阅读说明：本技术 具有用于热回火的优先破碎行为和高的热膨胀系数的未离子交换玻璃 (Non-ion exchanged glass with preferential fragmentation behavior and high coefficient of thermal expansion for thermal tempering ) 是由 T·M·格罗斯 P·J·莱齐 于 2018-11-30 设计创作，主要内容包括：本公开内容涉及玻璃组合物,其具有设计用于热回火的高的热膨胀系数和低的破碎韧度。理想地,当经受热回火时,这些玻璃适合产生“划割”式样,即使是薄的时候(<3mm)时也是如此。本文所揭示的玻璃在低温和高温下具有高的热膨胀,从而一旦淬冷产生增加的回火应力,结合低的破碎韧度,这促进了裂纹分叉和增强的脆性。还提供了此类玻璃的制造方法。(The present disclosure relates to glass compositions having a high coefficient of thermal expansion and low fracture toughness designed for thermal tempering. Ideally, these glasses are suitable for producing a "score" pattern when subjected to thermal tempering, even when thin (<3 mm). The glasses disclosed herein have high thermal expansion at low and high temperatures, thereby producing increased tempering stress upon quenching, combined with low fracture toughness, which promotes crack branching and enhanced brittleness. Methods of making such glasses are also provided.)

1. A glass composition comprising:

greater than 70 mol% SiO₂，

Greater than 0 to 20 mol% Al₂O₃，

More than 0 to 20 mole% of at least one alkaline earth oxide selected from the group consisting of: MgO, CaO, BaO or SrO,

3-16 mol% K₂O, and

>0-10 mol% B₂O₃。

2. The glass composition of claim 1, comprising 72-90 mol% SiO₂。

3. The glass composition of claim 1 or 2, further comprising:

0-16 mol% Na₂O, and

3-22 mol% Na₂O+K₂O。

4. The glass composition of any of claims 1-3, wherein the low temperature coefficient of thermal expansion is greater than 75x10 at 25-300 ℃^-7ppm/℃。

5. The glass composition of any of claims 1-4, wherein the high temperature coefficient of thermal expansion is greater than 250x10^{- 7}ppm/℃。

6. The glass composition of any of claims 1-5, wherein the fracture toughness K_ICLess than 0.65MPa-m^1/2。

7. The glass composition of any of claims 1-6, wherein the glass has a viscosity of 200kP at a temperature of 1000 ℃ and 1200 ℃.

8. The glass composition of any of claims 1-7, wherein the glass has a viscosity of 35kP at a temperature of 1100 ℃ and 1300 ℃.

9. The glass composition of any of claims 1-8, comprising 75-90 mol% SiO₂And 0.5 to 8 mol% or 1 to 5 mol% B₂O₃。

10. The glass composition of any one of claims 1-9, comprising>0-10 mol% or 3 to 10 mol% Al₂O₃。

11. The glass composition of any of claims 1-10, comprising 2 to 20 mol.% or 2 to 15 mol.% MO.

12. The glass composition of any of claims 1-11, comprising 8-16 mol% Na₂O+K₂O。

13. The glass composition of any of claims 1-12, comprising 5-15 mol% K₂O。

14. The glass composition of any one of claims 1-13, wherein the glass is thermally tempered and has a depth of compression of at least about 10 microns.

15. The glass composition of any of claims 1-14, wherein the glass is thermally tempered and has a surface compressive stress of at least 250 MPa.

16. The glass composition of any of claims 1-15, wherein the glass meets scribing standard astm c 1048.

17. A method of making the glass composition of any of claims 1-16, comprising treating SiO₂，Al₂O₃At least one alkaline earth oxide selected from the group consisting of: MgO, CaO, BaO or SrO, K₂O, and B₂O₃Mixing is carried out so as to produce a homogeneous melt.

18. The method of claim 17, wherein the melt is formed into a glass sheet and the glass sheet is subsequently thermally tempered.

19. The method of claim 17 or 18, wherein the glass composition meets the scribing standard ASTM C1048.

20. The method of any one of claims 17-19, wherein the glass is melted and maintained at a temperature in the range of 1100-1650 ℃ for a time in the range of about 6-16 hours, and annealed at about 500-650 ℃, wherein the glass is maintained at the temperature for about 1 hour and subsequently cooled for at least 6 hours.

Technical Field

This application claims priority from U.S. application serial No. 62/592,683 filed on 2017, 11, 30, 35 us.c. § 120, which is hereby incorporated by reference herein in its entirety.

The present disclosure relates to melt-formable glass having a high coefficient of thermal expansion and low fracture toughness designed for thermal tempering. Ideally, these glasses are suitable for producing a "scribing" pattern when subjected to thermal tempering, even at very thin thicknesses. They have high thermal expansion at low and high temperatures, producing increased tempering stress upon quenching, combined with low fracture toughness, which promotes crack branching and enhanced brittleness.

Background

Thermally tempered glass (sometimes referred to as safety glass) is often used in settings where safe breaking action is required to prevent injury in the event of a failure. For example, safety glass is used to reinforce side and rear windows of vehicles and objects such as rain doors. The property that makes tempered glass so desirable for safety applications is that when it breaks, it shatters into rock salt-like pieces that do not have sharp edges or needle-like points. This desirable breaking behavior is referred to as "scoring" and occurs when the glass achieves full tempering.

In addition to the safety aspects of thermally tempered glass, tempering the glass results in greater damage resistance and durability. Due to the increased durability, tempered glass can be used in applications where normal glass would rapidly break, such as vehicle windows where the glass may be impacted by stones or other hard materials. Due to the increase in glass for architectural, vehicle, and electronic device applications, there is a continuing need for thin, thermally strengthened glass that is durable but that breaks when broken in a 'safe' or scribe-break pattern. However, as glass becomes thinner, it becomes more difficult to create any thermal tempering stress at all, and the central tension required to safely "score" the break pattern increases, creating a complex challenge. The present disclosure addresses this unmet need by the disclosed glass, which produces increased temper stress, while achieving lower stress levels for scribing to occur.

Disclosure of Invention

In aspect (1), the present disclosure provides a glass composition comprising: greater than 70 mol% SiO₂Greater than 0 to 20 mol% Al₂O₃More than 0 to 20 mol% of at least one alkaline earth oxide selected from the group consisting of: MgO, CaO, BaO or SrO, 3-16 mol% K₂O，>0-10 mol% B₂O₃. In aspect (2), the present disclosure provides the glass composition of aspect (1), comprising 72 to 90 mol% SiO₂. In aspect (3), the present disclosure provides the glass composition of aspect (1) or (2), further comprising 0 to 16 mol% Na₂O and 3-22 mol% Na₂O+K₂And O. In aspect (4), the present disclosure provides the glass composition of any one of aspects (1) to (3), wherein the low temperature coefficient of thermal expansion from 25 to 300 ℃ is greater than 75x10^-7ppm/DEG C. In aspect (5), the present disclosure provides the glass composition of any one of aspects (1) to (4), wherein the high temperature coefficient of thermal expansion is greater than 250x10^-7ppm/DEG C. In aspect (6), the present disclosure provides the glass composition of any one of aspects (1) - (5), wherein the fracture toughness, KIC, is less than 0.65MPa-m^1/2. In aspect (7), the present disclosure provides the glass composition of any one of aspects (1) to (6), wherein the viscosity of the glass at a temperature of 1000-. In aspect (8), the present disclosure provides the glass composition of any one of aspects (1) to (7), wherein the viscosity of the glass at the temperature of 1100 ℃ and 1300 ℃ is 35 kP. In aspect (9), the present disclosure provides the glass composition of any one of aspects (1) to (8), comprising 0.5 to 8 mol% or 1 to 5 mol% B₂O₃. In aspect (10), the present disclosure provides the glass composition of any one of aspects (1) to (9), comprising>0-10 mol% or 3 to 10 mol% Al₂O₃. In aspect (11), the present disclosure provides the glass composition of any one of aspects (1) to (10), whichComprises 2-20 mol% or 2 to 15 mol% MO. In aspect (12), the present disclosure provides the glass composition of any one of aspects (1) to (11), comprising 8 to 16 mol% Na₂O+K₂And O. In aspect (13), the present disclosure provides the glass composition of any one of aspects (1) to (12), comprising 5 to 15 mol% K₂And O. In aspect (14), the present disclosure provides the glass composition of any one of aspects (1) - (13), wherein the glass is thermally tempered and has a depth of compression of at least about 10 microns. In aspect (15), the present disclosure provides the glass composition of any one of aspects (1) to (14), wherein the glass is thermally tempered and has a surface compressive stress of at least 250 MPa. In aspect (16), the present disclosure provides the glass composition of any one of aspects (1) - (15), wherein the glass meets the scribing standard ASTM C1048.

In aspect (17), the present disclosure provides a method of producing the glass composition of any one of aspects (1) to (16), the method comprising treating SiO₂，Al₂O₃At least one alkaline earth oxide selected from the group consisting of: MgO, CaO, BaO or SrO, K₂O, and B₂O₃Mixing is carried out so as to produce a homogeneous melt. In aspect (18), the present disclosure provides the method of aspect (17), wherein the melt is formed into a glass sheet and the glass sheet is subsequently thermally tempered. In aspect (19), the present disclosure provides the method of aspect (17) or aspect (18), wherein the glass composition meets the scribing standard ASTM C1048. In aspect (20), the present disclosure provides the method of any one of aspects (17) - (19), wherein the glass is melted and maintained at a temperature range of 1100-1650 ℃ for a time range of about 6-16 hours, and annealed at about 500-650 ℃, wherein the glass is maintained at the temperature for about 1 hour and subsequently cooled for at least 6 hours.

Detailed Description

In the following description, whenever a group is described as comprising at least one of a group of elements and combinations thereof, it is understood that the group may comprise, consist essentially of, or consist of any number of those listed elements, either individually or in combination with each other. Similarly, whenever a group is described as consisting of at least one of a group of elements or a combination thereof, it is understood that the group may consist of any number of those listed elements, either individually or in combination with each other. Unless otherwise indicated, a range of numerical values set forth includes both the upper and lower limits of the range, as well as any range between the stated ranges. As used herein, the indefinite article "a" or "an" and its corresponding definite article "the" mean "at least one" or "one or more", unless otherwise indicated. It is also to be understood that the various features disclosed in the specification and in the drawings may be used in any and all combinations.

Unless otherwise indicated in a specific context, the numerical ranges set forth herein include upper and lower values, and the ranges are intended to include the endpoints thereof and all integers and fractions within the range. It is not intended that the scope of the claims be limited to the specific values recited, when such ranges are defined. Further, when an amount, concentration, or other value or parameter is expressed in terms of a range, one or more preferred ranges, or an upper preferred numerical range and a lower preferred numerical range, it is understood that any range by combining any pair of an upper range limit or a preferred numerical value with any lower range limit or a preferred numerical value is specifically disclosed, regardless of whether such a combination is specifically disclosed. Finally, when the term "about" is used to describe a value or an endpoint of a range, it is to be understood that the disclosure includes the particular value or endpoint referenced. When a numerical range or an end point of a range does not recite "about," the end point of the numerical range or range is intended to include two embodiments: one modified with "about" and one not.

As used herein, the term "about" means that amounts, sizes, formulations, parameters and other variables and characteristics are not and need not be exact, but may be approximate and/or larger or smaller as desired, reflecting tolerances, conversion factors, rounding off and measurement errors and the like, and are known to those of skill in the artOf the other elements. It should be noted that the term "substantially" may be used herein to represent the inherent degree of uncertainty that may be attributed to any quantitative comparison, value, measurement, or other representation. The terms "comprises," "comprising," and any other variation thereof, are intended to cover a non-exclusive inclusion, such that a non-exclusive inclusion does not imply that all of the features and functions of the subject matter claimed herein are in fact, or even wholly, essential to the subject matter. Thus, "does not contain Al₂O₃"is a glass in which Al is not actively incorporated₂O₃Added or dosed to the glass, but may be present in very small amounts as contaminants (e.g., 500, 400, 300, 200, or 100 parts per million (ppm) or less).

All compositions are expressed as mole percent (mol%) unless otherwise indicated. Unless otherwise stated, the Coefficient of Thermal Expansion (CTE) is in units of 10^-7Low temperature CTE (L TCTE) was measured over a temperature range of 25 ℃ to 300 ℃ and has units of 10^-7V. C. The High Temperature CTE (HTCTE) is measured at a temperature above the glass transition region and has a unit of 10^-7The sum of the TCTE and HTCTE is in units of 10/. degree.C. L^-7V. C. Density is measured by the Archimedes (Archimedes) method (ASTM C693) in grams/cm³. Young's modulus, shear modulus and Poisson's ratio were measured by ASTM C623 standard.

Glass composition

In thermal tempering, the glass product is heated to near the softening temperature and then rapidly quenched by, for example, blowing cool air over the surface. As a result, the glass may have a lower surface temperature than the interior during cooling. Since the center of the glass cools to room temperature in a slower manner, it shrinks to a smaller specific volume (specific volume), while the high specific volume of the surface layer remains unchanged. This results in a surface compressive layer that gives the tempered glass its strength. The difference in specific volume is due to a combination of the difference in thermal expansion of the glass after cooling and the difference in fictive temperature between the surface and the body. For a preliminary approximation, the stress distribution in thermally tempered glass can be represented by a simple parabola, with the magnitude of the surface compressive stress being approximately equal to twice the central tension.

Unlike annealed glass, when thermally tempered glass breaks, it shatters into rock salt-like pieces that do not have sharp edges or needle-like shapes. This behavior is particularly useful for scenarios where safe breaking behavior is necessary, and for this reason it is of paramount importance to characterize the breaking behavior of thermally tempered glass. Desirable breakage behavior is referred to as "scoring" and occurs when the glass achieves full tempering. The score threshold of tempered glass is a somewhat arbitrarily defined breaking behavior that can be considered a "safe" situation for the user in the event of a glass failure. There are criteria for the scribing threshold worldwide, such as: ASTM C1048 and ANSI Z97.1 in the United states, EN12150-1 in Europe, GOST 5727-88 in Russia, JIS R3206 in Japan, and GB 15763.2 in China (all of which are incorporated herein by reference). The standards are similar across countries, which usually specify that for thick glass: (a), (b), and (c)>3mm), the crushed pieces of tempered soda-lime glass need to contain at least 30 to 40 pieces (1.6 pieces/cm) in an area of 50mm x 50mm²) The japanese standard, in particular, stipulates that in the case of thinner glass, at least 60 pieces are required.

The glasses disclosed herein have a high coefficient of thermal expansion, and a hot tempering process can be employed to obtain improved shatter behavior compared to commercially available thin glasses. The glasses described herein are needed to meet the growing demand for stronger but thinner thermally strengthened glasses for commercial electronic, vehicle, and architectural applications that require durability and/or scratch resistance as well as a "safe" break pattern. Furthermore, glasses must also retain significant chemical durability as they may be exposed to elements for extended periods of time.

It has been found that in order for thin glass (3mm or less, 2mm or less, or 1mm or less) to be thermally temperable and retain the desired shatter pattern, the low temperature coefficient of thermal expansion (L TCTE) should be 75x10^-7the/deg.C or greater and the High Temperature Coefficient of Thermal Expansion (HTCTE) should be 250x10^-7In some embodiments, it has been found that in addition to L TCTE and HTCTE limitations, the glass must also have a temperature of less than 0.65MPam^1/2Fracture toughness (K)_IC)。

In some embodiments, the glass comprises SiO₂、K₂O、Al₂O₃、B₂O₃And alkaline earth oxides. For example, embodiments may include: greater than 70 mol% SiO₂Greater than 0 mol% Al₂O₃Greater than 0 mol% B₂O₃Greater than 3 mol% K₂O, and greater than 0 mol% MO, wherein M is Ca, Ba, Sr, or Mg. In some embodiments, the glass can comprise: 72 mol% SiO₂，>0 to 10 mol% Al₂O₃0.5 to 5 mol% B₂O₃3 to 20 mol% K₂O, and 2 to 20 mol% MO, wherein M is Ca, Ba, Sr, or Mg. In other embodiments, the glass may comprise: 72 to 90 mol% SiO₂3 to 10 mol% Al₂O₃1 to 5 mol% B₂O₃8 to 18 mol% K₂O, and 2 to 15 mol% MO, wherein M is Ca, Ba, Sr, or Mg.

SiO₂Is the largest oxide component in practical glasses and may be included to provide high temperature stability and chemical durability. In some embodiments, the glass may comprise 70 mol% or more SiO₂. In some embodiments, the glass may comprise 72 mol% or more SiO₂. In some embodiments, the glass may comprise 72 to 90 weight percent SiO₂. In some embodiments, the glass may comprise 75 to 90 weight percent SiO₂. In some embodiments, the glass may comprise 70 to 92 mole%, 70 to 90 mole%, 70 to 85 mole%, 70 to 80 mole%, 72 to 92 mole%, 72 to 90 mole%, 72 to 85 mole%, 72 to 80 mole%, 75 to 92 mole%, 75 to 90 mole%, 75 to 85 mole%, or 75 to 80 mole% SiO₂. In some embodiments, the glass comprises 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, or 92 mole percent SiO₂。

Al₂O₃Can shadowDepending on the structure of the glass, the liquidus temperature and the thermal expansion coefficient may be lowered or the strain point may be increased. In some embodiments, the glass may comprise greater than 0 mol% Al₂O₃. In some embodiments, the glass can comprise>0 to 20 mol% Al₂O₃. In some embodiments, the glass can comprise>0 to 10 mol%, 3 to 10 mol% or 5 to 10 mol% Al₂O₃. In some embodiments, the glass can comprise>0 to 20 mol%,>0 to 18 mol%,>0 to 15 mol%,>0 to 12 mol%,>0 to 10 mol%,>0 to 8 mol%, 1 to 20 mol%, 1 to 18 mol%, 1 to 15 mol%, 1 to 12 mol%, 1 to 10 mol%, 1 to 8 mol%, 3 to 20 mol%, 3 to 18 mol%, 3 to 15 mol%, 3 to 12 mol%, 3 to 10 mol%, 3 to 8 mol%, 5 to 20 mol%, 5 to 18 mol%, 5 to 15 mol%, 5 to 12 mol%, 5 to 10 mol%, 7 to 20 mol%, 7 to 18 mol%, 7 to 15 mol%, 7 to 12 mol%, or 7 to 10 mol% of Al₂O₃. In some embodiments, the glass can comprise about>0.1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 mol% Al₂O₃。

Without being bound by theory, it is believed that B is incorporated into the glasses described herein₂O₃The coefficient of thermal expansion is influenced, particularly at high temperatures, and the temperability of the glass is improved. In some embodiments, when present, the glass can comprise>0 to 10 mol% B₂O₃. In some embodiments, the glass may comprise 0.5 to 10 mol%, 0.5 to 8 mol%, or 1 to 6 mol% B₂O₃. In some embodiments, the glass may comprise 1 to 5 weight percent B₂O₃. In some embodiments, the glass can comprise>0 to 10 mol%,>0 to 8 mol%,>0 to 6 mol%,>0 to 5 mol%,>0 to 4 mol%, 0.5 to 10 mol%, 0.5 to 8 mol%, 0.5 to 6 mol%, 0.5 to 5 mol%, 0.5 to 4 mol%, 1 to 10 mol%, 1To 8 mole%, 1 to 6 mole%, 1 to 5 mole%, 1 to 4 mole%, 2 to 10 mole%, 2 to 8 mole%, 2 to 6 mole%, 2 to 5 mole%, or 2 to 4 mole%. In some embodiments, the glass may comprise about 0,>0. 0.5, 1, 1.5, 2, 3, 4, 5, 6, 7, 8, 9 or 10 mol% B₂O₃。

Alkaline earth oxides can improve desirable properties in the material, including affecting young's modulus and coefficient of thermal expansion. In some embodiments, the glass comprises >0 mol% to about 20 mol% MO (0 mol% < MO ≦ 20 mol%), where M is the sum of the alkaline earth metals Mg, Ca, Sr, and Ba in the glass. In some embodiments, the glass may comprise 2 to 20 weight percent MO. In some embodiments, the glass may comprise 2 to 15 wt.% MO. In some embodiments, the glass can comprise about >0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 mol% MO.

In some embodiments, the glass comprises MgO, CaO, or SrO. In some embodiments, the glass may comprise greater than 0 mol.% MgO. In some embodiments, the glass may comprise >0 to 10 mol% MgO. In some embodiments, the glass may comprise 3 to 10 mole%, 5 at 10 mole%, 5 to 8 mole% MgO. In some embodiments, the glass can comprise >0 to 10 mole%, >0 to 8 mole%, >0 to 6 mole%, >0 to 4 mole%, >0 to 2 mole%, 1 to 10 mole%, 1 to 8 mole%, 1 to 6 mole%, 1 to 4 mole%, 1 to 2 mole%, 3 to 8 mole%, 3 to 6 mole%, 3 to 10 mole%, 5 to 8 mole%, 5 to 10 mole%, 7 to 10 mole%, or 8 to 10 mole% MgO. In some embodiments, the glass can comprise approximately >0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 mole percent MgO.

In some embodiments, the glass may include greater than 0 mol% CaO. In some embodiments, the glass may contain >0 to 15 mol% CaO. In some embodiments, the glass may comprise >0 to 5 mol%, 6 to 13 mol%, 5 to 15 mol%, 7 to 13 mol%, 7 to 11 mol%, 8 to 12 mol% CaO. In some embodiments, the glass may comprise >0 to 15 mol%, >0 to 13 mol%, >0 to 11 mol%, >0 to 9 mol%, >0 to 7 mol%, >0 to 5 mol%, 1 to 15 mol%, 1 to 13 mol%, 1 to 11 mol%, 1 to 9 mol%, 1 to 7 mol%, 1 to 5 mol%, 3 to 15 mol%, 3 to 13 mol%, 3 to 11 mol%, 3 to 9 mol%, 3 to 7 mol%, 3 to 5 mol%, 5 to 15 mol%, 5 to 13 mol%, 5 to 11 mol%, 5 to 9 mol%, 7 to 15 mol%, 7 to 13 mol%, 7 to 11 mol%, 7 to 9 mol%, 9 to 15 mol%, 9 to 13 mol%, 9 to 11 mol%, 11 to 15 mol%, or 11 to 13 mol% CaO. In some embodiments, the glass may comprise approximately >0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 mol% CaO.

In some embodiments, SrO may be present, and in such embodiments, the glass may comprise 0 to 10 weight percent SrO. In some embodiments, the glass may comprise >0 to 10 mol% SrO. In some embodiments, the glass may comprise 3 to 10 mole%, 5 at 10 mole%, 5 to 8 mole% SrO. In some embodiments, the glass may comprise >0 to 10 mol%, >0 to 8 mol%, >0 to 6 mol%, >0 to 4 mol%, >0 to 2 mol%, 1 to 10 mol%, 1 to 8 mol%, 1 to 6 mol%, 1 to 4 mol%, 1 to 2 mol%, 3 to 8 mol%, 3 to 6 mol%, 3 to 10 mol%, 5 to 8 mol%, 5 to 10 mol%, 7 to 10 mol% or 8 to 10 mol% SrO. In some embodiments, the glass may comprise about >0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 mol% SrO.

In some embodiments, BaO may be present, and in such embodiments, the glass may comprise 0 to 15 weight percent BaO. In some embodiments, the glass may comprise 0 to 10 mole%, >0 to 5 mole%, 6 to 13 mole%, 5 to 15 mole%, 7 to 13 mole%, 7 to 11 mole%, 8 to 12 mole% BaO. In some embodiments, the glass may comprise >0 to 15 mole%, >0 to 13 mole%, >0 to 11 mole%, >0 to 9 mole%, >0 to 7 mole%, >0 to 5 mole%, 1 to 15 mole%, 1 to 13 mole%, 1 to 11 mole%, 1 to 9 mole%, 1 to 7 mole%, 1 to 5 mole%, 3 to 15 mole%, 3 to 13 mole%, 3 to 11 mole%, 3 to 9 mole%, 3 to 7 mole%, 3 to 5 mole%, 5 to 15 mole%, 5 to 13 mole%, 5 to 11 mole%, 5 to 9 mole%, 7 to 15 mole%, 7 to 13 mole%, 7 to 11 mole%, 7 to 9 mole%, 9 to 15 mole%, 9 to 13 mole%, 9 to 11 mole%, 11 to 15 mole%, or 11 to 13 mole% BaO. In some embodiments, the glass may comprise approximately >0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 mol% BaO.

Na₂O and K₂O can improve the temperability of the glass and influence the coefficient of thermal expansion, especially at low temperatures. In some embodiments, the glass may comprise 0 to 10 mol% Na₂And O. In some embodiments, the glass can comprise>0 to 10 mol% Na₂And O. In some embodiments, the glass may comprise 0 to 8 mol% Na₂And O. In some embodiments, the glass may comprise 2 to 6 mol% Na₂And O. In some embodiments, the glass may comprise 0 to 10 mole percent, 0 to 8 mole percent, 0 to 6 mole percent, 0 to 4 mole percent, 0 to 2 mole percent,>0 to 10 mol%,>0 to 8 mol%,>0 to 6 mol%,>0 to 4 mol%,>0 to 2 mol%, 2 to 10 mol%, 2 to 8 mol%, 2 to 6 mol%, 2 to 4 mol%, 5 to 16 mol%, 5 to 10 mol%, 5 to 8 mol% or 8 to 10 mol% Na₂And O. In some embodiments, the glass can comprise 0,>0.1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 mol% Na₂O.。

In some embodiments, the glass may comprise 3 to 20 weight percent K₂And O. In some embodiments, the glass may comprise 5 to 18 mol% K₂And O. In some embodiments, the glass may comprise 8 to 12 mol% K₂And O. In some embodiments, the glass may comprise 3 to 20 mole%, 3 to 18 mole%, 3 to 15 mole%, 3 to 12 mole%, 3 to 10 mole%, 3 to 8 mole%, 5 to 20 mol%, 5 to 18 mol%, 5 to 15 mol%, 5 to 12 mol%, 5 to 10 mol%, 5 to 8 mol%, 8 to 20 mol%, 8 to 18 mol%, 8 to 15 mol%, 8 to 12 mol%, 8 to 10 mol%, 10 to 20 mol%, 10 to 18 mol%, 10 to 15 mol%, 10 to 12 mol%, 12 to 20 mol%, 12 to 18 mol% or 12 to 15 mol% K₂And O. In some embodiments, the glass can comprise 0,>0.1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 mol% K₂O。

In some embodiments, L i may be present₂O, and in such embodiments, the glass may comprise 0 to 5 mole% L i₂And O. In some embodiments, the glass can comprise>0 to 5 mol% L i₂And O. In some embodiments, the glass can comprise about>0 to 3.5 mol% L i₂O or 0.2 to 3 mol% L i₂In some embodiments, the glass may comprise 1 to 4 mol% L i₂And O. In some embodiments, the glass may comprise 0.2 to 5 mole percent, 0.2 to 4 mole percent, 0.2 to 3 mole percent, 0.2 to 2 mole percent,>0 to 5 mol%,>0 to 4 mol%,>0 to 3 mol%,>0 to 2 mol%, 1 to 5 mol%, 1 to 4 mol% or 1 to 3 mol% L i₂And O. In some embodiments, the glass may comprise about 0,>0.1, 2, 3, 4 or 5 mol% L i₂O。

In some embodiments, the alkaline substance Na₂O and K₂O or L i₂O、Na₂O and K₂The total amount of O is important for the glass properties. In some embodiments, the glass may comprise 3 to 22 mole% Na₂O+K₂O or L i₂O+Na₂O+K₂And O. In some embodiments, the glass may comprise 5 to 20 mole% Na₂O+K₂O or L i₂O+Na₂O+K₂And O. In some embodiments, the glass may comprise 5 to 15 mole% Na₂O+K₂O or L i₂O+Na₂O+K₂And O. In some embodiments, the glass can comprise8 to 16 mol% Na₂O+K₂O or L i₂O+Na₂O+K₂And O. In some embodiments, the glass may comprise 9 to 14 mole% Na₂O+K₂O or L i₂O+Na₂O+K₂And O. In some embodiments, the glass may comprise 3 to 22, 5 to 22, 8 to 22, 3 to 20, 5 to 20, 8 to 20, 3 to 15, 5 to 15, 8 to 15, 3 to 12, 5 to 12, or 8 to 12 mole percent Na₂O+K₂O or L i₂O+Na₂O+K₂And O. In some embodiments, the glass may comprise 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22 mole percent Na₂O+K₂O or L i₂O+Na₂O+K₂O。

Additional components may be incorporated into the glass to provide additional benefits, or may be incorporated as contaminants commonly found in commercially produced glasses. For example, the additional components may be added as colorants or fining agents (e.g., to facilitate removal of gaseous inclusions from molten batch materials used to produce the glass) and/or for other purposes. In some embodiments, the glass may comprise one or more compounds that act as absorbers of ultraviolet radiation. In some embodiments, the glass may comprise 3 mole% or less of: ZnO, TiO₂、CeO、MnO、Nb₂O₅、MoO₃、Ta₂O₅、WO₃、SnO₂、Fe₂O₃、As₂O₃、Sb₂O₃Cl, Br, or combinations thereof. In some examples, the glass may comprise 0 to about 3 mole%, 0 to about 2 mole%, 0 to about 1 mole%, 0 to 0.5 mole%, 0 to 0.1 mole%, 0 to 0.05 mole%, or 0 to 0.01 mole% ZnO, TiO₂、CeO、MnO、Nb₂O₅、MoO₃、Ta₂O₅、WO₃、SnO₂、Fe₂O₃、As₂O₃、Sb₂O₃Cl, Br, orCombinations thereof. According to some embodiments, the glass may also include various contaminants associated with the batch materials and/or various contaminants introduced into the glass by the melting, fining, and/or forming equipment used to produce the glass. For example, in some embodiments, the glass may comprise 0 to about 3 mole%, 0 to about 2 mole%, 0 to about 1 mole%, 0 to about 0.5 mole%, 0 to about 0.1 mole%, 0 to about 0.05 mole%, or 0 to about 0.01 mole% SnO₂Or Fe₂O₃Or a combination thereof.

Non-limiting examples of the amounts of precursor oxides used to form the embodiment glasses, as well as the properties of the resulting glasses, are set forth in table 1.

TABLE 1

TABLE 1 (continuation)

As noted above, glasses of one or more embodiments practiced may exhibit colors, in some embodiments, the glasses are desired to have green-yellow to gold to amber colors, in particular embodiments, these colors may be combined with the blue color of crystalline silicon photovoltaic cells to produce aesthetically pleasing dark blue to black colors, in some embodiments, the glasses exhibit the following colors (determined using reflectance spectroscopy measurements of a spectrophotometer, illuminant D65, and specular reflection excluded) present in the SCE color space coordinates, in the range of from about-10 to about 30 for a glass thickness of 2.7mm, b is from about 0 to about 30, and L > 80. in some embodiments, the glasses exhibit the following colors present in the SCI color space coordinates, a is from about-5 to about-1 for a glass thickness of 2.7mm, b is from about 5 to about 18, and 32 is combined with the reflectance spectra of a reflectance of a photovoltaic cells included in the scc-19, in the application range of from about 10 to about 10, and a is determined using a spectrophotometer as a reflectance spectroscopy measurement of a reflectance of a photovoltaic cells together with the SCE 19.

In some embodiments, the glass may be strengthened by thermal or chemical tempering. In some embodiments, the glass may be strengthened to include a Compressive Stress (CS) extending from a surface thereof to a depth of compression (DOC). The compressive stress region is balanced by a central portion exhibiting tensile stress. At the DOC, the stress is converted from positive (compressive) stress to negative (tensile) stress. Such strengthening methods include both thermal tempering and chemical tempering.

The glasses described herein are particularly capable of being thermally tempered. Thermal tempering processes are well known in the art. To thermally temper a glass article, the article is heated to near the softening temperature and then rapidly cooled or quenched. As a result, the glass may have a lower surface temperature than the interior during cooling. The temperature differential is maintained until the surface of the glass cools at least to its strain point or below (e.g., room temperature). Since the center of the glass cools in a slower manner, it shrinks to a smaller specific volume (specific volume), while the high specific volume of the surface layer remains unchanged. This results in a surface compressive layer that gives the tempered glass its strength. The difference in specific volume is partly due to the difference in thermal expansion of the glass after cooling and the difference in fictive temperature between the surface and the bulk (less influence). For a preliminary approximation, the stress distribution in thermally tempered glass can be represented by a simple parabola, with the magnitude of the surface compressive stress being approximately equal to twice the central tension.

As an alternative to thermal tempering, the glasses disclosed herein may be ion exchanged by immersion in at least one ion exchange bath containing a molten salt (e.g., nitrate, sulfide, halide, or the like) of at least one alkali metal (e.g., lithium, sodium, or potassium). Ion exchange is commonly used to perform glassAnd (4) chemically strengthening. In one particular example, the alkali cations in such cation sources (e.g., molten salts or "ion exchange" baths) are exchanged with smaller alkali cations within the glass, thereby achieving a layer under Compressive Stress (CS) that extends from the surface of the glass to a depth of compression (DOC) in the glass phase. For example, potassium ions from the cation source are typically exchanged with sodium and/or lithium ions in the glass phase, and K⁺The ion exchange bath may contain a single alkali metal salt (or salts) (e.g., L i, a sulfide, nitrate, or halide of Na or K) or two or more alkali metal salts (e.g., L i and a sulfide, nitrate, or halide of Na and K). ion exchange is performed in the ion exchange bath at a temperature range of about 390 ℃ to about 550 ℃ for a time period of about 0.5 hours to about 24 hours.

In some embodiments, the glass is ion exchanged and has a compressive layer that extends from the surface to a depth of compression (DOC) of at least about 10 μm, or in some embodiments, at least about 30 μm into the glass, or in some embodiments, up to about 10, 15, 20, or 25% into the glass, as measured in thickness (surface to center). In some embodiments, the compressive layer extends from the surface of the glass to a depth of up to about 20% of the thickness of the glass. In some embodiments, the glass can be strengthened to exhibit a surface compressive stress of 250MPa to 800MPa or greater.

In strengthened glass, the depth of the compressive layer can be determined by: electron microprobe, glow discharge optical emission spectroscopy (GDOES, a technique for measuring the depth distribution of constituent elements in a solid sample by sputtering the emission of atoms contained in a plasma), or similar techniques that can provide compositional data as a function of depth, where the data would show the incorporation of Na at the surface (Na in the glass phase) of a solid sample⁺Instead of L i⁺) DOC of precursor glass can be measured by a surface stress meter (FSM) using a commercial instrument such as FSM-6000 manufactured by Orihara Industrial Co., L td (Japan), manufactured by Japan K.K.. surface stress measurementRelies on the accurate measurement of the Stress Optical Coefficient (SOC), which is related to the birefringence of the glass. SOC is measured using methods known in the art, such as fiber and four-point bending methods, which are described in the subject "Standard Test Method for measuring Glass Stress-Optical Coefficient", and large cylinder methods]Is ASTM standard C770-98(2013), which is incorporated herein by reference in its entirety. CS can also be measured by FSM measurements. As used herein, CS may be the "maximum compressive stress," which is the highest value of compressive stress measured in the layer of compressive stress. In some embodiments, the maximum compressive stress is at the surface of the glass. In other embodiments, the maximum compressive stress may be generated at a depth below the surface, giving a compressive profile that appears as a "buried peak".

The thermally or chemically strengthened glass or article disclosed herein can be integrated into another article, such as an article (or display article) having a display screen (e.g., consumer electronics, including mobile phones, tablets, computers, navigation systems, and the like), a construction article (e.g., windows, skylights, strip roofs (shingles)), a transportation article (e.g., vehicles, trains, aircraft, marine, and the like), an electrical article, or any article that would benefit from transparency, scratch resistance, abrasion resistance, or a combination thereof. In other embodiments, the glass forms part of a consumer electronic product (e.g., a cell phone or smart phone, a laptop or tablet, etc.). Such consumer electronics typically include a housing having a front surface, a back surface, and side surfaces, and include electronic components, such as a power supply, a controller, a memory, or a display, located at least partially within the housing. In some embodiments, the glasses described herein comprise at least a portion of a protective element, such as, but not limited to, an enclosure and/or a display for consumer electronics.

Process for producing glass

Glasses having the oxide contents listed in table 1 can be produced by conventional methods. For example, in some embodiments, the precursor glass can be formed by thoroughly mixing the desired batch materials (e.g., using a tube mixer), thereby protecting the homogeneous melt, and then placed into a silica and/or platinum crucible. The crucible can be placed in a furnace and the glass batch melted and maintained at a temperature of 1250-. The melt may then be poured into a steel mold to obtain a glass slab. These slabs may then be immediately transferred to an annealer operating at about 500-. In another non-limiting example, the precursor glass is prepared by dry blending the appropriate oxides and mineral sources for a time sufficient to thoroughly mix the ingredients. The glass was melted in a platinum crucible at a temperature of about 1100 c to 1650 c and held at temperature for about 16 hours. The resulting glass melt was then poured onto a steel table for cooling. The precursor glass is then annealed at a suitable temperature.

Tempering of glass in practice is achieved using conventional processes in which the glass is heated to a predetermined temperature in a radiant energy or convection furnace (or a "combination mode" furnace using both techniques) and then gas cooled ("quench") by convection, typically by blowing large volumes of ambient air against or along the surface of the glass.

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