KR20240023043A - Colored glass articles with improved mechanical durability - Google Patents

Abstract

SiO ₂ of 50 mol% or more and 80 mol% or less; 7 mol% or more and 25 mol% or less of Al ₂ O ₃ ; 1 mol% or more and 15 mol% or less of B ₂ O ₃ ; 5 mol% or more and 20 mol% or less of Li ₂ O; Na ₂ O of 0.5 mol% or more and 15 mol% or less; K ₂ O greater than 0 mol% and less than or equal to 1 mol%; and a colored glass article comprising at least 1 x 10 ^-6 mol% and up to 1 mol% Au. R ₂ O - Al ₂ O ₃ is -5 mol% or more and 7 mol% or less, and R ₂ O is the sum of Li ₂ O, Na ₂ O, and K ₂ O.

Description

Colored glass articles with improved mechanical durability

This application is related to U.S. Patent Application No. 17/677,345, filed on February 22, 2022, U.S. Patent Application No. 17/677,375, filed on February 22, 2022, and U.S. Patent Application No. 17/677,375, filed on January 31, 2022. Claims priority to Patent Application No. 63/304,807, U.S. Provisional Patent Application No. 63/251,785, filed on October 4, 2021, and U.S. Provisional Patent Application No. 63/212,191, filed on June 18, 2021 , the entire contents of which are incorporated herein by reference.

This specification relates generally to glass compositions and glass articles, and in particular to glass compositions and ion-exchangeable colored glass articles formed therefrom.

Aluminosilicate glass articles can exhibit excellent ion-exchangeability and dropping performance. A variety of industries, including the consumer electronics industry, desire colored materials with identical or similar strength and fracture toughness properties. However, simply including a colorant in a conventional aluminosilicate glass composition may not produce the desired color.

Accordingly, a need exists for alternative colored glass articles with high strength and fracture toughness.

According to the first aspect (A1), the colored glass article contains 50 mol% or more and 80 mol% or less of SiO ₂ ; 7 mol% or more and 25 mol% or less of Al ₂ O ₃ ; 1 mol% or more and 15 mol% or less of B ₂ O ₃ ; 5 mol% or more and 20 mol% or less of Li ₂ O; 0.5 mol% or more and 12 mol% or less of Na ₂ O; K ₂ O greater than 0 mol% and less than or equal to 1 mol%; and 1 x 10 ^-6 mol% or more and 1 mol% or less of Au, where: R ₂ O - Al ₂ O ₃ is -5 mol% or more and 7 mol% or less, and R ₂ O is Li ₂ O , Na ₂ O, and K ₂ O.

According to the second first aspect (A1.1), the colored glass article comprises: at least 50 mol% but not more than 80 mol% SiO ₂ ; 7 mol% or more and 25 mol% or less of Al ₂ O ₃ ; 1 mol% or more and 15 mol% or less of B ₂ O ₃ ; Li ₂ O of 7 mol% or more and 20 mol% or less; 0.5 mol% or more and 12 mol% or less of Na ₂ O; K ₂ O greater than 0 mol% and less than or equal to 1 mol%; and 1 x 10 ^-6 mol% or more and 1 mol% or less of Au, where: R ₂ O - Al ₂ O ₃ is -5 mol% or more and 5 mol% or less, and R ₂ O is Li ₂ O , Na ₂ O, and K ₂ O.

The second viewpoint (A2) comprises a colored glass article according to the first viewpoint (A1) or the second first viewpoint (A1.1), said colored glass article under F2 illumination and a 10° standard observer angle. When measured at an article thickness of 1.33 mm: L* not less than 50 but not more than 100; a* of -15 or more and 25 or less; and b* of -25 or more and 25 or less; and a transmittance color coordinate in the CIELAB color space.

A third aspect (A3) comprises a colored glass article according to the second aspect (A2), wherein R ₂ O - Al ₂ O ₃ is at least -5 mol% and at most 1.5 mol%; b* is -25 or more and 10 or less.

A fourth aspect (A4) comprises a colored glass article according to the third aspect (A3), wherein R ₂ O - Al ₂ O ₃ is at least -3 mol% and at most 1.5 mol%; b* is -15 or more and 7 or less.

A fifth aspect (A5) comprises a colored glass article according to the second aspect (A2), wherein R ₂ O - Al ₂ O ₃ is greater than 1.5 mol% and up to 7 mol%; b* is between 0 and 25.

A sixth aspect (A6) comprises a colored glass article according to the fifth aspect (A5), wherein R ₂ O - Al ₂ O ₃ is greater than 1.5 mol% and up to 5 mol%; b* is 0 or more and 15 or less.

A seventh aspect (A7) comprises a colored article according to any one of the first to sixth aspects (A1-A6), wherein R ₂ O - Al ₂ O ₃ is at least -3 mol% and at most 5 mol%. .

An eighth aspect (A8) comprises a colored glass article according to the seventh aspect (A7), wherein R ₂ O - Al ₂ O ₃ is at least -1 mol% and at most 3 mol%.

A ninth aspect (A9) includes a colored article according to any one of the first to eighth aspects (A1-A8), wherein the colored glass article comprises at least 0.0001 mol% and not more than 0.1 mol% Au.

A tenth aspect (A10) comprises a colored article according to any one of the first to ninth aspects (A1-A9), wherein R ₂ O is at least 6 mol% and at most 25 mol%.

An eleventh aspect (A11) comprises a colored glass article according to the tenth aspect (A10), wherein R ₂ O is at least 8 mol% and at most 23 mol%.

A twelfth aspect (A12) comprises a colored article according to any one of the first to eleventh aspects (A1-A11), wherein the colored glass article comprises at least 0.01 mol% and at most 2 mol% ZrO ₂ .

A thirteenth aspect (A13) includes a colored glass article according to the twelfth aspect (A12), wherein the colored glass article comprises at least 0.1 mol% and at most 1.5 mol% ZrO ₂ .

A fourteenth aspect (A14) includes a colored article according to any one of the first to thirteenth aspects (A1-A13), wherein the colored glass article contains at least 0.01 mol% and not more than 1 mol% Fe ₂ O ₃ Includes.

A fifteenth aspect (A15) includes a colored article according to the fourteenth aspect (A14), wherein the colored glass article comprises at least 0.05 mol% and at most 0.5 mol% Fe ₂ O ₃ .

The sixteenth aspect (A16) comprises a colored article according to any one of the first to fifteenth aspects (A1-A15), wherein 5.72*Al ₂ O ₃ (mol%) - 21.4*ZnO (mol%) - 2.5*P ₂ O ₅ (mol%) - 35*Li ₂ O (mol%) - 16.6*B ₂ O ₃ (mol%) - 20.5*MgO (mol%) - 23.3*Na ₂ O (mol%) - 27.9*SrO (mol%) - 18.5*K ₂ O (mol%) - 26.3*CaO (mol%) is greater than -609 mol%.

A seventeenth aspect (A17) includes a colored glass article according to any one of the first to sixteenth aspects (A1-A16), wherein the colored glass article comprises at least 0.01 mol% and at most 1 mol% SnO ₂ do.

An eighteenth aspect (A18) includes a colored glass article according to the seventeenth aspect (A17_), wherein the colored glass article comprises at least 0.05 mol% and at most 0.75 mol% SnO ₂ .

A nineteenth aspect (A19) includes a colored glass article according to any one of the first to eighteenth aspects (A1-A18), wherein the colored glass article has MgO, CaO, ZnO, Cl, or a combination thereof. Practically none.

A twentieth aspect (A20) includes a colored glass article according to any one of the first to nineteenth aspects (A1-A19), wherein the colored glass article contains at least 7 mol% and not more than 18 mol% Li ₂ O. Includes.

A twenty-first aspect (A21) includes a colored glass article according to the twentieth aspect (A20), wherein the colored glass article comprises at least 9 mol% and at most 16 mol% Li ₂ O.

A twenty-second aspect (A22) includes a colored glass article according to any one of the first to twenty-first aspects (A1-A21), wherein the colored glass article contains at least 1 mol% but not more than 12 mol% Na ₂ O. Includes.

A twenty-third aspect (A23) includes a colored glass article according to the twenty-second aspect (A22), wherein the colored glass article comprises at least 2 mol% and at most 10 mol% Na ₂ O.

A twenty-fourth aspect (A24) includes a colored glass article according to any one of the first to twenty-third aspects (A1-A23), wherein the colored glass article contains at least 0.1 mol% and at most 0.5 mol% K ₂ O. Includes.

A twenty-fifth aspect (A25) includes a colored glass article according to any one of the first to twenty-fourth aspects (A1-A24), wherein the colored glass article has at least 9 mol% and not more than 23 mol% Al ₂ O ₃ Includes.

A twenty-sixth aspect (A26) includes a colored glass article according to the twenty-fifth aspect (A25), wherein the colored glass article comprises at least 11 mol% and at most 20 mol% Al ₂ O ₃ .

A twenty-seventh aspect (A27) includes a colored glass article according to any one of the first to twenty-sixth aspects (A1-A26), wherein the colored glass article has at least 2 mol% and up to 12 mol% of B ₂ O ₃ Includes.

A twenty-eighth aspect (A28) includes a colored glass article according to the twenty-seventh aspect (A27), wherein the colored glass article comprises at least 3 mol% and up to 10 mol% B ₂ O ₃

A twenty-ninth aspect (A29) includes a colored glass article according to any one of the first to twenty-eighth aspects (A1-A28), wherein the colored glass article comprises at least 52 mol% and at most 75 mol% SiO ₂ do.

The thirtieth aspect (A30) comprises the colored glass article according to any one of the first to twenty-ninth aspects (A1-A29), wherein the colored glass article has a thickness of at least 250 μm and at most 6 mm.

The thirty-first aspect (A31) includes a colored glass article according to any one of the first to the thirtieth aspects (A1-A30), wherein the colored glass article is an ion-exchanged colored glass article.

A thirty-second aspect A32 includes a colored glass article according to the thirty-first aspect A31, wherein the ion-exchanged colored glass article has a depth of compression of at least 10 μm.

A thirty-third aspect (A33) includes a colored glass article according to the thirty-first aspect (A31) or the thirty-second aspect (A32), wherein the ion-exchanged colored glass article has a thickness “t” and a compression of at least 0.15 t. It has depth.

A thirty-fourth aspect (A34) includes a colored glass article according to any one of the thirty-first to thirty-third aspects (A31-A33), wherein the ion-exchanged colored glass article has a surface compressive stress of at least 300 MPa.

A thirty-fifth aspect (A35) includes a colored glass article according to any one of the thirty-first to thirty-fourth aspects (A31-A34), wherein the ion-exchanged colored glass article has a maximum central tension of at least 40 MPa.

According to a thirty-sixth aspect (A36), a consumer electronic device includes a housing having a front, a back and a side; and an electrical component provided at least partially within the housing, the electrical component comprising at least a controller, a memory and a display, the display provided at or adjacent to the front of the housing; wherein the housing comprises a colored glass article according to any one of the first to thirty-fifth aspects (A1-A35).

According to the thirty-seventh aspect (A37), the glass composition includes: SiO ₂ of at least 50 mol% and not more than 80 mol%; 7 mol% or more and 25 mol% or less of Al ₂ O ₃ ; 1 mol% or more and 15 mol% or less of B ₂ O ₃ ; 5 mol% or more and 20 mol% or less of Li ₂ O; Na ₂ O of 0.5 mol% or more and 15 mol% or less; K ₂ O greater than 0 mol% and less than or equal to 1 mol%; It may contain 1 x 10 ^-6 mol% or more and 1 mol% or less of Au, where: R ₂ O - Al ₂ O ₃ is -5 mol% or more and 7 mol% or less, R ₂ O is Li ₂ O, It is the sum of Na ₂ O, and K ₂ O.

According to the second 27th aspect (A37.1), the glass composition comprises: at least 50 mol% but not more than 80 mol% SiO ₂ ; 7 mol% or more and 25 mol% or less of Al ₂ O ₃ ; 1 mol% or more and 15 mol% or less of B ₂ O ₃ ; Li ₂ O of 7 mol% or more and 20 mol% or less; 0.5 mol% or more and 12 mol% or less of Na ₂ O; K ₂ O greater than 0 mol% and less than or equal to 1 mol%; It may contain 1 x 10 ^-6 mol% or more and 1 mol% or less of Au, where: R ₂ O - Al ₂ O ₃ is -5 mol% or more and 5 mol% or less, R ₂ O is Li ₂ O, It is the sum of Na ₂ O, and K ₂ O.

A thirty-eighth aspect (A38) includes a glass composition according to the thirty-seventh aspect (A37) or the second thirty-seventh aspect (A37.1), wherein R ₂ O - Al ₂ O ₃ is -3 mol % or more than 5 mol. % or less.

A thirty-ninth aspect (A39) includes a glass composition according to the thirty-eighth aspect (A38), wherein R ₂ O - Al ₂ O ₃ is at least -1 mol% and at most 3 mol%.

A fortieth aspect (A40) includes the glass composition according to the thirty-seventh to thirty-ninth aspects (A37-A39), wherein the glass composition comprises at least 0.0001 mol% and not more than 0.1 mol% Au.

A forty-first aspect (A41) includes a glass composition according to any one of the thirty-seventh to fortieth aspects (A37-A40), wherein R ₂ O is less than or equal to 6 mol% and 25 mol%.

A forty-second aspect (A42) includes a glass composition according to the forty-first aspect (A41), wherein R ₂ O is at least 8 mol% and at most 23 mol%.

The forty-third aspect (A43) includes the glass composition according to any one of the thirty-seventh to forty-second aspects (A37-A42), wherein the glass composition comprises at least 0.01 mol% and not more than 2 mol% ZrO ₂ .

A forty-fourth aspect (A44) includes the glass composition of the forty-third aspect (A43), wherein the glass composition comprises at least 0.1 mol% and at most 1.5 mol% ZrO ₂ .

The forty-fifth aspect (A45) includes the glass composition of any one of the thirty-seventh to forty-fourth aspects (A37-A44), wherein the glass composition comprises at least 0.01 mol% and not more than 1 mol% Fe ₂ O ₃ .

A forty-sixth aspect (A46) includes the glass composition according to the forty-fifth aspect (A45), wherein the glass composition comprises at least 0.05 mol% and not more than 0.5 mol% Fe ₂ O ₃ .

A forty-seventh aspect (A47) comprises a glass composition according to any one of the thirty-seventh to forty-sixth aspects (A37-A46), wherein 5.72*Al ₂ O ₃ (mol%) - 21.4*ZnO (mol%) - 2.5 *P ₂ O ₅ (mol%) - 35*Li ₂ O (mol%) - 16.6*B ₂ O ₃ (mol%) - 20.5*MgO (mol%) - 23.3*Na ₂ O (mol%) - 27.9 *SrO (mol%) - 18.5*K ₂ O (mol%) - 26.3*CaO (mol%) is greater than -609 mol%.

A forty-eighth aspect (A48) includes the glass composition according to any one of the thirty-seventh to forty-seventh aspects (A37-A47), wherein the glass composition comprises at least 0.01 mol% and not more than 1 mol% SnO ₂ .

A forty-ninth aspect (A49) includes a glass composition according to the forty-eighth aspect (A48), wherein the glass composition comprises at least 0.05 mol% and at most 0.75 mol% SnO ₂ .

A fiftieth aspect (A50) includes the glass composition according to any one of the thirty-seventh to forty-ninth aspects (A37-A49), wherein the glass composition is substantially free of MgO, CaO, ZnO, Cl, or combinations thereof.

The fifty-first aspect (A51) includes the glass composition according to any one of the thirty-seventh to fifty-fifty aspects (A37-A50), wherein the glass composition comprises at least 7 mol% and at most 18 mol% Li ₂ O.

A fifty-second aspect (A52) includes a glass composition according to the fifty-first aspect (A51), wherein the glass composition comprises at least 9 mol% and at most 16 mol% Li ₂ O.

The fifty-third aspect (A53) includes the glass composition according to any one of the thirty-seventh to fifty-second aspects (A37-A52), wherein the glass composition comprises at least 1 mol% and at most 12 mol% Na ₂ O.

A fifty-fourth aspect (A54) includes the glass composition according to the fifty-third aspect (A53), wherein the glass composition comprises at least 2 mol% and at most 10 mol% Na ₂ O.

The fifty-fifth aspect (A55) includes the glass composition according to any one of the thirty-seventh to fifty-fourth aspects (A37-A54), wherein the glass composition comprises at least 0.1 mol% and at most 0.5 mol% K ₂ O.

The fifty-sixth aspect (A56) includes the glass composition according to any one of the thirty-seventh to fifty-fifth aspects (A37-A55), wherein the glass composition comprises at least 9 mol% and not more than 23 mol% Al ₂ O ₃ .

A fifty-seventh aspect (A57) includes the glass composition according to the fifty-sixth aspect (A56), wherein the glass composition comprises at least 11 mol% and at most 20 mol% Al ₂ O ₃ .

The fifty-eighth aspect (A58) includes the glass composition according to any one of the thirty-seventh to fifty-seventh aspects (A37-A57), wherein the glass composition comprises at least 2 mol% and not more than 12 mol% B ₂ O ₃ .

A fifty-ninth aspect (A59) includes a glass composition according to the fifty-eighth aspect (A58), wherein the glass composition comprises at least 3 mol% and at most 10 mol% B ₂ O ₃ .

A sixtieth aspect (A60) includes the glass composition according to any one of the thirty-seventh to fifty-ninth aspects (A37-A59), wherein the glass composition comprises at least 52 mol% and not more than 75 mol% SiO ₂ .

According to a sixty-first aspect (A61), a method of forming a colored glass article comprises: heat treating a glass composition to form a glass article, the glass composition comprising: at least 50 mol% and not more than 80 mol% SiO ₂ ; 7 mol% or more and 25 mol% or less of Al ₂ O ₃ ; 1 mol% or more and 15 mol% or less of B ₂ O ₃ ; 5 mol% or more and 20 mol% or less of Li ₂ O; Na ₂ O of 0.5 mol% or more and 15 mol% or less; K ₂ O greater than 0 mol% and less than or equal to 1 mol%; and 1 x 10 ^-6 mol% to 1 mol% Au, where: R ₂ O - Al ₂ O ₃ is -5 mol% to 7 mol%, and R ₂ O is Li ₂ O, Na. ₂ O, and K ₂ O; and subjecting the glass article to a heat treatment cycle at a temperature of 500°C or more and 800°C or less and a period of 0.25 hours or more and 24 hours or less to produce a colored glass article.

According to the second 61st aspect (A61.1), a method of forming a colored glass article comprises: heat treating a glass composition to form a glass article, wherein the glass composition has: 50 mol% or more and 80 mol% or less. of SiO ₂ ; 7 mol% or more and 25 mol% or less of Al ₂ O ₃ ; 1 mol% or more and 15 mol% or less of B ₂ O ₃ ; Li ₂ O of 7 mol% or more and 20 mol% or less; 0.5 mol% or more and 12 mol% or less of Na ₂ O; K ₂ O greater than 0 mol% and less than or equal to 1 mol%; and 1 x 10 ^-6 mol% to 1 mol% Au, where: R ₂ O - Al ₂ O ₃ is -5 mol% to 5 mol%, and R ₂ O is Li ₂ O, Na. ₂ O, and K ₂ O; and subjecting the glass article to a heat treatment cycle at a temperature of 500°C or more and 800°C or less and a period of 0.25 hours or more and 24 hours or less to produce a colored glass article.

A sixty-second aspect (A62) includes a method according to the sixty-first aspect (A61) or the second sixty-first aspect (A61.1), wherein the temperature of the heat treatment cycle is at least 550°C and at most 775°C.

A sixty-third aspect (A63) includes a method according to any one of the sixty-first to sixty-second aspects (A61-A62), wherein the duration of the heat treatment cycle is at least 0.5 hours and at most 16 hours.

The sixty-fourth aspect (A64) includes the method according to any one of the sixty-first to sixty-third aspects (A61-A63), comprising: comprising the steps of: It further includes strengthening the colored glass article to form an ion exchanged glass-ceramic article.

A sixty-fifth aspect (A65) includes a method according to sixty-fourth aspect (A64), wherein the ion exchange bath comprises KNO ₃ .

A sixty-sixth aspect (A66) includes a method according to the sixty-fifth aspect (A65), wherein the ion exchange bath comprises NaNO ₃ .

Additional features and advantages of the colored glass articles described herein will be set forth in the following detailed description, and will be apparent in part to those skilled in the art from the following detailed description, or which includes the accompanying drawings, as well as the following detailed description and claims. This will be readily appreciated by practicing the implementations described herein.

It will be understood that both the foregoing general description and the following detailed description are intended to illustrate various embodiments and 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 in and constitute a part of this specification. The drawings illustrate the various embodiments described herein and, together with the detailed description, serve to explain the principles and operation of the claimed subject matter.

1 is a top view of an electronic device including any one of the colored glass articles according to one or more embodiments described herein.
FIG. 2 is a perspective view of the electronic device of FIG. 1.
3 shows R ₂ O - Al ₂ O ₃ versus a* CIELAB space (x-axis: R ₂ O - Al ₂ ) of colored glass articles made from glass compositions according to one or more embodiments described herein and subjected to heat treatment. O ₃ ; y-axis: a*) plot.
4 shows R ₂ O - Al ₂ O ₃ versus b* CIELAB space (x-axis: R ₂ O - Al ₂ ) of colored glass articles made from glass compositions according to one or more embodiments described herein and subjected to heat treatment. O ₃ ; y-axis: b*) plot.

Reference will now be made in detail to various embodiments of glass compositions having desired colors and colored glass articles formed therefrom. According to embodiments, the colored glass article contains at least 50 mol% and up to 80 mol% SiO ₂ ; 7 mol% or more and 25 mol% or less of Al ₂ O ₃ ; 1 mol% or more and 15 mol% or less of B ₂ O ₃ ; 5 mol% or more and 20 mol% or less of Li ₂ O; Na ₂ O of 0.5 mol% or more and 15 mol% or less; K ₂ O greater than 0 mol% and less than or equal to 1 mol%; and 1 x 10 ^-6 mol% or more and 1 mol% or less of Au. R ₂ O - Al ₂ O ₃ is -5 mol% or more and 7 mol% or less, and R ₂ O is the sum of Li ₂ O, Na ₂ O, and K ₂ O. According to embodiments, the colored glass article contains at least 50 mol% but not more than 80 mol% SiO ₂ ; 7 mol% or more and 25 mol% or less of Al ₂ O ₃ ; 1 mol% or more and 15 mol% or less of B ₂ O ₃ ; Li ₂ O of 7 mol% or more and 20 mol% or less; 0.5 mol% or more and 12 mol% or less of Na ₂ O; K ₂ O greater than 0 mol% and less than or equal to 1 mol%; and 1 x 10 ^-6 mol% or more and 1 mol% or less of Au. R ₂ O - Al ₂ O ₃ is -5 mol% or more and 5 mol% or less, and R ₂ O is the sum of Li ₂ O, Na ₂ O, and K ₂ O.

Various embodiments of colored glass articles and methods of making the same will be described herein with specific reference to the accompanying drawings.

Ranges can be expressed herein from “about” one particular value, and/or to “about” another particular value. When such ranges are expressed, alternative embodiments include from one specific value and/or to the remaining specific value. Similarly, by the preceding use of “about,” it will be understood that when a value is expressed as an approximation, that particular value forms another embodiment. It will be further understood that each end point of the range is meaningful both in relation to and independently of the other end point.

Directional terms as used herein - e.g., up, down, right, left, front, back, top, bottom - are made with reference to the drawings as shown only and are not intended to imply absolute directions. No.

Unless otherwise stated, any method described herein is not intended to be construed as requiring that its steps be performed in a particular order or that any particular orientation is required in any device. Accordingly, either a method claim does not substantially describe the order in which its steps are followed, or any device claim does not substantially describe an order or orientation for the individual components, or the steps are limited to a particular order, or the configuration of the device. Unless a particular order or orientation of elements is specifically recited in the claims or detailed description, it is not intended that a particular order or orientation be assumed, in any respect. This is a matter of logic regarding the arrangement of steps, flow of operations, order of components, or direction of components; A general meaning derived from a grammatical construction or punctuation mark; and any possible non-expressive basis for interpretation, including the number or type of embodiments described herein.

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

In embodiments of the glass compositions described herein and the resulting colored glass articles, the concentration of constituents in oxide form (e.g., SiO ₂ , Al ₂ O ₃ , etc.) is on an oxide basis, unless otherwise specified. It is expressed as mol% (mol%).

In embodiments of the glass compositions and resulting colored glass articles described herein, the concentrations of Au and Cl are specified in mole percent (mol%), unless otherwise specified.

The term "substantially free", when used to describe the concentration and/or absence of a particular component in the glass composition and the resulting colored glass article, means that the component is intentionally present in the glass composition and the resulting colored glass article. This means that it is not added. However, the glass compositions and resulting colored glass articles may contain traces of contaminants or tramps in amounts less than 0.1 mole percent.

The terms "0 mole percent" and "free", used to describe the concentration and/or absence of a particular component in the glass composition and the resulting colored glass article, mean that the component is present in the glass composition and the resulting colored glass article. means that it is not present in colored glass articles.

Fracture toughness (K _1C ) refers to the ability of a glass composition to resist fracture. Just as K _1C values are measured prior to ion exchange (IOX) treatment of glass articles, fracture toughness is measured on unreinforced glass articles and thereby characterizes the glass substrate prior to IOX. The fracture toughness test method described here is not suitable for glass exposed to IOX treatment. However, fracture toughness measurements performed as described herein on the same glass (e.g., glass substrate) prior to IOX treatment are correlated to fracture toughness after IOX treatment and are therefore used as is. The chevron notch short bar (CNSB) method utilized to measure K _1C values is described in Reddy, K.P.R., et al., “Determination of Fracture Toughness of Glass and Ceramic Materials Using Chevron-Notchted Specimens,” J. Am. Ceram. Soc., 71 [6], C-310-C-313 (1988), provided that Y*m “Closed-shape expression for crack-entrance displacement and stress intensity factors”, NASA Technical Memorandum 83796, pp. It is calculated using equation 5 in 1-30 (October 1992). Unless otherwise specified, all fracture toughness values were measured by the Chevron Notched Short Bar (CNSB) method.

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

Surface compressive stress is measured using a surface stress meter (FSM), such as a commercially available instrument such as the FSM-6000 manufactured by Orihara Industrial Co., Ltd. (Japan). Surface stress measurements rely on measurement of the stress optical coefficient (SOC), which is related to the birefringence of the glass article. SOC is measured according to Procedure C (Glass Disk Method) described in ASTM Standard C770-16, entitled “Standard Test Method for Determination of Glass Stress-Optical Modulus,” the contents of which are incorporated herein by reference in their entirety. . Depth of compression (DOC) is also measured using FSM. Maximum central tension (CT) values are measured using scattered light polariscope (SCALP) techniques known in the art.

As used herein, the term “depth of compression” (DOC) refers to the location in the article where compressive stress converts to tensile stress.

As used herein, the term “CIELAB color space” refers to the color space defined in 1976 by the International Commission on Illumination (CIE). It expresses color as three values: L* for lightness from black (0) to white (100), a* for green (-) to red (+), and B* for blue (-). Indicates from to yellow (+).

As used herein, the term “color gamut” refers to the palette of colors that can be achieved by a colored glass article within the CIELAB color space.

As used herein, “optical transmission spectra” refers to an Agilent Cary 60 spectrometer with a scan range of 250 nm to 800 nm, a scan step of 2 nm, a signal average of 0.5 s, and a spot size of 2 mm. Obtained using a photometer. The obtained light transmission data is based on RS Berns's Billmeyer and Saltzman's Principles of Color Technology , 3rd. Ed., John Wiley & Sons, New York (2000).

Colorants have been added to existing aluminosilicate glass compositions to achieve colored glass articles with desired colors and improved mechanical properties. For example, gold (Au) doped glass articles typically appear red, orange, or purple. However, simply including a colorant in the aluminosilicate glass composition may not produce the desired color.

A glass composition that alleviates the above-mentioned problems and colored glass articles formed therefrom, such that Au can be added to an aluminosilicate glass composition to produce a colored glass article with a desired color while maintaining excellent ion-exchange and dropping performance. It is disclosed here. Specifically, the concentration of certain components can be adjusted to achieve the desired color and prevent precipitation of Au particles in the glass network.

The glass compositions and colored glass articles described herein may be described as aluminoborosilicate glass compositions and colored glass articles and may include SiO ₂ , Al ₂ O ₃ , and B ₂ O ₃ . In addition to SiO ₂ , Al ₂ O ₃ , and B ₂ O ₃ , the glass compositions and colored glass articles described herein include Au to produce colored glass articles with desired colors. The glass compositions and colored glass articles described herein also include alkali oxides such as Li ₂ O and Na ₂ O to enable ion-exchangeability of the colored glass articles. Additionally, the difference in R ₂ O and Al ₂ O ₃ (ie R ₂ O (mol%) - Al ₂ O ₃ (mol%)) in the glass compositions described herein and the resulting colored glass articles is as desired. It can be adjusted to produce an observable color (e.g., pink, purple, red, or orange). Moreover, the viscosity of the glass composition can be adjusted to prevent devitrification of the glass composition and precipitation of Au particles during the melting and forming steps, which can limit the color gamut that can be achieved.

SiO ₂ is the primary glass former in the glass compositions described herein and can function to stabilize the network structure of the colored glass article. The concentration of SiO ₂ in the glass composition and the resulting colored glass article should be sufficiently high to improve the chemical durability of the glass composition and, in particular, the resistance of the glass composition to decomposition upon exposure to acidic solutions, basic solutions and water. (e.g. more than 50 mol%). Because the melting point of pure SiO ₂ or high SiO ₂ glass is undesirably high, the amount of SiO ₂ can be limited (eg, to 80 mole % or less) to control the melting point of the glass composition. Accordingly, limiting the concentration of SiO ₂ can help improve the meltability and formability of the resulting colored glass article.

In embodiments, the glass composition and resulting colored glass article may include greater than or equal to 50 mol% and less than or equal to 80 mol% SiO ₂ . In embodiments, the glass composition and resulting colored glass article may include greater than or equal to 52 mol% and less than or equal to 75 mol% SiO ₂ . In embodiments, the concentration of SiO ₂ in the glass composition and the resulting colored glass article is at least 50 mol%, at least 52 mol%, at least 54 mol%, at least 56 mol%, at least 58 mol%, or even at least 60 mol%. It may be more than mol%. In embodiments, the concentration of SiO ₂ in the glass composition and the resulting colored glass article may be no more than 80 mol%, no more than 75 mol%, no more than 73 mol%, no more than 71 mol%, or even no more than 69 mol%. In embodiments, the concentration of SiO ₂ in the glass composition and the resulting colored glass article is greater than or equal to 50 mol% and less than or equal to 80 mol%, greater than or equal to 50 mol% and less than or equal to 75 mol%, greater than or equal to 50 mol% and less than or equal to 73 mol%, or less than or equal to 50 mol%. mol% or more but 71 mol% or less, 50 mol% or more but 69 mol% or less, 52 mol% or more but 80 mol% or less, 52 mol% or more but 75 mol% or less, 52 mol% or more and 73 mol% or less, 52 mol% or more 71 mol % or less, 52 mol% or more but 69 mol% or less, 54 mol% or more but 80 mol% or less, 54 mol% or more but 75 mol% or less, 54 mol% or more but 73 mol% or less, 54 mol% or more but 71 mol% or less, 54 mol % or more 69 mol% or less, 56 mol% or more but 80 mol% or less, 56 mol% or more but 75 mol% or less, 56 mol% or more but 73 mol% or less, 56 mol% or more but 71 mol% or less, 56 mol% or more 69 mol% or less, 58 mol% or more and 80 mol% or less, 58 mol% or more and 75 mol% or less, 58 mol% or more and 73 mol% or less, 58 mol% or more and 71 mol% or less, 58 mol% or more and 69 mol% or less, 50 mol% Not less than 80 mol% but not more than 75 mol%, not less than 60 mol% but not more than 73 mol%, not less than 60 mol% but not more than 71 mol%, or even at least 60 mol% and not more than 69 mol%, or any of these terminal points. It can be any and all sub-ranges formed from those of.

Like SiO ₂ , Al ₂ O ₃ can also stabilize the glass network and additionally provide improved mechanical properties and chemical durability to the glass composition and the resulting colored glass article. The amount of Al ₂ O ₃ can also be adjusted to control the viscosity of the glass composition. Al ₂ O ₃ may be included such that the resulting glass composition has a desired fracture toughness (eg, 0.7 MPa·m ^1/2 or greater). However, if the amount of Al ₂ O ₃ is too high (eg, greater than 25 mole %), the viscosity of the glass melt may increase, thereby reducing the formability of the colored glass article.

Accordingly, in embodiments, the glass composition and resulting colored glass article may include at least 7 mol% and up to 25 mol% Al ₂ O ₃ . In embodiments, the glass composition and resulting colored glass article may include greater than or equal to 9 mol% and less than or equal to 23 mol% Al ₂ O ₃ . In embodiments, the glass composition and resulting colored glass article may include from 11 mol% to 20 mol% Al ₂ O ₃ . In embodiments, the concentration of Al ₂ O ₃ in the glass composition and the resulting colored glass article may be at least 7 mol%, at least 9 mol%, at least 11 mol%, or even at least 13 mol%. In embodiments, the concentration of Al ₂ O ₃ in the glass composition and resulting colored glass article may be less than or equal to 25 mol%, less than or equal to 23 mol%, less than or equal to 20 mol%, or even less than or equal to 17 mol%. In embodiments, the concentration of Al ₂ O ₃ in the glass composition and the resulting colored glass article is greater than or equal to 7 mol% and less than or equal to 25 mol%, greater than or equal to 7 mol% and less than or equal to 23 mol%, or greater than or equal to 7 mol% and less than or equal to 20 mol%. , 7 mol% or more and 17 mol% or less, 9 mol% or more and 25 mol% or less, 9 mol% or more and 23 mol% or less, 9 mol% or more and 20 mol% or less, 9 mol% or more and 17 mol% or less, 11 mol% or more 25 mol% or less, 11 mol% or more but 23 mol% or less, 11 mol% or more but 20 mol% or less, 11 mol% or more but 17 mol% or less, 13 mol% or more and 25 mol% or less, 13 mol% or more and 23 mol% or less, It can be from 13 mol% to 20 mol%, from 13 mol% to 17 mol%, or any and all sub-ranges formed from any of these terminal points.

B ₂ O ₃ helps improve the damage resistance of the resulting colored glass article. Additionally, B ₂ O ₃ reduces the formation of non-bridging oxygens, which can reduce fracture toughness. The concentration of B ₂ O ₃ should be sufficiently high (eg, greater than 1 mol %) to reduce the melting point of the glass composition, improve formability, and increase fracture toughness of the colored glass article. However, if B ₂ O ₃ is too high (eg, greater than 15 mol%), the annealing point and strain point may decrease, which increases stress relaxation and reduces the overall strength of the colored glass article.

In embodiments, the glass composition and resulting colored glass article may include greater than or equal to 1 mol% and less than or equal to 15 mol% of B ₂ O ₃ . In embodiments, the glass composition and resulting colored glass article may include at least 2 mol% and up to 12 mol% B ₂ O ₃ . In embodiments, the glass composition and resulting colored glass article may include from 3 mol% to 10 mol% B ₂ O ₃ . In embodiments, the concentration of B ₂ O ₃ in the glass composition and the resulting colored glass article may be at least 1 mol%, at least 2 mol%, at least 3 mol%, or even at least 4 mol%. In embodiments, the concentration of B ₂ O ₃ in the glass composition and resulting colored glass article will be 15 mol% or less, 12 mol% or less, 10 mol% or less, 8 mol% or less, or even 6 mol% or less. You can. In embodiments, the concentration of B ₂ O ₃ in the glass composition and the resulting colored glass article is from 1 mol% to 15 mol%, from 1 mol% to 12 mol%, from 1 mol% to 10 mol%. , 1 mol% or more and 8 mol% or less, 1 mol% or more and 6 mol% or less, 2 mol% or more and 15 mol% or less, 2 mol% or more and 12 mol% or less, 2 mol% or more and 10 mol% or less, 2 mol% or more 8 mol% or less, 2 mol% or more but 6 mol% or less, 3 mol% or more and 15 mol% or less, 3 mol% or more and 12 mol% or less, 3 mol% or more and 10 mol% or less, 3 mol% or more and 8 mol% or less, 3 mol% or more and 6 mol% or less, 4 mol% or more and 15 mol% or less, 4 mol% or more and 12 mol% or less, 4 mol% or more and 10 mol% or less, 4 mol% or more and 8 mol% or less, or even 4 mol% It may be greater than or equal to 6 mol%, or any and all sub-ranges formed from any of these terminal points.

As mentioned above, the glass composition and resulting colored glass article may contain alkali oxides such as Li ₂ O, Na ₂ O, and K ₂ O to enable ion-exchangeability of the colored glass article. there is.

Li ₂ O helps the ion exchangeability of the colored glass article and also reduces the softening point of the glass composition, thereby increasing the moldability of the colored glass article. Additionally, Li ₂ O lowers the melting point of the glass composition, which may help improve Au retention. The concentration of Li ₂ O in the glass composition and the resulting colored glass article should be sufficiently high to lower the melting point of the glass composition and achieve the desired maximum central tension (e.g., 40 MPa and higher) after ion exchange. For example, 5 mol% or more). However, if the amount of Li ₂ O is too high (for example, more than 20 mol%), the liquidus temperature may increase, which may reduce the manufacturability of the colored glass water.

In embodiments, the glass composition and resulting colored glass article may include at least 5 mol% and up to 20 mol% Li ₂ O or at least 7 mol% and up to 20 mol% Li ₂ O. In embodiments, the glass composition and resulting colored glass article may include from 7 mol% to 18 mol% Li ₂ O. In embodiments, the glass composition and resulting colored glass article may include greater than or equal to 9 mol% and less than or equal to 16 mol% Li ₂ O. In embodiments, the concentration of Li ₂ O in the glass composition and the resulting colored glass article may be at least 5 mol%, at least 7 mol%, or even at least 9 mol%. In embodiments, the concentration of Li ₂ O in the glass composition and resulting colored glass article is 20 mol% or less, 18 mol% or less, 16 mol% or less, 16 mol% or less, 14 mol% or less, or even It may be 12 mol% or less. The concentration of Li ₂ O in the glass composition and the resulting colored glass article can be from 5 mol% to 20 mol%, from 5 mol% to 18 mol%, from 5 mol% to 16 mol%, from 5 mol% to 14 mol%. mol% or less, 5 mol% or more but 12 mol% or less, 7 mol% or more but 20 mol% or less, 7 mol% or more but 18 mol% or less, 7 mol% or more but 16 mol% or less, 7 mol% or more but 14 mol% or less, 7 more than 12 mol% but less than 20 mol%, more than 9 mol% but less than 20 mol%, more than 9 mol% but less than 18 mol%, more than 9 mol% but less than 16 mol%, more than 9 mol% but less than 14 mol%, or even more than 9 mol%. It may be up to 12 mol%, or any and all sub-ranges formed from any of these terminal points.

Na ₂ O improves the diffusivity of alkali ions in the glass, thereby reducing ion-exchange time and helping to achieve the desired surface compressive stress (e.g., greater than 300 MPa). Na ₂ O also improves the formability of colored glass articles. However, if too much Na ₂ O is added to the glass composition, the melting point may become too low. As such, in embodiments, the concentration of Li ₂ O present in the glass composition and the resulting colored glass article is greater than the concentration of Na ₂ O present in the glass composition and the resulting colored glass article. You can.

In embodiments, the glass composition and the resulting colored glass article may include from 0.5 mol% to 15 mol% Na ₂ O or from 0.5 mol% to 12 mol% Na ₂ O. In embodiments, the glass composition and resulting colored glass article may include greater than or equal to 1 mol% and less than or equal to 12 mol% Na ₂ O. In embodiments, the glass composition and resulting colored glass article may include greater than or equal to 2 mol% and less than or equal to 10 mol% Na ₂ O. In embodiments, the concentration of Na ₂ O in the glass composition and the resulting colored glass article may be at least 0.5 mol%, at least 1 mol%, at least 2 mol%, at least 3 mol%, or even at least 4 mol%. . In embodiments, the concentration of Na ₂ O in the glass composition and resulting colored glass article may be 15 mol% or less, 12 mol% or less, 10 mol% or less, 8 mol% or less, or even 6 mol% or less. there is. In embodiments, the concentration of Na ₂ O in the glass composition and the resulting colored glass article is from 0.5 mol% to 15 mol%, from 0.5 mol% to 12 mol%, from 0.5 mol% to 10 mol%, 0.5 mol% or more but 8 mol% or less, 0.5 mol% or more but 6 mol% or less, 1 mol% or more but 15 mol% or less, 1 mol% or more but 12 mol% or less, 1 mol% or more and 10 mol% or less, 1 mol% or more 8 mol% or less, 1 mol% or more but 6 mol% or less, 2 mol% or more but 15 mol% or less, 2 mol% or more but 12 mol% or less, 2 mol% or more but 10 mol% or less, 2 mol% or more but 8 mol% or less, 2 mol% or more but 6 mol% or less, 3 mol% or more but 15 mol% or less, 3 mol% or more but 12 mol% or less, 3 mol% or more and 10 mol% or less, 3 mol% or more and 8 mol% or less, 3 mol% or more 6 mol % or less, not less than 4 mol% but not more than 15 mol%, not less than 4 mol% but not more than 12 mol%, not less than 4 mol% but not more than 10 mol%, not less than 4 mol% but not more than 8 mol%, or even more than 4 mol% but not more than 6 mol%, or any and all sub-ranges formed from any of these terminal points.

K ₂ O can promote ion-exchange, increase the depth of compression, and reduce the melting point to improve the formability of colored glass articles. However, adding too much K ₂ O may cause the surface compressive stress and melting point to become too low. Accordingly, in embodiments, the amount of K ₂ added to the glass composition may be limited.

In embodiments, the glass composition and resulting colored glass article may include greater than 0 mol% and less than or equal to 1 mol% K ₂ O. In embodiments, the glass composition and resulting colored glass article may optionally include greater than 0.1 mol% and less than or equal to 0.5 mol% K ₂ O. In embodiments, the concentration of K ₂ O in the glass composition and the resulting colored glass article may be greater than 0 mol% or even greater than 0.1 mol%. In embodiments, the concentration of K ₂ O in the glass composition and the resulting colored glass article may be 1 mol% or less, 0.5 mol% or less, or even 0.25 mol% or less. In embodiments, the concentration of K ₂ O in the glass composition and the resulting colored glass article is greater than 0 mol% and up to 1 mol%, greater than 0 mol% and up to 0.5 mol%, greater than 0 mol% and up to 0.25 mol%, It can be from 0.1 mol% to 1 mol%, from 0.1 mol% to 0.5 mol%, or even from 0.1 mol% to 0.25 mol%, or any and all sub-ranges formed from any of these terminal points.

As used herein, R ₂ O is the sum of Na ₂ O, K ₂ O, and Li ₂ O (in mol%) present in the glass composition (i.e., R ₂ O = Na ₂ O (mol%) + K ₂ O (mol%) + Li ₂ O (mol%)). As used herein, alkali oxides such as Na ₂ O, K ₂ O, and Li ₂ O help reduce the softening point and molding temperature of the glass composition, thereby e.g. offsets the increase in softening point and molding temperature of the glass composition due to the larger amount of SiO ₂ . The reduction in softening point and molding temperature can be further reduced by including a combination of alkali oxides (e.g., two or more alkali oxides) in the glass composition, a phenomenon referred to as the “mixed alkali effect”. However, it has been found that if the amount of alkali oxide is too high, the average coefficient of thermal expansion of the glass composition increases beyond 100 x 10 ^-7 /°C, which may be undesirable.

In embodiments, the concentration of R ₂ O in the glass composition and the resulting colored glass article may be greater than or equal to 6 mol% and less than or equal to 25 mol%. In embodiments, the concentration of R ₂ O in the glass composition and the resulting colored glass article may be greater than or equal to 8 mol% and less than or equal to 23 mol%. In embodiments, the concentration of R ₂ O in the glass composition and resulting colored glass article can be at least 6 mol%, at least 8 mol%, at least 10 mol%, at least 12 mol%, or even at least 14 mol%. there is. In embodiments, the concentration of R ₂ O in the glass composition and resulting colored glass article may be less than or equal to 25 mol%, less than or equal to 23 mol%, less than or equal to 20 mol%, or even less than or equal to 18 mol%. In embodiments, the concentration of R ₂ O in the glass composition and the resulting colored glass article is from 6 mol% to 25 mol%, from 6 mol% to 23 mol%, from 6 mol% to 20 mol%, 6 mol% or more but 18 mol% or less, 8 mol% or more but 25 mol% or less, 8 mol% or more but 23 mol% or less, 8 mol% or more but 20 mol% or less, 8 mol% or more but 18 mol% or less, 10 mol% or more 25 mol% or less, 10 mol% or more but 23 mol% or less, 10 mol% or more but 20 mol% or less, 10 mol% or more but 18 mol% or less, 12 mol% or more but 25 mol% or less, 12 mol% or more but 23 mol% or less, 12 greater than or equal to 20 mol%, greater than or equal to 12 mol% but less than or equal to 18 mol%, greater than or equal to 14 mol% but less than or equal to 25 mol%, greater than or equal to 14 mol% and less than or equal to 23 mol%, greater than or equal to 14 mol% and less than or equal to 20 mol%, or even greater than or equal to 14 mol%. It may be up to 18 mol%, or any and all sub-ranges formed from any of these terminal points.

In embodiments, the difference between R ₂ O and Al ₂ O ₃ (i.e., R ₂ O (mol%) - Al ₂ O ₃ (mol%)) in the glass composition determines the desired observable color (e.g., pink). , purple, red, or orange). Together with the temperature and time of heat treatment, the analyzed R ₂ O - Al ₂ O ₃ of the resulting colored glass article correlates with the observable color of the colored glass article after heat treatment as discussed herein. There may be. In embodiments, R ₂ O - Al ₂ O ₃ in the glass composition and resulting colored glass article may be at least -5 mol% and at most 7 mol%, or at least -5 mol% and at most 5 mol%. In embodiments, R ₂ O - Al ₂ O ₃ in the glass composition and resulting colored glass article may be greater than -3 mol% and less than or equal to 6 mol%. In embodiments, R ₂ O - Al ₂ O ₃ in the glass composition and the resulting colored glass article may be greater than -1 mol% and less than or equal to 5 mol%. In embodiments, R ₂ O - Al ₂ O ₃ in the glass composition and resulting colored glass article may be greater than -5 mol% and less than or equal to 1.5 mol%. In embodiments, R ₂ O - Al ₂ O ₃ in the glass composition and resulting colored glass article may be greater than -3 mol% and less than or equal to 1.5 mol%. In embodiments, R ₂ O - Al ₂ O ₃ in the glass composition and resulting colored glass article may be greater than or equal to 1.5 mol% and less than or equal to 7 mol%. In embodiments, R ₂ O - Al ₂ O ₃ in the glass composition and resulting colored glass article may be greater than or equal to 1.5 mol% and less than or equal to 5 mol%. In embodiments, R ₂ O - Al ₂ O ₃ in the glass composition and resulting colored glass article is at least -5 mol%, at least -3, at least -1 mol%, at least 0 mol%, or even 1.5 mol%. It could be more than that. In embodiments, R ₂ O - Al ₂ O ₃ in the glass composition and resulting colored glass article can be 7 mol% or less, 5 mol% or less, 3 mol% or less, or even 1.5 mol% or less. In embodiments, R ₂ O - Al ₂ O ₃ in the glass composition and the resulting colored glass article is greater than or equal to -5 mol% but less than or equal to 7 mol%, greater than or equal to -5 mol% and less than or equal to 5 mol%, -5 mol%. More than 3 mol% and less, -5 mol% and less than 1.5 mol%, -3 mol% and more than 7 mol%, -3 mol% and less than 5 mol%, -3 mol% and more than 3 mol%, -3 mol% More than 1.5 mol% or less, -1 mol% or more but less than 7 mol%, -1 mol% or more but less than 5 mol%, -1 mol% or more but less than 3 mol%, -1 mol% or more and less than 1.5 mol%, more than 0 mol% 7 mol% or less, 0 mol% or more but 5 mol% or less, 0 mol% or more but 3 mol% or less, 0 mol% or more and 1.5 mol% or less, 1.5 mol% or more and 7 mol% or less, 1.5 mol% or more and 5 mol% or less, or even from 1.5 mol% to 3 mol%, or any and all sub-ranges formed from any of these terminal points.

The glass compositions described herein and the resulting colored glass articles may further include ZrO ₂ . ZrO ₂ can act as a colorant in addition to Au, producing colored glass articles that can be red, for example. In embodiments, the glass composition and resulting colored glass article can include at least 0.01 mol% and up to 2 mol% ZrO ₂ . In embodiments, the glass composition and resulting colored glass article can include at least 0.1 mol% and up to 1.5 mol% ZrO ₂ . In embodiments, the concentration of ZrO ₂ in the glass composition may be at least 0 mol%, at least 0.01 mol%, at least 0.1 mol%, or even at least 0.2 mol%. In embodiments, the concentration of ZrO ₂ in the glass composition may be 2 mol% or less, 1.5 mol% or less, 1 mol% or less, 0.75 mol% or less, or even 0.5 mol% or less. In embodiments, the concentration of ZrO ₂ in the glass composition is greater than or equal to 0 mol% and less than or equal to 2 mol%, greater than or equal to 0 mol% and less than or equal to 1.5 mol%, greater than or equal to 0 mol% and less than or equal to 1 mol%, greater than or equal to 0 mol% and less than or equal to 0.75 mol%, or 0 mol% or less. mol% or more 0.5 mol% or less, 0.01 mol% or more but 2 mol% or less, 0.01 mol% or more but 1.5 mol% or less, 0.01 mol% or more but 1 mol% or less, 0.01 mol% or more and 0.75 mol% or less, 0.01 mol% or more 0.5 mol % or less, 0.1 mol% or more but 2 mol% or less, 0.1 mol% or more but 1.5 mol% or less, 0.1 mol% or more but 1 mol% or less, 0.1 mol% or more but 0.75 mol% or less, 0.1 mol% or more but 0.5 mol% or less, 0.2 mol % but not less than 2 mol%, not less than 0.2 mol% but not more than 1.5 mol%, not less than 0.2 mol% but not more than 1 mol%, not less than 0.2 mol% but not more than 0.75 mol%, or even more than 0.2 mol% but not more than 0.5 mol%, or any of these terminal points. It can be any and all sub-ranges formed from any. In embodiments, the glass composition and resulting colored glass article may or may be substantially free of ZrO ₂ .

The glass compositions described herein and the resulting colored glass articles may further include Fe ₂ O ₃ . Fe ₂ O ₃ can also act as a colorant in addition to Au, producing colored glass articles that may, for example, be pink or red in color. In embodiments, the glass composition and resulting colored glass article may include greater than or equal to 0.01 mol% and less than or equal to 1 mol% of Fe ₂ O ₃ . In embodiments, the glass composition and the resulting colored glass article may include greater than or equal to 0.05 mol% and less than or equal to 1 mol% of Fe ₂ O ₃ . In embodiments, the concentration of Fe ₂ O ₃ in the glass composition may be at least 0 mol%, at least 0.01 mol%, or even at least 0.05 mol%. In embodiments, the concentration of Fe ₂ O ₃ in the glass composition may be 1 mol% or less, 0.75 mol% or less, 0.5 mol% or less, or even 0.25 mol% or less. In embodiments, the concentration of Fe ₂ O ₃ in the glass composition is from 0 mol% to 1 mol%, from 0 mol% to 0.75 mol%, from 0 mol% to 0.5 mol%, from 0 mol% to 0.25 mol%. , 0.01 mol% or more and 1 mol% or less, 0.01 mol% or more and 0.75 mol% or less, 0.01 mol% or more and 0.5 mol% or less, 0.01 mol% or more and 0.25 mol% or less, 0.05 mol% or more and 1 mol% or less, 0.05 mol% or more It can be up to 0.75 mol%, up to 0.05 mol% up to 0.5 mol%, or even up to 0.05 mol% up to 0.25 mol%, or any and all sub-ranges formed from any of these end points. In embodiments, the glass composition and resulting colored glass article may or may be substantially free of Fe ₂ O ₃ .

The glass compositions described herein and the resulting colored glass articles may further include one or more fining agents. In embodiments, the fining agent may include SnO ₂ , for example. In embodiments, the glass composition and resulting colored glass article may include at least 0.01 mol% and up to 1 mol% SnO ₂ . In embodiments, the glass composition and resulting colored glass article may include greater than or equal to 0.05 mol% and less than or equal to 0.75 mol% SnO ₂ . In embodiments, the concentration of SnO ₂ in the glass composition may be at least 0 mol%, at least 0.01 mol%, or at least 0.05 mol%. In embodiments, the concentration of SnO ₂ in the glass composition may be 1 mol% or less, 0.75 mol% or less, 0.5 mol% or less, or even 0.25 mol% or less. In embodiments, the concentration of SnO ₂ in the glass composition is greater than or equal to 0 mol% and less than or equal to 1 mol%, greater than or equal to 0 mol% and less than or equal to 0.75 mol%, greater than or equal to 0 mol% and less than or equal to 0.5 mol%, greater than or equal to 0 mol% and less than or equal to 0.25 mol%, or 0.01 mol% or greater. mol% or more but 1 mol% or less, 0.01 mol% or more but 0.75 mol% or less, 0.01 mol% or more but 0.5 mol% or less, 0.01 mol% or more and 0.25 mol% or less, 0.05 mol% or more but 1 mol% or less, 0.05 mol% or more 0.75 mol % or less, from 0.05 mol% to 0.5 mol%, or even from 0.01 mol% to 0.25 mol%, or any and all sub-ranges formed from any of these terminal points. In embodiments, the glass composition and resulting colored glass article may or may not be substantially free of SnO ₂ .

In embodiments, the glass composition and resulting colored glass article may include alkaline earth oxides such as MgO, ZnO, CaO, SrO, and BaO.

In embodiments, the concentration of MgO in the glass composition and resulting colored glass article may be greater than 0 mol% or even greater than 0.5 mol%. In embodiments, the concentration of MgO in the glass composition and resulting colored glass article may be 2 mol% or less or even 1 mol% or less. In embodiments, the concentration of MgO in the glass composition and the resulting colored glass article is at least 0 mol% but not more than 2 mol%, at least 0 mol% at most 1 mol%, at least 0.5 mol% at most 2 mol%, or even It can be from 0.5 mol% to 1 mol%, or any and all sub-ranges formed from any of these terminal points. In embodiments, the glass composition and resulting colored glass article may or may be substantially free of MgO.

In embodiments, the concentration of ZnO in the glass composition and resulting colored glass article may be greater than 0 mol% or even greater than 0.5 mol%. In embodiments, the concentration of ZnO in the glass composition and resulting colored glass article may be 2 mol% or less or even 1 mol% or less. In embodiments, the concentration of ZnO in the glass composition and the resulting colored glass article is greater than or equal to 0 mol% and less than or equal to 2 mol%, greater than or equal to 0 mol% and less than or equal to 1 mol%, greater than or equal to 0.5 mol% and less than or equal to 2 mol%, or even It can be from 0.5 mol% to 1 mol%, or even from 0.5 mol% to 1 mol%, or any and all sub-ranges formed from any of these terminal points. In embodiments, the glass composition and resulting colored glass article may or may not be substantially free of ZnO.

In embodiments, the concentration of CaO in the glass composition and the resulting colored glass article may be greater than 0 mol% or even greater than 0.5 mol%. In embodiments, the concentration of CaO in the glass composition and the resulting colored glass article may be less than or equal to 2 mol% or even less than or equal to 1 mol%. In embodiments, the concentration of CaO in the glass composition and the resulting colored glass article is greater than or equal to 0 mol% and less than or equal to 2 mol%, greater than or equal to 0 mol% and less than or equal to 1 mol%, greater than or equal to 0.5 mol% and less than or equal to 2 mol%, or even It can be from 0.5 mol% to 1 mol%, or any and all sub-ranges formed from any of these terminal points. In embodiments, the glass composition and resulting colored glass article may or may be substantially free of CaO.

In embodiments, the concentration of SrO in the glass composition and the resulting colored glass article may be greater than 0 mol% or even greater than 0.5 mol%. In embodiments, the concentration of SrO in the glass composition and resulting colored glass article may be less than or equal to 2 mol% or even less than or equal to 1 mol%. In embodiments, the concentration of SrO in the glass composition and the resulting colored glass article is greater than or equal to 0 mol% and less than or equal to 2 mol%, greater than or equal to 0 mol% and less than or equal to 1 mol%, greater than or equal to 0.5 mol% and less than or equal to 2 mol%, or even It can be from 0.5 mol% to 1 mol%, or any and all sub-ranges formed from any of these terminal points. In embodiments, the glass composition and resulting colored glass article may or may be substantially free of SrO.

In embodiments, the concentration of BaO in the glass composition and the resulting colored glass article may be at least 0 mol% or even at least 0.5 mol%. In embodiments, the concentration of BaO in the glass composition and resulting colored glass article may be 2 mol% or less or even 1 mol% or less. In embodiments, the concentration of BaO in the glass composition and the resulting colored glass article is greater than or equal to 0 mol% and less than or equal to 2 mol%, greater than or equal to 0 mol% and less than or equal to 1 mol%, greater than or equal to 0.5 mol% and less than or equal to 2 mol%, or even It can be from 0.5 mol% to 1 mol%, or any and all sub-ranges formed from any of these terminal points. In embodiments, the glass composition and resulting colored glass article may or may be substantially free of BaO.

In embodiments, the glass composition and resulting colored glass article may include Cl, which may specifically enable the growth of Au particles. In embodiments, the concentration of Cl in the glass composition and the resulting colored glass article may be at least 0 mol% or even at least 0.1 mol%. In embodiments, the concentration of Cl in the glass composition and the resulting colored glass article may be less than or equal to 0.5 mol% or even less than or equal to 0.25 mol%. In embodiments, the concentration of Cl in the glass composition and the resulting colored glass article is greater than or equal to 0 mol% and less than or equal to 0.5 mol%, greater than or equal to 0 mol% and less than or equal to 0.25 mol%, greater than or equal to 0.1 mol% and less than or equal to 0.5 mol%, or even It can be from 0.1 mol% to 0.25 mol%, or any and all sub-ranges formed from any of these terminal points. In implementations, the glass composition and resulting colored glass article may or may not be substantially free of Cl.

In implementations, the glass composition and resulting colored glass article may or may be substantially free of MgO, CaO, ZnO, Cl, or combinations thereof.

The glass compositions described herein and the resulting colored glass articles further include Au as a colorant to achieve the desired color. In embodiments, the glass composition and resulting colored glass article may include at least 1 x 10 ^-6 mol% and up to 1 mol% Au. In embodiments, the glass composition and resulting colored glass article can include at least 0.0001 mol% and up to 0.1 mol% Au. In embodiments, the concentration of Au in the glass composition and the resulting colored glass article is at least 1 x 10 ^-6 mol%, at least 1 x 10 ^-5 mol%, at least 0.0001 mol%, at least 0.0005 mol%, or It can even be more than 0.001 mol%. In embodiments, the concentration of Au in the glass composition and the resulting colored glass article is 1 mol% or less, 0.75 mol% or less, 0.5 mol% or less, 0.25 mol% or less, 0.1 mol% or less, 0.05 mol% or less. , or even less than 0.01. In embodiments, the concentration of Au in the glass composition and the resulting colored glass article is from 1 x 10 ^-6 mol% to 0.75 mol%, from 1 x 10 ^-6 mol% to 0.5 mol%, and from 1 x 10 to 10 mol%. ^-6 mol% or more 0.25 mol% or less, 1 x 10 ^-6 mol% or more 0.1 mol% or less, 1 x ^{10 -6} mol% or more 0.05 mol% or less, 1 More than x 10 ^-5 mol% but less than 1 mol%, more than 1 x 10 ^-5 mol% but less than 0.75 mol%, more than 1 x 10 ^-5 mol% but less than ^0.5 mol%, more than 1 , ¹ x 10 ^-5 mol% or more and 0.1 mol% or less, 1 x 10 ^-5 mol% or more and 0.05 mol% or less, 1 mol% or more 0.75 mol% or less, 0.0001 mol% or more but 0.5 mol% or less, 0.0001 mol% or more but 0.25 mol% or less, 0.0001 mol% or more 0.1 mol% or more, 0.0001 mol% or more but 0.05 mol% or less, 0.0001 mol% or more 0.01 mol % or less, 0.0005 mol% or more but 1 mol% or less, 0.0005 mol% or more but 0.75 mol% or less, 0.0005 mol% or more but 0.5 mol% or less, 0.0005 mol% or more but 0.25 mol% or less, 0.0005 mol% or more but 0.1 mol% or less, 0.0005 mol % or more 0.05 mol% or less, 0.0005 mol% or more but 0.01 mol% or less, 0.001 mol% or more but 1 mol% or less, 0.001 mol% or more but 0.75 mol% or less, 0.001 mol% or more but 0.5 mol% or less, 0.001 mol% or more 0.25 mol% or less, from 0.001 mol% to 0.1 mol%, from 0.001 mol% to 0.05 mol%, or even from 0.001 mol% to 0.01 mol%, or any and all sub-ranges formed from any of these terminal points. there is.

In embodiments, the glass compositions described herein and the resulting colored glass articles contain sulfur-based compounds such as TiO ₂ , MnO, MoO ₃ , WO ₃ , Y ₂ O ₃ , CdO, As ₂ O ₃ , sulfates, etc. , halogen, or a combination thereof may be further included. In embodiments, the glass compositions and resulting colored glass articles include TiO ₂ , MnO, MoO ₃ , WO ₃ , Y ₂ O ₃ , CdO, As ₂ O ₃ , sulfur-based compounds such as sulfates, halogens, It may be substantially free of tramp material, or a combination thereof. In embodiments, antibacterial ingredients, chemical fining agents, or other additional ingredients may be included in the glass composition and the resulting colored glass article.

In embodiments, the viscosity of the glass composition can be adjusted to prevent devitrification of the glass composition and formation of Au particles during melting and forming. The formation of Au particles before melting can limit the color range that can be achieved by heat treatment. Accordingly, in embodiments, to achieve the desired viscosity and thereby prevent the formation of Au particles prior to melting, the glass compositions described herein and the resulting glass articles have a concentration of 5.72*Al ₂ O ₃ (mol%) - 21.4*ZnO (mol%) - 2.5*P ₂ O ₅ (mol%) - 35*Li ₂ O (mol%) - 16.6*B ₂ O ₃ (mol%) - 20.5*MgO (mol%) - 23.3* Na ₂ O (mol%) - 27.9*SrO (mol%) - 18.5*K ₂ O (mol%) - 26.3*CaO (mol%) can satisfy the relationship of exceeding -609 mol%. In embodiments, the glass compositions described herein and the resulting glass articles have 5.72*Al ₂ O ₃ (mol%) - 21.4*ZnO (mol%) - 2.5*P ₂ O ₅ (mol%) - 35* Li ₂ O (mol%) - 16.6*B ₂ O ₃ (mol%) - 20.5*MgO (mol%) - 23.3*Na ₂ O (mol%) - 27.9*SrO (mol%) - 18.5*K ₂ O (mol%) - 26.3*CaO (mol%) may satisfy the relation greater than -609 mol%, greater than -575 mol%, greater than -550 mol%, or even greater than -525 mol%. In embodiments, the glass compositions described herein and the resulting glass articles have 5.72*Al ₂ O ₃ (mol%) - 21.4*ZnO (mol%) - 2.5*P ₂ O ₅ (mol%) - 35* Li ₂ O (mol%) - 16.6*B ₂ O ₃ (mol%) - 20.5*MgO (mol%) - 23.3*Na ₂ O (mol%) - 27.9*SrO (mol%) - 18.5*K ₂ O (mol%) - 26.3*CaO (mol%) may satisfy the relation of -400 mol% or less, -425 mol% or less, or even -450 mol% or less. In embodiments, the glass compositions described herein and the resulting glass articles have 5.72*Al ₂ O ₃ (mol%) - 21.4*ZnO (mol%) - 2.5*P ₂ O ₅ (mol%) - 35* Li ₂ O (mol%) - 16.6*B ₂ O ₃ (mol%) - 20.5*MgO (mol%) - 23.3*Na ₂ O (mol%) - 27.9*SrO (mol%) - 18.5*K ₂ O (mol%) - 26.3*CaO (mol%) is greater than -609 mol% and less than or equal to -400 mol%, greater than -609 mol% and less than or equal to -425 mol%, greater than -609 mol% and less than or equal to -450 mol%, and -575 mol%. More than -400 mol% or less, -575 mol% or more or less -425 mol% or less, -575 mol% or more and -450 mol% or less, -550 mol% or more and -400 mol% or less, -550 mol% or more and -425 mol% or less , -550 mol% or more and -450 mol% or less, -525 mol% or more and -400 mol% or less, -525 mol% or more and -425 mol% or less, or even -525 mol% or more and -450 mol% or less, or these terminals. Any and all sub-ranges formed from any of the points may be satisfied.

In embodiments, the process of making a glass article includes heat treating the glass composition described herein at one or more preselected temperatures for one or more preselected times to induce glass homogenization. In embodiments, the heat treatment to make a glass article includes (i) heating the glass composition at a rate of 1-100° C./min to the glass homogenization temperature; (ii) maintaining the glass composition at the glass homogenization temperature for a period of at least 0.25 hours but not more than 4 hours to produce a glass article; and (iii) cooling the formed glass article to room temperature. In embodiments, the glass homogenization temperature may be greater than or equal to 300°C and less than or equal to 700°C.

The glass composition described herein includes Au, R ₂ O, and Al ₂ O ₃ . The concentrations of R ₂ O and Al ₂ O ₃ are such that the difference between R ₂ O - Al ₂ O ₃ can be combined with Au to produce a colored glass article having a desired color (e.g., pink, purple, red or orange). It can be adjusted to create In embodiments, the colored glass article has: an L* of greater than or equal to 50 and less than or equal to 100, as measured at a 1.33 mm article thickness under F2 illumination and a 10° standard observer angle; a* of -15 or more and 25 or less; and b* of -25 or more and 25 or less; may have a transmittance color coordinate in the CIELAB color space.

Relatively smaller concentrations of R ₂ O - Al ₂ O ₃ (eg, 1.5 mol% or less) can produce blue or purple glass articles. Relatively high concentrations of R ₂ O - Al ₂ O ₃ (eg, greater than 1.5 mol%) can produce orange or red glass articles.

For example, in embodiments, R ₂ O - Al ₂ O ₃ may be -5 mol% or more and 1.5 mol% or less, and b* may be -25 or more and 10 or less. In embodiments, R ₂ O - Al ₂ O ₃ may be -3 mol% or more and 1.5 mol% or less, and b* may be -15 or more and 7 or less. In embodiments, R ₂ O - Al ₂ O ₃ is greater than -5 mol% and less than or equal to 1.5 mol%, greater than -3 mol% and less than or equal to 1.5 mol%, greater than -1 mol% and less than or equal to 1.5 mol%, or even greater than 0 mol%. may be up to 1.5 mol%, or any and all sub-ranges formed from any of these terminal points; and b* is -25 and 10 or less, -25 and 7 or less, -25 and 5 or less, -15 and 10 or less, -15 and 7 or less, -15 and 5 or less, -10 and 10 or less, -10 and 7 , or even from -10 to 5, or any and all sub-ranges formed from any of these end points.

In embodiments, R ₂ O - Al ₂ O ₃ may be greater than 1.5 mole % but not greater than 7 mole %, and b* may be greater than or equal to 0 and less than or equal to 25 mole %. In embodiments, R ₂ O - Al ₂ O ₃ may be greater than 1.5 mole % and less than or equal to 5 mole %, and b* may be greater than or equal to 0 and less than or equal to 15 mole %. In embodiments, R ₂ O - Al ₂ O ₃ is greater than or equal to 1.5 mol% and less than or equal to 7 mol%, greater than or equal to 1.5 mol% and less than or equal to 5 mol%, or even greater than or equal to 1.5 mol% and less than or equal to 3 mol%, or any of these terminal points. Can be any and all sub-ranges formed from; and b* is 0 to 25, 0 to 15, 0 to 10, 2.5 to 25, 2.5 to 15, 2.5 to 10, 5 to 25, 5 to 15, or even 5 to 10. , or any and all sub-ranges formed from any of these terminal points.

In embodiments, the glass composition and resulting colored glass article contain at least 60 mol% and up to 70 mol% SiO ₂ ; 11 mol% or more and 17 mol% or less of Al ₂ O ₃ ; 2 mol% or more and 8 mol% or less of B ₂ O ₃ ; Li ₂ O of 9 mol% or more and 14 mol% or less; 2 mol% or more and 6 mol% or less of Na ₂ O; 0.1 mol% or more and 0.5 mol% or less of K ₂ O; And it may include 1 x 10 ^-6 mol% or more and 0.05 mol% or less of Au. In embodiments, R ₂ O -Al ₂ O ₃ may be greater than 0 mol% and less than or equal to 3 mol%, and R ₂ O may be the sum of Li ₂ O, Na ₂ O, and K ₂ O.

Different color coordinates within the color gamut can be achieved by varying the heat treatment cycle used to produce the resulting colored glass article. The heat treatment cycle is characterized by the temperature of the environment (i.e., oven) and the duration of the cycle (i.e., the time the glass article is exposed to the heated environment). As used herein, the phrase “temperature of the heat treatment cycle” refers to the temperature of the environment (i.e., oven). In embodiments, glass articles formed from the glass compositions described herein are heat treated in an isothermal oven to produce the resulting colored glass article.

In embodiments, the temperature of the heat treatment cycle is at least 500°C, at least 550°C, at least 575°C, at least 600°C, at least 625°C, or even at least 650°C. In embodiments, the temperature of the heat treatment cycle is below 800°C, below 775°C, below 750°C, below 725°C, or even below 700°C. In embodiments, the temperature of the heat treatment cycle is 500°C to 800°C, 500°C to 775°C, 500°C to 750°C, 500°C to 725°C, 550°C to 700°C, 550°C to 800°C. ℃ or lower, 550℃ or higher 775℃ or lower, 550℃ or higher 750℃ or lower, 550℃ or higher or 725℃ or lower, 550℃ or higher 700℃ or lower, 575℃ or higher but 800℃ or lower, 575℃ or higher or higher 775℃ or lower, 575℃ or higher or 750℃ or less, 575℃ or more and 725℃ or less, 575℃ or more and 700℃ or less, 600℃ or more and 800℃ or less, 600℃ or more and 775℃ or less, 600℃ or more and 750℃ or less, 600℃ or more and 725℃ or less, 600℃ or more and 700℃ or less , 625℃ or higher and 800℃ or lower, 625℃ or higher and 775℃ or lower, 625℃ or higher and 750℃ or lower, 625℃ or higher and 725℃ or lower, 625℃ or higher and 700℃ or lower, 650℃ or higher and 800℃ or lower, 650℃ or higher and 775℃ or lower, from 650°C to 750°C, from 650°C to 725°C, or even from 650°C to 700°C, or any and all sub-ranges formed from any of these end points.

In embodiments, the duration of the heat treatment cycle is at least 0.25 hours, at least 0.5 hours, at least 1 hour, or even at least 2 hours. In embodiments, the duration of the heat treatment cycle is no more than 24 hours, no more than 16 hours, no more than 8 hours, or even no more than 4 hours. In embodiments, the duration of the heat treatment cycle is at least 0.25 hours but up to 24 hours, at least 0.25 hours at most 16 hours, at least 0.25 hours at most 8 hours, at least 0.25 hours at most 4 hours, at least 0.5 hours at most 24 hours, at least 0.5 hours. 16 hours or less, 0.5 hours or more but 8 hours or less, 0.5 hours or more but 4 hours or less, 1 hour or more but 24 hours or less, 1 hour or more but 16 hours or less, 1 hour but not more than 8 hours, 1 hour but more than 4 hours, 2 hours or more 24 hours or less, from 2 hours to 16 hours, from 2 hours to 8 hours, or even from 2 hours to 4 hours, or any and all sub-ranges formed from any of these end points.

Colored glass articles formed from the glass compositions described herein may be of any suitable thickness, which may vary depending on the particular application of the colored glass article. In embodiments, the colored glass article is at least 250 μm and up to 6 mm, at least 250 μm and up to 4 mm, at least 250 μm and up to 2 mm, at least 250 μm and up to 1 mm, at least 250 μm and up to 750 μm, at least 250 μm and up to 500 μm. 500 μm to 6 mm, 500 μm to 4 mm, 500 μm to 2 mm, 500 μm to 1 mm, 500 μm to 750 μm, 750 μm to 6 mm, 750 μm to 4 mm , 750 μm to 2 mm, 750 μm to 1 mm, 1 mm to 6 mm, 1 mm to 4 mm, 1 mm to 2 mm, 2 mm to 6 mm, 2 mm to 4 mm, or even from 4 mm to 6 mm, or any and all sub-ranges of thickness formed from any of these end points.

As discussed above, colored glass articles formed from the glass compositions described herein can have increased fracture toughness, such that the colored glass articles are more resistant to damage. In embodiments, the colored glass article can have a K _Ic fracture toughness, as measured by the CNSB method, prior to ion exchange, of at least 0.7 MPa·m ^1/2 . In embodiments, the colored glass article has, prior to ion exchange, at least 0.7 MPa·m ^1/2 , at least 0.8 MPa·m ^1/2 , at least 0.9 MPa·m ^1/2 , or It can even have a K _Ic fracture toughness of more than 1.0 MPa·m ^1/2 .

In embodiments, the glass compositions described herein are ion-exchangeable to facilitate strengthening colored glass articles made from the glass compositions. In a typical ion-exchange process, smaller metal ions in the glass composition are replaced or “exchanged” with larger metal ions of the same valence within a layer proximate the outer surface of a colored glass article made from the glass composition. Replacing smaller ions with larger ions creates compressive stresses within the layers of colored glass articles made from the glass composition. In embodiments, the metal ion is a monovalent metal ion (e.g., Li ⁺ , Na ⁺ , K ⁺ , etc.), and ion-exchange is used to transform a glass article made from the glass composition into a smaller metal within the colored glass article. This is achieved by immersing the ions in a bath containing at least one molten salt of a larger metal ion, which replaces the ions. Alternatively, other monovalent ions such as Ag ⁺ , Tl ⁺ , Cu ⁺ , etc. can be exchanged for the monovalent ion. The ion-exchange process or processes used to strengthen colored glass articles made from glass compositions may include contacting the colored glass article with an ion-exchange medium. In embodiments, the ion-exchange medium can be a molten salt bath. For example, but not limited to, the ion-exchange process may include immersion in a single bath or multiple baths of the same or different composition with optional washing and/or annealing steps between immersion steps.

When exposed to a colored glass article, the ion exchange solution (e.g., KNO ₃ and/or NaNO ₃ molten salt bath) has a temperature of at least 350° C. but not more than 500° C., at least 360° C. but not greater than 450° C., and at least 370° C., depending on embodiments. 440℃ and below, 360℃ and below 420℃, 370℃ and above 400℃, 375℃ and below 475℃, 400℃ and below 500℃, 410℃ and above 490℃, 420℃ and above 480℃, 430℃ and below 470 Celsius degrees Celsius or lower, or even between 440°C and 460°C, or any and all sub-ranges formed from any of these end points. In embodiments, the colored glass article has a temperature range of at least 2 hours and up to 24 hours, between 2 hours and up to 12 hours, between 2 hours and up to 6 hours, between 8 hours and up to 24 hours, between 6 hours and up to 24 hours, between 6 hours and up to 12 hours. The exposure to the ion exchange solution may be from 8 hours to 24 hours, or even from 8 hours to 12 hours, or for any and all sub-ranges of duration formed from any of these end points.

In embodiments, the colored glass article made from the glass composition is ion-exchanged to a size greater than 10 μm, at least 20 μm, at least 30 μm, at least 40 μm, at least 50 μm, at least 60 μm, at least 70 μm, at least 80 μm, A depth of compression of more than 90 μm, or more than 100 μm can be achieved. In embodiments, colored glass articles made from the glass composition can have a thickness “t” and can be ion exchanged to achieve a depth of compression of at least 0.15 t, at least 0.17 t, or even at least 0.2 t. In embodiments, colored glass articles made from the glass composition can have a thickness “t” and can be ion-exchanged to achieve a depth of compression of 0.3t or less, 0.27t or less, or even 0.25t or less. . In embodiments, colored glass articles made from the glass compositions described herein may have a thickness “t” and be ion-exchanged to form a thickness of 0.15 t or greater but 0.3 t or less, 0.15 t or greater but 0.27 t or less, 0.15 t or greater but 0.25 t or less, 0.17 t. t but not less than 0.3t, not less than 0.17t but not more than 0.27t, not less than 0.17t but not more than 0.25t, not less than 0.2t but not more than 0.3t, not less than 0.2t but not more than 0.27t, or even not less than 0.2t but not more than 0.25t, or any of these end points. Any and all sub-ranges of depth of compression formed from can be achieved.

The development of this surface compression layer is advantageous for achieving better crack resistance and higher bending strengths compared to non-ion-exchanged materials. The surface compression layer has a higher concentration of ions exchanged into the colored glass article compared to the concentration of ions exchanged into the colored glass article for the body of the colored glass article (i.e., the region not comprising surface compression). . In embodiments, colored glass articles made from the glass composition may have a surface compressive stress after ion-exchange strengthening of at least 300 MPa, at least 400 MPa, at least 500 MPa, or even at least 600 MPa. In embodiments, colored glass articles made from the glass composition may have a surface compressive stress of less than or equal to 1 GPa, less than or equal to 900 MPa, or even less than or equal to 800 MPa, after ion exchange strengthening. In embodiments, the colored glass article made from the glass composition has, after ion exchange strengthening, at least 300 MPa and up to 1 GPa, at least 300 MPa and up to 900 MPa, at least 300 MPa and up to 800 MPa, at least 400 MPa and up to 1 GPa, and at least 400 MPa. 900 MPa or less, 400 MPa or more 800 MPa or less, 500 MPa or more 1 GPa or less, 500 MPa or more 900 MPa or less, 500 MPa or more 800 MPa or less, 600 MPa or more 1 GPa or less, 600 MPa or more 900 MPa or less, 600 MPa or more 800 It may have a surface compressive stress of MPa or less.

In embodiments, colored glass articles made from the glass composition may have a maximum central tension after ion-exchange strengthening of at least 40 MPa, at least 60 MPa, at least 80 MPa, or even at least 100 MPa. In implementations, colored glass articles made from the glass composition can have a maximum central tension after ion-exchange strengthening of less than or equal to 250 MPa, less than or equal to 200 MPa, or even less than or equal to 150 MPa. In embodiments, the colored glass article made from the glass composition is, after ion-exchange strengthening, at least 40 MPa but not more than 250 MPa, at least 40 MPa but not more than 200 MPa, at least 40 MPa but not more than 150 MPa, at least 60 MPa but not more than 250 MPa, at least 60 MPa. 200 MPa or less, 60 MPa or more but less than 150 MPa, 80 MPa or more but less than 250 MPa, 80 MPa or more but less than 200 MPa, 80 MPa or more but less than 150 MPa, 100 MPa or more but less than 250 MPa, 100 MPa or more but less than 200 MPa, or even 100 MPa It may have a maximum central tension of no less than 150 MPa, or any and all sub-ranges formed from any of these end points. As used herein, central tension refers to the maximum central tension value unless otherwise specified.

The colored glass articles described herein can be used in a variety of applications, including, for example, back cover applications for consumer or commercial electronic devices such as smartphones, tablet computers, personal computers, ultrabooks, televisions, and cameras. Representative articles comprising any of the colored glass articles disclosed herein are shown in Figures 1 and 2. Specifically, Figures 1 and 2 show a housing 102 having a front 104, a back 106, and a side 108; electrical components (not shown) at least partially within the housing or entirely within the housing and including at least a controller, memory and display 110 on or adjacent to the front of the housing; A consumer electronic device 100 is shown including a cover substrate 112 at or above the front of the housing so as to overlie the display. In implementations, at least a portion of housing 102, such as back side 106, may include any of the colored glass articles disclosed herein.

Example

To make the various embodiments easier to understand, reference is made to the following examples that illustrate various embodiments of the colored glass articles described herein.

Table 1 shows exemplary compositions C1-C26 along with the analyzed concentrations (in terms of mol%) of the resulting colored glass articles.

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Referring now to Table 2, exemplary glass articles A1-A52 formed from exemplary compositions C2-C9 and C15-C23 shown in Table 1 were heat treated at the temperatures and for the periods shown in Table 2. The transmittance color coordinates in CIELAB color space measured at an article thickness of 1.33 mm under F2 illumination and a 10° standard viewing angle, and the observable colors of the resulting colored glass articles are shown in Table 2.

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Referring now to Table 3, exemplary glass articles A53-A114 were formed from the exemplary compositions C1-C14 and C24-C26 shown in Table 1 and heat treated for the temperatures and periods shown in Table 3. The observable colors of the resulting colored glass articles are shown in Table 3.

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Referring now to Figures 3 and 4, the plots show the relationships of R ₂ O-Al ₂ O ₃ and a* and b*, respectively, for exemplary glass articles A29-A44. As shown in FIG. 3, a* is a positive number regardless of the value of R ₂ O-Al ₂ O ₃ , which results in an observable color toward the red side in the CIELAB color space. As shown in Figure 4, as R ₂ O-Al ₂ O ₃ increased, b* increased, thereby shifting the observable color from blue to yellow. For example, exemplary glass articles A35 and A36 formed from exemplary compositions C8 and C9 with assayed R ₂ O - Al ₂ O ₃ of 0.07 mol% and 0.04 mol%, respectively, have b* of -9.39 and -8.92, respectively. , resulting in an observable purple glass article. Exemplary glass articles A29 and A30 formed from exemplary glass compositions C2 and C3 with assayed R ₂ O - Al ₂ O ₃ of 2.98 mol % and 2.02 mol %, respectively, have b* of 9.97 and 10.51, respectively, resulting in an observable This resulted in an orange glass article and an observable red glass article.

Moreover, exemplary glass articles A33 and A34 formed from exemplary glass compositions C6 and C7 comprising Fe ₂ O ₃ and ZrO ₂ , respectively, had an observable red color.

As shown by Tables 2 and 3 and Figures 3 and 4, the R ₂ O - Al ₂ O ₃ analyzed can be adjusted, additional components can be added to the glass composition, and the glass article can be the desired colored glass. The article may undergo certain heat treatments to provide it.

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

Claims (66)

As a colored glass article:
SiO ₂ of 50 mol% or more and 80 mol% or less;
7 mol% or more and 25 mol% or less of Al ₂ O ₃ ;
1 mol% or more and 15 mol% or less of B ₂ O ₃ ;
Li ₂ O of 7 mol% or more and 20 mol% or less;
0.5 mol% or more and 12 mol% or less of Na ₂ O;
K ₂ O greater than 0 mol% and less than or equal to 1 mol%; and
Containing at least 1 x 10 ^-6 mol% and not more than 1 mol% Au, where:
R ₂ O - Al ₂ O ₃ is not less than -5 mol% and not more than 5 mol%, and R ₂ O is the sum of Li ₂ O, Na ₂ O, and K ₂ O. In claim 1,
The colored glass article was measured at an article thickness of 1.33 mm under F2 illumination and a 10° standard observer angle:
L* of 50 or more and 100 or less;
a* of -15 or more and 25 or less; and
-25 or more and 25 or less b*; of
A colored glass article having transmittance color coordinates in the CIELAB color space. In claim 2,
R ₂ O - Al ₂ O ₃ is -5 mol% or more and 1.5 mol% or less; b* is -25 or more and 10 or less. In claim 3,
R ₂ O - Al ₂ O ₃ is -3 mol% or more and 1.5 mol% or less; b* is -15 or more and 7 or less. In claim 2,
R ₂ O - Al ₂ O ₃ is more than 1.5 mol% and not more than 5 mol%; b* is 0 or more and 25 or less. In claim 5,
R ₂ O - Al ₂ O ₃ is more than 1.5 mol% and not more than 5 mol%; b* is 0 or more and 15 or less. The method of any one of claims 1 to 6,
R ₂ O - Al ₂ O ₃ is -3 mol% or more and 5 mol% or less. In claim 7,
R ₂ O - Al ₂ O ₃ is -1 mol% or more and 3 mol% or less. The method of any one of claims 1 to 8,
The colored glass article comprises at least 0.0001 mol% and not more than 0.1 mol% Au. The method of any one of claims 1 to 9,
R ₂ O is 6 mol% or more and 25 mol% or less. In claim 10,
R ₂ O is at least 8 mol% and at most 23 mol%. The method of any one of claims 1 to 11,
The colored glass article comprises at least 0.01 mol% and not more than 2 mol% ZrO ₂ . In claim 12,
The colored glass article comprises at least 0.1 mol% and not more than 1.5 mol% ZrO ₂ . The method of any one of claims 1 to 13,
The colored glass article comprises at least 0.01 mol% and not more than 1 mol% Fe ₂ O ₃ . In claim 14,
The colored glass article comprises at least 0.05 mol% and not more than 0.5 mol% Fe ₂ O ₃ . The method of any one of claims 1 to 15,
5.72*Al ₂ O ₃ (mol%) - 21.4*ZnO (mol%) - 2.5*P ₂ O ₅ (mol%) - 35*Li ₂ O (mol%) - 16.6*B ₂ O ₃ (mol%) - 20.5*MgO (mol%) - 23.3*Na ₂ O (mol%) - 27.9*SrO (mol%) - 18.5*K ₂ O (mol%) - 26.3*CaO (mol%) exceeds -609 mol% Phosphorus, colored glass articles. The method of any one of claims 1 to 16,
The colored glass article comprises SnO ₂ of 0.01 mol% or more and 1 mol% or less. In claim 17,
The colored glass article comprises at least 0.05 mol% and not more than 0.75 mol% SnO ₂ . The method of any one of claims 1 to 18,
The colored glass article is substantially free of MgO, CaO, ZnO, Cl, or combinations thereof. The method of any one of claims 1 to 19,
The colored glass article comprises at least 7 mol% and not more than 18 mol% Li ₂ O. In claim 20,
The colored glass article comprises at least 9 mol% and not more than 16 mol% Li ₂ O. The method of any one of claims 1 to 21,
The colored glass article comprises at least 1 mol% and not more than 12 mol% Na ₂ O. In claim 22,
The colored glass article comprises at least 2 mol% and not more than 10 mol% Na ₂ O. The method of any one of claims 1 to 23,
The colored glass article comprises at least 0.1 mol% and up to 0.5 mol% K ₂ O. The method of any one of claims 1 to 24,
The colored glass article comprises not less than 9 mol% but not more than 23 mol% Al ₂ O ₃ . In claim 25,
The colored glass article comprises not less than 11 mol% but not more than 20 mol% Al ₂ O ₃ . The method of any one of claims 1 to 26,
The colored glass article comprises at least 2 mol% and not more than 12 mol% B ₂ O ₃ . In claim 27,
The colored glass article comprises at least 3 mol% and not more than 10 mol% B ₂ O ₃ . The method of any one of claims 1 to 28,
The colored glass article comprises at least 52 mol% and not more than 75 mol% SiO ₂ . The method of any one of claims 1 to 29,
The colored glass article has a thickness of 250 μm or more and 6 mm or less. The method of any one of claims 1 to 30,
The colored glass article is an ion-exchanged colored glass article. In claim 31,
The ion-exchanged colored glass article has a depth of compression of at least 10 μm. The method of claim 31 or 32,
wherein the ion-exchanged colored glass article has a thickness “t” and a depth of compression of at least 0.15 t. The method of any one of claims 30 to 32,
wherein the ion-exchanged colored glass article has a surface compressive stress of at least 300 MPa. The method of any one of claims 30 to 33,
wherein the ion-exchanged colored glass article has a maximum central tension of at least 40 MPa. As a consumer electronic device:
a housing having a front, back, and sides; and
comprising an electrical component provided at least partially within the housing, the electrical component including at least a controller, a memory and a display, the display provided at or adjacent to the front of the housing;
A consumer electronic device, wherein the housing comprises the colored glass article of any one of claims 1-35. As a glass composition:
SiO ₂ of 50 mol% or more and 80 mol% or less;
7 mol% or more and 25 mol% or less of Al ₂ O ₃ ;
1 mol% or more and 15 mol% or less of B ₂ O ₃ ;
Li ₂ O of 7 mol% or more and 20 mol% or less;
0.5 mol% or more and 12 mol% or less of Na ₂ O;
K ₂ O greater than 0 mol% and less than or equal to 1 mol%; and
Containing at least 1 x 10 ^-6 mol% and not more than 1 mol% Au, where:
R ₂ O - Al ₂ O ₃ is -5 mol% or more and 5 mol% or less, and R ₂ O is the sum of Li ₂ O, Na ₂ O, and K ₂ O. A glass composition. In claim 37,
A glass composition in which R ₂ O - Al ₂ O ₃ is -3 mol% or more and 5 mol% or less. In claim 38,
A glass composition in which R ₂ O - Al ₂ O ₃ is -1 mol% or more and 3 mol% or less. The method of any one of claims 37 to 39,
The glass composition includes 0.0001 mol% or more and 0.1 mol% or less of Au. The method of any one of claims 37 to 40,
R ₂ O is 6 mol% or more and 25 mol% or less. In claim 41,
R ₂ O is 8 mol% or more and 23 mol% or less. The method of any one of claims 37 to 42,
The glass composition includes 0.01 mol% or more and 2 mol% or less of ZrO ₂ . In claim 43,
The glass composition includes 0.1 mol% or more and 1.5 mol% or less of ZrO ₂ . The method of any one of claims 37 to 44,
The glass composition includes 0.01 mol% or more and 1 mol% or less of Fe ₂ O ₃ . In claim 45,
The glass composition includes 0.05 mol% or more and 0.5 mol% or less of Fe ₂ O ₃ . The method of any one of claims 37 to 46,
5.72*Al ₂ O ₃ (mol%) - 21.4*ZnO (mol%) - 2.5*P ₂ O ₅ (mol%) - 35*Li ₂ O (mol%) - 16.6*B ₂ O ₃ (mol%) - 20.5*MgO (mol%) - 23.3*Na ₂ O (mol%) - 27.9*SrO (mol%) - 18.5*K ₂ O (mol%) - 26.3*CaO (mol%) exceeds -609 mol% Phosphorus, glass composition. The method of any one of claims 37 to 47,
The glass composition includes 0.01 mol% or more and 1 mol% or less of SnO ₂ . In claim 48,
The glass composition includes SnO ₂ of 0.05 mol% or more and 0.75 mol% or less. The method of any one of claims 37 to 49,
The glass composition is substantially free of MgO, CaO, ZnO, Cl, or combinations thereof. The method of any one of claims 37 to 50,
The glass composition includes 7 mol% or more and 18 mol% or less of Li ₂ O. In claim 51,
The glass composition includes 9 mol% or more and 16 mol% or less of Li ₂ O. The method of any one of claims 37 to 52,
The glass composition includes 1 mol% or more and 12 mol% or less of Na ₂ O. In claim 53,
The glass composition includes 2 mol% or more and 10 mol% or less of Na ₂ O. The method of any one of claims 37 to 54,
The glass composition includes 0.1 mol% or more and 0.5 mol% or less of K ₂ O. The method of any one of claims 37 to 55,
The glass composition includes 9 mol% or more and 23 mol% or less of Al ₂ O ₃ . In claim 56,
The glass composition includes 11 mol% or more and 20 mol% or less of Al ₂ O ₃ . The method of any one of claims 37 to 57,
The glass composition includes 2 mol% or more and 12 mol% or less of B ₂ O ₃ . In claim 58,
The glass composition includes 3 mol% or more and 10 mol% or less of B ₂ O ₃ . The method of any one of claims 37 to 59,
The glass composition includes 52 mol% or more and 75 mol% or less of SiO ₂ . A method of forming a colored glass article comprising:
heat treating a glass composition to form a glass article, the glass composition comprising:
SiO ₂ of 50 mol% or more and 80 mol% or less;
7 mol% or more and 25 mol% or less of Al ₂ O ₃ ;
1 mol% or more and 15 mol% or less of B ₂ O ₃ ;
Li ₂ O of 7 mol% or more and 20 mol% or less;
0.5 mol% or more and 12 mol% or less of Na ₂ O;
K ₂ O greater than 0 mol% and less than or equal to 1 mol%; and
Containing at least 1 x 10 ^-6 mol% and not more than 1 mol% Au, where:
R ₂ O - Al ₂ O ₃ is -5 mol% or more and 5 mol% or less, R ₂ O is the sum of Li ₂ O, Na ₂ O, and K ₂ O; and
A method of forming a colored glass article comprising subjecting the glass article to a heat treatment cycle at a temperature of 500°C or higher and 800°C or lower and a period of time of 0.25 hours or longer and 24 hours or longer to produce the colored glass article. In claim 61,
A method of forming a colored glass article, wherein the temperature of the heat treatment cycle is greater than or equal to 550°C and less than or equal to 775°C. The method of claim 61 or 62,
A method of forming a colored glass article, wherein the duration of the heat treatment cycle is not less than 0.5 hours and not more than 16 hours. The method of any one of claims 61 to 63,
The method further comprises strengthening the colored glass article in an ion exchange bath at a temperature of 350° C. to 500° C. for a period of at least 2 hours and not more than 12 hours to form an ion-exchanged glass-ceramic article. Method for forming glass articles. In claim 64,
A method of forming a colored glass article, wherein the ion exchange bath comprises KNO ₃ . In claim 65,
The method of claim 1 , wherein the ion exchange bath comprises NaNO ₃ .