal to 6 hour and less than or equal to 16 hours, greater than or equal to 8 hour and less than or equal to 16 hours, greater than or equal to 10 hour and less than or equal to 16 hours, greater than or equal to 12 hour and less than or equal to 16 hours, greater than or equal to 14 hour and less than or equal to 16 hours, greater than or equal to 1 hour and less than or equal to 14 hours, greater than or equal to 2 hour and less than or equal to 14 hours, greater than or equal to 4 hour and less than or equal to 14 hours, greater than or equal to 6 hour and less than or equal to 14 hours, greater than or equal to 8 hour and less than or equal to 14 hours, greater than or equal to 10 hour and less than or equal to 14 hours, greater than or equal to 12 hour and less than or equal to 14 hours, greater than or equal to 1 hour and less than or equal to 12 hours, greater than or equal to 2 hour and less than or equal to 12 hours, greater than or equal to 4 hour and less than or equal to 12 hours, greater than or equal to 6 hour and less than or equal to 12 hours, greater than or equal to 8 hour and less than or equal to 12 hours, greater than or equal to 10 hour and less than or equal to 12 hours, greater than or equal to 1 hour and less than or equal to 10 hours,greater than or equal to 2 hour and less than or equal to 10 hours, greater than or equal to 4 hour and less than or equal to 10 hours, greater than or equal to 6 hour and less than or equal to 10 hours, greater than or equal to 8 hour and less than or equal to 10 hours, greater than or equal to 1 hour and less than or equal to 8 hours, greater than or equal to 2 hour and less than or equal to 8 hours, greater than or equal to 4 hour and less than or equal to 8 hours, greater than or equal to 6 hour and less than or equal to 8 hours, greater than or equal to 1 hour and less than or equal to 6 hours, greater than or equal to 2 hour and less than or equal to 6 hours, greater than or equal to 4 hour and less than or equal to 6 hours, greater than or equal to 1 hour and less than or equal to 4 hours, greater than or equal to 2 hour and less than or equal to 4 hours, or greater than or equal to 1 hour and less than or equal to 2 hours. It should be understood that the above ranges include all subranges within the explicitly disclosed ranges.

[0136] After an ion exchange process is performed, it should be understood that a composition at the surface of the glass-based articles may be different than the composition of the as-formed glass-based articles (i.e., the glass-based article before it undergoes an ion exchange process). This results from one type of alkali metal ion in the as-formed glass-based articles, such as, for example Li+or Na+, being replaced with larger alkali metal ions, such as, for example Na+or K+, respectively. However, the composition of the glass-based articles at or near the center of the depth of the glass-based articles article will, in embodiments, still have the composition of the as-formed glass-based articles. As utilized herein, the center of the glass article refers to any location in the glass article that is a distance of at least 0.5t from every surface thereof, where t is the thickness of the glass article.

[0137] In embodiments, various masking techniques may be used so that regions of the glass-based article is not exposed to the ion-exchange bath. For instance, in embodiments, the bendable amorphous region may be masked in one or more ion exchange steps so that the bendable amorphous region is not subjected to the ion exchange process. In embodiments, the crystal-containing region may be masked in one or more ion exchange steps so that the crystal- containing region is not subjected to the ion exchange process.

[0138] Using the above strengthening methods, the glass-based article has a compressive stress in the first crystal-containing region, in the second crystal-containing region, and in the bendable amorphous region. Because of the different phase structures of the crystal-containing regions and the bendable amorphous region, the compressive stress is, in embodiments, different in the crystal-containing regions and the bendable amorphous region. Likewise, theglass-based article has a Young’s modulus in the crystal-containing regions that is different than the Young’s modulus of the bendable amorphous region. Having a ratio of compressive stress to Young’s modulus (CS / E) that is greater in the bendable amorphous region than in the crystal-containing regions and allows the glass-based article to bend around the bendable amorphous region while keeping the crystal-containing regions comparatively straight.

[0139] Methods for forming bendable amorphous region and crystal-containing regions in a single, continuous glass-based article

[0140] Methods for forming the crystal-containing regions and the bendable amorphous region in the glass-based article will now be described.

[0141] In a first method for forming crystal-containing regions and the bendable amorphous region includes doping the glass-based articles with metallic nucleating agents (such as cerium, antimony, silver, copper, gold, oxides thereof, and combinations thereof) as described above. The method will now be described with reference to FIG.4. In a first step, a mask 410 is placed over a glass-based article 100 that has not been cerammed. The mask 410 is placed over a portion of the glass-based article 100 where the bendable amorphous region is to be located. The mask 410 may be directly deposited on the glass-based article 100 or employ a separate mask 410 that is placed on the glass surface and then removed after exposure and reused. After the mask 410 is in place, the glass-based article 100 is exposed to ultraviolet (UV) light 420 for a period of time sufficient to form metal droplets in the portions of the glass-based article 100 exposed to the UV light 420 (i.e., the portions of the glass-based article 100 that are not masked). These metal droplets are formed from the metallic nucleating agents that were doped into the composition of the glass-based article.

[0142] In a second step, the mask 410 is removed from the glass-based article 100 and the glass-based article 100 is subjected to a ceramming cycle, such as those described above. During the ceramming cycle crystals will grow on the metallic droplets but not on the masked region where no metallic droplets were formed. This will result in a final glass-based article with sharp demarcation between crystal-containing regions and bendable amorphous region enabling complex shapes and patterns of cerammed regions to be generated. In embodiments, this could be used to make a crystal-containing region with high retained strength that is not bent while leaving a portion of the article as a higher CS / E glassy region to facilitate bending,either in an elliptical bend, a “waterdrop” bend, or around a mandrel (such as in a slideable device).

[0143] Another embodiment for forming a glass-based article having crystal-containing regions and a bendable amorphous region comprises using a focused energy source, such as for example a laser, to form the bendable amorphous region.

[0144] To provide a bendable amorphous region while enabling the higher damage resistance of the crystal-containing regions requires different material properties in both the bendable amorphous region and the crystal-containing regions. Achieving this in a single, continuous glass-based article, requires additional processing to either ceram the glass-based article, then amorphize the bendable amorphous region or ceram only the crystal-containing regions from an amorphous sheet of glass. A focused energy source, such as a laser, may be used to achieve the different material properties.

[0145] In embodiments, a glass-based article may be cerammed as described above, subsequently, a focused energy source, such as a laser, is presented incident to the cerammed glass-based article where the bendable amorphous region is to be formed. The focused energy source causes the crystalline phases to revert back to amorphous phases, thereby forming a bendable amorphous region in the cerammed glass-based article. An ultrafast laser is good for glass surface texturing and internal modification from non-linear effects, however if the laser is used as a heating source to trigger linear absorption through the whole glass, a CW / QCW or diode laser with proper wavelength may be used. By using this process, the depth of the bendable amorphous region in the thickness of the glass may be controlled such that, in embodiments, the entire thickness of the bendable amorphous region may comprise predominantly amorphous phase. However, in embodiments, a thin crystal-containing layer may remain on a surface of the bendable amorphous region that is to be exposed to impart improved damage resistance. In embodiments, the bendable amorphous region may include layers of crystal-containing material and layers of amorphous material. By using this methodology, a glass-based article having a first crystal-containing region, a second crystal- containing region, and a bendable amorphous region positioned between the first crystal- containing region and the second crystal-containing region may be made.

[0146] In one or more embodiments, an amorphous glass-based article may be exposed to a focused energy source, such as a laser, where the bendable amorphous region is to be formed.This causes a shift in the portion of the amorphous glass-based article exposed to the focused energy source such that when the glass-based article is cerammed the portion of the glass-based article exposed to the focused energy source does not crystallize. Subsequent to exposure to the focused energy source, the amorphous glass-based article is subjected to a ceramming process, such as those disclosed above. By using this methodology, a glass-based article having a first crystal-containing region, a second crystal-containing region, and a bendable amorphous region positioned between the first crystal-containing region and the second crystal-containing region may be made.

[0147] In one or more embodiments, ion exchange treatment may be used to form a glass- based article having a first crystal-containing region, a second crystal-containing region, and a bendable amorphous region positioned between the first crystal-containing region and the second crystal-containing region. A glass-based composition having a high concentration of sodium and a low lithium concentration—such as being essentially free of lithium—maybe be formed. The glass-based article can then be ion exchanged in a lithium salt bath with the bendable amorphous region(s) masked to prevent lithium-ion penetration. The swap of a smaller lithium ion for larger sodium ion in the glass-based article will result in some tension, which will have to be managed, perhaps through ion exchanging at high temperatures to trigger stress relaxation. The crystal-containing regions will now have a gradient of lithium through the thickness, or a nearly uniform lithium concentration, which is possible because of the low thickness of the glass. The glass can then be creamed, such as through the processes disclosed above, with crystallization only happening in the crystal-containing regions that comprise the lithium. Using this method, the bendable amorphous region will remain a sodium-containing amorphous glass that is easily ion-exchangeable and should have a high CS / E ratio.

[0148] In one or more embodiments, ion exchange treatment may be used to form a glass- based article having a first crystal-containing region, a second crystal-containing region, and a bendable amorphous region positioned between the first crystal-containing region and the second crystal-containing region by using a targeted ion exchange medium at the bendable amorphous region. In such an embodiment, a glass article comprising lithium may be formed into a sheet. Subsequently, the bendable amorphous region is ion exchanged using an ion exchange medium that has a high potassium concentration—such as an ion exchange medium that is high in KNO3as disclosed above—without exposing the first crystal-containing region and second crystal-containing region to the ion exchange medium. This can be accomplishedby masking the first crystal-containing region and the second crystal-containing region thereby only exposing the bendable amorphous region to the ion exchange medium with a high potassium concentration. Alternatively, the ion exchange medium with a high potassium concentration may be targeted to the bendable amorphous region by precision applications such as spraying so that the ion exchange medium with a high potassium concentration does not contact the first crystal-containing region or the second crystal-containing region. The temperature and duration of the ion exchange treatment may be conducted as disclosed above. After the ion exchange treatment is complete, the glass sheet may be subjected to the ceramming processes disclosed herein. During this ceramming process, the first crystal- containing region and the second crystal-containing region become glass-ceramic regions comprising a crystalline phase and an amorphous phase while the bendable amorphous region remains as an amorphous region.

[0149] Without being bound by any particular theory, it is believed that by ion exchanging the bendable amorphous region with an ion exchange medium having a high potassium concentration, the lithium in the bendable amorphous region is replaced with potassium, thereby changing the concentration of the bendable amorphous region. Therefore, after the ion exchange is complete, the composition of the bendable amorphous region is low in lithium while the composition of the first crystal-containing region and the composition of the second crystal-containing region differ from the composition of the bendable amorphous region in that the first crystal-containing region and the second crystal-containing region comprise significantly more lithium than the bendable amorphous region. Accordingly, when the ceramming process is conducted, crystal nucleation and growth will occur in the first crystal- containing region and the second crystal-containing region that comprise lithium, but nucleation and growth will not occur—at least not significantly—in the bendable amorphous region that does not comprise lithium.

[0150] It is possible that lithium ions may be infused from the first crystal-containing region and / or the second crystal-containing region into the bendable amorphous region during or after the ion exchange in a potassium-rich ion exchange medium has been conducted. Therefore, in embodiments, the ion exchange medium may be directed to an area of the glass article that is greater than the intended area of the bendable amorphous region to ensure that lithium ions do not infuse into the region designed to be the bendable amorphous region.

[0151] The above phenomenon is depicted in the SEM images shown in FIG. 5A to FIG. 5C, which depict glass-based articles having a potassium rich surface. The glass-based articles shown in FIG. 5A to FIG. 5C, the glass-based articles have been subjected to a ceramming processes. However, as discussed in more detail below, the portions of the glass-based articles having a high potassium concentration (including K2O) did not undergo crystal nucleation and growth, whereas portions of the glass-based articles that do not have a high potassium concentration did undergo crystal nucleation and growth. In particular, FIG. 5A is an SEM image of a glass-based article that was ion exchanged with an ion exchange medium having a high potassium concentration for one hour. As shown by the black line in FIG.5A, the glass- based article has a K2O boundary at about 8 µm from the surface of the glass based article; meaning that the glass-based article depicted in FIG.5A has a high K2O concentration from its surface to a depth of about 8 µm into the thickness of the glass-based article. As seen in FIG. 5A, an amorphous portion (indicated by the lighter region) exists where there is a high K2O concentration (i.e., from the surface to about 8 µm into the thickness of the glass-based article), and a crystal-containing portion exists at depths greater than about 8 µm into the thickness of the glass-based article (indicated by a darker region). Likewise, FIG.5B is an SEM image of a glass-based article that was ion exchanged with an ion exchange medium having a high potassium concentration for two hours. As shown by the black line in FIG.5B, the glass-based article has a K2O boundary at about 12 µm from the surface of the glass based article; meaning that the glass-based article depicted in FIG.5B has a high K2O concentration from its surface to a depth of about 12 µm into the thickness of the glass-based article. As seen in FIG.5B, an amorphous portion (indicated by the lighter region) exists where there is a high K2O concentration (i.e., from the surface to about 12 µm into the thickness of the glass-based article), and a crystal-containing portion exists at depths greater than about 12 µm into the thickness of the glass-based article (indicated by a darker region). Similarly, FIG. 5C is an SEM image of a glass-based article that was ion exchanged with an ion exchange medium having a high potassium concentration for six hours. As shown by the black line in FIG. 5C, the glass-based article has a K2O boundary at about 24 µm from the surface of the glass based article; meaning that the glass-based article depicted in FIG.5C has a high K2O concentration from its surface to a depth of about 24 µm into the thickness of the glass-based article. As seen in FIG.5C, an amorphous portion (indicated by the lighter region) exists where there is a high K2O concentration (i.e., from the surface to about 24 µm into the thickness of the glass-based article), and a crystal-containing portion exists at depths greater than about 24 µm into the thickness of the glass-based article (indicated by a darker region).

[0152] As shown in FIG.5A to FIG.5C, in portions of the glass-based article that comprise a high K2O content, crystal nucleation and growth does not occur. Accordingly, in embodiments, ion exchange with a potassium-rich ion exchange medium at the bendable amorphous region of a glass sheet is used to modify the composition of the bendable amorphous region to have in increased amount of K2O, which can prevent crystal nucleation and growth in the bendable amorphous region while allowing crystal nucleation and growth in the first crystal-containing region and the second crystal-containing region, which do not have an increased amount of K2O.

[0153] Properties of the crystal-containing regions

[0154] The mechanic properties of crystal-containing regions disclosed herein are tested on strengthened glass-based articles unless otherwise indicated. Even though described in separate paragraphs below, the various mechanical properties are present in combination in glass-based articles of embodiments. The balance of these mechanical properties provide a durable, robust glass-based article that is difficult to achieve without sacrificing other mechanical properties. For instance, and as an example only, achieving high compressive stress alone is possible, but achieving high compressive stress and central tension can be more difficult.

[0155] In embodiments, DOC and DOC’ are individually greater than or equal to 0.15t and less than or equal to 0.25t, greater than or equal to 0.16t and less than or equal to 0.25t, greater than or equal to 0.17 and less than or equal to 0.25t, greater than or equal to 0.18t and less than or equal to 0.25t, greater than or equal to 0.19t and less than or equal to 0.25t, greater than or equal to 0.20t and less than or equal to 0.25t, greater than or equal to 0.21t and less than or equal to 0.25t, greater than or equal to 0.22t and less than or equal to 0.25t, greater than or equal to 0.23t and less than or equal to 0.25t, greater than or equal to 0.24t and less than or equal to 0.25t, greater than or equal to 0.15t and less than or equal to 0.24t, greater than or equal to 0.16t and less than or equal to 0.24t, greater than or equal to 0.17 and less than or equal to 0.24t, greater than or equal to 0.18t and less than or equal to 0.24t, greater than or equal to 0.19t and less than or equal to 0.24t, greater than or equal to 0.20t and less than or equal to 0.24t, greater than or equal to 0.21t and less than or equal to 0.24t, greater than or equal to 0.22t and less than or equal to 0.24t, greater than or equal to 0.23t and less than or equal to 0.24t, greater than or equal to 0.15t and less than or equal to 0.23t, greater than or equal to 0.16t and less than or equal to 0.23t, greater than or equal to 0.17 and less than or equal to 0.23t, greater than or equal to 0.18t and less than or equal to 0.23t, greater than or equal to 0.19t and less thanor equal to 0.23t, greater than or equal to 0.20t and less than or equal to 0.23t, greater than or equal to 0.21t and less than or equal to 0.23t, greater than or equal to 0.22t and less than or equal to 0.23t, greater than or equal to 0.15t and less than or equal to 0.22t, greater than or equal to 0.16t and less than or equal to 0.22t, greater than or equal to 0.17 and less than or equal to 0.22t, greater than or equal to 0.18t and less than or equal to 0.22t, greater than or equal to 0.19t and less than or equal to 0.22t, greater than or equal to 0.20t and less than or equal to 0.22t, greater than or equal to 0.21t and less than or equal to 0.22t, greater than or equal to 0.15t and less than or equal to 0.21t, greater than or equal to 0.16t and less than or equal to 0.21t, greater than or equal to 0.17 and less than or equal to 0.21t, greater than or equal to 0.18t and less than or equal to 0.21t, greater than or equal to 0.19t and less than or equal to 0.21t, greater than or equal to 0.20t and less than or equal to 0.21t, greater than or equal to 0.15t and less than or equal to 0.20t, greater than or equal to 0.16t and less than or equal to 0.20t, greater than or equal to 0.17 and less than or equal to 0.20t, greater than or equal to 0.18t and less than or equal to 0.20t, greater than or equal to 0.19t and less than or equal to 0.20t, greater than or equal to 0.15t and less than or equal to 0.19t, greater than or equal to 0.16t and less than or equal to 0.19t, greater than or equal to 0.17 and less than or equal to 0.19t, greater than or equal to 0.18t and less than or equal to 0.19t, greater than or equal to 0.15t and less than or equal to 0.18t, greater than or equal to 0.16t and less than or equal to 0.18t, greater than or equal to 0.17 and less than or equal to 0.18t, greater than or equal to 0.15t and less than or equal to 0.17t, greater than or equal to 0.16t and less than or equal to 0.17t, or greater than or equal to 0.15t and less than or equal to 0.16t.

[0156] Referring again to FIG. 3, there is also a central tension region 310 under tensile stress in between DOC and DOC’. Accordingly, stress transitions from compressive stress to tensile stress at DOC and DOC’, which are described hereinabove, measured from a surface toward a centerline of the strengthened glass-based article.

[0157] In embodiments, the glass-based articles may have a compressive stress (CS) of greater than or equal to 200 MPa and less than or equal to 400 MPa, such as greater than or equal to 225 MPa and less than or equal to 400 MPa, greater than or equal to 250 MPa and less than or equal to 400 MPa, greater than or equal to 275 MPa and less than or equal to 400 MPa, greater than or equal to 300 MPa and less than or equal to 400 MPa, greater than or equal to 325 MPa and less than or equal to 400 MPa, greater than or equal to 350 MPa and less than or equal to 400 MPa, greater than or equal to 375 MPa and less than or equal to 400 MPa, greaterthan or equal to 200 MPa and less than or equal to 375 MPa, greater than or equal to 225 MPa and less than or equal to 375 MPa, greater than or equal to 250 MPa and less than or equal to 375 MPa, greater than or equal to 275 MPa and less than or equal to 375 MPa, greater than or equal to 300 MPa and less than or equal to 375 MPa, greater than or equal to 325 MPa and less than or equal to 375 MPa, greater than or equal to 350 MPa and less than or equal to 375 MPa, greater than or equal to 200 MPa and less than or equal to 350 MPa, greater than or equal to 225 MPa and less than or equal to 350 MPa, greater than or equal to 250 MPa and less than or equal to 350 MPa, greater than or equal to 275 MPa and less than or equal to 350 MPa, greater than or equal to 300 MPa and less than or equal to 350 MPa, greater than or equal to 325 MPa and less than or equal to 350 MPa, greater than or equal to 200 MPa and less than or equal to 325 MPa, greater than or equal to 225 MPa and less than or equal to 325 MPa, greater than or equal to 250 MPa and less than or equal to 325 MPa, greater than or equal to 275 MPa and less than or equal to 325 MPa, greater than or equal to 300 MPa and less than or equal to 325 MPa, greater than or equal to 200 MPa and less than or equal to 300 MPa, greater than or equal to 225 MPa and less than or equal to 300 MPa, greater than or equal to 250 MPa and less than or equal to 300 MPa, greater than or equal to 275 MPa and less than or equal to 300 MPa, greater than or equal to 200 MPa and less than or equal to 275 MPa, greater than or equal to 225 MPa and less than or equal to 275 MPa, greater than or equal to 250 MPa and less than or equal to 275 MPa, greater than or equal to 200 MPa and less than or equal to 250 MPa, greater than or equal to 225 MPa and less than or equal to 250 MPa, or greater than or equal to 200 MPa and less than or equal to 225 MPa. It should be understood that the above ranges include all subranges within the explicitly disclosed ranges.

[0158] In embodiments, the maximum central tension (CT) is greater than or equal to 100 MPa and less than or equal to 170 MPa, such as greater than or equal to 110 MPa and less than or equal to 170 MPa, greater than or equal to 120 MPa and less than or equal to 170 MPa, greater than or equal to 130 MPa and less than or equal to 170 MPa, greater than or equal to 140 MPa and less than or equal to 170 MPa, greater than or equal to 150 MPa and less than or equal to 170 MPa, greater than or equal to 160 MPa and less than or equal to 170 MPa, greater than or equal to 100 MPa and less than or equal to 160 MPa, greater than or equal to 110 MPa and less than or equal to 160 MPa, greater than or equal to 120 MPa and less than or equal to 160 MPa, greater than or equal to 130 MPa and less than or equal to 160 MPa, greater than or equal to 140 MPa and less than or equal to 160 MPa, greater than or equal to 150 MPa and less than or equal to 160 MPa, greater than or equal to 100 MPa and less than or equal to 150 MPa,greater than or equal to 110 MPa and less than or equal to 150 MPa, greater than or equal to 120 MPa and less than or equal to 150 MPa, greater than or equal to 130 MPa and less than or equal to 150 MPa, greater than or equal to 140 MPa and less than or equal to 150 MPa, greater than or equal to 100 MPa and less than or equal to 140 MPa, greater than or equal to 110 MPa and less than or equal to 140 MPa, greater than or equal to 120 MPa and less than or equal to 140 MPa, greater than or equal to 130 MPa and less than or equal to 140 MPa, greater than or equal to 100 MPa and less than or equal to 130 MPa, greater than or equal to 110 MPa and less than or equal to 130 MPa, greater than or equal to 120 MPa and less than or equal to 130 MPa, greater than or equal to 100 MPa and less than or equal to 120 MPa, greater than or equal to 110 MPa and less than or equal to 120 MPa, or greater than or equal to 100 MPa and less than or equal to 110 MPa. It should be understood that the above ranges include all subranges within the explicitly disclosed ranges.

[0159] In embodiments, the glass-based articles have a ratio of CS to CT (CS / CT) that is greater than or equal to 1.5 and less than or equal to 3.0, such as greater than or equal to 1.8 and less than or equal to 3.0, greater than or equal to 2.0 and less than or equal to 3.0, greater than or equal to 2.2 and less than or equal to 3.0, greater than or equal to 2.5 and less than or equal to 3.0, greater than or equal to 2.8 and less than or equal to 3.0, greater than or equal to 1.5 and less than or equal to 2.8, such as greater than or equal to 1.8 and less than or equal to 2.8, greater than or equal to 2.0 and less than or equal to 2.8, greater than or equal to 2.2 and less than or equal to 2.8, greater than or equal to 2.5 and less than or equal to 2.8, greater than or equal to 1.5 and less than or equal to 2.5, such as greater than or equal to 1.8 and less than or equal to 2.5, greater than or equal to 2.0 and less than or equal to 2.5, greater than or equal to 2.2 and less than or equal to 2.5, greater than or equal to 1.5 and less than or equal to 2.2, such as greater than or equal to 1.8 and less than or equal to 2.2, greater than or equal to 2.0 and less than or equal to 2.2, greater than or equal to 1.5 and less than or equal to 2.0, such as greater than or equal to 1.8 and less than or equal to 2.0, or greater than or equal to 1.5 and less than or equal to 1.8. It should be understood that the above ranges include all subranges within the explicitly disclosed ranges.

[0160] Glass-based articles according to embodiments have a stress that decreases with increasing distance from the surface of the glass article toward the centerline of the glass article, and the stress decreases as a substantially linear function from a depth that is greater than or equal to 0.07t and less than or equal to 0.26t, greater than or equal to 0.10t and less than orequal to 0.26t, greater than or equal to 0.12t and less than or equal to 0.26t, greater than or equal to 0.15t and less than or equal to 0.26t, greater than or equal to 0.17t and less than or equal to 0.26t, greater than or equal to 0.20t and less than or equal to 0.26t, greater than or equal to 0.22t and less than or equal to 0.26t, greater than or equal to 0.25t and less than or equal to 0.26t, greater than or equal to 0.07t and less than or equal to 0.25t, greater than or equal to 0.10t and less than or equal to 0.25t, greater than or equal to 0.12t and less than or equal to 0.25t, greater than or equal to 0.15t and less than or equal to 0.25t, greater than or equal to 0.17t and less than or equal to 0.25t, greater than or equal to 0.20t and less than or equal to 0.25t, greater than or equal to 0.22t and less than or equal to 0.25t, greater than or equal to 0.07t and less than or equal to 0.22t, greater than or equal to 0.10t and less than or equal to 0.22t, greater than or equal to 0.12t and less than or equal to 0.22t, greater than or equal to 0.15t and less than or equal to 0.22t, greater than or equal to 0.17t and less than or equal to 0.22t, greater than or equal to 0.20t and less than or equal to 0.22t, greater than or equal to 0.07t and less than or equal to 0.20t, greater than or equal to 0.10t and less than or equal to 0.20t, greater than or equal to 0.12t and less than or equal to 0.20t, greater than or equal to 0.15t and less than or equal to 0.20t, greater than or equal to 0.17t and less than or equal to 0.20t, greater than or equal to 0.07t and less than or equal to 0.17t, greater than or equal to 0.10t and less than or equal to 0.17t, greater than or equal to 0.12t and less than or equal to 0.17t, greater than or equal to 0.15t and less than or equal to 0.17t, greater than or equal to 0.07t and less than or equal to 0.15t, greater than or equal to 0.10t and less than or equal to 0.15t, greater than or equal to 0.12t and less than or equal to 0.15t, greater than or equal to 0.07t and less than or equal to 0.12t, greater than or equal to 0.10t and less than or equal to 0.12t, or greater than or equal to 0.07t and less than or equal to 0.10t. It should be understood that the above ranges include all subranges within the explicitly disclosed ranges.

[0161] According to embodiments, the stress in the glass-based article transitions from compressive stress to tensile stress at a depth measured from a surface of the class-ceramic article toward the centerline of the glass-based article that is greater than or equal to 0.18t and less than or equal to 0.25t, greater than or equal to 0.19t and less than or equal to 0.25t, greater than or equal to 0.20t and less than or equal to 0.25t, greater than or equal to 0.21t and less than or equal to 0.25t, greater than or equal to 0.22t and less than or equal to 0.25t, greater than or equal to 0.23t and less than or equal to 0.25t, greater than or equal to 0.24t and less than or equal to 0.25t, greater than or equal to 0.18t and less than or equal to 0.24t, greater than or equal to 0.19t and less than or equal to 0.24t, greater than or equal to 0.20t and less than orequal to 0.24t, greater than or equal to 0.21t and less than or equal to 0.24t, greater than or equal to 0.22t and less than or equal to 0.24t, greater than or equal to 0.23t and less than or equal to 0.24t, greater than or equal to 0.18t and less than or equal to 0.23t, greater than or equal to 0.19t and less than or equal to 0.23t, greater than or equal to 0.20t and less than or equal to 0.23t, greater than or equal to 0.21t and less than or equal to 0.23t, greater than or equal to 0.22t and less than or equal to 0.23t, greater than or equal to 0.18t and less than or equal to 0.22t, greater than or equal to 0.19t and less than or equal to 0.22t, greater than or equal to 0.20t and less than or equal to 0.22t, greater than or equal to 0.21t and less than or equal to 0.22t, greater than or equal to 0.18t and less than or equal to 0.21t, greater than or equal to 0.19t and less than or equal to 0.21t, greater than or equal to 0.20t and less than or equal to 0.21t, greater than or equal to 0.18t and less than or equal to 0.20t, greater than or equal to 0.19t and less than or equal to 0.20t, or greater than or equal to 0.18t and less than or equal to 0.19t. It should be understood that the above ranges include all subranges within the explicitly disclosed ranges.

[0162] According to embodiments, the glass-based article has a maximum central tension (mCT) and the absolute value of the surface compressive stress measured at a surface of the glass-based article is greater than or equal to 1.5 mCT and less than or equal to 2.5 mCT, greater than or equal to 1.7 mCT and less than or equal to 2.5 mCT, greater than or equal to 2.0 mCT and less than or equal to 2.5 mCT, greater than or equal to 2.2 mCT and less than or equal to 2.5 mCT, greater than or equal to 1.5 mCT and less than or equal to 2.2 mCT, greater than or equal to 1.7 mCT and less than or equal to 2.2 mCT, greater than or equal to 2.0 mCT and less than or equal to 2.2 mCT, greater than or equal to 1.5 mCT and less than or equal to 2.0 mCT, greater than or equal to 1.7 mCT and less than or equal to 2.0 mCT, or greater than or equal to 1.5 mCT and less than or equal to 1.7 mCT. It should be understood that the above ranges include all subranges within the explicitly disclosed ranges.

[0163] In embodiments, the stored strain energy of the glass-based article is greater than or equal to 22 J / m2and less than or equal to 60 J / m2, such as greater than or equal to 25 J / m2and less than or equal to 60 J / m2, greater than or equal to 30 J / m2and less than or equal to 60 J / m2, greater than or equal to 35 J / m2and less than or equal to 60 J / m2, greater than or equal to 40 J / m2and less than or equal to 60 J / m2, greater than or equal to 45 J / m2and less than or equal to 60 J / m2, greater than or equal to 50 J / m2and less than or equal to 60 J / m2, greater than or equal to 55 J / m2and less than or equal to 60 J / m2, greater than or equal to 22 J / m2and less thanor equal to 55 J / m2, such as greater than or equal to 25 J / m2and less than or equal to 55 J / m2, greater than or equal to 30 J / m2and less than or equal to 55 J / m2, greater than or equal to 35 J / m2and less than or equal to 55 J / m2, greater than or equal to 40 J / m2and less than or equal to 55 J / m2, greater than or equal to 45 J / m2and less than or equal to 55 J / m2, greater than or equal to 50 J / m2and less than or equal to 55 J / m2, greater than or equal to 22 J / m2and less than or equal to 50 J / m2, such as greater than or equal to 25 J / m2and less than or equal to 50 J / m2, greater than or equal to 30 J / m2and less than or equal to 50 J / m2, greater than or equal to 35 J / m2and less than or equal to 50 J / m2, greater than or equal to 40 J / m2and less than or equal to 50 J / m2, greater than or equal to 45 J / m2and less than or equal to 50 J / m2, greater than or equal to 22 J / m2and less than or equal to 45 J / m2, such as greater than or equal to 25 J / m2and less than or equal to 45 J / m2, greater than or equal to 30 J / m2and less than or equal to 45 J / m2, greater than or equal to 35 J / m2and less than or equal to 45 J / m2, greater than or equal to 40 J / m2and less than or equal to 45 J / m2, greater than or equal to 22 J / m2and less than or equal to 40 J / m2, such as greater than or equal to 25 J / m2and less than or equal to 40 J / m2, greater than or equal to 30 J / m2and less than or equal to 40 J / m2, greater than or equal to 35 J / m2and less than or equal to 40 J / m2, greater than or equal to 22 J / m2and less than or equal to 35 J / m2, such as greater than or equal to 25 J / m2and less than or equal to 35 J / m2, greater than or equal to 30 J / m2and less than or equal to 35 J / m2, greater than or equal to 22 J / m2and less than or equal to 30 J / m2, such as greater than or equal to 25 J / m2and less than or equal to 30 J / m2, or greater than or equal to 22 J / m2and less than or equal to 25 J / m2. It should be understood that the above ranges include all subranges within the explicitly disclosed ranges. The glass-based achieves the aforementioned stored strain energy with no bifurcation in crack pattern.

[0164] In embodiments, the glass-based article has a thickness t that is greater than or equal to 0.1 mm and less than or equal to 2.0 mm, greater than or equal to 0.3 mm and less than or equal to 2.0 mm, greater than or equal to 0.5 mm and less than or equal to 2.0 mm, greater than or equal to 0.8 mm and less than or equal to 2.0 mm, greater than or equal to 1.0 mm and less than or equal to 2.0 mm, greater than or equal to 1.3 mm and less than or equal to 2.0 mm, greater than or equal to 1.5 mm and less than or equal to 2.0 mm, greater than or equal to 1.8 mm and less than or equal to 2.0 mm, greater than or equal to 0.1 mm and less than or equal to 1.8 mm, greater than or equal to 0.3 mm and less than or equal to 1.8 mm, greater than or equal to 0.5 mm and less than or equal to 1.8 mm, greater than or equal to 0.8 mm and less than or equal to 1.8 mm, greater than or equal to 1.0 mm and less than or equal to 1.8 mm, greater than or equal to 1.3 mm and less than or equal to 1.8 mm, greater than or equal to 1.5 mm and lessthan or equal to 1.8 mm, greater than or equal to 0.1 mm and less than or equal to 1.5 mm, greater than or equal to 0.3 mm and less than or equal to 1.5 mm, greater than or equal to 0.5 mm and less than or equal to 1.5 mm, greater than or equal to 0.8 mm and less than or equal to 1.5 mm, greater than or equal to 1.0 mm and less than or equal to 1.5 mm, greater than or equal to 1.3 mm and less than or equal to 1.5 mm, greater than or equal to 0.1 mm and less than or equal to 1.3 mm, greater than or equal to 0.3 mm and less than or equal to 1.3 mm, greater than or equal to 0.5 mm and less than or equal to 1.3 mm, greater than or equal to 0.8 mm and less than or equal to 1.3 mm, greater than or equal to 1.0 mm and less than or equal to 1.3 mm, greater than or equal to 0.1 mm and less than or equal to 1.0 mm, greater than or equal to 0.3 mm and less than or equal to 1.0 mm, greater than or equal to 0.5 mm and less than or equal to 1.0 mm, greater than or equal to 0.8 mm and less than or equal to 1.0 mm, greater than or equal to 0.1 mm and less than or equal to 0.8 mm, greater than or equal to 0.3 mm and less than or equal to 0.8 mm, greater than or equal to 0.5 mm and less than or equal to 0.8 mm, greater than or equal to 0.1 mm and less than or equal to 0.5 mm, greater than or equal to 0.3 mm and less than or equal to 0.5 mm, or greater than or equal to 0.1 mm and less than or equal to 0.3 mm. It should be understood that the above ranges include all subranges within the explicitly disclosed ranges.

[0165] In embodiments, the glass-based article may be substantially planar and flat. In other embodiments, the glass-based article may be shaped, for example it may have a 2.5D or 3D shape. In embodiments, the glass-based article may have a uniform thickness and in other embodiments, the glass-based article may not have a uniform thickness.

[0166] In embodiments, the fracture toughness of the glass-based article is greater than or equal to 1.0 MPa√m and less than or equal to 2.0 MPa√m, greater than or equal to 1.2 MPa√m and less than or equal to 2.0 MPa√m, greater than or equal to 1.4 MPa√m and less than or equal to 2.0 MPa√m, greater than or equal to 1.5 MPa√m and less than or equal to 2.0 MPa√m, greater than or equal to 1.6 MPa√m and less than or equal to 2.0 MPa√m, greater than or equal to 1.8 MPa√m and less than or equal to 2.0 MPa√m, greater than or equal to 1.0 MPa√m and less than or equal to 1.8 MPa√m, greater than or equal to 1.2 MPa√m and less than or equal to 1.8 MPa√m, greater than or equal to 1.4 MPa√m and less than or equal to 1.8 MPa√m, greater than or equal to 1.5 MPa√m and less than or equal to 1.8 MPa√m, greater than or equal to 1.6 MPa√m and less than or equal to 1.8 MPa√m, greater than or equal to 1.0 MPa√m and less than or equal to 1.6 MPa√m, greater than or equal to 1.2 MPa√m and less than or equalto 1.6 MPa√m, greater than or equal to 1.4 MPa√m and less than or equal to 1.6 MPa√m, greater than or equal to 1.5 MPa√m and less than or equal to 1.6 MPa√m, greater than or equal to 1.0 MPa√m and less than or equal to 1.5 MPa√m, greater than or equal to 1.2 MPa√m and less than or equal to 1.5 MPa√m, greater than or equal to 1.4 MPa√m and less than or equal to 1.5 MPa√m, greater than or equal to 1.0 MPa√m and less than or equal to 1.4 MPa√m, greater than or equal to 1.2 MPa√m and less than or equal to 1.4 MPa√m, or greater than or equal to 1.0 MPa√m and less than or equal to 1.2 MPa√m. It should be understood that the above ranges include all subranges within the explicitly disclosed ranges.

[0167] In embodiments, the Young’s modulus (also referred to as elastic modulus) of the non-chemically strengthened glass-based article is greater than or equal to 90 GPa and less than or equal to 200 GPa, such as greater than or equal to 100 GPa and less than or equal to 200 GPa, greater than or equal to 120 GPa and less than or equal to 200 GPa, greater than or equal to 140 GPa and less than or equal to 200 GPa, greater than or equal to 160 GPa and less than or equal to 200 GPa, greater than or equal to 180 GPa and less than or equal to 200 GPa, greater than or equal to 90 GPa and less than or equal to 180 GPa, such as greater than or equal to 100 GPa and less than or equal to 180 GPa, greater than or equal to 120 GPa and less than or equal to 180 GPa, greater than or equal to 140 GPa and less than or equal to 180 GPa, greater than or equal to 160 GPa and less than or equal to 180 GPa, greater than or equal to 90 GPa and less than or equal to 160 GPa, such as greater than or equal to 100 GPa and less than or equal to 160 GPa, greater than or equal to 120 GPa and less than or equal to 160 GPa, greater than or equal to 140 GPa and less than or equal to 160 GPa, greater than or equal to 90 GPa and less than or equal to 140 GPa, such as greater than or equal to 100 GPa and less than or equal to 140 GPa, greater than or equal to 120 GPa and less than or equal to 140 GPa, greater than or equal to 90 GPa and less than or equal to 120 GPa, such as greater than or equal to 100 GPa and less than or equal to 120 GPa, or greater than or equal to 90 GPa and less than or equal to 100 GPa. It should be understood that the above ranges include all subranges within the explicitly disclosed ranges.

[0168] In embodiments, the non-chemically strengthened glass-based articles have a Poisson’s ratio that is greater than or equal to 0.15 and less than or equal to 0.25, greater than or equal to 0.17 and less than or equal to 0.25, greater than or equal to 0.20 and less than or equal to 0.25, greater than or equal to 0.22 and less than or equal to 0.25, greater than or equal to 0.15 and less than or equal to 0.22, greater than or equal to 0.17 and less than or equal to0.22, greater than or equal to 0.20 and less than or equal to 0.22, greater than or equal to 0.15 and less than or equal to 0.20, greater than or equal to 0.17 and less than or equal to 0.20, or greater than or equal to 0.15 and less than or equal to 0.17. It should be understood that the above ranges include all subranges within the explicitly disclosed ranges.

[0169] In embodiments, the non-chemically strengthened glass-based articles have a shear modulus that is greater than or equal to 40 GPa and less than or equal to 50 GPa, greater than or equal to 43 GPa and less than or equal to 50 GPa, greater than or equal to 45 GPa and less than or equal to 50 GPa, greater than or equal to 48 GPa and less than or equal to 50 GPa, greater than or equal to 40 GPa and less than or equal to 48 GPa, greater than or equal to 43 GPa and less than or equal to 48 GPa, greater than or equal to 45 GPa and less than or equal to 48 GPa, greater than or equal to 40 GPa and less than or equal to 45 GPa, greater than or equal to 43 GPa and less than or equal to 45 GPa, or greater than or equal to 40 GPa and less than or equal to 43 GPa. It should be understood that the above ranges include all subranges within the explicitly disclosed ranges.

[0170] The fracture stress was measured by applied fracture stress to failure with a 4 point bending test after introducing about 80 μm deep flaws using sand paper impact via an 1000 grit, 180 grit, and 80 grit slapper. Testing was performed using an apparatus comprising a simple pendulum-based dynamic impact test having a surface ranging from flat to curved, where the glass-based article test specimen is mounted to a bob of a pendulum, which is then used to cause the test specimen to contact a roughened impact surface. The apparatus is described in detail in International Application Publication No. WO2017 / 100646, which is hereby incorporated by reference in its entirety. To perform the test, the sample is loaded on the holder and then pulled backwards from the pendulum equilibrium position and released to make a dynamic impact on the impact surface.

[0171] The fracture stress of the glass-based according to embodiments measured on a glass- based article having a thickness of 0.6 mm using 1000 grit is greater than or equal to 450 MPa and less than or equal to 550 MPa, greater than or equal to 475 MPa and less than or equal to 550 MPa, greater than or equal to 500 MPa and less than or equal to 550 MPa, greater than or equal to 525 MPa and less than or equal to 550 MPa, greater than or equal to 450 MPa and less than or equal to 525 MPa, greater than or equal to 475 MPa and less than or equal to 525 MPa, greater than or equal to 500 MPa and less than or equal to 525 MPa, greater than or equal to 450 MPa and less than or equal to 500 MPa, greater than or equal to 475 MPa and less than orequal to 500 MPa, or greater than or equal to 450 MPa and less than or equal to 475 MPa. It should be understood that the above ranges include all subranges within the explicitly disclosed ranges.

[0172] The fracture strength of the glass-based according to embodiments measured on a glass-based article having a thickness of 0.5 mm using 1000 grit is greater than or equal to 475 MPa and less than or equal to 550 MPa, greater than or equal to 500 MPa and less than or equal to 550 MPa, greater than or equal to 525 MPa and less than or equal to 550 MPa, greater than or equal to 475 MPa and less than or equal to 525 MPa, greater than or equal to 500 MPa and less than or equal to 525 MPa, or greater than or equal to 475 MPa and less than or equal to 500 MPa, It should be understood that the above ranges include all subranges within the explicitly disclosed ranges.

[0173] The fracture strength of the glass-based according to embodiments measured on a glass-based article having a thickness of 0.6 mm using 180 grit is greater than or equal to 400 MPa and less than or equal to 500 MPa, greater than or equal to 425 MPa and less than or equal to 500 MPa, greater than or equal to 450 MPa and less than or equal to 500 MPa, greater than or equal to 475 MPa and less than or equal to 500 MPa, greater than or equal to 400 MPa and less than or equal to 475 MPa, greater than or equal to 425 MPa and less than or equal to 475 MPa, greater than or equal to 450 MPa and less than or equal to 475 MPa, greater than or equal to 400 MPa and less than or equal to 450 MPa, greater than or equal to 425 MPa and less than or equal to 450 MPa, or greater than or equal to 400 MPa and less than or equal to 425 MPa. It should be understood that the above ranges include all subranges within the explicitly disclosed ranges.

[0174] The fracture strength of the glass-based according to embodiments measured on a glass-based article having a thickness of 0.5 mm using 180 grit is greater than or equal to 350 MPa and less than or equal to 450 MPa, greater than or equal to 375 MPa and less than or equal to 450 MPa, greater than or equal to 400 MPa and less than or equal to 450 MPa, greater than or equal to 425 MPa and less than or equal to 450 MPa, greater than or equal to 350 MPa and less than or equal to 425 MPa, greater than or equal to 375 MPa and less than or equal to 425 MPa, greater than or equal to 400 MPa and less than or equal to 425 MPa, greater than or equal to 350 MPa and less than or equal to 400 MPa, greater than or equal to 375 MPa and less than or equal to 400 MPa, or greater than or equal to 350 MPa and less than or equal to 375 MPa. Itshould be understood that the above ranges include all subranges within the explicitly disclosed ranges.

[0175] The fracture strength of the glass-based according to embodiments measured on a glass-based article having a thickness of 0.6 mm using 80 grit is greater than or equal to 350 MPa and less than or equal to 450 MPa, greater than or equal to 375 MPa and less than or equal to 450 MPa, greater than or equal to 400 MPa and less than or equal to 450 MPa, greater than or equal to 425 MPa and less than or equal to 450 MPa, greater than or equal to 350 MPa and less than or equal to 425 MPa, greater than or equal to 375 MPa and less than or equal to 425 MPa, greater than or equal to 400 MPa and less than or equal to 425 MPa, greater than or equal to 350 MPa and less than or equal to 400 MPa, greater than or equal to 375 MPa and less than or equal to 400 MPa, or greater than or equal to 350 MPa and less than or equal to 375 MPa. It should be understood that the above ranges include all subranges within the explicitly disclosed ranges.

[0176] The fracture strength of the glass-based according to embodiments measured on a glass-based article having a thickness of 0.5 mm using 80 grit is greater than or equal to 300 MPa and less than or equal to 400 MPa, greater than or equal to 325 MPa and less than or equal to 400 MPa, greater than or equal to 350 MPa and less than or equal to 400 MPa, greater than or equal to 375 MPa and less than or equal to 400 MPa, greater than or equal to 300 MPa and less than or equal to 375 MPa, greater than or equal to 325 MPa and less than or equal to 375 MPa, greater than or equal to 350 MPa and less than or equal to 375 MPa, greater than or equal to 300 MPa and less than or equal to 350 MPa, greater than or equal to 325 MPa and less than or equal to 350 MPa, or greater than or equal to 300 MPa and less than or equal to 325 MPa. It should be understood that the above ranges include all subranges within the explicitly disclosed ranges.

[0177] The Drop Test Method is used to determine the drop strength of the glass or glass- based. The Drop Test Method involves performing face-drop testing on a puck with a glass or glass ceramic article attached thereto. The glass or glass ceramic article to be tested has a thickness similar or equal to the thickness that will be used in a given hand-held consumer electronic device. A puck refers to a structure meant to mimic the size, shape, and weight distribution of a given device, such as a cell phone. Hereinafter, the term “puck,” refers to a structure that has a weight of 126.0 grams, a length of 133.1 mm, a width of 68.2 mm, and a height of 9.4 mm.

[0178] An exemplary device-drop machine that may be used to conduct the Drop Test Method will now be described. The device-drop machine includes a chuck having chuck jaws. The puck is staged in the chuck jaws with the glass-based article attached thereto and facing downward. The chuck is ready to fall from, for example, an electro-magnetic chuck lifter. The chuck is released and during its fall, the chuck jaws are triggered to open by, for example, a proximity sensor. As the chuck jaws open, the puck is released. The falling puck strikes a drop surface. The drop surface may be sandpaper, such as 180 grit sandpaper (however other grit sandpaper may be used as disclosed herein). If the glass or glass-based article attached to the puck survives the fall (i.e., does not crack), the chuck is set at an increased height and the test is repeated. The failure height is then the lowest height from which the puck including the glass or glass-based article is dropped and the glass or glass-based composition fails.

[0179] In embodiments the drop strength of a 0.6 mm thick glass-based article is greater than or equal to 190 cm and less than or equal to 250 cm, greater than or equal to 200 cm and less than or equal to 250 cm, greater than or equal to 210 cm and less than or equal to 250 cm, greater than or equal to 220 cm and less than or equal to 250 cm, greater than or equal to 230 cm and less than or equal to 250 cm, greater than or equal to 240 cm and less than or equal to 250 cm, greater than or equal to 190 cm and less than or equal to 240 cm, greater than or equal to 200 cm and less than or equal to 240 cm, greater than or equal to 210 cm and less than or equal to 240 cm, greater than or equal to 220 cm and less than or equal to 240 cm, greater than or equal to 230 cm and less than or equal to 240 cm, greater than or equal to 190 cm and less than or equal to 230 cm, greater than or equal to 200 cm and less than or equal to 230 cm, greater than or equal to 210 cm and less than or equal to 230 cm, greater than or equal to 220 cm and less than or equal to 230 cm, greater than or equal to 190 cm and less than or equal to 220 cm, greater than or equal to 200 cm and less than or equal to 220 cm, greater than or equal to 210 cm and less than or equal to 220 cm, greater than or equal to 190 cm and less than or equal to 210 cm, greater than or equal to 200 cm and less than or equal to 210 cm, or greater than or equal to 190 cm and less than or equal to 200 cm. It should be understood that the above ranges include all subranges within the explicitly disclosed ranges.

[0180] In embodiments the drop strength of a 0.5 mm thick glass-based article is greater than or equal to 180 cm and less than or equal to 240 cm, greater than or equal to 190 cm and less than or equal to 240 cm, greater than or equal to 200 cm and less than or equal to 240 cm, greater than or equal to 210 cm and less than or equal to 240 cm, greater than or equal to 220cm and less than or equal to 240 cm, greater than or equal to 230 cm and less than or equal to 240 cm, greater than or equal to 180 cm and less than or equal to 230 cm, greater than or equal to 190 cm and less than or equal to 230 cm, greater than or equal to 200 cm and less than or equal to 230 cm, greater than or equal to 210 cm and less than or equal to 230 cm, greater than or equal to 220 cm and less than or equal to 230 cm, greater than or equal to 180 cm and less than or equal to 220 cm, greater than or equal to 190 cm and less than or equal to 220 cm, greater than or equal to 200 cm and less than or equal to 220 cm, greater than or equal to 210 cm and less than or equal to 220 cm, greater than or equal to 180 cm and less than or equal to 210 cm, greater than or equal to 190 cm and less than or equal to 210 cm, greater than or equal to 200 cm and less than or equal to 210 cm, greater than or equal to 180 cm and less than or equal to 200 cm, greater than or equal to 190 cm and less than or equal to 200 cm, or greater than or equal to 180 cm and less than or equal to 190 cm. It should be understood that the above ranges include all subranges within the explicitly disclosed ranges.

[0181] Non-strengthened glass-based articles according to embodiments disclosed and described herein are also scratch resistant and have an onset load for lateral cracking that is greater than or equal to 0.50 Newtons (N) and less than or equal to 0.75 N, such as greater than or equal to 0.55 N and less than or equal to 0.75 N, greater than or equal to 0.60 N and less than or equal to 0.75 N, greater than or equal to 0.65 N and less than or equal to 0.75 N, greater than or equal to 0.70 N and less than or equal to 0.75 N, greater than or equal to 0.50 N and less than or equal to 0.70 N, greater than or equal to 0.55 N and less than or equal to 0.70 N, greater than or equal to 0.60 N and less than or equal to 0.70 N, greater than or equal to 0.65 N and less than or equal to 0.70 N, greater than or equal to 0.50 N and less than or equal to 0.65 N, greater than or equal to 0.55 N and less than or equal to 0.65 N, greater than or equal to 0.60 N and less than or equal to 0.65 N, greater than or equal to 0.50 N and less than or equal to 0.60 N, greater than or equal to 0.55 N and less than or equal to 0.60 N, or greater than or equal to 0.50 N and less than or equal to 0.55 N. It should be understood that the above ranges include all subranges within the explicitly disclosed ranges.

[0182] Glass-based articles according to embodiments have a Vickers Hardness (at 200g load) measured on an unstrengthened glass-based that is greater than or equal to 740 Kgf / mm2and less than or equal to 820 Kgf / mm2, such as greater than or equal to 760 Kgf / mm2and less than or equal to 820 Kgf / mm2, greater than or equal to 780 Kgf / mm2and less than or equal to 820 Kgf / mm2, greater than or equal to 800 Kgf / mm2and less than or equal to 820 Kgf / mm2,greater than or equal to 740 Kgf / mm2and less than or equal to 800 Kgf / mm2, such as greater than or equal to 760 Kgf / mm2and less than or equal to 800 Kgf / mm2, greater than or equal to 780 Kgf / mm2and less than or equal to 800 Kgf / mm2, greater than or equal to 740 Kgf / mm2and less than or equal to 780 Kgf / mm2, such as greater than or equal to 760 Kgf / mm2and less than or equal to 780 Kgf / mm2, or greater than or equal to 740 Kgf / mm2and less than or equal to 760 Kgf / mm2. It should be understood that the above ranges include all subranges within the explicitly disclosed ranges.

[0183] Embodiments of glass-based articles have an annealing point that is greater than or equal to 750 °C and less than or equal to 770 °C, greater than or equal to 755 °C and less than or equal to 770 °C, greater than or equal to 760 °C and less than or equal to 770 °C, greater than or equal to 765 °C and less than or equal to 770 °C, greater than or equal to 750 °C and less than or equal to 765 °C, greater than or equal to 755 °C and less than or equal to 765 °C, greater than or equal to 760 °C and less than or equal to 765 °C, greater than or equal to 750 °C and less than or equal to 760 °C, greater than or equal to 755 °C and less than or equal to 760 °C, or greater than or equal to 750 °C and less than or equal to 755 °C. It should be understood that the above ranges include all subranges within the explicitly disclosed ranges.

[0184] Glass-based articles according to embodiments have a strain point that is greater than or equal to 700 °C and less than or equal to 750 °C, greater than or equal to 710 °C and less than or equal to 750 °C, greater than or equal to 720 °C and less than or equal to 750 °C, greater than or equal to 725 °C and less than or equal to 750 °C, greater than or equal to 730 °C and less than or equal to 750 °C, greater than or equal to 740 °C and less than or equal to 750 °C, greater than or equal to 700 °C and less than or equal to 740 °C, greater than or equal to 710 °C and less than or equal to 740 °C, greater than or equal to 720 °C and less than or equal to 740 °C, greater than or equal to 725 °C and less than or equal to 740 °C, greater than or equal to 730 °C and less than or equal to 740 °C, greater than or equal to 700 °C and less than or equal to 730 °C, greater than or equal to 710 °C and less than or equal to 730 °C, greater than or equal to 720 °C and less than or equal to 730 °C, greater than or equal to 725 °C and less than or equal to 730 °C, greater than or equal to 700 °C and less than or equal to 725 °C, greater than or equal to 710 °C and less than or equal to 725 °C, greater than or equal to 720 °C and less than or equal to 725 °C, greater than or equal to 700 °C and less than or equal to 720 °C, greater than or equal to 710 °C and less than or equal to 720 °C, or greater than or equal to 700°C and less than or equal to 710 °C. It should be understood that the above ranges include all subranges within the explicitly disclosed ranges.

[0185] According to embodiments, glass-based articles have a refraction index (measured at wavelengths of 598 nm) that is greater than or equal to 1.500 and less than or equal to 1.600, greater than or equal to 1.520 and less than or equal to 1.600, greater than or equal to 1.540 and less than or equal to 1.600, greater than or equal to 1.550 and less than or equal to 1.600, greater than or equal to 1.560 and less than or equal to 1.600, greater than or equal to 1.580 and less than or equal to 1.600, greater than or equal to 1.500 and less than or equal to 1.580, greater than or equal to 1.520 and less than or equal to 1.580, greater than or equal to 1.540 and less than or equal to 1.580, greater than or equal to 1.550 and less than or equal to 1.580, greater than or equal to 1.560 and less than or equal to 1.580, greater than or equal to 1.500 and less than or equal to 1.560, greater than or equal to 1.520 and less than or equal to 1.560, greater than or equal to 1.540 and less than or equal to 1.560, greater than or equal to 1.550 and less than or equal to 1.560, greater than or equal to 1.500 and less than or equal to 1.550, greater than or equal to 1.520 and less than or equal to 1.550, greater than or equal to 1.540 and less than or equal to 1.550, greater than or equal to 1.500 and less than or equal to 1.540, greater than or equal to 1.520 and less than or equal to 1.540, or greater than or equal to 1.500 and less than or equal to 1.520. It should be understood that the above ranges include all subranges within the explicitly disclosed ranges.

[0186] The stress optical coefficient (measured at a wavelength of 546 nm) of glass-based articles according to embodiments is greater than or equal to 25.5 nm / cm / MPa and less than or equal to 26.5 nm / cm / MPa, greater than or equal to 25.8 nm / cm / MPa and less than or equal to 26.5 nm / cm / MPa, greater than or equal to 26.0 nm / cm / MPa and less than or equal to 26.5 nm / cm / MPa, greater than or equal to 26.2 nm / cm / MPa and less than or equal to 26.5 nm / cm / MPa, greater than or equal to 26.4 nm / cm / MPa and less than or equal to 26.5 nm / cm / MPa, greater than or equal to 25.5 nm / cm / MPa and less than or equal to 26.4 nm / cm / MPa, greater than or equal to 25.8 nm / cm / MPa and less than or equal to 26.4 nm / cm / MPa, greater than or equal to 26.0 nm / cm / MPa and less than or equal to 26.4 nm / cm / MPa, greater than or equal to 26.2 nm / cm / MPa and less than or equal to 26.4 nm / cm / MPa, greater than or equal to 25.5 nm / cm / MPa and less than or equal to 26.2 nm / cm / MPa, greater than or equal to 25.8 nm / cm / MPa and less than or equal to 26.2 nm / cm / MPa, greater than or equal to 26.0 nm / cm / MPa and less than or equal to 26.2nm / cm / MPa, greater than or equal to 25.5 nm / cm / MPa and less than or equal to 26.0 nm / cm / MPa, greater than or equal to 25.8 nm / cm / MPa and less than or equal to 26.0 nm / cm / MPa, or greater than or equal to 25.5 nm / cm / MPa and less than or equal to 25.8 nm / cm / MPa. It should be understood that the above ranges include all subranges within the explicitly disclosed ranges.

[0187] According to embodiments, the glass-based articles have a density that is greater than or equal to 2.40 g / cm3and less than or equal to 2.60 g / cm3, greater than or equal to 2.42 g / cm3and less than or equal to 2.60 g / cm3, greater than or equal to 2.45 g / cm3and less than or equal to 2.60 g / cm3, greater than or equal to 2.48 g / cm3and less than or equal to 2.60 g / cm3, greater than or equal to 2.50 g / cm3and less than or equal to 2.60 g / cm3, greater than or equal to 2.52 g / cm3and less than or equal to 2.60 g / cm3, greater than or equal to 2.55 g / cm3and less than or equal to 2.60 g / cm3, greater than or equal to 2.58 g / cm3and less than or equal to 2.60 g / cm3, greater than or equal to 2.40 g / cm3and less than or equal to 2.58 g / cm3, greater than or equal to 2.42 g / cm3and less than or equal to 2.58 g / cm3, greater than or equal to 2.45 g / cm3and less than or equal to 2.58 g / cm3, greater than or equal to 2.48 g / cm3and less than or equal to 2.58 g / cm3, greater than or equal to 2.50 g / cm3and less than or equal to 2.58 g / cm3, greater than or equal to 2.52 g / cm3and less than or equal to 2.58 g / cm3, greater than or equal to 2.55 g / cm3and less than or equal to 2.58 g / cm3, greater than or equal to 2.40 g / cm3and less than or equal to 2.55 g / cm3, greater than or equal to 2.42 g / cm3and less than or equal to 2.55 g / cm3, greater than or equal to 2.45 g / cm3and less than or equal to 2.55 g / cm3, greater than or equal to 2.48 g / cm3and less than or equal to 2.55 g / cm3, greater than or equal to 2.50 g / cm3and less than or equal to 2.55 g / cm3, greater than or equal to 2.52 g / cm3and less than or equal to 2.55 g / cm3, greater than or equal to 2.40 g / cm3and less than or equal to 2.52 g / cm3, greater than or equal to 2.42 g / cm3and less than or equal to 2.52 g / cm3, greater than or equal to 2.45 g / cm3and less than or equal to 2.52 g / cm3, greater than or equal to 2.48 g / cm3and less than or equal to 2.52 g / cm3, greater than or equal to 2.50 g / cm3and less than or equal to 2.52 g / cm3, greater than or equal to 2.40 g / cm3and less than or equal to 2.50 g / cm3, greater than or equal to 2.42 g / cm3and less than or equal to 2.50 g / cm3, greater than or equal to 2.45 g / cm3and less than or equal to 2.50 g / cm3, greater than or equal to 2.48 g / cm3and less than or equal to 2.50 g / cm3, greater than or equal to 2.40 g / cm3and less than or equal to 2.48 g / cm3, greater than or equal to 2.42 g / cm3and less than or equal to 2.48 g / cm3, greater than or equal to 2.45 g / cm3and less than or equal to 2.48 g / cm3, greater than or equal to 2.40 g / cm3and less than or equal to 2.45 g / cm3, greater than or equal to 2.42 g / cm3and less than or equal to 2.45 g / cm3, or greater than or equalto 2.40 g / cm3and less than or equal to 2.42 g / cm3. It should be understood that the above ranges include all subranges within the explicitly disclosed ranges.

[0188] End products

[0189] The glass-based articles disclosed herein may be incorporated into another article such as an article with a display (or display articles) (e.g., consumer electronics, including mobile phones, tablets, computers, navigation systems, wearable devices (e.g., watches) and the like). An exemplary article incorporating any of the strengthened glass-based articles disclosed herein is shown in FIGS.13A and 13B.

[0190] Specifically, FIGS. 13A and 13B show a consumer electronic device 200 including a housing 202 having front 204, back 206, and side surfaces 208; electrical components (not shown) that are at least partially inside or entirely within the housing and including at least a controller, a memory, and a display 210 at or adjacent to the front surface of the housing; and a cover substrate 212 at or over the front surface of the housing such that it is over the display. In some embodiments, at least one of the cover substrate 212 or a portion of housing 202 may include any of the glass-based strengthened articles disclosed herein. EXAMPLES

[0191] Embodiments will be further clarified by the following examples. EXAMPLE 1

[0192] After composition and ceram cycle optimization of a glass-based article, the crystallization of the exposed vs. unexposed regions can be altered as can be seen in FIG. 6. The glass-based article had the following composition in addition to 2.5 wt.% of a metallic nucleating agent package comprising cerium oxide and other nucleating agents: Composition (wt.%) SiO2 72.3 Al2O3 7.2 Li2O 11.6 Na2O 0.07 K2O 0.12 ZrO2 5.97 Fe2O3 0.06CaO 0.7

[0193] On the left image of FIG.6, a simple “line” mask on part of the sample was used to highlight the difference in transparency in exposed vs. unexposed regions. The darker circular pattern with lines is the exposed region and clearly shows enhanced transparency relative to the unexposed surrounding region. Similarly, a “bear” mask was used in the image on the right of FIG.6 to show more complex designs that can utilize this technique. These samples were exposed for 1 hour using a low power lamp in and then heat treated for 35 minutes at 545°C, and then rapidly ramped to 745°C for a 15-minute hold. This thermal cycle was designed to undernucleate the composition (as evidenced by the dense white regions in the unexposed areas). The regions exposed to the UV light, however, were able to ceram into a clear state, which is expected. EXAMPLE2

[0194] A glass-ceramic article was exposed to different laser conditions, which resulted in an amorphous regions begin formed in the areas exposed to the laser conditions. The results are shown in FIG.7. It was found that an ultrafast laser is good for glass surface texturing and internal modification from non-linear effects; however, if the laser is used as a heating source to trigger linear absorption through the whole glass, a CW / QCW or diode laser with proper wavelength may be more effective. EXAMPLE3

[0195] A fracture mechanics model was scripted in FEA for Abaqus, which calculates the stress intensity factor and retained strength as a function of residual stress profile, flaw length, material properties, residual stress profile, and applied bending stress, if applicable. The model is shown in FIG. 8, which is a Schematic illustration of the retained strength model. The retained strength equation as a function of applied bending load is shown (P is the applied load at one of the four load points, L is the distance between the load and support point, d is the depth into the sheet, and t is the thickness of the glass).

[0196] A typical residual stress profile for 150-micron glass is shown in FIG.9 and was used for the model calculations as shown in FIG.10. Using the stress profile shown in FIG. 9, the model was used to calculate the stress intensity factor as a function of flaw length for materialswith the toughness of a glass and a glass ceramic (0.7 and 1.15 MPa m0.5measured from the chevron notched beam, respectively). The glass ceramic had a significant advantage for retained strength, as shown in FIG.10. As can be seen in FIG.10, the glass ceramic has over 100 MPa more strength for nearly all flaw depths.

[0197] The stress intensity factor without any applied bending is a good indicator of the materials’ resistance to flaws in an unbent state. The modeled results for the conditions considered in FIG. 9 are shown in FIG. 11. The stress intensity factor divided by the stress intensity factor without bending is significantly reduced for the glass ceramic material.

[0198] In addition to the material benefits shown from modeling, it has been observed for thicker cover glass materials that glass ceramics are more likely to dissipate energy through crushing during a scratch event than through cracking. Scratch testing results are shown in FIG.11.

[0199] When compared to a glass the glass ceramic (GC) has a low Knoop Scratch Threshold. However, at higher loads, the glass ceramic transitions to crushing rather than cracking. It is therefore expected that a glass ceramic will be less likely to initiate cover glass failing median cracks during a scratch-like contact event than glass.

[0200] 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. Thus, it is intended that the specification cover the modifications and variations of the various embodiments described herein provided such modification and variations come within the scope of the appended claims and their equivalents.

Claims

What is claimed is:

1. A glass-based article comprising: a first crystal-containing region; a second crystal-containing region; and a bendable amorphous region positioned between the first crystal-containing region and the second crystal-containing region, wherein the glass-based article is a continuous glass-based article, and the bendable amorphous region is configured so that the glass-based article bends about the bendable amorphous region.

2. The glass-based article of claim 1, wherein the bendable amorphous region is configured so that when a bending force is applied to one or more of the first crystal-containing region and the second crystal-containing region: the bendable amorphous region is in a bent position; and the first crystal-containing region and the second crystal-containing region are not bent.

3. The glass-based article of any one of claims 1 or 2, wherein the bendable amorphous region comprises a first edge adjacent to the first crystal-containing region and a second edge adjacent to the second crystal-containing region, wherein the bendable amorphous region is configured so that: the first edge, the second edge, the first crystal-containing region, and the second crystal-containing region are planar to one another when the glass-based article is not in a bent position, and the first crystal-containing layer and the second crystal-containing layer are not planar when the glass-based article is in a bent position.

4. The glass-based article of claim 3, wherein the bendable amorphous region is configured so that the first edge is planar to the first crystal-containing region and the second edge is planar to the second crystal-containing region when the glass-based article is in a bent position.

5. The glass-based article of any one of claims 3 or 4, wherein the bendable amorphous region is configured so that the first edge is adjacent to the second edge when the glass-based article is in a bent position.

6. The glass-based article of any one of claims 1 to 5, wherein the glass-based article comprises more than one bendable amorphous region and more than two crystal- containing regions.

7. The glass-based article of any one of claims 1 to 6, wherein a number of crystal- containing regions is n+1, where n is the number of amorphous bendable regions.

8. The glass-based article of any one of claims 1 to 7, wherein the first crystal- containing region and the second crystal-containing region individually comprise greater than or equal to 75 wt% and less than or equal to 95 wt% crystalline phase.

9. The glass-based article of any one of claims 1 to 8, wherein the bendable amorphous region comprises up to 10 wt% crystalline phase.

10. The glass-based article of any one of claims 1 to 9, wherein the bendable amorphous region comprises 100 wt% amorphous glass.

11. The glass-based article of any one of claims 1 to 9, wherein the bendable amorphous region comprises a crystal-containing layer on a surface of the bendable amorphous region.

12. The glass-based article of any one of claims 1 to 11, wherein the first crystal- containing region, the second crystal-containing region, and the bendable amorphous region have a uniform thickness.

13. The glass-based article of any one of claims 1 to 11, wherein a thickness of the bendable amorphous region is less than a thickness of at least one of the first crystal-containing region and the second crystal containing region.

14. The glass-based article of any one of claims 1 to 13, wherein the bendable amorphous region has a ratio of compressive stress to Young’s modulus (CS / E) that is less than a CS / E of the first crystal-containing region and a CS / E of the second crystal-containing region.

15. The glass-based article of any one of claims 1 to 14, wherein the glass-based article comprises: greater than or equal to 65.00 wt.% and less than or equal to 80.00 wt.% SiO2; greater than 4.00 wt.% and less than or equal to 12.00 wt.% Al2O3;greater than or equal to 8.00 wt.% and less than or equal to 17.00 wt.% Li2O; greater than or equal to 4.00 wt.% and less than or equal to 15.00 wt.% ZrO2; and greater than or equal to 0.05 wt.% and less than or equal to 4.00 wt.% CaO.

16. The glass-based article of any one of claims 1 to 15, wherein the glass-based article comprises greater than or equal to 0.10 wt.% and less than or equal to 3.5 wt.% P2O5.

17. The glass-based article of any one of claims 1 to 16, wherein the glass-based article comprises metallic nucleating agents.

18. The glass-based article of claim 17, wherein the metallic nucleating agents are selected from the group consisting of cerium, antimony, silver, copper, gold, oxides thereof, and combinations thereof.

19. The glass-based article of any one of claims 1 to 18, wherein the glass-based article has a thickness that is greater than or equal to 0.1 mm and less than or equal to 2.0 mm.

20. An electronic device comprising: a housing; a display; and a cover substrate adjacent to the display, wherein the cover substrate comprises the glass-based article of any one of claims 1 to 19.

Images