阅读说明：本技术 化学耐久性铝硅酸盐玻璃组合物及由其形成的玻璃制品 (Chemically durable aluminosilicate glass compositions and glass articles formed therefrom ) 是由 N·T·罗恩罗斯 马丽娜 R·A·绍特 于 2020-03-04 设计创作，主要内容包括：在实施方式中,玻璃组合物可以包括：大于或等于71摩尔％且小于或等于83摩尔％的SiO-(2)；大于或等于1摩尔％且小于或等于11摩尔％的Al-(2)O-(3)；大于或等于5摩尔％且小于或等于18摩尔％的碱金属氧化物,碱金属氧化物包含大于3摩尔％的Li-(2)O以及Na-(2)O和K-(2)O中的至少一者；大于或等于1摩尔％且小于或等于8摩尔％的碱土金属氧化物,碱土金属氧化物包含MgO以及CaO、BaO和SrO中的至少一者；以及TiO-(2)、ZrO-(2)、HfO-(2)、La-(2)O-(3)和Y-(2)O-(3)中的至少一者,其中TiO-(2)+ZrO-(2)+HfO-(2)+La-(2)O-(3)+Y-(2)O-(3)大于0摩尔％且小于或等于6摩尔％,并且Al-(2)O-(3)+TiO-(2)+ZrO-(2)+HfO-(2)+La-(2)O-(3)+Y-(2)O-(3)大于或等于2摩尔％且小于或等于12摩尔％。(In embodiments, the glass composition may comprise: 71 mol% or more and 83 mol% or less of SiO 2 (ii) a1 mol% or more and 11 mol% or less of Al 2 O 3 (ii) a Greater than or equal to 5 mol% and less than or equal to 18 mol% of an alkali metal oxide comprising greater than 3 mol% Li 2 O and Na 2 O and K 2 At least one of OA step of; greater than or equal to 1 mol% and less than or equal to 8 mol% of an alkaline earth oxide comprising MgO and at least one of CaO, BaO, and SrO; and TiO 2 、ZrO 2 、HfO 2 、La 2 O 3 And Y 2 O 3 At least one of (1), wherein TiO 2 +ZrO 2 +HfO 2 +La 2 O 3 +Y 2 O 3 Greater than 0 mol% and less than or equal to 6 mol%, and Al 2 O 3 +TiO 2 +ZrO 2 +HfO 2 +La 2 O 3 +Y 2 O 3 2 mol% or more and 12 mol% or less.)

1. A glass composition comprising:

71 mol% or more and 83 mol% or less of SiO₂；

1 mol% or more and 11 mol% or less of Al₂O₃；

Greater than or equal to 5 mol% and less than or equal to 18 mol% of an alkali metal oxide comprising greater than 3 mol% Li₂O and Na₂O and K₂At least one of O;

greater than or equal to 1 mol% and less than or equal to 8 mol% of an alkaline earth oxide comprising MgO and at least one of CaO, BaO, and SrO; and

TiO₂、ZrO₂、HfO₂、La₂O₃and Y₂O₃At least one of (1), wherein TiO₂(mol%) + ZrO₂(mol%) + HfO₂(mol%) + La₂O₃(mol%) + Y₂O₃(mol%) is more than 0 mol% and 6 mol% or less, and Al₂O₃(mol%) + TiO₂(mol%) + ZrO₂(mol%) + HfO₂(mol%) + La₂O₃(mol%) + Y₂O₃(mol%) is 2 mol% or more and 12 mol% or less.

2. The glass composition of claim 1, wherein the SiO₂(mol%) + Al₂O₃(mol%) + TiO₂(mol%) + ZrO₂(mol%) + HfO₂(mol%) + La₂O₃(mol%) + Y₂O₃(mol%) + B₂O₃(mol%) is less than or equal to 90 mol%.

3. The glass composition of claim 1, wherein the glass composition comprises TiO₂And ZrO₂。

4. The glass composition of claim 3, wherein the TiO₂(mol%) + ZrO₂(mol%) is less than or equal to 6 mol%.

5. The glass composition of claim 3, wherein the TiO₂(mol%) + ZrO₂(mol%) is less than or equal to 4 mol%.

6. The glass composition of claim 3, wherein the TiO₂(mol%) + ZrO₂(mol%) is less than or equal to 2 mol%.

7. The glass composition of claim 1, wherein the glass composition comprises TiO₂、ZrO₂And HfO₂。

8. The glass composition of claim 7, wherein the TiO₂(mol%) + ZrO₂(mol%) + HfO₂(mol%) is less than or equal to 6 mol%.

9. The glass composition of claim 7, wherein the TiO₂(mol%) + ZrO₂(mol%) + HfO₂(mol%) is less than or equal to 5 mol%.

10. The glass composition of claim 1, wherein the glass composition comprises ZrO₂And HfO₂。

11. The glass composition according to claim 10, wherein ZrO₂(mol%) + HfO₂(mol%) is less than or equal to 4.0 mol%.

12. As claimed in claim10 of the glass composition, wherein ZrO₂(mol%) + HfO₂(mol%) is less than or equal to 2.0 mol%.

13. The glass composition according to claim 10, wherein ZrO₂(mol%) + HfO₂(mol%) is less than or equal to 0.5 mol%.

14. The glass composition of claim 1, wherein the glass composition comprises La₂O₃And La₂O₃Is less than or equal to 1 mole%.

15. The glass composition of claim 1, wherein the glass composition comprises ZrO₂And is ZrO₂Is greater than 1 mole%.

16. The glass composition of claim 15, wherein the glass composition comprises ZrO₂And is ZrO₂Is less than or equal to 5 mole%.

17. The glass composition of claim 1, wherein the glass composition comprises HfO₂And HfO₂Is less than or equal to 4 mole%.

18. The glass composition of claim 1, wherein the glass composition comprises TiO₂And TiO 2₂Is greater than 1 mole%.

19. The glass composition of claim 18, wherein the glass composition comprises TiO₂And TiO 2₂Is less than or equal to 6 mole%.

20. The glass composition of claim 1, wherein the glass composition comprises Y₂O₃And Y is₂O₃Is less than or equal to 1 mole%.

21. The glass composition of claim 1, wherein the SiO₂Greater than or equal to 72 mol% and less than or equal to 79 mol%.

22. The glass composition of claim 1, wherein the SiO₂73 mol% or more and 78 mol% or less.

23. The glass composition of claim 1, wherein Al is₂O₃2 mol% or more and 8 mol% or less.

24. The glass composition of claim 1, wherein Al is₂O₃4 mol% or more and 8 mol% or less.

25. The glass composition of claim 1, wherein Al is₂O₃5 mol% or more and 7 mol% or less.

26. The glass composition of claim 1, wherein Li₂O (mol%) > Na₂O (mol%) > K₂O (mol%).

27. The glass composition of claim 1, wherein the alkali metal oxide is greater than or equal to 5 mol% and less than or equal to 13 mol%.

28. The glass composition of claim 1, wherein Li₂O is 3 mol% or more and 10 mol% or less.

29. The glass composition of claim 28, wherein Li₂O is less than or equal to 8 mol%.

30. The glass composition of claim 1, wherein Na₂O is 1 mol% or more and 5 mol% or less.

31. The glass composition of claim 30, wherein Na₂O is less than 3 mol%.

32. The glass composition of claim 30, wherein Na₂O is less than 2.5 mol%.

33. The glass composition of claim 30, wherein Na₂O is less than 2.0 mol%.

34. The glass composition of claim 1, wherein K is₂O is 1 mol% or more and 7 mol% or less.

35. The glass composition of claim 34, wherein K is₂O is less than 5 mol%.

36. The glass composition of claim 1, wherein alkaline earth oxide comprises greater than or equal to 4 mol% and less than or equal to 8 mol% MgO and less than or equal to 1 mol% of at least one of CaO, BaO, and SrO.

37. The glass composition of claim 36, wherein the alkaline earth oxide comprises less than or equal to 0.5 mol% CaO.

38. The glass composition of claim 1, further comprising greater than or equal to about 0.01 mol.% and less than or equal to 0.5 mol.% fining agent.

39. The glass composition of claim 38, wherein the fining agent is SnO₂。

40. Such asThe glass composition of claim 1, wherein the glass composition has a temperature range of about 20 ℃ to about 300 ℃ of less than or equal to 65 x 10^-7Average coefficient of thermal expansion per deg.C.

41. The glass composition of claim 1, wherein the glass composition has a temperature range of about 20 ℃ to about 300 ℃ of less than or equal to 62 x 10^-7A temperature of 50 x 10 or higher^-7Average coefficient of thermal expansion per deg.C.

42. The glass composition of claim 1, wherein the glass composition has a hydrolysis resistance of grade HGA1 according to ISO720:1985 prior to strengthening by ion exchange.

43. The glass composition of claim 42, wherein the glass composition has a hydrolysis resistance according to ISO720:1985 grade HGA1 after strengthening by ion exchange.

44. The glass composition of claim 1, wherein the glass composition has an alkali resistance of grade a1 or grade a2 according to ISO695:1991 prior to strengthening by ion exchange.

45. The glass composition of claim 44, wherein the glass composition has an alkali resistance of grade A1 or grade A2 according to ISO695:1991 after strengthening by ion exchange.

46. The glass composition of claim 1, wherein the glass composition, prior to strengthening by ion exchange, has an acid resistance of grade S2 or grade S1 according to DIN12116 (2001).

47. The glass composition of claim 46, wherein the glass composition, after strengthening by ion exchange, has an acid resistance of grade S2 or grade S1 according to DIN12116 (2001).

48. A glass pharmaceutical package formed from the glass composition of any of claims 1 to 47.

Technical Field

The present description relates generally to aluminosilicate glass compositions, and in particular, to chemically durable aluminosilicate glass compositions and glass articles formed therefrom.

Background

Historically, glass has been the preferred material for packaging pharmaceuticals because of its hermeticity, optical clarity and excellent chemical durability relative to other materials. In particular, glass used for pharmaceutical packaging must have sufficient chemical durability so as not to affect the stability of the pharmaceutical composition contained therein. Glasses having suitable chemical durability include those of the ASTM standards "type IA" and "type 1B" glass compositions, which are aluminoborosilicate glasses.

It has been found that aluminoborosilicate glasses may exhibit a tendency to delaminate. This tendency to delaminate is associated with the higher concentration of borate species in aluminoborosilicate glasses. It is believed that reducing or eliminating borate species in the glass may reduce the tendency to delaminate.

Accordingly, there is a need for aluminosilicate glasses that exhibit chemical durability.

Disclosure of Invention

According to a first aspect a1, a glass composition may include: 71 mol% or more and 83 mol% or less of SiO₂(ii) a1 mol% or more and 11 mol% or less of Al₂O₃(ii) a Greater than or equal to 5 mol% and less than or equal to 18 mol% of an alkali metal oxide comprising greater than 3 mol% Li₂O and Na₂O and K₂At least one of O; greater than or equal to 1 mol% and less than or equal to 8 mol% of an alkaline earth oxide comprising MgO and at least one of CaO, BaO, and SrO; and TiO₂、ZrO₂、HfO₂、La₂O₃And Y₂O₃At least one of (1), wherein TiO₂(mol%) + ZrO₂(mol%) + HfO₂(mol%) + La₂O₃(mol%) + Y₂O₃(mol%) is more than 0 mol% and 6 mol% or less, and Al₂O₃(mol%) + TiO₂(mol%) + ZrO₂(mol%) + HfO₂(mol%) + La₂O₃(mol%) + Y₂O₃(mol%) is 2 mol% or more and 12 mol% or less.

A second aspect A2 includes the glass composition of the first aspect A1 wherein the SiO₂(mol%) + Al₂O₃(mol%) + TiO₂(mol%) + ZrO₂(mol%) + HfO₂(mol%) + La₂O₃(mol%) + Y₂O₃(mol%) + B₂O₃(mol%) is less than or equal to 90 mol%.

The third aspect A3 includes the glass composition of the first aspect a1 or the second aspect a2, wherein the glass composition includes TiO₂And ZrO₂。

The fourth aspect A4 includesThe glass composition of any of aspects a1-A3, wherein the TiO₂(mol%) + ZrO₂(mol%) is less than or equal to 6 mol%.

The fifth aspect A5 includes the glass composition of any one of the first to fourth aspects A1-A4, wherein the TiO₂(mol%) + ZrO₂(mol%) is less than or equal to 4 mol%.

The sixth aspect A6 includes the glass composition of any one of the first to fifth aspects A1-A5 wherein the TiO₂(mol%) + ZrO₂(mol%) is less than or equal to 2 mol%.

The seventh aspect A7 includes the glass composition of any one of the first to sixth aspects A1-A6, wherein the glass composition comprises TiO₂、ZrO₂And HfO₂。

The eighth aspect A8 includes the glass composition of any one of the first to seventh aspects A1-A7, wherein the TiO₂(mol%) + ZrO₂(mol%) + HfO₂(mol%) is less than or equal to 6 mol%.

The ninth aspect A9 includes the glass composition of any one of the first to eighth aspects A1-A8 wherein the TiO₂(mol%) + ZrO₂(mol%) + HfO₂(mol%) is less than or equal to 5 mol%.

The tenth aspect A10 includes the glass composition of any one of the first to ninth aspects A1-A9, wherein the glass composition comprises ZrO₂And HfO₂。

The eleventh aspect A11 includes the glass composition of any one of the first to tenth aspects A1-A10, wherein ZrO₂(mol%) + HfO₂(mol%) is less than or equal to 4.0 mol%.

The twelfth aspect A12 includes the glass composition of any one of the first to eleventh aspects A1-A11, wherein ZrO₂(mol%) + HfO₂(mol%) is less than or equal to 2.0 mol%.

A thirteenth aspect A13 includes the glass composition of any one of the first to twelfth aspects A1-A12, wherein ZrO₂(mol%) + HfO₂(mol%) is less than or equal to 0.5 mol%.

A fourteenth aspect a14 includes the glass composition of any one of the first to thirteenth aspects a1-a13, wherein the glass composition comprises La₂O₃And La₂O₃Is less than or equal to 1 mole%.

Fifteenth aspect a15 includes the glass composition of any one of the first to fourteenth aspects a1-a14, wherein the glass composition comprises ZrO₂And is ZrO₂Is greater than 1 mole%.

A sixteenth aspect A16 includes the glass composition of any one of the first to fifteenth aspects A1-A15, wherein the glass composition comprises ZrO₂And is ZrO₂Is less than or equal to 5 mole%.

A seventeenth aspect A17 includes the glass composition of any one of the first to sixteenth aspects A1-A16, wherein the glass composition comprises HfO₂And HfO₂Is less than or equal to 4 mole%.

The eighteenth aspect a18 includes the glass composition of any one of the first to seventeenth aspects a1-a17, wherein the glass composition comprises TiO₂And TiO 2₂Is greater than 1 mole%.

Nineteenth aspect a19 includes the glass composition of eighteenth aspect a18, wherein the glass composition comprises TiO₂Glass composition, and TiO₂Is less than or equal to 6 mole%.

A twentieth aspect a20 includes the glass composition of any one of the first to nineteenth aspects a1-a19, wherein the glass composition comprises Y₂O₃And Y is₂O₃Is less than or equal to 1 mole%.

The twenty-first aspect A21 includes the glass composition of any one of the first to twentieth aspects A1-A20, wherein the SiO₂Greater than or equal to 72 mol% and less than or equal to 79 mol%.

The twenty-second aspect a22 includes the first aspect toThe glass composition of any of the twenty-first aspects A1-A21, wherein the SiO₂73 mol% or more and 78 mol% or less.

The twenty-third aspect A23 includes the glass composition of any one of the first to twenty-second aspects A1-A22, wherein Al₂O₃2 mol% or more and 8 mol% or less.

A twenty-fourth aspect A24 includes the glass composition of any one of the first to twenty-third aspects A1-A23, wherein Al₂O₃4 mol% or more and 8 mol% or less.

The twenty-fifth aspect a25 includes the glass composition of any one of the first to twenty-fourth aspects a1-a24, wherein Al₂O₃5 mol% or more and 7 mol% or less.

A twenty-sixth aspect A26 includes the glass composition of any one of the first to twenty-fifth aspects A1-A25, wherein Li₂O (mol%)>Na₂O (mol%)>K₂O (mol%).

A twenty-seventh aspect a27 includes the glass composition of any one of the first to twenty-sixth aspects a1-a26, wherein the alkali metal oxide is greater than or equal to 5 mol% and less than or equal to 13 mol%.

A twenty-eighth aspect A28 includes the glass composition of any one of the first to twenty-seventh aspects A1-A27, wherein Li₂O is 3 mol% or more and 10 mol% or less.

A twenty-ninth aspect A29 includes the glass composition of the twenty-eighth aspect A28, wherein Li₂O is less than or equal to 8 mol%.

A thirtieth aspect a30 includes the glass composition of any one of the first to twenty-ninth aspects a1-a29, wherein Na₂O is 1 mol% or more and 5 mol% or less.

A thirty-first aspect A31 includes the glass composition of the thirty-first aspect A30 wherein Na₂O is less than 3 mol%.

The thirty-second aspect A32 includes the glass composition of the thirty-first aspect A30 wherein Na₂O is less than 2.5 mol%.

A thirty-third aspect a33 includes the glass composition of the thirty-third aspect a30 wherein Na₂O is less than 2.0 mol%.

A thirty-fourth aspect A34 includes the glass composition of any one of the first to thirty-third aspects A1-A33 wherein K₂O is 1 mol% or more and 7 mol% or less.

A thirty-fifth aspect A35 includes the glass composition of the thirty-fourth aspect A34, wherein K₂O is less than 5 mol%.

A thirty-sixth aspect a36 includes the glass composition of any one of the first to thirty-fifth aspects a1-a35, wherein the alkaline earth metal oxide comprises greater than or equal to 4 mol% and less than or equal to 8 mol% MgO and less than or equal to 1 mol% of at least one of CaO, BaO, and SrO.

A thirty-seventh aspect a37 includes the glass composition of the thirty-sixth aspect a36 wherein the alkaline earth oxide includes less than or equal to 0.5 mol% CaO.

A thirty-eighth aspect a38 includes the glass composition of any one of the first to thirty-seventh aspects a1-a37, further comprising greater than or equal to about 0.01 mol% and less than or equal to 0.5 mol% fining agent.

A thirty-ninth aspect A39 includes the glass composition of the thirty-eighth aspect A38 wherein the fining agent is SnO₂。

The fortieth aspect a40 includes the glass composition of any one of the first to thirty-ninth aspects a1-a39, wherein the glass composition has a temperature range of about 20 ℃ to about 300 ℃ of less than or equal to 65 x 10^-7Average coefficient of thermal expansion per deg.C.

A forty-first aspect a41 includes the glass composition of any one of the first to fortieth aspects a1-a40, wherein the glass composition has a temperature range of about 20 ℃ to about 300 ℃ of less than or equal to 62 x 10^-7A temperature of 50 x 10 or higher^-7Average thermal expansion coefficient at/° CAnd (4) counting.

A forty-second aspect a42 includes the glass composition of any one of the first to fortieth aspects a1-a41, wherein the glass composition has a hydrolysis resistance of HGA grade 1 according to ISO720:1985 prior to strengthening by ion exchange.

The forty-third aspect a43 includes the glass composition of the forty-second aspect a42, wherein the glass composition has a hydrolysis resistance according to ISO720:1985 of HGA grade 1 after strengthening by ion exchange.

A forty-fourth aspect a44 includes the glass composition of any one of the first to forty-third aspects a1-a43, wherein the glass composition has an alkali resistance of grade a1 or grade a2 according to ISO695:1991 prior to strengthening by ion exchange.

The forty-fifth aspect a45 includes the forty-fourth aspect a44 glass composition wherein the glass composition has an alkali resistance of grade a1 or grade a2 according to ISO695:1991 after strengthening by ion exchange.

The forty-sixth aspect a46 includes the glass composition of any one of the first to forty-fifth aspects a1-a45, wherein the glass composition has an acid resistance of grade S2 or grade S1 according to DIN12116(2001) prior to strengthening by ion exchange.

The forty-seventh aspect a47 includes the forty-sixth aspect a46 glass composition wherein the glass composition has an acid resistance of grade S2 or grade S1 according to DIN12116(2001) after strengthening by ion exchange.

A forty-eighth aspect a48 is a glass pharmaceutical package formed from the glass composition of any one of the first through forty-seventh aspects a1-a 47.

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

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

Detailed Description

Reference will now be made in detail to various embodiments of the chemically durable aluminosilicate glass compositions. According to one embodiment, a glass composition may include: 71 mol% or more and 83 mol% or less of SiO₂(ii) a1 mol% or more and 11 mol% or less of Al₂O₃(ii) a Greater than or equal to 5 mol% and less than or equal to 18 mol% of an alkali metal oxide comprising greater than 3 mol% Li₂O and Na₂O and K₂At least one of O; greater than or equal to 1 mol% and less than or equal to 8 mol% of an alkaline earth oxide comprising MgO and at least one of CaO, BaO, and SrO; and TiO₂、ZrO₂、HfO₂、La₂O₃And Y₂O₃At least one of (1), wherein TiO₂+ZrO₂+HfO₂+La₂O₃+Y₂O₃Greater than 0 mol% and less than or equal to 6 mol%, and Al₂O₃+TiO₂+ZrO₂+HfO₂+La₂O₃+Y₂O₃2 mol% or more and 12 mol% or less. Various embodiments of aluminosilicate glass compositions and their properties will be described in further detail herein with reference to illustrative examples.

The term "softening point" as used herein means that the viscosity of the glass composition is 1X 10^7.6Temperature at poise.

As used herein, the term "annealing point" refers to a viscosity of the glass composition of 1X 10¹³Temperature at poise.

As used herein, the terms "strain point" and "T_{Strain of}"means that the viscosity of the glass composition is 3X 10¹⁴Temperature at poise.

The term "liquidus temperature" as used herein refers to the highest temperature at which crystals can coexist with molten glass in a glass melt at thermodynamic equilibrium.

The elastic modulus (also referred to as young's modulus) of the glass composition is provided in gigapascals (GPa) units. The elastic modulus of the glass was determined by resonance ultrasonic spectroscopy on a large number of samples of each glass composition according to ASTM C623.

The term "CTE" as used herein refers to the coefficient of thermal expansion of the glass composition over a temperature range of about 20 ℃ to about 300 ℃.

Shear modulus was measured by resonance ultrasound spectroscopy according to ASTM C623.

Strain and anneal points were measured according to ASTM C598 based on the Beam bending viscometry, which measures from 10 for inorganic glasses as a function of temperature¹²To 10¹⁴Viscosity of poise.

The softening point is measured according to the parallel position viscometry, which measures from 10 for inorganic glasses as a function of temperature, similar to ASTM C1351M⁷To 10⁹Viscosity of poise.

The liquidus temperature is measured using a gradient furnace method according to ASTM C829-81.

Compressive stresses, including surface compressive stresses, are measured using a surface stress meter (FSM) [ e.g., a commercially available instrument such as FSM-6000 manufactured by Orihara Industrial co. Surface stress measurements depend on the accurate measurement of the Stress Optical Coefficient (SOC) related to the birefringence of the glass. SOC was further measured according to protocol C (Glass disk Method) described in ASTM Standard C770-16 entitled "Standard Test Method for measuring Glass Stress-Optical Coefficient", which is hereby incorporated by reference in its entirety. Depth of compression (DOC) is also measured with FSM. The maximum Central Tension (CT) value was measured using the scattered light polarizer (scapp) technique known in the art.

The phrase "depth of compression" and the abbreviation "DOC" refer to the location in the glass where compressive stress is converted into tensile stress.

In embodiments of the glass compositions described herein, the constituent components (e.g., SiO) unless otherwise specified₂、Al₂O₃And the like) are specified in mole percent (mol%) based on the oxide.

When the terms "free" and "substantially free" are used to describe the concentration of a particular constituent component in a glass composition and/or to describe its absence in a glass composition, it is intended that the constituent component is not intentionally added to the glass composition. However, the glass composition may contain trace constituent components as contaminants or inclusions in an amount of less than 0.01 mol%.

The term "chemical durability" as used herein refers to the ability of a glass composition to resist deterioration after exposure to specified chemical conditions. Specifically, the chemical durability of the glass compositions described herein is evaluated according to three established material testing standards: DIN12116 entitled "Testing of glass-Resistance to attack by a binding aqueous solution of hydrochloric acid-Method of test and classification" in 3.2001; ISO695:1991 entitled "Glass- -Resistance to attack by adhesion of aqueous solution of mixed bases of mixed alkali of mixture of viscosity and classification"; and ISO720:1985 entitled "Glass- -Hydraulic resistance of Glass grains at 121degrees C- -Method of test and classification (Glass- -hydrolysis resistance of Glass particles at 121 ℃ C. - -test Method and classification)". In addition to the above-mentioned reference standards, the chemical durability of the Glass can also be evaluated according to ISO 719:1985 "Glass- -hydraulic resistance of Glass grains at 98degrees C- -Method of test and classification (Glass- -hydrolysis resistance of Glass particles at 98 ℃ C. - -test Method and classification)". The ISO 719 standard is a less stringent version of the ISO720 standard, and thus it is believed that a given class of glass that conforms to the ISO720 standard should also conform to a corresponding class of the ISO 719 standard. The categories associated with each criterion will be described in further detail herein.

The term "colorless" as used herein means that a sample of the glass composition having a thickness of 10mm has a transmission of greater than 80% in the visible portion of the electromagnetic spectrum (i.e., wavelengths from 380nm to 740 nm).

Ranges can be expressed herein as from "about" one particular value, and/or to "about" another particular value. When such a range is expressed, another embodiment includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent "about," it will be understood that the particular value forms another embodiment. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint.

Directional terms used herein, such as upper, lower, left, right, front, rear, top, bottom, are used only with reference to the drawings, and are not intended to imply absolute orientations.

Unless specifically stated otherwise, any methods described herein should not be construed as requiring that their steps be performed in a particular order, or that any apparatus be specifically oriented. Accordingly, if a method claim does not actually recite an order to be followed by its steps, or any apparatus does not actually recite an order or orientation to the components, or it is not otherwise specifically stated in the claims or descriptions that the steps are to be limited to a specific order, or a specific order or orientation to the components of an apparatus is not recited, then no order or orientation is to be inferred, in any respect. This applies to any possible non-expressive basis for interpretation, including: a logical problem related to the arrangement of steps, a flow of operations, an order of components, or an orientation of components; obvious meaning derived from grammatical organization or punctuation, and quantity or type of implementation described in the specification.

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

Because of the tendency of boron containing glasses to delaminate, aluminosilicate glasses have been investigated as alternatives to conventional type 1B aluminoborosilicate glasses. Although aluminosilicate glasses have been identified as being spall resistant, having excellent chemical durability, and being strengthened by ion exchange processes, the spall resistant aluminosilicate glasses of the present disclosure may be strengthened by ion exchange, and may be strengthened by the addition of TiO₂、ZrO₂、HfO₂、La₂O₃And Y₂O₃At least one of (a) to further enhance chemical durability.

In embodiments of the glass compositions described herein, SiO₂Is the largest component of the composition and is therefore the major component of the resulting glass network. I.e. SiO₂Is the primary network former. SiO 2₂The chemical durability of the glass, specifically, the decomposition resistance of the glass composition in acid and the decomposition resistance of the glass composition in water are enhanced. Therefore, high SiO is generally desirable₂And (4) concentration. However, if SiO₂Too high, the formability of the glass may be reduced because of the higher concentration of SiO₂Increasing the difficulty of melting the glass and adversely affecting the formability of the glass.

In embodiments described herein, the glass composition comprises greater than or equal to 71 mol% SiO₂To enhance the chemical durability of the glass composition. SiO 2₂The amount may be less than or equal to 83 mole percent so that the glass composition can be easily melted and shaped. Thus, in the embodiments described herein, the glass composition comprises SiO₂The amount of (a) is generally greater than or equal to 71 mol% and less than or equal to 83 mol%. In embodiments, the SiO in the glass composition₂The lower limit of the amount of (B) may be greater than or equal toEqual to 72 mol%, greater than or equal to 73 mol%, greater than or equal to 74 mol%, greater than or equal to 75 mol%, or even greater than or equal to 76 mol%. In embodiments, the SiO in the glass composition₂The upper limit of the amount of (b) may be less than or equal to 82 mole%, less than or equal to 81 mole%, less than or equal to 80 mole%, or even less than or equal to 79 mole%. It is understood that SiO in the glass composition₂In amounts that can be found in the SiO described herein₂Any one of the lower limits of (1) and SiO₂Within a range formed by any of the upper limits of (1).

For example, and without limitation, in embodiments, the glass composition may include greater than or equal to 72 mol% and less than or equal to 79 mol% SiO₂. In embodiments, the glass composition may include greater than or equal to 73 mol% and less than or equal to 79 mol% SiO₂. In embodiments, the glass composition may include greater than or equal to 72 mol% and less than or equal to 78 mol% SiO₂. In embodiments, the glass composition may include greater than or equal to 73 mol% and less than or equal to 78 mol% SiO₂. In embodiments, the glass composition may include greater than or equal to 74 mol% and less than or equal to 79 mol% SiO₂. In embodiments, the glass composition may include greater than or equal to 74 mol% and less than or equal to 78 mol% SiO₂。

The glass compositions described herein may further include Al₂O₃。Al₂O₃Can be used as a network forming agent and a modifying agent. For example, Al₂O₃With alkali metal oxides (e.g. Li) present in the glass composition₂O、Na₂O and/or K₂O) together improve the sensitivity of the glass to ion exchange strengthening. Addition of Al to glass composition₂O₃The chemical durability of the glass is also improved. However, if Al is present in the glass composition₂O₃Too high, the acid erosion resistance of the glass composition is reduced. Further, if Al is contained in the glass composition₂O₃Too high an amountLa in the glass₂O₃And ZrO₂May decrease in solubility (when the glass includes these ingredients).

In the embodiments described herein, the glass composition includes Al₂O₃Is greater than or equal to 1 mol% to enhance the ion-exchangeable property of the glass composition. Al (Al)₂O₃Is less than or equal to 11 mole percent so that the acid erosion resistance of the glass composition is not reduced. Thus, in the embodiments described herein, the glass composition comprises Al₂O₃The amount of (B) is generally greater than or equal to 1 mol% and less than or equal to 11 mol%. In an embodiment, Al in the glass composition₂O₃The lower limit of the amount of (d) may be greater than or equal to 2 mole%, greater than or equal to 3 mole%, greater than or equal to 4 mole%, greater than or equal to 5 mole%, or even greater than or equal to 6 mole%. In an embodiment, Al in the glass composition₂O₃The upper limit of the amount of (b) may be less than or equal to 10 mole%, less than or equal to 9 mole%, or even less than or equal to 8 mole%. It is understood that Al in the glass composition₂O₃In amounts that can be described herein for Al₂O₃Any one of the lower limits of (1) and Al₂O₃Within a range formed by any of the upper limits of (1).

For example, and not by way of limitation, Al is included in the glass compositions described herein₂O₃The amount of (c) may be greater than or equal to 2 mol% and less than or equal to 8 mol%. In an embodiment, Al in the glass composition₂O₃The amount of (b) is greater than or equal to 4 mol% and less than or equal to 8 mol%. In some embodiments, Al in the glass composition₂O₃The amount of (b) is greater than or equal to 5 mol% to less than or equal to 7 mol%. In an embodiment, Al in the glass composition₂O₃The amount of (b) is greater than or equal to 6 mol% to less than or equal to 8 mol%.

The glass compositions described herein also include alkali metal oxides, e.g., Li₂O、Na₂O and/or K₂And O. Alkali metal oxide promoted glassIon-exchangeable property of the composition. As described in further detail herein, alkali metal oxides may also enhance other properties of the glass. In embodiments described herein, the glass composition may include at least one alkali metal oxide, e.g., Li₂O、Na₂O and/or K₂At least one of O. In some embodiments described herein, the alkali metal oxide may include Li₂O and Na₂O and K₂At least one of O. In some embodiments described herein, the amount of alkali metal oxide can be greater than 2 mole% and less than or equal to 18 mole%. In embodiments, the lower limit of the amount of alkali metal oxide in the glass composition may be greater than or equal to 2 mole%, greater than or equal to 3 mole%, greater than or equal to 4 mole%, greater than or equal to 5 mole%, greater than or equal to 6 mole%, greater than or equal to 7 mole%, or even greater than or equal to 8 mole%. In embodiments, the upper limit of the amount of alkali metal oxide in the glass composition may be less than or equal to 18 mole%, less than or equal to 17 mole%, less than or equal to 16 mole%, less than or equal to 15 mole%, less than or equal to 14 mole%, less than or equal to 13 mole%, less than or equal to 12 mole%, or even less than or equal to 11 mole%. It is to be understood that the amount of alkali metal oxide in the glass composition can be within a range formed by any of the lower limits of the alkali metal oxide described herein and any of the upper limits of the alkali metal oxide.

For example, and without limitation, the glass composition may include alkali metal oxide in an amount greater than or equal to 5 mol% and less than or equal to 15 mol%. In an embodiment, the amount of alkali metal oxide in the glass composition is greater than or equal to 5 mol% and less than or equal to 13 mol%. In embodiments, the amount of alkali metal oxide in the glass composition is greater than or equal to 6 mol% to less than or equal to 18 mol%. In an embodiment, the amount of alkali metal oxide in the glass composition is greater than or equal to 6 mol% and less than or equal to 15 mol%. In an embodiment, the amount of alkali metal oxide in the glass composition is greater than or equal to 6 mol% and less than or equal to 13 mol%. In embodiments, the amount of alkali metal oxide in the glass composition is greater than or equal to 7 mol% to less than or equal to 18 mol%. In an embodiment, the amount of alkali metal oxide in the glass composition is greater than or equal to 7 mol% and less than or equal to 15 mol%. In an embodiment, the amount of alkali metal oxide in the glass composition is greater than or equal to 7 mol% and less than or equal to 13 mol%. In an embodiment, the amount of alkali metal oxide in the glass composition is greater than or equal to 8 mol% and less than or equal to 18 mol%. In an embodiment, the amount of alkali metal oxide in the glass composition is greater than or equal to 8 mol% and less than or equal to 15 mol%. In an embodiment, the amount of alkali metal oxide in the glass composition is greater than or equal to 8 mol% and less than or equal to 13 mol%. In an embodiment, the amount of alkali metal oxide in the glass composition is greater than or equal to 9 mol% and less than or equal to 18 mol%. In an embodiment, the amount of alkali metal oxide in the glass composition is greater than or equal to 9 mol% and less than or equal to 15 mol%. In an embodiment, the amount of alkali metal oxide in the glass composition is greater than or equal to 9 mol% and less than or equal to 13 mol%. In embodiments, the amount of alkali metal oxide in the glass composition is greater than or equal to 10 mol% to less than or equal to 18 mol%. In an embodiment, the amount of alkali metal oxide in the glass composition is greater than or equal to 10 mol% and less than or equal to 15 mol%. In an embodiment, the amount of alkali metal oxide in the glass composition is greater than or equal to 10 mol% and less than or equal to 13 mol%.

The glass compositions described herein include an alkali metal oxide, Li₂O。Li₂O provides a mechanism for strengthening glass by ion exchange. Specifically, Li is added to the glass₂O improves the kinetics of the ion exchange process and reduces the time for the ion exchange process to achieve the desired surface compressive stress and depth of compression at a given ion exchange temperature. It is also considered that Li is added to the glass composition₂O, the amount of stored energy in the glass composition after ion exchange is greater. Li₂O-further strengthened glass compositionSome other property of (a). For example, Li₂The addition of O lowers the softening point of the glass, thereby improving the formability of the glass. Because of Li₂O offsets the higher SiO₂The amount of (A) causes an increase in the melting point of the glass, for a composition comprising a larger amount of SiO₂For the glass composition of (1), Li₂The addition of O is particularly advantageous. Li₂The addition of O also reduces the coefficient of thermal expansion of the glass composition. Reducing the coefficient of thermal expansion improves the survivability of the glass under thermal cycling or thermal stress conditions compared to glass compositions having a relatively higher coefficient of thermal expansion. Finally, Li₂The addition of O improves the hydrolysis resistance of the glass, thereby providing a glass with higher chemical durability.

Li present in glass compositions₂The amount of O may be greater than 0 mole%, for example, greater than or equal to 3 mole%. In embodiments, Li is present in the glass composition₂The amount of O may be greater than or equal to 3 mol% and less than or equal to 10 mol%. In an embodiment, Li in the glass composition₂The lower limit of the amount of O may be greater than or equal to 4 mole%, greater than or equal to 5 mole%, or even greater than or equal to 6 mole%. In an embodiment, Na in the glass composition₂The upper limit of the amount of O may be less than or equal to 9 mole%, less than or equal to 8 mole%, less than or equal to 7 mole%, less than or equal to 6 mole%, less than or equal to 5 mole%, or even less than or equal to 4 mole%. It is understood that Li in the glass composition₂The amount of O can be Li as described herein₂Any of the lower limits of O and Li₂Any of the upper limits of O.

For example and without limitation, Li is included in the glass compositions described herein₂The amount of O may be greater than or equal to 3 mol% and less than or equal to 9 mol%. In an embodiment, Li in the glass composition₂The amount of O is greater than or equal to 3 mol% and less than or equal to 8 mol%. In some embodiments, Li in the glass composition₂The amount of O is 4 mol% or more and 10 mol% or less. In an embodiment, Li in the glass composition₂The amount of O is 4 mol% or more and 9 mol% or less. In an embodiment, Li in the glass composition₂The amount of O is 4 mol% or more and 8 mol% or less. In an embodiment, Li in the glass composition₂The amount of O is 5 mol% or more and 10 mol% or less. In an embodiment, Li in the glass composition₂The amount of O is 5 mol% or more and 9 mol% or less. In an embodiment, Li in the glass composition₂The amount of O is 5 mol% or more and 8 mol% or less.

When alkali metal oxide Na is included₂O, alkali metal oxide Na₂O enhances the ion-exchangeable property of the glass composition and improves the meltability of the glass composition. If Na₂If the amount of O is too low, the liquidus temperature of the glass composition may increase, making it difficult to melt the glass composition. However, if Na₂If the concentration of O is too high, the chemical durability of the glass composition is lowered. In the case where the alkali metal oxide comprises Na₂In the O embodiment, Na is present in the glass composition₂The amount of O may be greater than 0 mol%, for example, greater than or equal to 0.5 mol%, and less than or equal to 13 mol%. In an embodiment, Na in the glass composition₂The lower limit of the amount of O may be greater than or equal to 1 mole%, greater than or equal to 1.25 mole%, greater than or equal to 1.5 mole%, greater than or equal to 1.75 mole%, greater than or equal to 2.0 mole%, greater than or equal to 2.25 mole%, greater than or equal to 2.5 mole%, greater than or equal to 2.75 mole%, greater than or equal to 3 mole%, greater than or equal to 3.25 mole%, greater than or equal to 3.5 mole%, or even greater than or equal to 3.75 mole%. In an embodiment, Na in the glass composition₂The upper limit of the amount of O may be less than or equal to 12 mole%, less than or equal to 11 mole%, less than or equal to 10 mole%, less than or equal to 9 mole%, less than or equal to 8 mole%, less than or equal to 7 mole%, less than or equal to 6 mole%, less than or equal to 5 mole%, less than or equal to 4 mole%, less than or equal to 3 mole%, less than or equal to 2.5 mole%, or even less than or equal to 2 mole%. It is understood that Na in the glass composition₂The amount of O can be Na as described herein₂Any one of the lower limits of O and Na₂Any of the upper limits of O.

For example and without limitation, Na is included in the glass compositions described herein₂The amount of O may be greater than or equal to 1 mol% and less than or equal to 12 mol%. In an embodiment, Na in the glass composition₂The amount of O is greater than or equal to 1 mol% and less than or equal to 11 mol%. In an embodiment, Na in the glass composition₂The amount of O is greater than or equal to 1 mol% and less than or equal to 10 mol%. In an embodiment, Na in the glass composition₂The amount of O is greater than or equal to 1 mol% and less than or equal to 9 mol%. In an embodiment, Na in the glass composition₂The amount of O is greater than or equal to 1 mol% and less than or equal to 8 mol%. In an embodiment, Na in the glass composition₂The amount of O is greater than or equal to 1 mol% and less than or equal to 7 mol%. In an embodiment, Na in the glass composition₂The amount of O is greater than or equal to 1 mol% and less than or equal to 6 mol%. In an embodiment, Na in the glass composition₂The amount of O is greater than or equal to 1 mol% and less than or equal to 5 mol%. In an embodiment, Na in the glass composition₂The amount of O is greater than or equal to 1 mol% and less than or equal to 4 mol%. In an embodiment, Na in the glass composition₂The amount of O is greater than or equal to 1 mol% and less than or equal to 3 mol%. In an embodiment, Na in the glass composition₂The amount of O is greater than or equal to 1 mol% and less than or equal to 2.5 mol%. In an embodiment, Na in the glass composition₂The amount of O is greater than or equal to 1 mol% to less than or equal to 2.0 mol%.

As described above, the alkali metal oxide in the glass composition may further include K₂And O. Similar to Na₂O, K present in the glass composition₂The amount of O is also related to the ion-exchangeable property of the glass composition and the meltability of the glass. In particular, as a function of K present in the glass composition₂The amount of O is increased by dissociationThe compressive stress that can be achieved with sub-exchange is reduced. Furthermore, if K₂If the amount of O is too large, the glass composition is difficult to melt. Therefore, it is desirable to limit the K present in the glass composition₂The amount of O.

In the presence of an alkali metal oxide comprising K₂In the O embodiment, K is present in the glass composition₂The amount of O may be greater than 0 mole%, for example, greater than or equal to 0.5 mole%, and less than or equal to 10 mole%. In an embodiment, K in the glass composition₂The lower limit of the amount of O may be greater than or equal to 1 mole%, greater than or equal to 1.25 mole%, greater than or equal to 1.5 mole%, greater than or equal to 1.75 mole%, greater than or equal to 2.0 mole%, greater than or equal to 2.25 mole%, greater than or equal to 2.5 mole%, greater than or equal to 2.75 mole%, greater than or equal to 3 mole%, greater than or equal to 3.25 mole%, greater than or equal to 3.5 mole%, or even greater than or equal to 3.75 mole%. In an embodiment, K in the glass composition₂The upper limit of the amount of O may be less than or equal to 10 mole%, less than or equal to 9 mole%, less than or equal to 8 mole%, less than or equal to 7 mole%, less than or equal to 6 mole%, less than or equal to 5 mole%, less than or equal to 4 mole%, less than or equal to 3 mole%, less than or equal to 2.5 mole%, or even less than or equal to 2 mole%. It is understood that K in the glass composition₂The amount of O can be K as described herein₂Any of the lower limits of O and K₂Any of the upper limits of O.

For example and without limitation, K is included in the glass compositions described herein₂The amount in O may be greater than or equal to 1 mol% to less than or equal to 9 mol%. In an embodiment, K in the glass composition₂The amount of O is greater than or equal to 1 mol% and less than or equal to 8 mol%. In an embodiment, K in the glass composition₂The amount of O is greater than or equal to 1 mol% and less than or equal to 7 mol%. In an embodiment, K in the glass composition₂The amount of O is greater than or equal to 1 mol% and less than or equal to 6 mol%. In an embodiment, K in the glass composition₂The amount of O is greater than or equal to1 mol% or more and 5 mol% or less. In an embodiment, K in the glass composition₂The amount of O is greater than or equal to 1 mol% and less than or equal to 4 mol%. In an embodiment, K in the glass composition₂The amount of O is greater than or equal to 1 mol% and less than or equal to 3 mol%. In an embodiment, K in the glass composition₂The amount of O is greater than or equal to 1 mol% and less than or equal to 2.5 mol%. In an embodiment, K in the glass composition₂The amount of O is greater than or equal to 1 mol% and less than or equal to 2.0 mol%.

In embodiments where the glass composition is used to form a glass article and the glass article is to be subsequently strengthened by ion exchange, Li in the glass article₂The amount of O is greater than the amount of Na present in the glass article₂O in an amount greater than K present in the glass article₂The amount of O. Similarly, Na in the glass product₂The amount of O is greater than the amount of K present in the glass article₂The amount of O. For example, the glass article contains Li₂O、Na₂O and K₂In the case of O, Li₂O (mol%)>Na₂O (mol%)>K₂O (mol%); including Li in glass articles₂O and Na₂In the case of O, Li₂O (mol%) > Na₂O (mol%); and inclusion of Li in the glass article₂O and K₂In the case of O, Li₂O (mol%) > K₂O (mol%).

Alkaline earth metal oxides (e.g., MgO, CaO, BaO, and SrO) may be present in the glass composition to improve the meltability of the glass batch material and increase the chemical durability of the glass composition. In the glass compositions described herein, the total amount (mol%) of alkaline earth metal oxides present in the glass composition is generally less than the total amount (mol%) of alkali metal oxides present in the glass composition to improve the ion-exchangeable properties of the glass composition. In the glass compositions described herein, the alkaline earth metal oxide can include MgO and at least one of CaO, BaO, and SrO.

In some embodiments described herein, the amount of alkaline earth metal oxide can be greater than or equal to 1 mole% and less than or equal to 8 mole%. In embodiments, the lower limit of the amount of alkaline earth metal oxide in the glass composition may be greater than or equal to 2 mole%, greater than or equal to 3 mole%, greater than or equal to 4 mole%, or even greater than or equal to 5 mole%, or even greater than or equal to 6 mole%. In embodiments, the upper limit of the amount of alkaline earth metal oxide in the glass composition may be less than or equal to 8 mole%, less than or equal to 7 mole%, less than or equal to 6 mole%, or even less than or equal to 5 mole%. It is to be understood that the amount of alkaline earth oxide in the glass composition can be within a range formed by any of the lower limits of the alkaline earth oxide described herein and any of the upper limits of the alkaline earth oxide.

For example, and without limitation, the glass composition may include an alkaline earth oxide in an amount greater than or equal to 2 mol% and less than or equal to 8 mol%. In embodiments, the glass compositions described herein may include greater than or equal to 3 mol% and less than or equal to 8 mol% alkaline earth metal oxide. In embodiments, the glass compositions described herein may include greater than or equal to 4 mol% and less than or equal to 8 mol% alkaline earth metal oxide. In embodiments, the glass compositions described herein may include greater than or equal to 5 mol% and less than or equal to 8 mol% alkaline earth metal oxide. In embodiments, the glass compositions described herein may include greater than or equal to 4 mol% and less than or equal to 7 mol% alkaline earth metal oxide. In embodiments, the glass compositions described herein may include greater than or equal to 4 mol% and less than or equal to 6 mol% alkaline earth oxide. In embodiments, the glass compositions described herein may include greater than or equal to 4 mol% and less than or equal to 5 mol% alkaline earth metal oxide.

In embodiments described herein, the alkaline earth oxide in the glass composition comprises MgO. In addition to improving the formability and meltability of the glass composition, MgO may also improve the ion exchange efficiency of the glass composition. MgO also improves La₂O₃And ZrO₂In the case of a glass composition comprising these ingredients.

In some embodiments described herein, the amount of MgO in the glass composition may be greater than or equal to 1 mol.% and less than or equal to 8 mol.%. In embodiments, the lower limit of the amount of MgO in the glass composition may be greater than or equal to 2 mol%, greater than or equal to 3 mol%, greater than or equal to 4 mol%, greater than or equal to 5 mol%, or even greater than or equal to 6 mol%. In embodiments, the upper limit of the amount of MgO in the glass composition may be less than or equal to 7 mol%, less than or equal to 6 mol%, or even less than or equal to 5 mol%. It is understood that the amount of MgO in the glass composition can be within a range formed by any of the lower limits of MgO described herein and any of the upper limits of MgO.

For example, and without limitation, the glass composition may include MgO in an amount greater than or equal to 2 mol% and less than or equal to 8 mol%. In embodiments, the glass compositions described herein may include greater than or equal to 3 mol.% and less than or equal to 8 mol.% MgO. In embodiments, the glass compositions described herein may include greater than or equal to 4 mol.% and less than or equal to 8 mol.% MgO. In embodiments, the glass compositions described herein may include greater than or equal to 2 mol.% and less than or equal to 7 mol.% MgO. In embodiments, the glass compositions described herein may include greater than or equal to 2 mol.% and less than or equal to 6 mol.% MgO. In embodiments, the glass compositions described herein may include greater than or equal to 2 mol.% and less than or equal to 5 mol.% MgO.

In embodiments described herein, the alkaline earth metal oxide in the glass composition may include at least one of CaO, BaO, and SrO in addition to MgO. CaO, BaO, and SrO improve the formability of the glass composition and also improve the chemical durability of the glass composition.

In some embodiments described herein, the total amount of CaO, BaO, and SrO in the glass composition (i.e., CaO (mol%) + BaO (mol%) + SrO (mol%) in the glass composition) may be greater than or equal to 0.10 mol% and less than or equal to 2 mol%. In embodiments, the lower limit of the total amount of CaO, BaO, and SrO in the glass composition may be greater than or equal to 0.15 mol%, greater than or equal to 0.20 mol%, greater than or equal to 0.25 mol%, greater than or equal to 0.30 mol%, greater than or equal to 0.35 mol%, greater than or equal to 0.40 mol%, greater than or equal to 0.45 mol%, or even greater than or equal to 0.50 mol%. In embodiments, the upper limit of the total amount of CaO, BaO, and SrO in the glass composition may be less than or equal to 2 mol%, less than or equal to 1.75 mol%, less than or equal to 1.5 mol%, less than or equal to 1.25 mol%, less than or equal to 1.0 mol%, or even less than or equal to 0.75 mol%. It is to be understood that the total amount of CaO, BaO, and SrO in the glass composition can be within a range formed by any of the lower limits of the total amount of CaO, BaO, and SrO and any of the upper limits of the total amount of CaO, BaO, and SrO described herein.

For example, and without limitation, the total amount of CaO, BaO, and SrO in the glass composition may be greater than or equal to 0.10 mol% and less than or equal to 1.5 mol%. In embodiments, the total amount of CaO, BaO, and SrO in the glass compositions described herein may be greater than or equal to 0.10 mol% and less than or equal to 1.25 mol%. In embodiments, the total amount of CaO, BaO, and SrO in the glass compositions described herein may be greater than or equal to 0.10 mol% and less than or equal to 1.0 mol%. In embodiments, the total amount of CaO, BaO, and SrO in the glass compositions described herein may be greater than or equal to 0.10 mol% and less than or equal to 0.75 mol%.

In the embodiments described herein, the glass composition is generally MgO-rich (i.e., the concentration of MgO in the glass composition is greater than the total concentration of other alkaline earth metal oxides in the glass composition). Forming the glass composition such that the glass composition is rich in MgO improves the hydrolysis resistance of the resulting glass. Furthermore, MgO-rich glass compositions generally exhibit improved ion exchange properties relative to glass compositions rich in other alkaline earth oxides. In particular, MgO-rich glass compositions generally form glasses having greater diffusivity than glass compositions rich in other alkaline earth oxides. Greater diffusivity enables deeper depth of layer formation in the glass. MgO-rich glass compositions are also capable of achieving higher compressive stresses in the surface of the glass than glass compositions rich in other alkaline earth oxides (e.g., CaO, BaO, and SrO, or combinations thereof). Furthermore, it is generally understood that as the ion exchange process proceeds and the alkali ions penetrate deeper into the glass, the maximum compressive stress achieved at the surface of the glass may decrease over time. However, glasses formed from MgO-rich glass compositions exhibit less reduction in compressive stress than glasses formed from glass compositions that are rich in other alkaline earth metal oxides or combinations of other alkaline earth metal oxides (i.e., MgO-poor glasses). Thus, MgO-rich glass compositions can produce higher compressive stress at the surface and have greater depth of compression than glasses that are rich in other alkaline earth oxides or combinations of other alkaline earth oxides.

In order to adequately realize the benefits of MgO in the glass compositions described herein, it has been determined that the ratio of the total concentration of CaO, BaO, and SrO in mole percent relative to the sum of the concentration of CaO, BaO, and SrO and the concentration of MgO (i.e., ((CaO + BaO + SrO)/(CaO + BaO + SrO + MgO)) should be minimized.

The glass compositions described herein may include one or more additional metal oxides to further improve the chemical durability of the glass compositions. In particular, it has been found that the addition of TiO₂、ZrO₂、HfO₂、La₂O₃And Y₂O₃Can further increase the chemical durability of the glass composition to yield a glass composition having good chemical durability prior to ion exchange strengthening, particularly with respect to glass in alkaline solutionChemical durability of glass. It has also been found that the addition of TiO₂、ZrO₂、HfO₂、La₂O₃And Y₂O₃The average coefficient of thermal expansion of the glass composition is advantageously reduced.

Without wishing to be bound by theory, it is believed that the addition of TiO₂、ZrO₂、HfO₂、La₂O₃And Y₂O₃By strengthening Al in the glass composition₂O₃The functionality of (a) improves the properties of the glass. As described herein, Al is added to the glass composition₂O₃The sensitivity of the glass to ion exchange strengthening is improved and the chemical durability of the glass is also improved. Regarding chemical durability, it is considered that Al is added to the glass composition₂O₃The amount of non-bridging oxygen in the glass composition is reduced, thereby improving the chemical durability of the glass. However, it has been found that if Al is present in the glass composition₂O₃Too much, the acid-erosion resistance of the glass composition decreases. It has now been found that, in addition to Al₂O₃In addition, comprise TiO₂、ZrO₂、HfO₂、La₂O₃And Y₂O₃Further reduces the amount of non-bridging oxygen in the glass composition, further improving the chemical durability of the glass over the addition of Al alone₂O₃Chemical durability that can be achieved.

The glass compositions described herein include TiO₂、ZrO₂、HfO₂、La₂O₃And Y₂O₃To further enhance the chemical durability of the glass composition. In embodiments, TiO in the glass composition₂、ZrO₂、HfO₂、La₂O₃And Y₂O₃Total amount of (i.e., TiO)₂(mol%) + ZrO₂(mol%) + HfO₂(mol%) + La₂O₃(mol%) + Y₂O₃(mol%) is greater than 0 mol% and less than or equal to 6 mol%. In factIn embodiments, TiO in the glass composition₂、ZrO₂、HfO₂、La₂O₃And Y₂O₃The lower limit of the total amount of (b) may be greater than or equal to 0.25 mole%, greater than or equal to 0.30 mole%, greater than or equal to 0.35 mole%, greater than or equal to 0.40 mole%, greater than or equal to 0.45 mole%, greater than or equal to 0.50 mole%, greater than or equal to 0.55 mole%, greater than or equal to 0.60 mole%, greater than or equal to 0.65 mole%, greater than or equal to 0.70 mole%, greater than or equal to 0.75 mole%, greater than or equal to 0.80 mole%, greater than or equal to 0.85 mole%, greater than or equal to 0.90 mole%, greater than or equal to 0.95 mole%, or even greater than or equal to 1.0 mole%. In embodiments, TiO in the glass composition₂、ZrO₂、HfO₂、La₂O₃And Y₂O₃The upper limit of the total amount of (b) may be less than or equal to 5 mole%, less than or equal to 4.5 mole%, less than or equal to 4.0 mole%, less than or equal to 3.5 mole%, less than or equal to 3.0 mole%, less than or equal to 2.5 mole%, or even less than or equal to 2.0 mole%. It is understood that TiO in the glass composition₂、ZrO₂、HfO₂、La₂O₃And Y₂O₃May be TiO as described herein₂、ZrO₂、HfO₂、La₂O₃And Y₂O₃Any one of the lower limits of the total amount of (A) and TiO₂、ZrO₂、HfO₂、La₂O₃And Y₂O₃Within a range formed by any of the upper limits of the total amount of (a).

For example, but not by way of limitation, TiO in the glass composition₂、ZrO₂、HfO₂、La₂O₃And Y₂O₃The total amount of (a) may be greater than or equal to 0.30 mol% and less than or equal to 6 mol%. Although it has been found that TiO can be added to the glass composition₂、ZrO₂、HfO₂、La₂O₃And/or Y₂O₃The chemical durability of the glass composition can be improved, but stillNow individually or together more than 6 mol% TiO₂、ZrO₂、HfO₂、La₂O₃And Y₂O₃May cause a reduction in the formability and acid resistance of the glass. Thus, in embodiments, the TiO in the glass compositions described herein₂、ZrO₂、HfO₂、La₂O₃And Y₂O₃The total amount of (a) may be greater than or equal to 0.30 mol% and less than or equal to 5.5 mol%. In embodiments, the TiO in the glass composition described herein₂、ZrO₂、HfO₂、La₂O₃And Y₂O₃The total amount of (a) may be greater than or equal to 0.30 mol% and less than or equal to 5.0 mol%. In embodiments, the TiO in the glass composition described herein₂、ZrO₂、HfO₂、La₂O₃And Y₂O₃The total amount of (a) may be greater than or equal to 0.30 mol% and less than or equal to 4.5 mol%. In embodiments, the TiO in the glass composition described herein₂、ZrO₂、HfO₂、La₂O₃And Y₂O₃The total amount of (a) may be greater than or equal to 0.30 mol% and less than or equal to 3.0 mol%. In embodiments, the TiO in the glass composition described herein₂、ZrO₂、HfO₂、La₂O₃And Y₂O₃The total amount of (a) may be greater than or equal to 0.30 mol% and less than or equal to 2.5 mol%. In embodiments, the TiO in the glass composition described herein₂、ZrO₂、HfO₂、La₂O₃And Y₂O₃The total amount of (a) may be greater than or equal to 0.30 mol% and less than or equal to 2.0 mol%. In embodiments, the TiO in the glass composition described herein₂、ZrO₂、HfO₂、La₂O₃And Y₂O₃The total amount of (a) may be greater than or equal to 0.30 mol% and less than or equal to 1.5 mol%. In embodiments, the TiO in the glass composition described herein₂、ZrO₂、HfO₂、La₂O₃And Y₂O₃The total amount of (a) may be greater than or equal to 0.30 mol% and less than or equal to 1.0 mol%.

In embodiments, the glass composition may optionally include TiO₂. It has been found that the addition of TiO to the glass composition₂Improves the hydrolysis resistance of the glass composition and improves the ion exchange performance of the glass. Including TiO in glass compositions₂In an embodiment of (1), TiO is present in the glass composition₂The amount may be greater than or equal to 0.01 mole%, greater than or equal to 0.1 mole%, greater than or equal to 0.2 mole%, greater than or equal to 0.3 mole%, greater than or equal to 0.4 mole%, greater than or equal to 0.5 mole%, greater than or equal to 0.6 mole%, greater than or equal to 0.7 mole%, greater than or equal to 0.8 mole%, greater than or equal to 0.9 mole%, greater than or equal to 1.0 mole%, greater than or equal to 1.5 mole%, or even greater than or equal to 2 mole%. In embodiments, TiO in the glass composition₂The upper limit of the amount of (d) can be less than or equal to 6.0 mole%, less than or equal to 5.75 mole%, less than or equal to 5.5 mole%, less than or equal to 5 mole%, less than or equal to 4.5 mole%, less than or equal to 4.0 mole%, less than or equal to 3.5 mole%, less than or equal to 3.0 mole%, less than or equal to 2.5 mole%, or even less than or equal to 2.0 mole%. It is understood that TiO in the glass composition₂In amounts that may be the TiO described herein₂Any one of the lower limits of (1) and TiO₂Within a range formed by any of the upper limits of (1).

For example and without limitation, the glass composition includes TiO₂The amount of (c) may be greater than or equal to 0.01 mol% and less than or equal to 5.5 mol%. In embodiments, the glass compositions described herein may include greater than or equal to 0.01 mol% and less than or equal to 5.0 mol% TiO₂. In embodiments, the glass compositions described herein may include greater than or equal to 0.01 mol% and less than or equal to 4.5 mol% TiO₂. In embodiments, the glass compositions described herein may include greater than or equal to 0.01 mol.% and less than or equal to 4.0 mol.%TiO₂. In embodiments, the glass compositions described herein may include greater than or equal to 0.01 mol% and less than or equal to 3.5 mol% TiO₂. In embodiments, the glass compositions described herein may include greater than or equal to 0.01 mol% and less than or equal to 3.0 mol% TiO₂. In embodiments, the glass compositions described herein may include greater than or equal to 0.01 mol% and less than or equal to 2.5 mol% TiO₂. In embodiments, the glass compositions described herein may include greater than or equal to 0.01 mol% and less than or equal to 2.0 mol% TiO₂. In embodiments, the glass compositions described herein may include greater than or equal to 1.0 mol% and less than or equal to 6.0 mol% TiO₂. In embodiments, the glass compositions described herein may include greater than or equal to 1.0 mol% and less than or equal to 5.5 mol% TiO₂. In embodiments, the glass compositions described herein may include greater than or equal to 1.0 mol% and less than or equal to 5.0 mol% TiO₂. In embodiments, the glass compositions described herein may include greater than or equal to 1.0 mol% and less than or equal to 4.5 mol% TiO₂. In embodiments, the glass compositions described herein may include greater than or equal to 1.0 mol% and less than or equal to 3.0 mol% TiO₂. In embodiments, the glass compositions described herein may include greater than or equal to 1.0 mol% and less than or equal to 2.5 mol% TiO₂. In embodiments, the glass compositions described herein may include greater than or equal to 1.0 mol% and less than or equal to 2.0 mol% TiO₂。

Addition of ZrO to glass compositions₂The alkali resistance of the glass composition is improved without imparting color to the glass composition (i.e., ZrO)₂Helps to maintain the glass "colorless," as determined by the transmittance of the glass). Including ZrO in the glass composition₂In an embodiment of (1), ZrO present in the glass composition₂The amount of (c) may be greater than or equal to 0.01 mol% and less than or equal to 6 mol%. In the embodimentZrO in glass compositions₂The lower limit of the amount of (d) may be greater than or equal to 0.01 mole%, greater than or equal to 0.1 mole%, greater than or equal to 0.2 mole%, greater than or equal to 0.3 mole%, greater than or equal to 0.4 mole%, greater than or equal to 0.5 mole%, greater than or equal to 0.6 mole%, greater than or equal to 0.7 mole%, greater than or equal to 0.8 mole%, greater than or equal to 0.9 mole%, greater than or equal to 1.0 mole%, greater than or equal to 1.5 mole%, or even greater than or equal to 2 mole%. In an embodiment, ZrO in the glass composition₂The upper limit of the amount of (d) can be less than or equal to 6.0 mole%, less than or equal to 5.75 mole%, less than or equal to 5.5 mole%, less than or equal to 5 mole%, less than or equal to 4.5 mole%, less than or equal to 4.0 mole%, less than or equal to 3.5 mole%, less than or equal to 3.0 mole%, less than or equal to 2.5 mole%, or even less than or equal to 2.0 mole%. It is understood that ZrO in the glass composition₂In amounts that can be described herein as ZrO₂Any one of the lower limits of (1) and ZrO₂Within a range formed by any of the upper limits of (1).

For example, but not by way of limitation, ZrO included in the glass composition₂The amount of (c) may be greater than or equal to 0.01 mol% and less than or equal to 5.5 mol%. In embodiments, the glass compositions described herein may include greater than or equal to 0.01 mol% and less than or equal to 5.0 mol% ZrO₂. In embodiments, the glass compositions described herein may include greater than or equal to 0.01 mol% and less than or equal to 4.5 mol% ZrO₂. In embodiments, the glass compositions described herein may include greater than or equal to 0.01 mol% and less than or equal to 4.0 mol% ZrO₂. In embodiments, the glass compositions described herein may include greater than or equal to 0.01 mol% and less than or equal to 3.5 mol% ZrO₂. In embodiments, the glass compositions described herein may include greater than or equal to 0.01 mol% and less than or equal to 3.0 mol% ZrO₂. In embodiments, the glass compositions described herein may include greater than or equal to 0.01 mol% and less than or equal to 2.5 mol% ZrO₂. In embodiments, the glass compositions described herein may include greater than or equal to 0.01 mol% and less than or equal to 2.0 mol% ZrO₂. In embodiments, the glass compositions described herein may include greater than or equal to 1.0 mol% and less than or equal to 6.0 mol% ZrO₂. In embodiments, the glass compositions described herein may include greater than or equal to 1.0 mol% and less than or equal to 5.5 mol% ZrO₂. In embodiments, the glass compositions described herein may include greater than or equal to 1.0 mol% and less than or equal to 5.0 mol% ZrO₂. In embodiments, the glass compositions described herein may include greater than or equal to 1.0 mol% and less than or equal to 4.5 mol% ZrO₂. In embodiments, the glass compositions described herein may include greater than or equal to 1.0 mol% and less than or equal to 3.0 mol% ZrO₂. In embodiments, the glass compositions described herein may include greater than or equal to 1.0 mol% and less than or equal to 2.5 mol% ZrO₂. In embodiments, the glass compositions described herein may include greater than or equal to 1.0 mol% and less than or equal to 2.0 mol% ZrO₂。

Similar to ZrO₂Adding HfO to the glass composition₂The alkali resistance of the glass composition is also improved without imparting color to the glass composition. Including HfO in a glass composition₂In an embodiment, HfO is present in the glass composition₂The amount of (c) may be greater than or equal to 0.01 mol% and less than or equal to 6 mol%. In embodiments, HfO in the glass composition₂The lower limit of the amount of (d) may be greater than or equal to 0.01 mole%, greater than or equal to 0.1 mole%, greater than or equal to 0.2 mole%, greater than or equal to 0.3 mole%, greater than or equal to 0.4 mole%, greater than or equal to 0.5 mole%, greater than or equal to 0.6 mole%, greater than or equal to 0.7 mole%, greater than or equal to 0.8 mole%, greater than or equal to 0.9 mole%, greater than or equal to 1.0 mole%, greater than or equal to 1.5 mole%, or even greater than or equal to 2 mole%. In embodiments, HfO in the glass composition₂Amount of (2)The upper limit of (d) may be less than or equal to 6.0 mole%, less than or equal to 5.75 mole%, less than or equal to 5.5 mole%, less than or equal to 5 mole%, less than or equal to 4.5 mole%, less than or equal to 4.0 mole%, less than or equal to 3.5 mole%, less than or equal to 3.0 mole%, less than or equal to 2.5 mole%, or even less than or equal to 2.0 mole%. It is understood that HfO in the glass composition₂May be HfO as described herein₂Any one of the lower limits of (1) and HfO₂Within a range formed by any of the upper limits of (1).

For example and without limitation, the glass composition includes HfO₂The amount of (c) may be greater than or equal to 0.01 mol% and less than or equal to 5.5 mol%. In embodiments, the glass compositions described herein may include greater than or equal to 0.01 mol% and less than or equal to 5.0 mol% HfO₂. In embodiments, the glass compositions described herein may include greater than or equal to 0.01 mol% and less than or equal to 4.5 mol% HfO₂. In embodiments, the glass compositions described herein may include greater than or equal to 0.01 mol% and less than or equal to 4.0 mol% HfO₂. In embodiments, the glass compositions described herein may include greater than or equal to 0.01 mol% and less than or equal to 3.5 mol% HfO₂. In embodiments, the glass compositions described herein may include greater than or equal to 0.01 mol% and less than or equal to 3.0 mol% HfO₂. In embodiments, the glass compositions described herein may include greater than or equal to 0.01 mol% and less than or equal to 2.5 mol% HfO₂. In embodiments, the glass compositions described herein may include greater than or equal to 0.01 mol% and less than or equal to 2.0 mol% HfO₂. In embodiments, the glass compositions described herein may include greater than or equal to 1.0 mol% and less than or equal to 6.0 mol% HfO₂. In embodiments, the glass compositions described herein may include greater than or equal to 1.0 mol% and less than or equal to 5.5 mol% HfO₂. In embodiments, the glass compositions described herein may include greater than or equal to 1.0 molar% and less than or equal to 5.0 mol% of HfO₂. In embodiments, the glass compositions described herein may include greater than or equal to 1.0 mol% and less than or equal to 4.5 mol% HfO₂. In embodiments, the glass compositions described herein may include greater than or equal to 1.0 mol% and less than or equal to 3.0 mol% HfO₂. In embodiments, the glass compositions described herein may include greater than or equal to 1.0 mol% and less than or equal to 2.5 mol% HfO₂. In embodiments, the glass compositions described herein may include greater than or equal to 1.0 mol% and less than or equal to 2.0 mol% HfO₂。

Adding La to glass composition₂O₃The hydrolysis resistance of the glass composition is improved. In a glass composition comprising La₂O₃In an embodiment of (1), La present in the glass composition₂O₃The amount of (c) may be greater than or equal to 0.01 mol% and less than or equal to 6 mol%. In an embodiment, the La in the glass composition₂O₃The lower limit of the amount of (d) may be greater than or equal to 0.01 mole%, greater than or equal to 0.1 mole%, greater than or equal to 0.2 mole%, greater than or equal to 0.3 mole%, greater than or equal to 0.4 mole%, greater than or equal to 0.5 mole%, greater than or equal to 0.6 mole%, greater than or equal to 0.7 mole%, greater than or equal to 0.8 mole%, greater than or equal to 0.9 mole%, greater than or equal to 1.0 mole%, greater than or equal to 1.5 mole%, or even greater than or equal to 2 mole%. In an embodiment, the La in the glass composition₂O₃The upper limit of the amount of (d) can be less than or equal to 6.0 mole%, less than or equal to 5.75 mole%, less than or equal to 5.5 mole%, less than or equal to 5 mole%, less than or equal to 4.5 mole%, less than or equal to 4.0 mole%, less than or equal to 3.5 mole%, less than or equal to 3.0 mole%, less than or equal to 2.5 mole%, less than or equal to 2.0 mole%, less than or equal to 1.5 mole%, or even less than or equal to 1.0 mole%. It is understood that La in the glass composition₂O₃Can be La as described herein₂O₃Any one of the lower limits of (1) and La₂O₃Within a range formed by any of the upper limits of (1).

For example and without limitation, the glass composition includes La₂O₃The amount of (c) may be greater than or equal to 0.01 mol% and less than or equal to 5.5 mol%. In embodiments, the glass compositions described herein may include greater than or equal to 0.01 mol.% and less than or equal to 5.0 mol.% La₂O₃. In embodiments, the glass compositions described herein may include greater than or equal to 0.01 mol.% and less than or equal to 4.5 mol.% La₂O₃. In embodiments, the glass compositions described herein may include greater than or equal to 0.01 mol.% and less than or equal to 4.0 mol.% La₂O₃. In embodiments, the glass compositions described herein may include greater than or equal to 0.01 mol.% and less than or equal to 3.5 mol.% La₂O₃. In embodiments, the glass compositions described herein may include greater than or equal to 0.01 mol.% and less than or equal to 3.0 mol.% La₂O₃. In embodiments, the glass compositions described herein may include greater than or equal to 0.01 mol.% and less than or equal to 2.5 mol.% La₂O₃. In embodiments, the glass compositions described herein may include greater than or equal to 0.01 mol.% and less than or equal to 2.0 mol.% La₂O₃. In embodiments, the glass compositions described herein may include greater than or equal to 0.01 mol.% and less than or equal to 1.5 mol.% La₂O₃. In embodiments, the glass compositions described herein may include greater than or equal to 0.01 mol.% and less than or equal to 1.0 mol.% La₂O₃. In embodiments, the glass compositions described herein may include greater than or equal to 0.01 mol.% and less than or equal to 2.0 mol.% La₂O₃. In embodiments, the glass compositions described herein may include greater than or equal to 1.0 mol.% and less than or equal to 6.0 mol.% La₂O₃. In embodiments, the glass compositions described herein may include greater than or equal to 1.0 mol.% andless than or equal to 5.5 mol% of La₂O₃. In embodiments, the glass compositions described herein may include greater than or equal to 1.0 mol.% and less than or equal to 5.0 mol.% La₂O₃. In embodiments, the glass compositions described herein may include greater than or equal to 1.0 mol.% and less than or equal to 4.5 mol.% La₂O₃. In embodiments, the glass compositions described herein may include greater than or equal to 1.0 mol.% and less than or equal to 3.0 mol.% La₂O₃. In embodiments, the glass compositions described herein may include greater than or equal to 1.0 mol.% and less than or equal to 2.5 mol.% La₂O₃. In embodiments, the glass compositions described herein may include greater than or equal to 1.0 mol.% and less than or equal to 2.0 mol.% La₂O₃。

Adding Y to a glass composition₂O₃Improves the hydrolysis resistance, acid resistance and alkali resistance of the glass composition. In a glass composition comprising Y₂O₃In an embodiment of (1), Y is present in the glass composition₂O₃The amount of (c) may be greater than or equal to 0.01 mol% and less than or equal to 6 mol%. In an embodiment, Y in the glass composition₂O₃The lower limit of the amount of (d) may be greater than or equal to 0.01 mole%, greater than or equal to 0.1 mole%, greater than or equal to 0.2 mole%, greater than or equal to 0.3 mole%, greater than or equal to 0.4 mole%, greater than or equal to 0.5 mole%, greater than or equal to 0.6 mole%, greater than or equal to 0.7 mole%, greater than or equal to 0.8 mole%, greater than or equal to 0.9 mole%, greater than or equal to 1.0 mole%, greater than or equal to 1.5 mole%, or even greater than or equal to 2 mole%. In an embodiment, Y in the glass composition₂O₃The upper limit of the amount of (b) can be less than or equal to 6.0 mole%, less than or equal to 5.75 mole%, less than or equal to 5.5 mole%, less than or equal to 5 mole%, less than or equal to 4.5 mole%, less than or equal to 4.0 mole%, less than or equal to 3.5 mole%, less than or equal to 3.0 mole%, less than or equal to 2.5 mole%, or even less than or equal toAt 2.0 mol%. It is understood that Y in the glass composition₂O₃May be Y as described herein₂O₃Any one of the lower limits of (1) and Y₂O₃Within a range formed by any of the upper limits of (1).

For example and without limitation, Y included in the glass composition₂O₃The amount of (c) may be greater than or equal to 0.01 mol% and less than or equal to 5.5 mol%. In embodiments, the glass compositions described herein may include greater than or equal to 0.01 mol.% and less than or equal to 5.0 mol.% Y₂O₃. In embodiments, the glass compositions described herein may include greater than or equal to 0.01 mol.% and less than or equal to 4.5 mol.% Y₂O₃. In embodiments, the glass compositions described herein may include greater than or equal to 0.01 mol.% and less than or equal to 4.0 mol.% Y₂O₃. In embodiments, the glass compositions described herein may include greater than or equal to 0.01 mol.% and less than or equal to 3.5 mol.% Y₂O₃. In embodiments, the glass compositions described herein may include greater than or equal to 0.01 mol.% and less than or equal to 3.0 mol.% Y₂O₃. In embodiments, the glass compositions described herein may include greater than or equal to 0.01 mol.% and less than or equal to 2.5 mol.% Y₂O₃. In embodiments, the glass compositions described herein may include greater than or equal to 0.01 mol.% and less than or equal to 2.0 mol.% Y₂O₃. In embodiments, the glass compositions described herein may include greater than or equal to 1.0 mol.% and less than or equal to 6.0 mol.% Y₂O₃. In embodiments, the glass compositions described herein may include greater than or equal to 1.0 mol.% and less than or equal to 5.5 mol.% Y₂O₃. In embodiments, the glass compositions described herein may include greater than or equal to 1.0 mol.% and less than or equal to 5.0 mol.% Y₂O₃. In embodiments, the glass compositions described herein may include greater than or equal to 1.0 mol.% and less thanOr equal to 4.5 mol% of Y₂O₃. In embodiments, the glass compositions described herein may include greater than or equal to 1.0 mol.% and less than or equal to 3.0 mol.% Y₂O₃. In embodiments, the glass compositions described herein may include greater than or equal to 1.0 mol.% and less than or equal to 2.5 mol.% Y₂O₃. In embodiments, the glass compositions described herein may include greater than or equal to 1.0 mol.% and less than or equal to 2.0 mol.% Y₂O₃。

In embodiments, the glass composition may include TiO₂、ZrO₂、HfO₂、La₂O₃And Y₂O₃A combination of at least two of the above. For example, and without limitation, in embodiments, the glass composition may include TiO₂And ZrO₂Combinations of (a) and (b). In these embodiments, the TiO₂+ZrO₂Total amount of (i.e., TiO)₂(mol%) + ZrO₂(mole%)) may be greater than 0 and less than or equal to 6 mole%, greater than 0 and less than or equal to 5 mole%, greater than 0 and less than or equal to 4 mole%, greater than 0 and less than or equal to 3 mole%, greater than 0 and less than or equal to 2 mole%, or even greater than 0 and less than or equal to 1 mole%. As another example, in embodiments, the glass composition may include TiO₂、ZrO₂And HfO₂Combinations of (a) and (b). In these embodiments, the TiO₂+ZrO₂+HfO₂Total amount of (i.e., TiO)₂(mol%) + ZrO₂(mol%) + HfO₂(mole%)) may be greater than 0 and less than or equal to 6 mole%, greater than 0 and less than or equal to 5 mole%, greater than 0 and less than or equal to 4 mole%, greater than 0 and less than or equal to 3 mole%, greater than 0 and less than or equal to 2 mole%, or even greater than 0 and less than or equal to 1 mole%. As another example, in embodiments, the glass composition may include ZrO₂And HfO₂Combinations of (a) and (b). In these embodiments, ZrO₂+HfO₂Total amount of (i.e., ZrO)₂(mol%) + HfO₂(% by mole)) may be more than 0 and 5 or less by mole%, greater than 0 and less than or equal to 4 mole%, greater than 0 and less than or equal to 3 mole%, greater than 0 and less than or equal to 2 mole%, or even greater than 0 and less than or equal to 1 mole%. As another example, in embodiments, the glass composition may include ZrO₂And Y₂O₃Combinations of (a) and (b). In these embodiments, ZrO₂+Y₂O₃Total amount of (i.e., ZrO)₂(mol%) + Y₂O₃(mole%)) may be greater than 0 and less than or equal to 5 mole%, greater than 0 and less than or equal to 4 mole%, greater than 0 and less than or equal to 3 mole%, greater than 0 and less than or equal to 2 mole%, or even greater than 0 and less than or equal to 1 mole%. As another example, in embodiments, the glass composition may include TiO₂And Y₂O₃Combinations of (a) and (b). In these embodiments, the TiO₂+Y₂O₃Total amount of (i.e., TiO)₂(mol%) + Y₂O₃(mole%)) may be greater than 0 and less than or equal to 5 mole%, greater than 0 and less than or equal to 4 mole%, greater than 0 and less than or equal to 3 mole%, greater than 0 and less than or equal to 2 mole%, or even greater than 0 and less than or equal to 1 mole%. As another example, in embodiments, the glass composition may include La₂O₃And Y₂O₃Combinations of (a) and (b). In these embodiments, La₂O₃+Y₂O₃Total amount of (i.e., La)₂O₃(mol%) + Y₂O₃(mole%)) may be greater than 0 and less than or equal to 5 mole%, greater than 0 and less than or equal to 4 mole%, greater than 0 and less than or equal to 3 mole%, greater than 0 and less than or equal to 2 mole%, or even greater than 0 and less than or equal to 1 mole%. As another example, in embodiments, the glass composition may include ZrO₂And La₂O₃Combinations of (a) and (b). In these embodiments, ZrO₂+La₂O₃Total amount of (i.e., ZrO)₂(mol%) + La₂O₃(mol%)) may be greater than 0 and less than or equal to 5 mol%, greater than 0 and less than or equal to 4 mol%, greater than 0 and less than or equal to 3 mol%Greater than 0 and less than or equal to 2 mole percent, or even greater than 0 and less than or equal to 1 mole percent. As another example, in embodiments, the glass composition may include TiO₂And La₂O₃Combinations of (a) and (b). In these embodiments, the TiO₂+La₂O₃Total amount of (i.e., TiO)₂(mol%) + La₂O₃(mole%)) may be greater than 0 and less than or equal to 5 mole%, greater than 0 and less than or equal to 4 mole%, greater than 0 and less than or equal to 3 mole%, greater than 0 and less than or equal to 2 mole%, or even greater than 0 and less than or equal to 1 mole%.

In embodiments of the glass compositions described herein, the Al in the glass composition₂O₃、TiO₂、ZrO₂、HfO₂、La₂O₃And Y₂O₃Total amount of (i.e., Al)₂O₃(mol%) + TiO₂(mol%) + ZrO₂(mol%) + HfO₂(mol%) + La₂O₃(mol%) + Y₂O₃(mol%)) greater than or equal to 2 mol% and less than or equal to 12 mol%, greater than or equal to 3 mol% and less than or equal to 12 mol%, greater than or equal to 4 mol% and less than or equal to 12 mol%, greater than or equal to 5 mol% and less than or equal to 12 mol%, greater than or equal to 6 mol% and less than or equal to 11 mol%, greater than or equal to 6 mol% and less than or equal to 10 mol%, greater than or equal to 6 mol% and less than or equal to 9 mol%, or even greater than or equal to 6 mol% and less than or equal to 8 mol%.

Boron oxide (B)₂O₃) Are glass formers that may be added to the glass composition to reduce the viscosity at a given temperature (e.g., strain temperature, annealing temperature, and softening temperature), thereby improving the formability of the glass. However, it has been found that the addition of boron significantly reduces the diffusivity of sodium and potassium ions in the glass composition, thereby adversely affecting the ion exchange properties of the resulting glass. In particular, it has been found that the glass composition is relatively boron-freeThe addition of boron significantly increases the time required to reach a given depth of compression. Thus, in some embodiments described herein, the amount of boron added to the glass composition is minimized to improve the ion exchange properties of the glass composition.

Can be controlled by controlling B₂O₃Relative to the alkali metal oxide (i.e., R)₂O, where R is an alkali metal) to the difference between the alumina (i.e., B)₂O₃(mol%)/(R)₂O (mol%) -Al₂O₃(mole%)) to mitigate the effect of boron on the ion exchange properties of the glass composition. Specifically, it has been determined that when B₂O₃/(R₂O-Al₂O₃) Is greater than or equal to about 0 and less than about 0.3 or even less than about 0.2, the diffusivity of the alkali metal oxide in the glass composition is not reduced and, thus, the ion exchange performance of the glass composition is maintained. Thus, in some embodiments, B₂O₃/(R₂O-Al₂O₃) Is greater than 0 and less than or equal to 0.3. In some of these embodiments, B₂O₃/(R₂O-Al₂O₃) Is greater than 0 and less than or equal to 0.2. In some embodiments, B₂O₃/(R₂O-Al₂O₃) Is greater than 0 and less than or equal to 0.15, or even less than or equal to 0.1. In some other embodiments, B₂O₃/(R₂O-Al₂O₃) The ratio of (d) may be greater than 0 and less than or equal to 0.05. Maintaining the ratio B₂O₃/(R₂O-Al₂O₃) Less than or equal to 0.3 or even less than or equal to 0.2 allows the inclusion of B₂O₃To lower the strain point, annealing point and softening point of the glass composition, and B₂O₃Without adversely affecting the ion exchange properties of the glass.

In embodiments, the glass composition may optionally include B, as described herein₂O₃To reduce the viscosity of the glass composition at a given temperature. In these casesIn embodiments, the glass composition may include greater than 0 mol% B₂O₃And comprises less than or equal to 3 mol% of B₂O₃So that B is₂O₃Without degrading the ion exchange performance of the glass composition. In an embodiment, B in the glass composition₂O₃Is greater than 0 mole% and less than or equal to 3 mole%, greater than 0 mole% and less than or equal to 2 mole%, or even greater than 0 mole% and less than or equal to 1 mole%. For example, in B₂O₃In embodiments present in the glass composition, B₂O₃The concentration of (b) may be greater than 0.01 mole% and less than or equal to 3 mole%. In some embodiments, B₂O₃The amount present may be greater than or equal to 0.01 mole% and less than or equal to 2 mole%, or even less than or equal to 1.5 mole%. Alternatively, B₂O₃The amount present may be greater than or equal to 1 mole% and less than or equal to 3 mole%, greater than or equal to 1 mole% and less than or equal to 2 mole%, or even greater than or equal to 1 mole% and less than or equal to 1.5 mole%. In some embodiments, B₂O₃The concentration of (b) may be greater than or equal to 0.1 mol% and less than or equal to 1.0 mol%.

Although in some embodiments B in the glass composition₂O₃Is minimized to improve the forming properties of the glass without compromising the ion exchange performance of the glass, but the glass composition in some embodiments is free of boron and boron compounds (e.g., B)₂O₃). In particular, it has been determined that forming glass compositions that are free of boron or boron compounds improves the ion-exchange properties of the glass compositions by reducing the treatment time and/or temperature required to achieve a specified compressive stress value and/or depth of compression.

In the embodiments described herein, the total amount of network formers (i.e., SiO) in the glass composition₂(mol%) + Al₂O₃(mol%) + TiO₂(mol%) + ZrO₂(mol%) + HfO₂(mol%) + La₂O₃(mol%) + Y₂O₃(mol%) + B₂O₃(mol%)) less than or equal to 90 mol%. For example, and without limitation, in embodiments, the total amount of network formers in the glass composition is greater than or equal to 72 mol% and less than or equal to 90 mol%. In an embodiment, the total amount of network formers in the glass composition is greater than or equal to 82 mol% and less than or equal to 88 mol%.

For example, the glass compositions described herein may optionally further comprise one or more fining agents [ e.g., SnO₂、As₂O₃、F^-、Ce₂O₃、Fe₂O₃、H₂O and/or Cl^-(from NaCl or the like)]. When present in the glass composition, the fining agent may be present in an amount less than or equal to 1 mole percent, or even less than or equal to 0.5 mole percent. In embodiments, the fining agent may be present in the glass composition in an amount greater than or equal to 0.01 mol%, or even 0.05 mol%, and less than or equal to 0.5 mol%. In embodiments, the fining agent may be present in the glass composition in an amount greater than or equal to 0.1 mol% and less than or equal to 0.5 mol%. For example, in some embodiments, the glass composition may include SnO₂To act as a clarifying agent. In these embodiments, the SnO present in the glass composition₂The amount may be greater than 0 mole% and less than or equal to 1 mole%, or even greater than or equal to 0.1 mole% and less than or equal to 0.50 mole%.

As described herein, the presence of alkali metal oxides in the glass composition aids in chemically strengthening the glass by ion exchange. In particular, alkali metal ions (e.g., lithium, potassium, and/or sodium ions) are sufficiently mobile in the glass to facilitate ion exchange. In some embodiments, the glass composition is ion-exchangeable to form a compressive stress layer having a depth of layer greater than or equal to 10 μm. In some embodiments, the depth of layer may be greater than or equal to 25 μm, or even greater than or equal to 50 μm. In some other embodiments of the present invention, the substrate is,the depth of layer may be greater than or equal to 75 μm, or even greater than or equal to 100 μm. In other embodiments, the depth of layer may be greater than or equal to 10 μm and less than or equal to 100 μm. 100% molten KNO at a temperature of 350 ℃ to 500 ℃ in a glass composition₃100% molten NaNO₃Or comprising KNO₃And NaNO₃After a treatment time of less than 30 hours or even less than 20 hours in the salt bath of the mixed bath, the associated surface compressive stress may be greater than or equal to 250MPa, greater than or equal to 300MPa, or even greater than or equal to 350 MPa.

Furthermore, as described above, the glass compositions described herein are chemically durable and resistant to degradation in acidic solutions, alkaline solutions, and water, as determined by DIN12116, ISO695, and ISO 720/ISO 719. The chemical durability of the glass composition makes the glass composition particularly suitable as a packaging material, e.g., glass vials, cartridges, ampoules and other containers for packaging pharmaceutical compositions.

Specifically, the DIN12116 standard is a measure of the resistance of the glass to decomposition when the glass is placed in an acidic solution. In brief, the DIN12116 standard utilizes a polished glass sample of known surface area, placed in contact with boiling hydrochloric acid after weighing. The sample was then removed from the solution, dried and weighed again. The glass mass lost during exposure to the acidic solution is a measure of the acid durability of the sample, with lower values indicating greater durability. The results of the tests are reported in units of half the mass per surface area (in particular mg/dm)²). The DIN12116 standard is divided into stages. Grade S1 indicates a weight loss of up to 0.7mg/dm²(ii) a Grade S2 indicating a weight loss of 0.7mg/dm²Up to 1.5mg/dm²(ii) a Grade S3 indicating a weight loss of 1.5mg/dm²Up to 15mg/dm²(ii) a And S4 grade indicates a weight loss of more than 15mg/dm²。

The ISO695 standard is a measure of the resistance of a glass to decomposition when placed in an alkaline solution. Briefly, the ISO695 standard utilizes polished glass samples, which after weighing are placed in boiling NaOH and Na₂CO₃In the solution of (1). Subsequently from the solutionThe sample was removed, dried and weighed again. The glass mass lost during exposure to the alkaline solution is a measure of the alkali durability of the sample, with lower numbers indicating greater durability. As with the DIN12116 standard, the results of the ISO695 standard are reported in units of mass per surface area, in particular mg/dm². The ISO695 standard is divided into stages. Grade A1 shows weight loss up to 75mg/dm²(ii) a Grade A2 representing a weight loss of 75mg/dm²Up to 175mg/dm²(ii) a Grade A3 indicates a weight loss of more than 175mg/dm²。

ISO720 standard is that the glass is placed in the absence of CO₂Is measured for resistance to deterioration in purified water. Briefly, the ISO720 standard protocol utilizes cullet particles that are placed in contact with a CO-free atmosphere of 121 ℃ and 2 atmospheres₂Is contacted with purified water. The solution was then colorimetrically titrated to neutral pH with HCl. Subsequently, the amount of HCl needed for titration to a neutral solution was converted to Na extracted from the glass₂Equivalent of O, and reported as μ g Na₂A smaller value indicates a higher durability in terms of O/glass weight. The ISO720 standard is divided into various types. Type HGA1 denotes Na per gram of glass tested₂The extraction equivalent of O is as much as 62 mug; type HGA2 denotes Na per gram of glass tested₂The extraction equivalent of O is more than 62 μ g and up to 527 μ g; and HGA3 type indicates Na per gram of glass tested₂The extraction equivalent of O is more than 527. mu.g and as much as 930. mu.g.

ISO 719 Standard is glass left free of CO₂Is measured for resistance to deterioration in purified water. Briefly, the ISO 719 standard protocol utilizes cullet particles, which are placed in contact with 98 ℃ and 1 atmosphere of pressure and are free of CO₂Is contacted with purified water. The solution was then colorimetrically titrated to neutral pH using dilute HCl. Subsequently, the amount of HCl needed for titration to a neutral solution was converted to Na extracted from the glass₂Equivalent of O, and reported as μ g Na₂A smaller value indicates a higher durability in terms of O/glass weight. The ISO 719 standard is divided into various types. The ISO 719 standard is divided into various types. HGB1 type represents Na₂The extraction equivalent of O is as much as 31 mug; HGB2 type represents Na₂The extraction equivalent of O is more than 31 μ g and up to 62 μ g; HGB3 type represents Na₂The extraction equivalent of O exceeds 62 μ g and up to 264 μ g; HGB4 type represents Na₂The extraction equivalent of O exceeds 264 mug and is as much as 620 mug; HGB5 type represents Na₂The extraction equivalent of O is over 620 μ g and up to 1085 μ g. The glass compositions described herein have ISO 719 hydrolysis resistance of type HGB2 or higher, and in some embodiments have hydrolysis resistance of type HGB 1.

The glass compositions described herein have acid resistance according to DIN12116 of grade S2 or grade S1 prior to ion exchange strengthening. In embodiments, the glass compositions described herein have acid resistance according to DIN12116, either class S2 or class S1, both before and after ion exchange strengthening. Further, the glass compositions described herein have an alkali resistance of grade a2 or even grade a1 according to ISO695 prior to ion exchange strengthening. In embodiments, the glass compositions described herein have an alkali resistance of grade a2 or even grade a1 according to ISO695 both before and after ion exchange strengthening. The glass compositions described herein have hydrolysis resistance of either the ISO720 HGA2 or HGA1 type prior to ion exchange strengthening. In embodiments, the glass compositions described herein also have hydrolysis resistance of ISO720 type HGA2 or HGA1 before and after ion exchange strengthening. The glass compositions described herein have previously had a hydrolysis resistance of type HGB1 according to ISO 719. In embodiments, the glass compositions described herein have hydrolysis resistance of type HGB1 of ISO 719, both before and after ion exchange strengthening.

In embodiments described herein, the glass composition has a temperature range of less than 65 x 10 ℃ in the range of 20 ℃ to 300 ℃^-7/° c or even less than 62 x 10^-7Average Coefficient of Thermal Expansion (CTE) at/° C. For example, in embodiments, the glass composition has a temperature range of 20 ℃ to 300 ℃ of less than or equal to 62 x 10^-7A temperature of 50 x 10 or higher^-7Average CTE per degree C. These relatively low CTE values improve the survivability of the glass under thermal cycling or thermal stress conditions compared to glass compositions having relatively high CTE.

In embodiments described herein, the glass composition has an elastic modulus of greater than or equal to 75 GPa. For example, in embodiments, the glass composition has an elastic modulus of greater than or equal to 78GPa and less than or equal to 88 GPa. In an embodiment, the glass composition has an elastic modulus greater than or equal to 80GPa and less than or equal to 86 GPa.

In embodiments described herein, the glass composition has a shear modulus of greater than or equal to 30 GPa. For example, in embodiments, the glass composition has a shear modulus of greater than or equal to 30GPa and less than or equal to 40 GPa. In an embodiment, the glass composition has a shear modulus of greater than or equal to 32GPa and less than or equal to 36 GPa.

The glass compositions described herein may generally have a strain point greater than or equal to about 500 ℃ and less than or equal to about 650 ℃ (or even less than or equal to 620 ℃). The glass composition may also have an anneal point greater than or equal to about 550 ℃ and less than or equal to about 725 ℃ (or even less than or equal to 680 ℃). The glass compositions described herein can have a softening point greater than or equal to about 830 ℃ and less than or equal to about 900 ℃. Due to the addition of TiO which may raise the liquidus temperature₂、ZrO₂、HfO₂、La₂O₃And Y₂O₃The glass composition can also have a liquidus temperature greater than or equal to 800 ℃ and less than or equal to 1350 ℃. In embodiments, the liquidus temperature may be less than or equal to 1350 ℃, less than or equal to 1150 ℃, less than or equal to 1000 ℃, or even less than or equal to 900 ℃.

The glass compositions described herein are prepared by combining batches of glass raw materials (e.g., SiO)₂、Al₂O₃Powders of alkali metal oxides, alkaline earth metal oxides, and the like) are mixed so that the batch of glass raw materials has a desired composition. Thereafter, the batch of glass raw materials is heated to form a molten glass composition, followed by cooling and solidification to form the glass composition. The glass composition can be shaped during curing (i.e., when the glass composition can be plastically deformed) using standard shaping techniquesTo shape the glass composition into a desired final form. Alternatively, the glass articles may be formed into stock form (e.g., sheet, tube, or the like), and subsequently reheated and formed into the desired final form.

The glass compositions described herein can be formed into glass articles (e.g., sheets, tubes, or the like) having various forms. However, in view of the chemical durability of the glass compositions, the glass compositions described herein are particularly suitable for forming glass articles that are pharmaceutical packages or pharmaceutical containers that contain pharmaceutical compositions (e.g., liquids, powders, and the like). For example, the glass compositions described herein may be used to form glass containers having various shapes and forms, including but not limited toA cartridge, syringe, ampoule, bottle, flask, vial, tube, beaker, vial or the like. In addition, the ability to chemically strengthen the glass composition by ion exchange can be exploited to improve the mechanical durability of such pharmaceutical packages or glass articles formed from the glass composition. Thus, it is understood that in at least one embodiment, the glass composition is included in a pharmaceutical package to improve the chemical durability and/or mechanical durability of the pharmaceutical package.

Examples

The embodiments described herein will be further clarified by the following examples.

Glass samples listed in table 1 were formed and the properties of each sample were measured. Specifically, the shear modulus (GPa), the elastic modulus (GPa), the strain point (. degree. C.), the annealing point (. degree. C.), the softening point (. degree. C.), the liquidus temperature (. degree. C.), the CTE (. times.10) were determined^-7/° c), hydrolysis resistance according to ISO720, acid resistance according to DIN12116, and alkali resistance according to ISO695 to evaluate the addition of TiO₂、ZrO₂、HfO₂、La₂O₃And Y₂O₃The effect of one or more of (a) on the properties of the glass composition. The properties (measured) of each glass composition are reported in table 2. Practice ofExamples 26-33 are comparative examples (i.e., not including TiO)₂、ZrO₂、HfO₂、La₂O₃And Y₂O₃At least one of the above).

Table 1: glass composition

Table 2: properties of

As shown in Table 2, TiO was added₂Generally improves the hydrolysis resistance of the glass composition while causing a slight increase in the average coefficient of thermal expansion of the glass. ZrO (ZrO)₂The addition of (b) generally improves the alkali resistance of the glass while also reducing the average coefficient of thermal expansion of the glass. HfO₂The addition of (b) improves the alkali resistance and hydrolysis resistance of the glass composition while also reducing the average coefficient of thermal expansion of the glass composition. Y is₂O₃The addition of (b) improves the acid and alkali resistance of the glass composition while maintaining the hydrolysis resistance of the glass at an acceptable level. Adding La into glass₂O₃Glasses are provided having acceptable acid, alkali and hydrolysis resistance.

Examples 1-11 and 17 can be compared with example 26 to illustrate the addition of TiO₂、ZrO₂And HfO₂Thereby improving the chemical durability of the glass composition. In particular, TiO compared to example 26₂、ZrO₂And/or HfO₂Is added and changedThe hydrolysis resistance and alkali resistance of the glass composition are improved, and the glass composition with higher chemical durability is obtained.

Examples 12 and 14 can be compared with example 27 to illustrate the addition of ZrO₂And HfO₂Thereby improving the chemical durability of the glass composition. Specifically, ZrO relative to example 27₂And HfO₂The addition of (b) improves the hydrolysis resistance and alkali resistance of the glass composition, thereby resulting in a glass composition with higher chemical durability.

Examples 13, 15 and 16 can be compared with example 28 to illustrate the addition of ZrO₂And HfO₂Thereby improving the chemical durability of the glass composition, and due to the addition of La₂O₃Thereby improving the chemical durability of the glass composition. Specifically, ZrO relative to example 28₂And HfO₂Addition of (2) and La₂O₃The addition of (b) improves the alkali resistance of the glass composition, thereby resulting in a glass composition with higher chemical durability.

Example 18 can be compared to example 29 to illustrate the improved chemical durability of the glass composition due to the modification to the glass composition of example 29. Specifically, Al is reduced₂O₃And increase ZrO₂、HfO₂And SiO₂The concentration of (a) improves the alkali resistance of the glass composition and lowers the liquidus temperature.

Example 19 can be compared to example 30 to illustrate the improved chemical durability of the glass composition due to the modification to the glass composition of example 30. Specifically, Al is reduced₂O₃And increase ZrO₂、HfO₂And SiO₂The concentration of (a) improves the acid and alkali resistance of the glass composition and lowers the low liquidus temperature.

It will be apparent to those skilled in the art that various modifications and variations can be made to the embodiments described herein without departing from the spirit and scope of the claimed subject matter. Thus, it is intended that the present description cover the modifications and variations of the various embodiments described herein provided they come within the scope of the appended claims and their equivalents.