USRE49530E1 - Crack and scratch resistant glass and enclosures made therefrom - Google Patents

Abstract

A glass and an enclosure, including windows, cover plates, and substrates for mobile electronic devices comprising the glass. The glass has a crack initiation threshold that is sufficient to withstand direct impact, has a retained strength following abrasion that is greater than soda lime and alkali aluminosilicate glasses, and is resistant to damage when scratched. The enclosure includes cover plates, windows, screens, and casings for mobile electronic devices and information terminal devices.

Description

CROSS REFERENCE TO RELATED APPLICATIONS

More than one reissue application has been filed for the reissue of U.S. Pat. No. 9,290,407. The reissue applications are the present application and U.S. patent application Ser. No. 15/862,353. This application is a continuation reissue application of U.S. patent application Ser. No. 15/862,353, filed Apr. 1, 2018, which is an application for reissue of U.S. Pat. No. 9,290,407, issued Mar. 22, 2016, filed as U.S. patent application Ser. No. 14/082,847 on Nov. 18, 2013, which is a continuation application of U.S. patent application Ser. No. 12/858,490, filed Aug. 18, 2010, now U.S. Pat. No. 8,586,492, which claims the benefit of U.S. Provisional Application No. 61/235,767, filed Aug. 21, 2009, each of which is incorporated herein by reference.

BACKGROUND

The disclosure is related to glass enclosures, including windows, cover plates, and substrates for electronic devices. More particularly, the disclosure relates to crack- and scratch-resistant enclosures.

Glass is being designed into electronic devices, such as telephones, and entertainment devices, such as games, music players and the like, and information terminal (IT) devices, such as laptop computers. A predominant cause of breakage of cover glass in mobile devices is point contact or sharp impact. The solution for this problem has been to provide a bezel or similar protective structure to hold and protect the glass from such impacts. In particular, the bezel provides protection from impact on the edge of the glass. The edge of the cover glass is most vulnerable to fragmentation by direct impact. Incorporation of the bezel limits the use of glass to flat pieces in the device and prevents utilization of designs that exploit the crystal-like appearance of glass.

SUMMARY

A glass and a glass enclosure, including windows, cover plates, and substrates for mobile electronic devices comprising the glass are provided. The glass has a crack initiation threshold that is sufficient to withstand direct impact, a retained strength following abrasion that is greater than soda lime and alkali aluminosilicate glasses, and is more resistant to damage when scratched. The enclosure includes cover plates, windows, screens, touch panels, casings, and the like for electronic devices and information terminal devices. The glass can also be used in other applications, such as a vehicle windshield, where light weight, high strength, and durable glass is be desired.

Accordingly, one aspect of the disclosure is to provide an aluminoborosilicate glass comprising at least 50 mol % SiO₂ in some embodiments, at least 58 mol % SiO₂, in other embodiments, and at least 60 mol % SiO₂ in still other embodiments, and at least one modifier selected from the group consisting of alkali metal oxides and alkaline earth metal oxides. The aluminoborosilicate glass is ion exchangeable, and exhibits the ratio

$\frac{{\mathrm{Al}}_2{O}_3\left(\mathrm{mol}\%\right)+{\mathrm{<figure-callout\; id="2"\; label="B"\; filenames="USRE049530-20230516-D00008.png"\; state="\{\{state\}\}">B</figure-callout>}}_2{O}_3\left(\mathrm{mol}\%\right)}{\Sigma modi\mathrm{fiers}\left(\mathrm{mol}\%\right)}>1.$

A second aspect of the disclosure is to provide an aluminoborosilicate glass. The aluminoborosilicate glass comprises: 50-72 mol % SiO₂; 9-17 mol % Al₂O₃; 2-12 mol % B₂O₃; 8-16 mol % Na₂O; and 0-4 mol % K₂O, wherein the ratio

$\frac{{\mathrm{Al}}_2{O}_3\left(\mathrm{mol}\%\right)+{\mathrm{<figure-callout\; id="2"\; label="B"\; filenames="USRE049530-20230516-D00008.png"\; state="\{\{state\}\}">B</figure-callout>}}_2{O}_3\left(\mathrm{mol}\%\right)}{\Sigma modi\mathrm{fiers}\left(\mathrm{mol}\%\right)}>1,$
where the modifiers are selected from the group consisting of alkali metal oxides and alkaline earth metal oxides. The aluminoborosilicate glass is ion exchangeable.

A third aspect of the disclosure is to provide a glass enclosure for use in an electronic device. The glass enclosure comprises a strengthened glass that, when scratched with a Knoop diamond at a load of at least 5 N to form a scratch of width w, is free of chips having a size greater than three times the width w.

These and other aspects, advantages, and salient features will become apparent from the following detailed description, the accompanying drawings, and the appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1a is an schematic representation of a prior art glass cover plate held in place by a bezel;

FIG. 1b is a schematic representation of glass cover plate that is proud of the bezel;

FIG. 2a is a microscopic image of an ion exchanged alkali aluminosilicate glass of the prior art having a scratch formed with a Knoop diamond at a load of 10 N;

FIG. 2b is a microscopic image of a strengthened aluminoborosilicate glass having a scratch formed with a Knoop diamond at a load of 10 N;

FIG. 3a is a top view of a 1 kilogram force (kgf) Vickers indentation 305 in a soda lime silicate glass of the prior art that had not been ion exchanged;

FIG. 3b is a side or cross-sectional view of a 1 kgf Vickers indentation in a soda lime silicate glass of the prior art that had not been ion exchanged;

FIG. 4 is a side or cross-sectional view of a 1 kgf Vickers indentation of an ion-exchanged soda lime silicate glass of the prior art;

FIG. 5a is a top view of a 1 kgf Vickers indentation in an aluminoborosilicate glass that had not been ion exchanged;

FIG. 5b is a side or cross-sectional view of a 1 kgf Vickers indentation in an aluminoborosilicate glass that had not been ion exchanged;

FIG. 6 is top view of a 30 kgf Vickers indentation of a ion exchanged aluminoborosilicate glass; and

FIG. 7 is a plot of crack initiation thresholds measured of aluminoborosilicate glasses as a function of Al₂O₃+B₂O₃—Na₂O.

DETAILED DESCRIPTION

In the following description, like reference characters designate like or corresponding parts throughout the several views shown in the figures. It is also understood that, unless otherwise specified, terms such as “top,” “bottom,” “outward,” “inward,” and the like are words of convenience and are not to be construed as limiting terms. In addition, whenever a group is described as comprising at least one of a group of elements and combinations thereof, it is understood that the group may comprise, consist essentially of, or consist of any number of those elements recited, either individually or in combination with each other. Similarly, whenever a group is described as consisting of at least one of a group of elements or combinations thereof, it is understood that the group may consist of any number of those elements recited, either individually or in combination with each other. Unless otherwise specified, a range of values, when recited, includes both the upper and lower limits of the range as well as any sub-ranges therebetween. Unless otherwise specified, all compositions and relationships that include constituents of compositions described herein are expressed in mole percent (mol %).

Referring to the drawings in general, it will be understood that the illustrations are for the purpose of describing particular embodiments and are not intended to limit the disclosure or appended claims thereto. The drawings are not necessarily to scale, and certain features and views of the drawings may be shown exaggerated in scale or in schematic in the interest of clarity and conciseness.

As used herein, the terms “enclosure,” “cover plate,” and “window” are used interchangeably and refer to glass articles, including windows, cover plates, screens, panels, and substrates, that form the outer portion of a display screen, window, or structure for mobile electronic devices.

Glass is being designed into mobile electronic devices, such as telephones, and entertainment devices, including games, music players and the like; information terminal (IT) devices, such as laptop computers; and analogous stationary versions of such devices.

In some instances, such designs are limited to a flat piece of glass that is protected by a bezel; i.e., a rim that is used to hold and protect a glass window or cover plate in a given device. An example of a glass cover plate or window that is held in place by a bezel is schematically shown in FIG. 1a. Cover plate 110 rests in rim 122 of bezel 120, which holds cover plate 110 in place on body 105 of device 100 and protects the edge 112 of cover plate 110 from sharp impacts.

In order to exploit the crystal-like appearance of glass windows, cover plates, and the like in such devices, designs are being extended to make the glass “proud” of the bezel. The term “proud of the bezel” means that the glass extends to the edge of the device and protrudes above and beyond any bezel or rim of the device. FIG. 1b schematically shows an example of a glass cover plate 110 that is proud of the bezel 120 and is affixed to body 105 of device 100. Glass cover plate 110 is mounted on the surface of bezel 120 such that edges 112 of glass cover plate 110 are exposed and otherwise not covered by bezel 120. Edges 112 of cover plate 110 extend to the edges of 107 of body 105.

The primary limitation to implementing a cover plate or window that is proud of the bezel in such designs is the inability of glass cover plate 110—particularly edges 112—to withstand direct impact, thus necessitating protection of edge 112 of glass cover plate 110 by bezel 120 (FIG. 1a). Furthermore, a glass cover plate 110 that is proud of the bezel 120 (FIG. 1b) will have a greater chance of being scratched during handling and use due to exposure of edge 112 of glass cover plate 110. In order to implement the aforementioned new designs, a glass cover plate must therefore be better able to withstand direct impacts than those glasses that are presently used in such applications. Moreover, a glass must also be resistant to scratching and should have a high retained strength after being scratched or abraded.

The predominant cause of glass breakage in applications such as windshields or cover glass in electronic devices is point contact or sharp impact. To serve as a cover glass or other enclosure in such applications, the crack initiation load of the glass has to be sufficiently high so that it can withstand direct impact. The depth of the surface layers of the glass that are under compressive stress has to be sufficient to provide a high retained strength and increased resistance to damage incurred upon being scratched or abraded.

Accordingly, a glass or glass article that is more resistant to sharp impact and is be able to withstand direct or point impacts is provided. Such glass articles include a windshield or glass enclosure such as, but not limited to, a cover plate, window, casing, screen, touch panel, or the like, for electronic devices. The glass enclosure comprises a strengthened glass which does not exhibit lateral damage such as, but not limited to, chipping when scratched at a rate of 0.4 mm/s with a Knoop diamond that is oriented so that the angle between the leading and trailing edges of the tip of the Knoop diamond is 172°30′ at a load of 5 N and, in some embodiments, at a load of 10 N. As used herein, “chipping” refers to the removal or ejection of glass fragments from a surface of a glass when the surface is scratched with an object such as a stylus. As used herein, “chip” can refer to either a glass fragment removed during scratching of the glass surface or the region on the surface from which the chip is removed. In the latter sense, a chip is typically characterized as a depression in the vicinity of the scratch. When scratched, the glass article described herein does not exhibit chipping (i.e., chips are not generated, or the glass is free of chips) beyond a region extending laterally on either side of the scratch track (i.e., the scratch formed by the Knoop diamond) formed for a distance d that is greater than twice the width w of the scratch and, in another embodiment, three times the width w of the scratch. In other words, chipping generated by scratching is limited to a region bordering either side of the scratch track, wherein the width of the region is no greater than twice (in some embodiment, no greater than three times) the width w of the scratch. In one embodiment, the glass enclosure is proud of a bezel, extending above and protruding beyond the bezel, in those instances where a bezel is present. In one embodiment, the glass enclosure has a thickness in a range from about 0.1 mm up to about 2.0 mm. In another embodiment, the glass enclosure has a thickness in a range from about 0.1 mm up to about 2.3 mm and, in other embodiments, the glass enclosure has a thickness of up to about 5.0 mm.

The scratch resistance or response of a glass enclosure to scratching is illustrated in FIG. 2a. The glass shown in FIG. 2a is an alkali aluminosilicate glass having the composition 66 mol % SiO₂, 10.3 mol % Al₂O₃, 0.6 mol % B₂O₃, 14 mol % Na₂O, 2.45 mol % K₂O, and 0.21 mol % SnO₂, wherein the ratio (Al₂O₃+B₂O₃)/Σ(modifiers), expressed in mol %, is 0.66. The glass was strengthened by ion exchange by immersion in a molten KNO₃ salt bath at 410° C. for 8 hrs. FIG. 2a is a microscopic image of the glass having a scratch 210 of width w formed at a rate of 0.4 mm/s with a Knoop diamond at a load of 10 N. Numerous chips 220 are formed along scratch 210, with some chips extending from scratch 210 for a distance d exceeding twice the width w (2w) of scratch 210. In contrast to the behavior of the glass shown in FIG. 2a, the response of the glass enclosure and glasses described herein to scratching is illustrated in FIG. 2b. FIG. 2b is a microscopic image of an aluminoborosilicate glass (64 mol % SiO₂, 14.5 mol % Al₂O₃, 8 mol % B₂O₃, 11.5 mol % Na₂O, 0.1 mol % SnO₂; wherein the ratio (Al₂O₃+B₂O₃)/Σ(modifiers), wherein Al₂O₃, B₂O₃, and Na₂O modifier concentrations are expressed in mol %, is 1.96) that is representative of those aluminoborosilicate glasses described herein. The glass shown in FIG. 2b was ion exchanged by immersion in a molten KNO₃ salt bath at 410° C. for 8 hrs. The glass shown in FIG. 2b has a scratch 210 of width w formed with a Knoop diamond at a load of 10 N. The chips 220 formed in the aluminoborosilicate glass shown in FIG. 2b are significantly smaller than those seen in FIG. 2a. In FIG. 2b, chip formation is limited to a zone extending from an edge 212 of scratch 210 to a distance d. The width d of the zone or region in which such chipping occurs is significantly less than 2w. In other words, most of the chips 220 seen in FIG. 2b extend for a distance d, which is less than about width w from crack 210. The glass retains at least 30% of its original load at failure and, in some embodiments, at least 50% of its original load at failure as a determined by ring on ring measurements after scratching with a 3 N Vickers load at a rate of 0.4 mm/s.

The glass enclosures described herein comprise a strengthened glass that deforms upon indentation under an indentation load of at least 500 gf primarily by densification rather than by shear faulting. The glass is free of subsurface faulting and radial and median cracks upon deformation and is consequently more resistant to damage than typical ion-exchangeable glasses. In addition, the glass is more resistant to crack initiation by shear faulting when strengthened by ion exchange. In one embodiment, the glass enclosure comprises an ion exchanged glass and has a Vickers median/radial crack initiation threshold of at least 10 kilogram force (kgf). In a second embodiment, the glass enclosure has a Vickers median/radial crack initiation threshold of at least about 20 kgf and, in a third embodiment, the glass enclosure has a Vickers median/radial crack initiation threshold of at least about 30 kgf. Unless otherwise specified, the Vickers median/radial crack threshold is determined by measuring the onset of median or radial cracks in 50% relative humidity at room temperature.

In another embodiment, the glass enclosures described herein are non-frangible. As used herein, the term “non-frangible” means that the glass enclosures and the glass comprising the glass enclosures do not exhibit forceful fragmentation upon fracture. Such forceful fragmentation is typically characterized by multiple crack branching with ejection or “tossing” of small glass pieces and/or particles from the glass enclosure in the absence of any external restraints, such as coatings, adhesive layers, or the like. More specifically frangible behavior is characterized by at least one of: breaking of the strengthened glass article (e.g., a plate or sheet) into multiple small pieces (e.g., ≤1 mm); the number of fragments formed per unit area of the glass article; multiple crack branching from an initial crack in the glass article; and violent ejection of at least one fragment a specified distance (e.g., about 5 cm, or about 2 inches) from its original location; and combinations of any of the foregoing breaking (size and density), cracking, and ejecting behaviors. The glass enclosure and the glass comprising the enclosure are deemed to be substantially non-frangible if they do not exhibit any of the foregoing criteria.

The strengthened glass comprising the glass enclosure can be strengthened by either thermal or chemical processes known in the art. The glass, in one embodiment, can be thermally tempered by heating the glass at a temperature that is between the strain point and the softening point of the glass, followed by cooling to room temperature. In another embodiment, the glass is chemically strengthened by ion exchange in which smaller metal ions in the glass are replaced or “exchanged” by larger metal ions of the same valence within a layer of the glass that extends from the outer surface of the glass to a depth below the surface (commonly referred to as the “depth of layer” or “DOL”). The replacement of smaller ions with larger ions creates a compressive stress within the layer. In one embodiment, the metal ions are monovalent alkali metal ions (e.g., Na⁺, K⁺, Rb+, and the like), and ion exchange is accomplished by immersing the glass in a bath comprising at least one molten salt (e.g., KNO₃, K₂SO₄, KCl, or the like) of the larger metal ion that is to replace the smaller metal ion or ions (e.g., Na⁺ ions) in the glass. Alternatively, other monovalent cations such as Ag⁺, Tl⁺, Cu⁺, and the like can be exchanged for the alkali metal cations in the glass. The ion exchange process or processes that are used to strengthen the glass can include, but are not limited to, immersion in a single bath or multiple baths of like or different compositions with washing and/or annealing steps between immersions.

The depth of the compressive stress layer (depth of layer) present in ion-exchanged glasses prevents the propagation of flaws at or near the surface of the glass. Glasses such as soda lime silicate and alkali aluminosilicate glasses deform with a high shear band density. Such behavior is known to lead to crack nucleation and propagation in the non-ion exchanged versions of such glasses. An example of shear fault formation and crack initiation is shown in FIGS. 3a and 3b. FIGS. 3a and 3b are top and side (i.e., cross-sectional) views, respectively, of a 1 kilogram force (kgf) Vickers indentation 305 in a soda lime silicate glass that has not been ion exchanged. Radial cracks 310 extend from the Vickers indentation 305 (FIG. 3a) and shear deformation zone A. Lateral cracks 317, median cracks 319, and subsurface shear faults 315 are seen in the side view of the glass (FIG. 3b). Shear faults 315 serve as initiation sites for lateral and median cracks 317, 319.

The compressive stress created in the surface layers of ion exchanged glasses prevents or mitigates the propagation of nucleated cracks, but does not totally eliminate shear deformation. FIG. 4 is a cross-sectional view of a 1 kgf Vickers indentation of an ion-exchanged soda lime silicate glass having a compressive stress of 400 MPa and a depth of layer of 13 μm. Although mitigated, deformation still occurs by the shearing mechanism and leads to crack initiation, as seen in the shear deformation zone A. The compressive layer prevents radial cracks 310 from extending far away from their nucleation sites in the shear deformation zone A. Under flexural loading, subsurface cracks 415 overcome the compressive stress created by ion exchange and propagate into the central tensile region of the glass, thereby causing failure.

To improve the mechanical properties of glass enclosures beyond those of currently available ion-exchanged glasses, a glass having higher damage resistance is needed. Accordingly, the glass enclosure described herein comprises an ion-exchanged glass that does not exhibit deformation by subsurface shear faulting, but instead exhibits indentation deformation by densification when submitted to an indentation load of at least 500 gf, which makes flaw/crack initiation more difficult. An example of deformation by densification is shown in FIGS. 5a and 5b, which are top and side views, respectively, of a 1 kilogram force (kgf) Vickers indentation in an alkaline earth aluminoborosilicate (EAGLE XG™, manufactured by Corning, Inc.) glass that has not been strengthened by ion exchange. The top view (FIG. 5a) shows no radial cracks extending from the Vickers indentation 505. As seen in the cross-sectional view (FIG. 5b), the glass deforms primarily by densification (region “B” in FIG. 5b) with no shear faulting. A top view of a 30 kgf Vickers indentation of an aluminoborosilicate glass having the composition: 64 mol % SiO₂, 14.5 mol % Al₂O₃, 8 mol % B₂O₃, 11.5 mol % Na₂O, and 0.1 mol % SnO₂; wherein the ratio (Al₂O₃+B₂O₃)/Σ(modifiers), with Al₂O₃, B₂O₃, and Na₂O modifier concentrations expressed in mol %, is 1.96, and strengthened by ion exchange by immersion in a molten KNO₃ salt bath at 410° C. for 8 hours is shown in FIG. 6 . At maximum load, the indenter tip has a depth of about 48 μm. No radial cracks extend from Vickers indentation 605.

The densification mechanism described hereinabove can be attributed to the absence or lack of non-bridging oxygens (NBOs) in the glass structure, high molar volume (at least 27 cm³/mol), and low Young's modulus (less than about 69 GPa) of the glass. In the aluminoborosilicate glasses described herein, a structure having substantially no non-bridging oxygens (NBO-free) is achieved through compositions in which the relationship

$\begin{array}{cc}\frac{{\mathrm{<figure-callout\; id="2"\; label="Al"\; filenames="USRE049530-20230516-D00008.png"\; state="\{\{state\}\}">Al</figure-callout>}}_2{O}_3\left(\mathrm{mol}\%\right)+{\mathrm{<figure-callout\; id="2"\; label="B"\; filenames="USRE049530-20230516-D00008.png"\; state="\{\{state\}\}">B</figure-callout>}}_2{O}_3\left(\mathrm{mol}\%\right)}{\mathrm{\Sigma modifiers}\left(\mathrm{mol}\%\right)}>1,& \left(1\right)\end{array}$
where Al₂O₃ and B₂O₃ are intermediate glass formers and alkali metal (e.g., Li₂O, Na₂O, K₂O, Rb₂O, Cs₂O) and alkaline earth metal oxides (e.g., MgO, CaO, SrO, BaO) are modifiers, is satisfied. Such modifiers are intentionally or actively included in the glass composition, and do not represent impurities that are inadvertently present in the batched material used to form the glass. To obtain sufficient depth of layer and compressive stress by ion exchange, it is preferable that 0.9<R₂O/Al₂O₃<1.3, wherein Al₂O₃ and R₂O modifier concentrations are expressed in mol %. Given a particular compressive stress and compressive depth of layer, any ion-exchangeable silicate glass composition that obeys equation (1) and contains alkali metals (e.g., Li⁺, Na⁺, K⁺) should have a high resistance to both crack initiation and crack propagation following ion exchange. Prior to ion exchange, such aluminoborosilicate glasses have a Vickers median/radial crack initiation threshold of at least 500 gf and, in one embodiment, the glasses have Vickers median/radial crack initiation threshold of at least 1000 gf.

In some embodiments, the glass enclosure comprises, consists essentially of, or consists of a strengthened glass that, when ion exchanged, is resistant to damage, such as crack initiation and propagation. The glass comprises at least 50 mol % SiO₂ in some embodiments, at least 58 mol % SiO₂ in some embodiments, at least 60 mol % SiO₂ in other embodiments, and includes at least one alkali metal modifier, wherein the ratio (Al₂O₃+B₂O₃)/Σ(modifiers)>1, wherein Al₂O₃, B₂O₃, and modifier concentrations are expressed in mol %, and wherein the modifiers are selected from the group consisting of alkali metal oxides and alkaline earth metal oxides. In some embodiments, (Al₂O₃+B₂O₃)/Σ(modifiers)≥1.45. As the value of this ratio increases, the damage resistance of the glass increases. In addition, an increase in the ratio or a substitution of B₂O₃ for Al₂O₃ results in a decrease in Young's modulus. In one embodiment, the Young's modulus of the aluminoborosilicate glass is less than about 69 GPa. In one embodiment, the Young's modulus of the aluminoborosilicate glass is less than about 65 GPa. In another embodiment, the Young's modulus of the aluminoborosilicate glass is in a range from about 57 GPa up to about 69 GPa. In another embodiment, the strengthened glass of the glass enclosure has a compressive stress of at least about 400 MPa and a depth of layer of at least about 15 μm, in another embodiment, at least about 25 μm, and, in yet another embodiment, at least about 30 μm.

In one embodiment, the glass enclosure comprises, consists essentially of, or consists of an ion exchangeable aluminoborosilicate glass that has been strengthened, for example, by ion exchange. As used herein, “ion exchangeable” means that a glass is capable of exchanging cations located at or near the surface of the glass with cations of the same valence that are either larger or smaller in size. In a particular embodiment, the aluminoborosilicate glass comprises, consists essentially of, or consists of: 50-72 mol % SiO₂; 9-17 mol % Al₂O₃; 2-12 mol % B₂O₃; 8-16 mol % Na₂O; and 0-4 mol % K₂O, wherein (Al₂O₃+B₂O₃)/Σ(modifiers)>1, and has a molar volume of at least 27 cm³/mol. In another embodiment, the aluminoborosilicate glass comprises, consists essentially of, or consists of: 60-72 mol % SiO₂; 9-16 mol % Al₂O₃; 5-12 mol % B₂O₃; 8-16 mol % Na₂O; and 0-4 mol % K₂O, wherein the ratio of concentrations of Al₂O₃ and B₂O₃ to the total concentrations of modifiers, (Al₂O₃+B₂O₃)/Σ(modifiers), is greater than 1, and has a molar volume of at least 27 cm³/mol. In the above embodiments, the modifiers are selected from alkali metal oxides (e.g., Li₂O, Na₂O, K₂O, Rb₂O, Cs₂O) and alkaline earth metal oxides (e.g., MgO, CaO, SrO, BaO). In some embodiments, the glass further includes 0-5 mol % of at least one of P₂O₅, MgO, CaO, SrO, BaO, ZnO, and ZrO₂. In other embodiments, the glass is batched with 0-2 mol % of at least one fining agent selected from a group that includes Na₂SO₄, NaCl, NaF, NaBr, K₂SO₄, KCl, KF, KBr, and SnO₂. The aluminoborosilicate glass is, in some embodiments, substantially free of lithium, whereas in other embodiments, the aluminoborosilicate glass is substantially free of at least one of arsenic, antimony, and barium. In other embodiments, the aluminoborosilicate glass is down-drawable by processes known in the art, such as slot-drawing, fusion drawing, re-drawing, and the like, and has a liquidus viscosity of at least 130 kilopoise.

Various non-limiting compositions of the aluminoborosilicate glasses described herein are listed in Table 1. Table 1 also includes properties measured for these glass compositions. Crack initiation thresholds were measured by making multiple indentations (indents) in the glass using a Vickers diamond indenter loaded onto the surface. The load was increased until formation of median or radial cracks extending out from the corners of the indent impression was observed at the surface of the glass in greater than 50% of indents. Crack initiation thresholds for the samples listed in Table 1 are plotted in FIG. 7 as a function of Al₂O₃+B₂O₃—Na₂O in the glass samples.

Samples a, b, c, and d in Table 1 have compositions that are nominally free of non-bridging oxygens; i.e., Al₂O₃+B₂O₃═Na₂O, or Al₂O₃+B₂O₃—Na₂O=0 (i.e. (Al₂O₃+B₂O₃)/Σ(modifiers)=1). Regardless of whether B₂O₃ or Al₂O₃ is used to consume the NBOs created by the presence of the Na₂O modifier in these sample compositions, all of the above samples exhibited low (i.e., 100-300 gf) crack initiation thresholds.

In samples e and f, however, an excess of B₂O₃ is created by increasing the Al₂O₃ content while decreasing the concentration of alkali metal oxide modifiers. For samples e and f, (Al₂O₃+B₂O₃)/Σ(modifiers)>1. In these samples, the crack initiation threshold increases dramatically, as shown in FIG. 7 . Specifically, sample e exhibited a crack initiation threshold of 700 gf prior to strengthening by ion exchange, whereas sample f exhibited a crack initiated threshold of 1000 gf prior to strengthening.

Non-limiting examples of the aluminoborosilicate glasses described herein are listed Table 2, which lists various compositions and properties of glasses. Several compositions (34, 35, 36, 37, 38, and 39), when ion exchanged, have crack initiation thresholds that are less than 10 kgf. These compositions are therefore outside the scope of the disclosure and appended claims and thus serve as comparative examples. Among the properties listed in Table 2 is the coefficient of thermal expansion (CTE), given in units of 1×10⁻⁷/° C. CTE is one consideration that is taken into account when designing devices that develop minimal thermal stresses upon temperature changes. Glasses having lower CTEs are desirable for down-draw processes (e.g., fusion-draw and slot-draw) to minimize sheet distortion during the drawing process. The liquidus temperature and corresponding liquidus viscosity (expressed in kP (kilopoise) or MP (megapoise)) indicate the suitability of glass compositions for hot forming the glass into sheets or other shapes. For down-draw processes, it is desirable that the aluminoborosilicate glasses glass described herein have a liquidus viscosity of at least 130 kP. The 200P temperature is the temperature at which the glass has a viscosity of 200 Poise, and is the process temperature typically used in manufacturing to remove gaseous inclusions (fining) and melt any remaining batch materials. The columns labeled 8 and 15 hr DOL and CS in Table 2 are the depth of the compressive layer and the surface compressive stress resulting from ion exchange in 100% KNO₃ at 410° C. in 8 and 15 hours, respectively.

To maintain desirable ion exchange properties for the glasses described herein, the total alkali metal oxide modifier concentration should equal that of Al₂O₃ and any excess (Al₂O₃+B₂O₃) that is needed should be made up with B₂O₃ alone to increase the crack initiation load. For optimum ion exchange, the aluminoborosilicate glass should the total concentration of alkali metal oxide modifiers should equal that of alumina—i.e., (Li₂O+Na₂O+K₂O+Rb₂O+Cs₂O)═Al₂O₃— to achieve the greatest compressive stress and depth of layer, with excess B₂O₃ to improve damage resistance of the glass. However, excess B₂O₃ content should be balanced against the rate of ion exchange. For deep (e.g., >20 μm) ion exchange, the B₂O₃ concentration should, in some embodiments, be less than that of Al₂O₃. To achieve the lowest level of melting defects such as undissolved batch or gaseous inclusions, it is best to that R₂O/Al₂O₃>1.0 and, preferably, between 1.05≥R₂O/Al₂O₃≥1.2. Since this condition would create NBOs, given by R₂O—Al₂O₃, enough B₂O₃ should, in some embodiments, be added to consume the excess modifiers (i.e., B₂O₃>R₂O—Al₂O₃) to maintain damage resistance. More preferably, B₂O₃>2(R₂O—Al₂O₃).

Divalent cations can be added to lower the 200 P temperature (i.e., the typical melting viscosity) of the aluminoborosilicate glass and eliminate defects such as undissolved and/or unmelted batch materials. Smaller divalent cations, such as Mg²⁺, Zn²⁺, or the like are preferable, as they have beneficial impact on the compressive stress developed during ion exchange of the glass. Larger divalent cations such as Ca²⁺, Sr²⁺, and Ba²⁺ decrease the ion exchange rate and the compressive stress achieved by ion exchange. Likewise, the presence of smaller monovalent cations such as Li⁺ in the glass can have a positive effect on the crack initiation threshold, whereas larger ions such as K⁺ are not as desirable. In addition, whereas small amounts of K₂O can increase the depth of layer of the compressive stress region, high concentrations of larger monovalent ions such as K⁺ decrease compressive stress and should therefore be limited to less than 4%.

The aluminoborosilicate glass described herein comprises at least 50 mol %, 58 mol % SiO₂ in some embodiments, and in other embodiments, at least 60 mol % SiO₂. The SiO₂ concentration plays a role in controlling the stability and viscosity of the glass. High SiO₂ concentrations raise the viscosity of the glass, making melting of the glass difficult. The high viscosity of high SiO₂-containing glasses frustrates mixing, dissolution of batch materials, and bubble rise during fining. High SiO₂ concentrations also require very high temperatures to maintain adequate flow and glass quality. Accordingly, the SiO₂ concentration in the glass should not exceed 72 mol %.

As the SiO₂ concentration in the glass decreases below 60 mol %, the liquidus temperature increases. The liquidus temperature of SiO₂—Al₂O₃—Na₂O compositions rapidly increases to temperatures exceeding 1500° C. at SiO₂ contents of less than 50 mol %. As the liquidus temperature increases, the liquidus viscosity (the viscosity of the molten glass at the liquidus temperature) of the glass decreases. While the presence of B₂O₃ suppresses the liquidus temperature, the SiO₂ content should be maintained at greater than 50 mol % to prevent the glass from having excessively high liquidus temperature and low liquidus viscosity. In order to keep the liquidus viscosity from becoming too low or too high, the SiO₂ concentration of the gasses described herein should therefore be within the range between 50 mol % and 72 mol %, between 58 mol % in some embodiments, and between 60 mol % and 72 mol % in other embodiments.

The SiO₂ concentration also provides the glass with chemical durability with respect to mineral acids, with the exception of hydrofluoric acid (HF). Accordingly, the SiO2 concentration in the glasses described herein should be greater than 50 mol % in order to provide sufficient durability.

TABLE 1
Compositions and properties of alkali aluminoborosilicate glasses.

Mol %	a	b	c	d	e	f

SiO2	64	64	64	64	64	64
Al2O3	0	6	9	15	12	13.5
B2O3	18	12	9	3	9	9
Na2O	18	18	18	18	15	13.5
SnO2	0.1	0.1	0.1	0.1	0.1	0.1
Al2O3 + B2O3 − Na2O	0	0	0	0	6	9
Strain Point (° C.)	537	527	524	570	532	548
Anneal Point (° C.)	575	565	564	619	577	605
Softening Point (° C.)	711	713	730	856	770	878
Coefficient of Thermal Expansion (×10−7/	81.7	81.8	84.8	88.2	78	74.1
° C.)
Density (g/cm3)	2.493	2.461	2.454	2.437	2.394	2.353
Crack Initiation Load (gf)	100	200	200	300	700	1100
Vickers Hardness at 200 gf		511	519	513	489	475
Indentation Toughness (MPa m{circumflex over ( )}0.5)		0.64	0.66	0.69	0.73	0.77
Brittleness (μm{circumflex over ( )}0.5)		7.8	7.6	7.3	6.6	6
IX at 410° C. for 8 hrs in 100% KNO3
DOL (μm)	10.7	15.7	20.4	34.3	25.6	35.1
CS (MPa)	874	795	773	985	847	871

TABLE 2
Table 2. Compositions, expressed in mol %, and properties of alkali aluminoborosilicate glasses.

Composition (mol %)

Sample	SiO2	Al2O3	B2O3	Li2O	Na2O	K2O	MgO	CaO	P2O5	SnO2	ZnO	ZrO2
1	64.0	13.5	8.9		13.4	0.0	0.0	0.0		0.10		0.00
2	65.7	12.3	9.0		11.5	1.3	0.0	0.0		0.10		0.00
3	65.7	12.3	9.0		9.5	3.3	0.0	0.0		0.10		0.00
4	65.7	12.3	9.0		12.8	0.0	0.0	0.0		0.10		0.00
5	64.0	13.0	8.9		13.9	0.00	0.02	0.05		0.10		0.00
6	64.0	13.5	8.9		13.4	0.00	0.02	0.04		0.10		0.00
7	64.0	14.0	8.9		12.9	0.00	0.02	0.04		0.10		0.00
8	64.0	14.5	7.9		13.4	0.00	0.02	0.04		0.10		0.00
9	64.0	12.5	9.9		13.4	0.00	0.02	0.04		0.10		0.00
10	64.0	13.5	8.9		11.4	2.01	0.02	0.04		0.10		0.00
11	64.0	14.5	7.0		14.4	0.00	0.00	0.05		0.10		0.00
12	64.0	13.5	7.9		13.4	0.00	1.00	0.05		0.10		0.00
13	63.3	12.3	9.8		12.3	0.99	0.00	0.02		0.15		0.02
14	64.0	13.5	8.5		14.0	0.00				0.10
15	64.0	12.5	10.0		13.0	0.50				0.10
16	64.0	13.5	9.0		12.5	1.00				0.10
17	64.0	13.5	9.0		13.5	0.00				0.10
18	65.7	11.8	9.5		11.5	1.3	0.0	0.0		0.05		0.00
19	64.0	12.5	10.9		12.4	0.00	0.00	0.04		0.10		0.00
20	64.0	13.5	8.0		14.5	0.00				0.10
21	64.0	13.5	8.9		13.4	0.0	0.0	0.0		0.10		0.00
22	63.9	13.0	5.0		11.0	3.0	4.0	0.0		0.10		0.00
23	65.7	11.8	10.0		11.0	1.30	0.02	0.04		0.05		0.00
24	65.7	11.3	10.0		11.5	1.3	0.0	0.0		0.05		0.00
25	65.7	10.7	10.6		11.5	1.30	0.02	0.05		0.05		0.00
26	64.0	13.5	6.0		13.4	0.00	3.02	0.06		0.10		0.00
27	64.0	13.5	7.0		15.5	0.00				0.10
28	65.7	12.3	10.0		10.5	1.30	0.02	0.04		0.05		0.00
29	64.0	12.0	11.9		11.9	0.00	0.00	0.04		0.10		0.00
30	64.0	14.0	6.0		11.4	2.50	2.02	0.05		0.10		0.00
31	64.0	13.5	7.0		13.4	0.00	2.01	0.06		0.10		0.00
32	64.0	12.0	8.9		14.9	0.0	0.0	0.0		0.10		0.00
33	62.0	14.0	6.0		12.9	3.01	2.01	0.05		0.10		0.00
34	64.1	13.2	5.6		12.2	2.83	1.89	0.05		0.09		0.00
35	64.0	12.5	6.0		12.9	2.50	2.02	0.05		0.10		0.00
36	63.1	13.6	5.8		12.6	2.92	1.95	0.05		0.10		0.00
37	64.0	12.5	5.5		14.9	3.0	0.0	0.0		0.10		0.00
38	64.0	13.0	6.0		12.4	2.50	2.01	0.05		0.10		0.00
39	65.7	10.3	11.0		11.5	1.30	0.02	0.05		0.05		0.00
40	61.8	12.9	10.3	0.0	13.9	1.03	0.00	0.0	0.0	0.12	0.00	0.0
41	62.6	12.6	10.1	0.0	13.6	1.01	0.00	0.0	0.0	0.12	0.00	0.0
42	63.3	12.4	9.9	0.0	13.4	0.99	0.00	0.0	0.0	0.12	0.00	0.0
43	64.0	12.1	9.7	0.0	13.1	0.97	0.00	0.0	0.0	0.12	0.00	0.0
44	63.3	11.4	9.9	0.0	13.4	0.99	0.00	0.0	1.0	0.12	0.00	0.0
45	63.3	10.4	9.9	0.0	13.4	0.99	0.00	0.0	2.0	0.12	0.00	0.0
46	62.7	12.2	9.8	0	12.2	0.98	1.96	0.00	0	0.12	0.00	0
47	61.5	12.0	9.6	0	12.0	0.96	3.84	0.00	0	0.12	0.00	0
48	62.7	12.2	9.8	0	12.2	0.98	0.00	0.00	0	0.12	2.0	0
49	61.5	12.0	9.6	0	12.0	0.96	0.00	0.00	0	0.12	3.8	0
50	62.7	12.2	9.8	0	12.2	0.98	0.98	0.00	0	0.12	0.98	0
51	63.9	12.5	10.0	0	12.5	1.00	0.00	0.00	0	0.12	0.00	0
52	64.1	16.9	2.1		15.6	1.01	0.02	0.12		0.10
53	64.0	16.4	2.1		16.3	1.01	0.02	0.13		0.10
54	59.9	16.5	6.6		16.2	0.5	0.0	0.1		0.1		0.0
55	50.5	20.2	9.8		19.4					0.1
56	52.3	19.4	9.3		18.9					0.1
57	55.2	20.3	9.7		14.6					0.1

		(R2O +		(Al2O3 +		Molar
		RO)/(Al2O3 +		B2O3)/(R2O +	Density	Volume
Sample	Total	B2O3)	R2O/Al2O3	RO)	g/cm3	cm3/mol
1	100.0	0.602	0.997	1.661	2.353	28.44
2	100.0	0.606	1.046	1.651	2.347	28.47
3	100.0	0.606	1.046	1.651	2.345	28.77
4	100.0	0.605	1.045	1.652	2.346	28.31
5	100.0	0.639	1.074	1.564	2.363	28.23
6	100.0	0.602	0.997	1.661	2.355	28.41
7	100.0	0.567	0.926	1.764	2.335	28.74
8	100.0	0.602	0.929	1.661	2.363	28.45
9	100.0	0.602	1.076	1.662	2.354	28.29
10	100.0	0.602	0.998	1.660	2.356	28.67
11	100.0	0.676	0.997	1.480	2.376	28.27
12	100.0	0.676	0.997	1.479	2.369	28.12
13	99.00	0.601	1.077	1.665	2.346	28.41
14	100.1	0.636	1.037	1.571
15	100.1	0.600	1.080	1.667
16	100.1	0.600	1.000	1.667
17	100.1	0.600	1.000	1.667
18	100.0	0.606	1.090	1.652	2.346	28.4
19	100.0	0.533	0.996	1.877	2.353	28.34
20	100.1	0.674	1.074	1.483
21	100.0	0.602	0.997	1.661	2.354	28.43
22	100.0	1.002	1.076	0.998	2.407	27.62
23	100.0	0.569	1.048	1.759	2.336	28.54
24	100.0	0.606	1.138	1.651	2.347	28.32
25	100.0	0.606	1.203	1.651	2.349	28.21
26	100.0	0.850	0.997	1.176	2.395	27.56
27	100.1	0.756	1.148	1.323
28	100.0	0.533	0.964	1.875	2.331	28.68
29	100.0	0.502	0.997	1.994	2.326	28.62
30	100.0	0.804	0.998	1.244	2.392	28.11
31	100.0	0.758	0.996	1.319	2.385	27.81
32	100.0	0.717	1.246	1.395	2.394	27.7
33	100.0	0.903	1.141	1.108	2.418	27.89
34	100.0	0.903	1.141	1.108	2.409	27.82
35	100.0	0.949	1.237	1.053	2.414	27.61
36	100.0	0.903	1.141	1.108	2.411	27.88
37	100.0	1.002	1.438	0.998	2.444	27.5
38	100.0	0.897	1.151	1.115	2.406	27.78
39	100.0	0.606	1.249	1.651	2.431	27.21
40	100.0	0.644	1.160	1.552	2.358
41	100.0	0.644	1.160	1.552	2.355	28.48
42	100.0	0.644	1.160	1.552	2.352	28.46
43	100.0	0.644	1.160	1.552	2.350	28.42
44	100.0	0.644	1.261	1.552	2.356
45	100.0	0.644	1.381	1.552	2.358
46	100.0	0.689	1.080	1.452	2.369	28.03
47	100.0	0.778	1.080	1.286	2.386	27.62
48	100.0	0.600	1.080	1.667	2.395	28.06
49	100.0	0.600	1.080	1.667	2.432	27.75
50	100.0	0.644	1.080	1.552	2.383	28.04
51	100.0	0.600	1.080	1.667	2.354	28.04
52	100.0	0.877	0.979	1.141	2.425	28.07
53	100.0	0.940	1.052	1.064	2.433	27.89
54	100.0	0.727	1.013	1.375	2.399	28.32
55	100.0	0.647	0.960	1.546	2.412	28.97
56	100.0	0.659	0.974	1.519	2.413	28.73
57	99.9	0.487	0.719	2.055	2.399	29.09

						Liquidus	200	Elastic	Shear
	Strain	Anneal	Softening	CTE ×	Liquidus	Viscosity	poise T	modulus	modulus
Sample	pt. (° C.)	pt. (° C.)	pt. (° C.)	107 K−1	T (° C.)	(Mpoise)	(° C.)	(GPa)	(GPa)
1	548	605	878	74.1				62.3	25.6
2	543	603					1694
3	524	580
4	538	593					1690
5	539	590	824	76.0	<750	>1786	1680	63.4	26.1
6	548	605	864	72.8	<750	>9706	1684	62.2	25.6
7	559	618	885	69.9	<750			62.7	25.7
8	566	625	893	72.1				63.3	26.1
9	528	577	804	74.0	<730	>474	1650	62.9	25.7
10	534	590	864	78.4	<745			62.3	25.8
11	563	620	900	80.0	<715	>132346	1732	64.0	26.3
12	546	599	864	74.8	<715	>11212	1655	64.4	26.4
13	542	597		75.4			1669	61.6	25.4
14	547	600		75.7	<720
15	523	574			<745
16	539	595			<720
17	569	628			<720
18	518	570	820	72.8			1692	63.2	26.1
19	522	578	874	70.3	<705			60.6	24.8
20	545	596		78.2	<700
21	546	604	871	72.0	<700	>100	1665	62.6	25.7
22	556	608	864	81.8	1115
23	521	575	831	73.8				62.4	25.5
24	517	568	798	75.2			1702	64.1	26.3
25	513	561	777	73.2			1663	64.6	26.6
26	564	616	872	73.0	1050			67.6	27.8
27	547	594			<745
28	528	587	883	68.9				61.8	25.3
29	509	563	826	69.9	<745	>663	1648	59.6	24.4
30	557	613	882	79.5	975	4.72	1689	67.4	27.6
31	550	603	862	75.4	945			66.2	27.2
32	532	577	770	78.0	865			67.4	27.8
33	538	587	830	87.7	<710		1614	68.8	28.3
34	540	591	839	82.1	<730	>885	1671	69.0	28.4
35	533	581	803	84.9	<710	>518	1634	69.0	28.5
36	538	588	830	85.7	<720	>1212	1663	68.4	28.1
37	522	564	754	91.2	<710			72.1	29.7
38	537	586	827	82.1	<720	>1698	1653	68.1	28.2
39	521	561	739	83.7	820	1.26	1480	72.5	29.9
40	517	567	805	79.4	<720			62.7
41	518	569	811	75.4	<710	1662	1668	62.7
42	520	572	831	74.0	<745			62.6
43	519	571	824	76.4	<700	2053	1679	62.2
44	508	556	785	76.0	<710			63.6
45	500	547	785	75.7	<745			63.5
46	524	573	809	74.5	<750
47	526	573	791	74.8
48	507	557	796	74.7	<700
49	507	554	781	74.0	955
50	513	562	795	75.4	<730
51	489	539	791		<710
52	666	726	1016	88.8	<930	>500	1743
53	620	679	969	89.3	1010	8.2	1727
54	588	643	905	87.4	1050	0.86	1628
55	559.0	609.0	849.5	74.4
56	559.0	610.0	841.0	92.4
57	577.0	631.0	877.7	68.9

		Pre-IX Crack	CS1	DOL1	CS2	DOL2,
	Poisson	initiation	IX 8 hrs	IX 8 hrs	IX 15 hrs	IX 15 hrs	Damage
Sample	ratio	load (gf)	(MPa)	(μm)	(MPa)	(μm)	Threshold (gf)3
1	0.219	1100	871	35.1			>30000
2		600					>30000
3		600					29000
4		800					>30000
5	0.213	500-1000	803	38.8	762	51.5
6	0.215	500-1000	816	38.8	782	51.8
7	0.219	500-1000	803	36.1	761	50.5
8	0.213	500-1000	868	40.3	840	53.6
9	0.223		752	34.8	707	47.2
10	0.209		722	47.8	687	65.1
11	0.216		924	46	877	60.9
12	0.219		839	36.2	790	48.8
13	0.214		775	43.5	732	60.8
14			850	38.5	792	50.7
15			738	33.7	686	47.2
16			763	40.7	716	55.5
17			808	40.5	757	55.4
18	0.212						25000
19	0.224		691	33.7	641	46.6
20			868	37.1	810	52.1
21	0.217		824	35.8
22			771	50.6	747	66
23	0.222						21000
24	0.218						20000
25	0.216						20000
26	0.217		887	34.8	864	46.7
27			887	34.7	835	48
28	0.221						18000
29	0.219		623	31.3	557	43
30	0.219	500-1000	791	54.1	772	67.5
31	0.217		870	35.2	833	46.9
32	0.21	600	847	25.6
33	0.216	500-1000	814	50.8	773	67
34	0.217	300-500	825	46.3	792	63.6
35	0.21	300-500	794	45.5	750	60.6
36	0.217	300-500	801	51.2	779	66.2
37	0.215	200-300	747	43.9	698	56.5
38	0.208	200-300	803	46.4	761	63.3
39	0.213						5000
40			694	38.1	668	54.2
41			707	40.1	654	50.6
42			690	39.9	643	52.6
43			689	38.6	627	55
44			611	37.5	555	51.2
45			533	37.4	502	50.4
46			806	40.1	705	71.7
47			753	27	716	36.3
48			712	29.3	670	37.2
49			720	25	688	34.8
50			716	30.4	680	39.5
51			574	32.5	540	43.1
52
53
54			1029	51.2
55			901	38.3	858	57.5	10000-15000
56			967	37.8	964	50.7	10000-15000
57			832	18.3	790	29	10000-15000

	Sample	Damage Threshold (gf)4	Damage Threshold (gf)5	Damage Threshold (gf)
	1			30
	2			30
	3			29
	4			30
	5	>30000		30
	6	>30000		30
	7	>30000		30
	8	>30000		30
	9	>30000		30
	10	>30000		30
	11	>30000		30
	12	>30000		30
	13	>30000		30
	14	>30000		30
	15	>30000		30
	16	>30000		30
	17	>30000		30
	18			25
	19	25000		25
	20	25000		25
	21		23000	23
	22	20000-25000		22
	23			21
	24			20
	25			20
	26	20000		20
	27	<25000		20
	28			18
	29	18000		18
	30	15000		15
	31	13000		13
	32		11000	11
	33	10000		10
	34	9000		9
	35	8000		8
	36	8000		8
	37	6000		6
	38	6000		6
	39			5
	40	19000		19
	41	22000		22
	42	>30000		30
	43
	44	20000-25000		22.5
	45
	46	15000-20000		17.5
	47	>30000		>30
	48	>30000		>30
	49	>30000		>30
	50	>30000		>30
	51	20000-25000		22.5
	52			13.5
	53			11.5
	54	10000-15000		12.5
	55	10000-15000		12.5
	56	<10000		12.5
	57	10000-15000		12.5
1Compressive stress (CS) and depth of layer (DOL) after ion exchange (IX) in 100% KNO3 at 410° C. for 8 hrs.
3Compressive stress (CS) and depth of layer (DOL) after ion exchange (IX) in 100% KNO3 at 410° C. for 15 hrs.
3After ion exchange (IX) in 100% KNO3 at 410° C. for 8 hrs.
4After ion exchange (IX) in 100% KNO3 at 410° C. for 15 hrs.
5After ion exchange (IX) in 100% KNO3 at 370° C. for 64 hrs.

Example

The following example illustrates features and advantages of the glasses described herein, and is in no way intended to limit the disclosure or appended claims thereto.

The purpose of this example was to verify that pre-ion exchange crack resistance improves post-ion exchange crack resistance in a glass. Samples of crack resistant aluminoborosilicate glass having composition e in Table 1 (64 mol % SiO₂, 13.5 mol % Al₂O₃, 9 mol % B₂O₃, 13.5 mol % Na₂O, 0.1 mol % SnO₂) and a pre-ion exchange crack initiation threshold of 1100 gram force (gf), were ion exchanged by immersion in a molten KNO₃ salt bath at 410° C. for 8 hrs to achieve depths of layer DOL and compressive stresses CS. One sample had a DOL of 55.8 μm and a CS of 838 MPa, and another sample had a DOL of 35.1 μm and a CS of 871 MPa.

For purposes of comparison, samples of Corning GORILLA™ Glass (an alkali aluminosilicate glass having the composition: 66.4 mol % SiO₂; 10.3 mol % Al₂O₃; 0.60 mol % B₂O₃; 4.0 mol % Na₂O; 2.10 mol % K₂O; 5.76 mol % MgO; 0.58 mol % CaO; 0.01 mol % ZrO₂; 0.21 mol % SnO₂; and 0.007 mol % Fe₂O₃) with a pre-ion exchange crack initiation threshold of 300 gf were then ion exchanged to closely match the compressive stress and depths of layer of the samples having composition f, listed in Table 1. One sample had a DOL of 54 μm and a CS of 751 MPa, and another sample had a DOL of 35 μm and a CS of 790 MPa. Compressive stresses and depths of layer of the ion exchanged samples of composition f and GORILLA Glass are listed in Table 3.

Following ion exchange, Vickers crack initiation loads were measured for each of composition f in Table 1 and the GORILLA Glass samples. Post-ion exchange crack initiation loads were measured using a Vickers diamond indenter as previously described herein and are listed in Table 3. The results of the crack initiation testing listed in Table 3 demonstrate that greater pre-ion exchange crack resistance improves post-ion exchange crack resistance. The GORILLA Glass 55 samples required loads of 5,000-7,000 gf to initiate median/radial crack systems, whereas the composition f samples required loads of greater than 30,000 gf, or 4-6 times the load needed to initiate such cracks in GORILLA Glass samples, to initiate median/radial crack systems. The GORILLA Glass samples fractured into several pieces when the indentation load exceeded the measured crack initiation loads, and in all cases fracture was observed by the point at which the load exceeded 10,000 gf. In contrast, the composition f samples did not fracture at any of the indentation loads (3,000 up to 30,000 gf) studied.

TABLE 3
Crack initiation loads of ion-exchanged glasses having
composition f (listed in Table 1) and Gorilla ® Glasses.

	Pre-Ion-Exchange			Post-Ion-
	Crack			Exchange Crack
	Initiation Load	DOL	Compressive	Initiation Load
Glass	(gf)	(microns)	Stress (MPa)	(gf)

Comp. f	1100	55.8	838	30000+
Gorilla	300	54	751	7000
Glass
Comp. f	1100	35.1	871	30000+
Gorilla	300	35	790	5000
Glass

While typical embodiments have been set forth for the purpose of illustration, the foregoing description should not be deemed to be a limitation on the scope of the disclosure or appended claims. Accordingly, various modifications, adaptations, and alternatives may occur to one skilled in the art without departing from the spirit and scope of the present disclosure or appended claims.

Claims (33)

The invention claimed is:

1. A glass comprising:

at least 58 mol % SiO₂;

at least 8 mol % Na₂O;

5.5-12 mol % B₂O₃; and

Al₂O₃;

wherein a ratio

$\frac{{\mathrm{Al}}_2{O}_3\left(\mathrm{mol}\%\right)+B_2{O}_3\left(\mathrm{mol}\%\right)}{\sum \mathrm{modifiers}\left(\mathrm{mol}\%\right)}>1,$

the modifiers are one or more alkali metal oxide (R₂O) and one or more alkaline earth oxide (RO);

wherein Al₂O₃ (mol %)>B₂O₃ (mol %) and 0.9<R₂O/Al₂O₃<1.3, wherein the glass is substantially free of Li₂O.

2. The glass of claim 1, wherein the glass is ion exchanged and has a layer under a compressive stress of at least about 600 MPa, the layer extending from a surface of the glass into the glass to a depth of layer of at least about 30 μm.

3. The glass of claim 2, wherein the compressive stress is at least about 800 MPa.

4. The glass of claim 2, wherein the glass has a Vickers crack initiation threshold of at least about 30 kgf.

5. The glass of claim 1, wherein the glass is defined by the equation

$\frac{{\mathrm{Al}}_2{O}_3\left(\mathrm{mol}\%\right)+B_2{O}_3\left(\mathrm{mol}\%\right)}{\sum \mathrm{modifiers}\left(\mathrm{mol}\%\right)}\ge 1.45.$

6. The glass of claim 1, wherein the glass comprises from about 60 to 72 mol % SiO₂, about 9 mol % to about 17 mol % Al₂O₃, and about 8 mol % to about 20 mol % Na₂O.

7. The glass of claim 1, wherein the glass comprises at least one of MgO, ZnO, CaO, SrO, and BaO.

8. The glass of claim 1, wherein the glass comprises 5.5-10 mol % B₂O₃.

9. The glass of claim 1, wherein the glass comprises from 0 mol % to about 4 mol % K₂O.

10. The glass of claim 1, wherein the glass is defined by the following equation −5.7 mol %<Σ modifiers−Al₂O₃<2.99 mol %.

11. The glass of claim 1, wherein the glass is defined by the following equation 1.0<R₂O/Al₂O₃<1.3.

12. The glass of claim 1, wherein the glass has a Young's modulus of less than about 69 GPa.

13. A glass comprising:

at least 58 mol % SiO₂;

at least 8 mol % Na₂O;

2-12 mol % B₂O₃; and

Al₂O₃;

wherein a ratio

$\frac{{\mathrm{Al}}_2{O}_3\left(\mathrm{mol}\%\right)+B_2{O}_3\left(\mathrm{mol}\%\right)}{\sum \mathrm{modifiers}\left(\mathrm{mol}\%\right)}>1,$

the modifiers are one or more alkali metal oxide (R₂O) and one or more alkaline earth oxide (RO);

wherein 0.9<R₂O/Al₂O3<1.3, Al₂O₃ (mol %)>B₂O₃ (mol %), and wherein the glass is defined by the following equation −5.7 mol %<Σ modifiers−Al₂O₃<2.17 mol %.

14. The glass of claim 13, wherein the glass is defined by the equation

$\frac{{\mathrm{Al}}_2{O}_3\left(\mathrm{mol}\%\right)+B_2{O}_3\left(\mathrm{mol}\%\right)}{\sum \mathrm{modifiers}\left(\mathrm{mol}\%\right)}\ge 1.45.$

15. The glass of claim 13, wherein the glass comprises from about 60 to 72 mol % SiO₂, about 9 mol % to about 17 mol % Al₂O₃, and about 8 mol % to about 20 mol % Na₂O.

16. The glass of claim 13, wherein the glass comprises at least one of MgO, ZnO, CaO, SrO, and BaO.

17. The glass of claim 13, wherein the glass comprises 3-10 mol % B₂O₃.

18. The glass of claim 13, wherein the glass is defined by the following equation 1.0<R₂O/Al₂O₃<1.3.

19. The glass of claim 13, wherein the glass has a Young's modulus of less than about 69 GPa.

20. A glass comprising:

at least 58 mol % SiO₂;

at least 8 mol % Na₂O;

2-10 mol % B₂O₃;

Al₂O₃; and

wherein a ratio

$\frac{{\mathrm{Al}}_2{O}_3\left(\mathrm{mol}\%\right)+B_2{O}_3\left(\mathrm{mol}\%\right)}{\sum \mathrm{modifiers}\left(\mathrm{mol}\%\right)}>1,$

the modifiers are one or more alkali metal oxide (R₂O) and one or more alkaline earth oxide (RO);

wherein 0.9<R₂O/Al₂O₃<1.3, and wherein the glass is defined by the following equation −5.7 mol %<Σ modifiers−Al₂O₃<2.17 mol %.

21. The glass of claim 20, wherein the glass is defined by the equation

$\frac{{\mathrm{Al}}_2{O}_3\left(\mathrm{mol}\%\right)+B_2{O}_3\left(\mathrm{mol}\%\right)}{\sum \mathrm{modifiers}\left(\mathrm{mol}\%\right)}\ge 1.45.$

22. The glass of claim 20, wherein the glass comprises from about 60 to 72 mol % SiO₂, about 9 mol % to about 17 mol % Al₂O₃, and about 8 mol % to about 20 mol % Na₂O.

23. The glass of claim 20, wherein the glass comprises at least one of MgO, ZnO, CaO, SrO, and BaO.

24. The glass of claim 20, wherein the glass comprises 3-10 mol % B₂O₃.

25. The glass of claim 20, wherein the glass is defined by the following equation 1.0<R₂O/Al₂O₃<1.3.

26. An aluminoborosilicate glass comprising:

at least 58 mol % SiO₂;

9-17 mol % Al₂O₃;

2-12 mol % B₂O₃;

8-16 mol % Na₂O;

>0-2 mol % SnO₂; and

0 mol % P₂O₅,

wherein

$\frac{{\mathrm{Al}}_2{O}_3\left(\mathrm{mol}\%\right)+B_2{O}_3\left(\mathrm{mol}\%\right)}{\Sigma \mathrm{modifiers}\left(\mathrm{mol}\%\right)}>1,$

wherein the modifiers are one or more alkali metal oxide (R₂O) and one or more alkaline earth metal oxide (RO),

wherein Al₂O₃ (mol %)>B₂O₃ (mol %),

wherein 1<R₂O (mol %)/Al₂O₃ (mol %)<1.3,

wherein the glass has a Vickers crack initiation threshold of greater than 500 gf, and

wherein the glass is substantially free of lithium.

27. The glass of claim 26, wherein the glass comprises from 60 to 72 mol % SiO₂.

28. The glass of claim 26, wherein the glass is defined by the equation wherein B₂O₃ (mol %)>(R₂O (mol %)−Al₂O₃ (mol %)).

29. The glass of claim 26, wherein the glass is defined by the equation

$1<\frac{{\mathrm{Al}}_2{O}_3\left(\mathrm{mol}\%\right)+B_2{O}_3\left(\mathrm{mol}\%\right)}{\Sigma \mathrm{modifiers}\left(\mathrm{mol}\%\right)}<1.45.$

30. The glass of claim 26, wherein the glass has a molar volume of at least 27 cm³/mol.

31. The glass of claim 26, wherein the glass is free of at least one of arsenic, antimony, and barium.

32. The glass of claim 26, wherein the glass has a Vickers crack initiation threshold of at least 1000 gf.

33. The glass of claim 26, wherein the glass, when ion exchanged, has a Vickers crack initiation threshold of at least 30 kgf.

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