Glass compositions with improved chemical and mechanical durability

Abstract

To provide chemically and mechanically durable glass compositions and glass articles formed of the glass compositions.SOLUTION: In one embodiment, a glass composition may include about 70 mol% to about 80 mol% of SiO2; about 3 mol% to about 13 mol% of alkaline earth oxide; X mol% of Al2O3; and Y mol% of alkali oxide. The alkali oxide may include Na2O in an amount greater than about 8 mol%. A ratio of Y:X may be greater than 1 and the glass composition may be free of boron and compounds of boron. In some embodiments, the glass composition may also be free of phosphorous and compounds of phosphorous. Glass articles formed of the glass composition may have at least a class S3 acid resistance according to DIN 12116, at least a class A2 base resistance according to ISO 695, and a type HGA1 hydrolytic resistance according to ISO 720.SELECTED DRAWING: None

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This invention claims priority to U.S. Provisional Patent Application No. 61 / 551,163, entitled "Glass Compositions With Improved Chemical and Mechanical Durability," filed October 25, 2011 (Attorney Docket No. SP11-240P), which is incorporated herein by reference in its entirety. [Technical Field]

[0002] FIELD OF THE INVENTION This specification relates generally to glass compositions, and more particularly to glass compositions having chemical and mechanical durability that are suitable for use in pharmaceutical packaging. [Background technology]

[0003] Historically, glass has been used as a preferred material for packaging pharmaceuticals due to its hermeticity, optical clarity, and superior chemical durability compared to other materials. Specifically, glass used in pharmaceutical packaging must have adequate chemical durability so as not to affect the stability of the pharmaceutical composition contained therein. Glasses with suitable chemical durability include those glass compositions that fall within the ASTM standard "Type 1B" glass compositions, which have historically proven chemical durability.

[0004] However, the use of glass for such applications is limited by the mechanical performance of glass. Specifically, in the pharmaceutical industry, glass breakage is a safety concern for end users because broken packages can injure them. Breakage within a filling line can be costly for pharmaceutical manufacturers because nearby, unbroken containers may also contain debris from the broken container and must be discarded. Breakage can also require the filling line to be slowed or stopped, reducing yield. Furthermore, breakage results in the loss of active drug product, increasing costs. Furthermore, non-catastrophic breakage (i.e., glass that is cracked but not broken) can compromise the sterility of the contents, which in turn can result in costly product recalls.

[0005] One approach to improving the mechanical durability of glass packages is to thermally temper them. Thermal tempering strengthens the glass by inducing surface compressive stresses during rapid cooling after forming. This technique works well for glass articles with flat geometries (e.g., windows), glass articles with thicknesses greater than 2 mm, and glass compositions with high thermal expansion. However, pharmaceutical glass packages typically have complex geometries (vials, tubing, ampoules, etc.), thin walls (approximately 1-1.5 mm), and are made of low-expansion glass (30-55×10). -7 K -1 ), which makes glass pharmaceutical packaging unsuitable for strengthening by thermal tempering.

[0006] Chemical tempering also strengthens glass by introducing surface compressive stress. The stress is introduced by immersing the article in a molten salt bath. Ions from the glass are replaced by larger ions from the molten salt, inducing compressive stress within the surface of the glass. The advantages of chemical tempering are that it can be used on complex geometries, thin samples, and is relatively insensitive to the thermal expansion characteristics of the glass substrate. However, glass compositions that are only slightly sensitive to chemical tempering also have low chemical durability, and vice versa. Summary of the Invention [Problem to be solved by the invention]

[0007] Therefore, a need exists for glass compositions that are chemically durable and amenable to chemical strengthening by ion exchange for use in glass pharmaceutical packaging and similar applications. [Means for solving the problem]

[0008] According to one embodiment, the glass composition may include SiO2 at a concentration greater than about 70 mol% and alkali oxides at Y mol%. The alkali oxides may include Na2O in an amount greater than about 8 mol%. The glass composition may be free of boron and boron compounds.

[0009] According to another embodiment, the glass composition may include greater than about 68 mol% SiO, X mol% AlO, Y mol% alkali oxides, and BO. The alkali oxides may include NaO in an amount greater than about 8 mol%. The ratio (BO (mol%) / (Y mol%-X mol%)) may be greater than 0 and less than 0.3.

[0010] In yet another embodiment, the glass article may have a hydrolysis resistance of Type HGB1 according to ISO 719. The glass article may include greater than about 8 mol% Na2O and less than about 4 mol% B2O3.

[0011] In yet another embodiment, the glass pharmaceutical package may include SiO2 in an amount greater than about 70 mol%, Al2O3 in X mol%, and alkali oxides in Y mol%. The alkali oxides may include Na2O in an amount greater than about 8 mol%. The ratio of the concentration (mol%) of B2O3 in the glass pharmaceutical package to (Y mol% - X mol%) may be less than 0.3. The glass pharmaceutical package may have a hydrolysis resistance of Type HGB1 according to ISO 719.

[0012] In another embodiment, the glass composition may include about 70 mol% to about 80 mol% SiO, about 3 mol% to about 13 mol% alkaline earth oxides, X mol% AlO, and Y mol% alkali oxides. The alkali oxides may include NaO in an amount greater than about 8 mol%. The Y:X ratio may be greater than 1, and the glass composition may be free of boron and boron compounds.

[0013] In yet another embodiment, the glass composition may include about 72 mol% to about 78 mol% SiO2, about 4 mol% to about 8 mol% alkaline earth oxides, X mol% Al2O3, and Y mol% alkali oxides. The amount of alkaline earth oxides may be about 4 mol% or more and about 8 mol% or less. The alkali oxides may include Na2O in an amount about 9 mol% or more and about 15 mol% or less. The ratio of Y:X may be greater than 1. The glass composition may be free of boron and boron compounds.

[0014] In yet another embodiment, the glass composition may include about 68 mol% to about 80 mol% SiO, about 3 mol% to about 13 mol% alkaline earth oxides, X mol% AlO, and Y mol% alkali oxides. The alkali oxides may include NaO in an amount greater than about 8 mol%. The glass composition may also include B0. The ratio (B0 (mol%) / (Y mol%-X mol%)) may be greater than 0 and less than 0.3, and the ratio of Y:X may be greater than 1.

[0015] In another embodiment, the glass composition may include about 70 mol% to about 80 mol% SiO, about 3 mol% to about 13 mol% alkaline earth oxides, X mol% AlO, and Y mol% alkali oxides. The alkaline earth oxides may include CaO in an amount of about 0.1 mol% to about 1.0 mol%. X may be about 2 mol% to about 10 mol%. The alkali oxides may include about 0.01 mol% to about 1.0 mol% KO. The ratio of Y:X may be greater than 1. The glass composition may be free of boron and boron compounds.

[0016] In yet another embodiment, the glass composition may include SiO in an amount of about 70 mol% or more and about 80 mol% or less, alkaline earth oxides in an amount of about 3 mol% to about 13 mol%, Al2O3 in an amount of X mol%, and alkali oxides in an amount of Y mol%. The alkali oxides may include Na2O in an amount greater than about 8 mol%. The ratio of the concentration (mol%) of B2O3 to (Y mol% - X mol%) in the glass composition may be less than 0.3. The Y:X ratio may be greater than 1.

[0017] In another embodiment, the glass article may have a hydrolysis resistance of Type HGB1 according to ISO 719. The glass article may also have a hydrolysis resistance of 16 μm at temperatures up to 450° C. 2 1 / hr.

[0018] In yet another embodiment, the glass article may have a hydrolysis resistance of Type HGB1 according to ISO 719. The glass article may also have a depth of layer greater than 25 μm and a surface compressive stress of 350 MPa or greater. The glass article may be strengthened by ion exchange, which may include treating the glass article in a molten salt bath at a temperature of 450° C. or less for a time period of 5 hours or less.

[0019] Additional features and advantages are set forth in the following detailed description, and in part will be readily apparent to those skilled in the art from this description, or may be learned by practicing the embodiments described herein, including the following detailed description, claims, and accompanying drawings.

[0020] It should 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 content and features of the claimed subject matter. The accompanying drawings are included to provide a further understanding of the various embodiments, and are incorporated into and constitute a part of this specification. The drawings illustrate various embodiments described herein and, together with the description, serve to explain the principles and operation of the claimed subject matter. [Brief explanation of the drawings]

[0021] [Figure 1] 1 is a graph depicting the relationship between the alkali oxide to alumina ratio (x-axis) and the strain point, annealing point, and softening point (y-axis) for glass compositions according to the invention and comparative glass compositions. [Figure 2] 1 is a graph depicting the relationship between the alkali oxide to alumina ratio (x-axis) and maximum compressive stress and stress change (y-axis) for glass compositions according to the invention and comparative glass compositions. [Figure 3] 1 is a graph showing the relationship between the alkali oxide to alumina ratio (x-axis) and hydrolysis resistance (y-axis) as determined from ISO 720 standard for glass compositions according to the invention and comparative glass compositions. [Figure 4] 1 is a graph showing the diffusivity D (y-axis) as a function of the (CaO / (CaO+MgO)) ratio (x-axis) for glass compositions according to the invention and comparative glass compositions. [Figure 5] 1 is a graph showing maximum compressive stress (y-axis) as a function of the (CaO / (CaO+MgO)) ratio (x-axis) for glass compositions according to the invention and comparative glass compositions. [Figure 6] 1 is a graph showing the diffusivity D (y-axis) as a function of the (B2O3 / (R2O-Al2O3)) ratio (x-axis) for glass compositions according to the invention and comparative glass compositions. [Figure 7]1 is a graph showing the hydrolysis resistance percentage (y-axis) determined from the ISO 720 standard as a function of the (B2O3 / (R2O-Al2O3)) ratio (x-axis) for glass compositions according to the invention and comparative glass compositions. DETAILED DESCRIPTION OF THE INVENTION

[0022] Reference will now be made in detail to various embodiments of glass compositions that exhibit improved chemical and mechanical durability. Such glass compositions are suitable for use in a variety of applications, including, but not limited to, use as pharmaceutical packaging materials. The glass compositions may also be chemically strengthened to impart increased mechanical durability to the glass. The glass compositions described herein generally may include silica (SiO), alumina (AlO), alkaline earth oxides (e.g., MgO and / or CaO), and alkali oxides (e.g., NaO and / or KO) in amounts that impart chemical durability to the glass composition. Additionally, alkali oxides present in the glass composition facilitate chemical strengthening of the glass composition by ion exchange. Various embodiments of glass compositions are described herein and further illustrated with reference to specific examples.

[0023] As used herein, the term "softening point" refers to the point at which the viscosity of a glass composition reaches 1×10 7.6 This means the temperature at which the force is in poise.

[0024] As used herein, the term "annealing point" refers to the point at which the viscosity of a glass composition reaches 1×10 13 This refers to the temperature at which the volume becomes poise.

[0025] As used herein, the terms "strain point" and "T strain The term "glass composition" refers to a glass composition having a viscosity of 3×10 14 This means the temperature at which the force is in poise.

[0026] As used herein, the term "CTE" refers to the coefficient of thermal expansion of a glass composition over a temperature range from about room temperature (RT) to about 300°C.

[0027] In the glass composition embodiments described herein, concentrations of components (e.g., SiO2, Al2O3, etc.) are specified in mole percentage (mol%) units on an oxide basis unless otherwise specified.

[0028] The terms "free of" and "substantially free of," when used to describe the concentration and / or absence of a particular component in a glass composition, mean that the component is not intentionally added to the glass composition. However, the glass composition may contain trace amounts of the component as a contaminant or adventitious element in amounts less than 0.01 mole percent.

[0029] As used herein, the term "chemical durability" refers to the ability of a glass composition to resist degradation when exposed to specified chemical conditions. Specifically, the chemical durability of the glass compositions described herein was assessed in accordance with three established materials testing standards: DIN 12116, dated March 2001, entitled "Testing of glass—Resistance to attack by a boiling aqueous solution of hydrochloric acid—Method of test and classification"; ISO 695:1991, entitled "Glass—Resistance to attack by a boiling aqueous solution of mixed alkali—Method of test and classification"; and ISO 720:1985, entitled "Glass—Hydrolytic resistance of glass grains at 121 degrees C—Method of test and classification." The chemical durability of glass may also be assessed in accordance with ISO 719:1985, "Glass--Hydrolytic resistance of glass grains at 98 degrees C--Method of test and classification," in addition to the standards mentioned above. The ISO 719 standard is a less stringent version of the ISO 720 standard, and as such, glass that meets the specified classifications in the ISO 720 standard is also considered to meet the corresponding classifications in the ISO 719 standard. The classifications associated with each standard are described in more detail herein.

[0030] The glass compositions described herein are generally alkali aluminosilicate glass compositions that may include a combination of SiO and one or more alkali oxides, such as NaO and / or KO. The glass compositions may also include AlO and at least one alkaline earth oxide. In some embodiments, the glass compositions may be free of boron and boron-containing compounds. The glass compositions are resistant to chemical degradation and are also suitable for chemical strengthening by ion exchange. In some embodiments, the glass compositions may further include small amounts of one or more additional oxides, such as SnO, ZrO, ZnO, TiO, AsO, etc. These components may be added as fining agents and / or to further enhance the chemical durability of the glass composition.

[0031] In embodiments of the glass compositions described herein, SiO is the largest component of the composition and, therefore, the major component of the resulting glass network. SiO enhances the chemical durability of the glass, specifically its resistance to decomposition in acid and in water. Therefore, a high SiO concentration is generally desirable. However, if the SiO content is excessively high, the formability of the glass may decrease because the high SiO concentration increases the glass's melting difficulty, which in turn adversely affects the formability of the glass. In embodiments described herein, the glass composition generally comprises SiO in an amount of at least 67 mol% and at most about 80 mol%, or even at most 78 mol%. In some embodiments, the amount of SiO in the glass composition may be greater than about 68 mol%, greater than about 69 mol%, or even greater than about 70 mol%. In other embodiments, the amount of SiO in the glass composition may be greater than 72 mol%, greater than 73 mol%, or even greater than 74 mol%. For example, in some embodiments, the glass composition may comprise about 68 mol% to about 80 mol%, or even up to about 78 mol% SiO2. In other embodiments, the glass composition may comprise about 69 mol% to about 80 mol%, or even up to about 78 mol% SiO2. In other embodiments, the glass composition may comprise about 70 mol% to about 80 mol%, or even up to about 78 mol% SiO2. In still other embodiments, the glass composition comprises SiO2 in an amount of 70 mol% or more and 78 mol% or less. In some embodiments, SiO2 may be present in the glass composition in an amount of about 72 mol% to about 78 mol%. In other embodiments, SiO2 may be present in the glass composition in an amount of about 73 mol% to about 78 mol%. In other embodiments, SiO2 may be present in the glass composition in an amount of about 74 mol% to about 78 mol%. In still other embodiments, SiO2 may be present in the glass composition in an amount of about 70 mol% to about 76 mol%.

[0032] The glass compositions described herein may further include Al2O3. Al2O3, along with alkali oxides, such as Na2O, present in the glass composition, improve the glass's susceptibility to ion-exchange strengthening. In the embodiments described herein, Al2O3 is present in the glass composition at X mole percent, while alkali oxides are present in the glass composition at Y mole percent. The Y:X ratio in the glass compositions described herein is greater than 1 to promote the aforementioned susceptibility to ion-exchange strengthening. Specifically, the diffusion coefficient or diffusivity D of a glass composition is related to the rate at which alkali ions penetrate into the glass surface during ion exchange. Glasses having a Y:X ratio greater than about 0.9, or even greater than about 1, have greater diffusivities than glasses having a Y:X ratio less than 0.9. Glasses in which the alkali ions have a greater diffusivity can achieve a greater depth of layer for a given ion-exchange time and temperature compared to glasses in which the alkali ions have a lower diffusivity. Furthermore, as the Y:X ratio increases, the strain point, annealing point, and softening point of the glass decrease, making the glass more easily formable. Furthermore, for a given ion-exchange time and ion-exchange temperature, the compressive stress induced in glasses having a Y:X ratio greater than about 0.9 and less than or equal to 2 is generally greater than that produced in glasses having a Y:X ratio less than 0.9 or greater than 2. Thus, in some embodiments, the Y:X ratio is greater than 0.9, or even greater than 1. In some embodiments, the Y:X ratio is greater than 0.9, or even greater than 1, and less than or equal to about 2. In still other embodiments, the Y:X ratio may be greater than or equal to about 1.3 and less than or equal to about 2.0 to maximize the amount of compressive stress induced in the glass for a specified ion-exchange time and a specified ion-exchange temperature.

[0033] However, if the amount of Al2O3 in the glass composition is too high, the resistance of the glass composition to acid attack decreases. Thus, the glass compositions described herein generally include Al2O3 in an amount of about 2 mol% or more and about 10 mol% or less. In some embodiments, the amount of Al2O3 in the glass composition is about 4 mol% or more and about 8 mol% or less. In some other embodiments, the amount of Al2O3 in the glass composition is about 5 mol% or more and about 7 mol% or less. In some other embodiments, the amount of Al2O3 in the glass composition is about 6 mol% or more and about 8 mol% or less. In still other embodiments, the amount of Al2O3 in the glass composition is about 5 mol% or more and about 6 mol% or less.

[0034] The glass composition also includes one or more alkali oxides, such as Na2O and / or KO. The alkali oxides promote the ion exchange capacity of the glass composition, thereby facilitating chemical strengthening of the glass. The alkali oxides may include one or more of Na2O and KO. The alkali oxides are generally present in the glass composition at a total concentration of Y mol%. In some embodiments described herein, Y may be greater than about 2 mol% and less than or equal to about 18 mol%. In some other embodiments, Y may be greater than about 8 mol%, greater than about 9 mol%, greater than about 10 mol%, or even greater than about 11 mol%. For example, in some embodiments described herein, Y is greater than about 8 mol% and less than or equal to about 18 mol%. In still other embodiments, Y may be greater than about 9 mol% and less than or equal to about 14 mol%.

[0035] The ion exchange capacity of a glass composition is primarily imparted to the glass composition by the amount of alkali oxide NaO initially present in the glass composition prior to ion exchange. Accordingly, in embodiments of the glass compositions described herein, the alkali oxide present in the glass composition includes at least NaO. Specifically, to achieve the desired compressive strength and depth of layer in the glass composition upon strengthening by ion exchange, the glass composition includes NaO in an amount of about 2 mol % to about 15 mol %, based on the molecular weight of the glass composition. In some embodiments, the glass composition includes at least about 8 mol % NaO, based on the molecular weight of the glass composition. For example, the concentration of NaO may be greater than 9 mol %, greater than 10 mol %, or even greater than 11 mol %. In some embodiments, the concentration of NaO may be 9 mol % or greater, or even 10 mol % or greater. For example, in some embodiments, the glass composition may include NaO in an amount of about 9 mol % or greater and about 15 mol % or less, or even about 9 mol % or greater and about 13 mol % or less.

[0036] As noted above, the alkali oxides in the glass composition can further include K2O. The amount of K2O present in the glass composition likewise relates to the ion exchange capacity of the glass composition. Specifically, as the amount of K2O present in the glass composition increases, the compressive stress obtainable through ion exchange decreases as a result of the exchange of potassium and sodium ions. Therefore, it is desirable to limit the amount of K2O present in the glass composition. In some embodiments, the amount of K2O is 0 mol% or more and 3 mol% or less. In some embodiments, the amount of K2O is 2 mol% or less, or even 1.0 mol% or less. In embodiments in which the glass composition includes K2O, K2O can be present at a concentration of about 0.01 mol% or more and about 3.0 mol% or less, or even about 0.01 mol% or more and about 2.0 mol% or less. In some embodiments, the amount of K2O present in the glass composition is about 0.01 mol% or more and about 1.0 mol% or less. Therefore, it should be understood that K2O need not be present in the glass composition. However, if K2O is included in the glass composition, the amount of K2O is generally less than about 3 mole percent based on the molecular weight of the glass composition.

[0037] Alkaline earth oxides may be present in the glass composition to improve the meltability of the glass batch materials and increase the chemical durability of the glass composition. In the glass compositions described herein, the total mole percent of alkaline earth oxides present in the glass composition is generally less than the total mole percent of alkali oxides present in the glass composition to improve the ion exchange capacity of the glass composition. In the embodiments described herein, the glass composition generally includes from about 3 mole percent to about 13 mole percent alkaline earth oxides. In some of these embodiments, the amount of alkaline earth oxides in the glass composition may be from about 4 mole percent to about 8 mole percent, or even from about 4 mole percent to about 7 mole percent.

[0038] The alkaline earth oxides in the glass composition may include MgO, CaO, SrO, BaO, or a combination thereof. In some embodiments, the alkaline earth oxides include MgO, CaO, or a combination thereof. For example, in the embodiments described herein, the alkaline earth oxide includes MgO. MgO is present in the glass composition in an amount of about 3 mol% or more and about 8 mol% or less. In some embodiments, MgO may be present in the glass composition in an amount of about 3 mol% or more and about 7 mol% or less, or even 4 mol% or more and about 7 mol% or less, by molecular weight of the glass composition.

[0039] In some embodiments, the alkaline earth oxide may further include CaO. In these embodiments, CaO is present in the glass composition in an amount of about 0 mol % to about 6 mol % or less by weight of the glass composition. For example, the amount of CaO present in the glass composition may be 5 mol % or less, 4 mol % or less, 3 mol % or less, or even 2 mol % or less. In some of these embodiments, CaO may be present in the glass composition in an amount of about 0.1 mol % or more and about 1.0 mol % or less. For example, CaO may be present in the glass composition in an amount of about 0.2 mol % or more and about 0.7 mol % or less, or even about 0.3 mol % or more and about 0.6 mol % or less.

[0040] In the embodiments described herein, the glass compositions are generally rich in MgO (i.e., the concentration of MgO in the glass composition is higher than the concentrations of other alkaline earth oxides in the glass composition, including, but not limited to, CaO). Forming the glass composition so that it is rich in MgO improves the hydrolytic resistance of the resulting glass, particularly after strengthening by ion exchange. Moreover, MgO-rich glass compositions generally exhibit improved ion exchange performance compared to glass compositions rich in other alkaline earth oxides. Specifically, glasses formed from MgO-rich glass compositions generally have a greater diffusivity than glass compositions rich in other alkaline earth oxides, such as CaO. The greater diffusivity allows for the formation of greater depths of layers in the glass. MgO-rich glass compositions also allow for a higher compressive stress to be achieved at the surface of the glass compared to glass compositions rich in other alkaline earth oxides, such as CaO. Furthermore, it is generally understood that as the ion exchange process progresses 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 compressive stress reduction than glasses formed from CaO-rich glass compositions or glass compositions rich in other alkaline earth oxides (i.e., glasses low in MgO). Thus, MgO-rich glass compositions enable glasses with higher surface compressive stresses and greater depths of layer than glasses rich in other alkaline earth oxides.

[0041] To fully realize the benefits of MgO in the glass compositions described herein, it has been determined that the ratio of the concentration of CaO to the sum of the concentrations of CaO and MgO in mole percent (i.e., (CaO / (CaO+MgO)) should be minimized. Specifically, it has been determined that (CaO / (CaO+MgO)) should be 0.5 or less. In some embodiments, (CaO / (CaO+MgO)) is 0.3 or less, or even 0.2 or less. In some other embodiments, (CaO / (CaO+MgO)) may even be 0.1 or less.

[0042] Boron oxide (BO) is a fluxing agent that may be added to reduce the viscosity at a given concentration (e.g., strain, annealing, and softening temperatures) to improve 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, which in turn adversely affects the ion exchange performance of the resulting glass. Specifically, it has been discovered that the addition of boron significantly increases the time required to achieve a given depth of layer compared to a boron-free glass composition. Therefore, in some embodiments described herein, the amount of boron added to the glass composition is minimized to improve the ion exchange performance of the glass composition.

[0043] For example, it has been determined that the effect of boron on the ion exchange performance of a glass composition is mitigated by controlling the ratio of the concentration of B2O3 to the difference between the total concentration of alkali oxides (i.e., R2O, where R is an alkali metal) and the concentration of alumina (i.e., B2O3 (mol %) / (R2O (mol %)-Al2O3 (mol %)). Specifically, it has been determined that when the ratio of 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 alkali oxides in the glass composition is not reduced, and therefore the ion exchange performance of the glass composition is maintained. Accordingly, in some embodiments, the ratio of B2O3 / (R2O In some of these embodiments, the ratio of B2O3 / (R2O-Al2O3) is greater than 0 and less than or equal to 0.3. In some of these embodiments, the ratio of B2O3 / (R2O-Al2O3) is greater than 0 and less than or equal to 0.2. In some embodiments, the ratio of 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, the ratio of B2O3 / (R2O-Al2O3) can be greater than 0 and less than or equal to 0.05. Maintaining a B2O3 / (R2O-Al2O3) ratio less than or equal to 0.3, or even less than or equal to 0.2, allows the inclusion of B2O3 to lower the strain point, annealing point, and softening point of the glass composition without adversely affecting the ion exchange performance of the glass.

[0044] In the embodiments described herein, the concentration of B2O3 in the glass composition is generally about 4 mol% or less, about 3 mol% or less, about 2 mol% or less, or even 1 mol% or less. For example, in embodiments in which B2O3 is present in the glass composition, the concentration of B2O3 may be about 0.01 mol% or more and 4 mol% or less. In some of these embodiments, the concentration of B2O3 may be greater than about 0.01 mol% and 3 mol% or less. In some embodiments, B2O3 may be present in an amount of about 0.01 mol% or more and 2 mol% or less, or even 1.5 mol% or less. Alternatively, B2O3 may be present in an amount of about 1 mol% or more and 4 mol% or less, about 1 mol% or more and 3 mol% or less, or even about 1 mol% or more and 2 mol% or less. In some of these embodiments, the B2O3 concentration may be about 0.1 mol% or more and 1.0 mol% or less.

[0045] In some embodiments, the concentration of B2O3 in the glass composition is minimized to improve the forming characteristics of the glass without impairing the ion exchange performance of the glass, while in some other embodiments, the glass composition is free of boron and boron compounds such as B2O3. Specifically, it has been determined that forming the glass composition without boron and boron compounds improves the ion exchange capacity of the glass composition by reducing the process time and / or temperature required to achieve a particular value of compressive stress and / or depth of layer.

[0046] In some embodiments of the glass compositions described herein, the glass compositions are free of phosphorus and phosphorus-containing compounds, including but not limited to P2O5. Specifically, it has been determined that formulating the glass compositions without phosphorus or phosphorus compounds increases the chemical durability of the glass compositions.

[0047] In addition to SiO, AlO, alkali oxides and alkaline earth oxides, the glass compositions described herein optionally further comprise one or more fining agents, such as SnO, AsO, and / or Cl. -The glass composition may include fining agents (such as from NaCl). When a fining agent is present in the glass composition, the fining agent may be present in an amount of about 1 mol% or less, or even about 0.4 mol% or less. For example, in some embodiments, the glass composition may include SnO2 as a fining agent. In these embodiments, SnO2 may be present in the glass composition in an amount of about 0 mol% or more and about 1 mol% or less, or even about 0.01 mol% or more and about 0.30 mol% or less.

[0048] Additionally, the glass compositions described herein may include one or more additional metal oxides to further improve the chemical durability of the glass composition. For example, the glass composition may further include ZnO, TiO, or ZrO, each of which further improves the glass composition's resistance to chemical attack. In these embodiments, the additional metal oxide may be present in an amount of about 0 mol% or more and about 2 mol% or less. For example, if the additional metal oxide is ZnO, ZnO may be present in an amount of about 1 mol% or more and about 2 mol% or less. If the additional metal oxide is ZrO or TiO, ZrO or TiO may be present in an amount of about 1 mol% or less.

[0049] As noted above, the presence of alkali oxides in the glass composition facilitates chemical strengthening of the glass by ion exchange. Specifically, alkali ions, such as potassium and sodium ions, have sufficient mobility in the glass composition to facilitate ion exchange. In some embodiments, the glass composition has ion exchange capacity to form a compressive stress layer having a depth of layer of 10 μm or greater. In some embodiments, the depth of layer may be about 25 μm or greater, or even about 50 μm or greater. In other embodiments, the depth of layer may be 75 μm or greater, or even 100 μm or greater. In still other embodiments, the depth of layer may be 10 μm or greater and about 100 μm or less. The associated surface compressive stress may be about 250 MPa or greater, 300 MPa or greater, or even about 350 MPa or greater after the glass composition is treated in a salt bath of 100% molten KNO at temperatures between 350°C and 500°C for a time period of less than about 30 hours, or even less than about 20 hours.

[0050] In addition to having improved mechanical properties due to ion exchange strengthening, glass articles formed from the glass compositions described herein may have hydrolysis resistance of HGB2 or even HGB1 under ISO 719 and / or HGA2 or even HGA1 under ISO 720 (as described further herein). In some embodiments described herein, the glass article may have a compressive stress layer extending into the glass article from the surface to a depth of 25 μm or more, or even 35 μm or more. In some embodiments, the depth of layer may be 40 μm or more or even 50 μm or more. The surface compressive stress of the glass article may be 250 MPa or more, 350 MPa or more, or even 400 MPa or more. The glass compositions described herein facilitate achieving the aforementioned depth of layer and surface compressive stress more quickly and / or at lower temperatures than conventional glass compositions due to the enhanced alkali ion diffusivity of the glass compositions described above. For example, depths of layer (i.e., 25 μm or greater) and compressive stresses (i.e., 250 MPa or greater) may be achieved by ion-exchanging the glass article in a molten salt bath of 100% KNO (or a mixed salt bath of KNO and NaNO) at temperatures of 500°C or less, or even 450°C or less, for a time period of 5 hours or less, or even 4.5 hours or less. In some embodiments, the time period for achieving these depths of layer and compressive stresses may be 4 hours or less, or even 3.5 hours or less. The temperature for achieving these depths of layer and compressive stresses may be 400°C or less, or even 350°C or less.

[0051] These improved ion exchange properties are due to the fact that the glass composition has a crystalline structure of about 16 μm at temperatures below 450°C. 2 / hr, and even below 20 μm at temperatures below 450°C. 2 This is achievable with a threshold diffusivity of greater than about 25 μm / hr at temperatures up to 450° C. 2 / hr or more, and 30 μm at temperatures below 450°C 2 In some other embodiments, the threshold diffusivity is about 35 μm / hr at temperatures of 450° C. or less. 2 / hr or more, and 40μm at temperatures below 450℃ 2 In yet another embodiment, the threshold diffusivity is about 45 μm / hr at temperatures up to 450° C. 2 / hr or more, and 50μm at temperatures below 450℃ 2 / hr.

[0052] The glass compositions described herein generally may have a strain point of about 525° C. or more and about 650° C. or less. The glasses may also have an annealing point of about 560° C. or more and about 725° C. or less and a softening point of about 750° C. or more and about 960° C. or less.

[0053] In the embodiments described herein, the glass composition is about 70×10 -7 K -1 Less than about 60 x 10 -7 K -1 These lower CTE values ​​improve the glass's ability to survive thermal cycling or thermal stress conditions compared to glass compositions with higher CTEs.

[0054] Additionally, as noted above, the glass composition is chemically durable and resistant to degradation as determined by DIN 12116, ISO 695 and ISO 720 standards.

[0055] Specifically, the DIN 12116 standard is a measure of the resistance of glass to degradation when placed in an acidic solution. Briefly, the DIN 12116 standard uses a polished glass sample of known surface area, which is weighed and then placed in contact with a proportional amount of 6M boiling hydrochloric acid for six hours. The sample is then removed from the solution, dried, and reweighed. The mass of glass lost during exposure to the acidic solution is a measure of the sample's acid resistance, with smaller numbers representing greater resistance. The test results are expressed as half mass per surface area, specifically mg / dm 2 The DIN 12116 standard is subdivided into individual classes: Class S1 is 0.7 mg / dm 2Class S2 represents a weight loss of up to 0.7 mg / dm 2 ~1.5mg / dm 2 Class S3 represents a weight loss of 1.5 mg / dm 2 ~15mg / dm 2 Class S4 represents a weight loss of 15 mg / dm 2 represents a weight loss of more than 1000kJ / kg.

[0056] The ISO 695 standard is a measure of the resistance of glass to degradation when placed in a basic solution. Briefly, the ISO 695 standard uses a polished glass sample, which is weighed and then placed in boiling 1M NaOH + 0.5M Na2CO3 for 3 hours. The sample is then removed from the solution, dried, and reweighed. The mass of glass lost during exposure to the basic solution is a measure of the sample's basic durability, with smaller numbers representing greater durability. As with DIN 12116, the ISO 695 results are expressed as mass per surface area, specifically mg / dm 2 The ISO 695 standard is subdivided into individual classes: Class A1 is 75 mg / dm 2 Class A2 represents a weight loss of up to 75 mg / dm 2 ~175mg / dm 2 Class A3 represents a weight loss of 175 mg / dm 2 represents a weight loss of more than 1000kJ / kg.

[0057] The ISO 720 standard is a measure of glass's resistance to degradation in CO2-free purified water. Briefly, the ISO 720 protocol uses crushed glass particles placed in contact with CO2-free purified water for 30 minutes under autoclave conditions (121°C, 2 atm). The solution is then colorimetrically titrated with dilute HCl to a neutral pH. The amount of HCl required to titrate to a neutral solution is then converted to the Na2O equivalent extracted from the glass and reported in μg Na2O per weight of glass, with lower values ​​representing greater durability. The ISO 720 standard is subdivided into individual types. Type HGA1 represents up to 62 μg extracted NaO equivalent per gram of glass tested, Type HGA2 represents greater than 62 μg and up to 527 μg extracted NaO equivalent per gram of glass tested, and Type HGA3 represents greater than 527 μg and up to 930 μg extracted NaO equivalent per gram of glass tested.

[0058] The ISO 719 standard is a measure of glass's resistance to degradation in CO2-free purified water. Briefly, the ISO 719 protocol uses crushed glass particles placed in contact with CO2-free purified water at 98°C for 30 minutes at 1 atmosphere of pressure. The solution is then colorimetrically titrated with dilute HCl to a neutral pH. The amount of HCl required to titrate to a neutral solution is then converted to the Na2O equivalent extracted from the glass and reported in μg Na2O per weight of glass, with lower values ​​representing greater durability. The ISO 719 standard is subdivided into individual types. Type HGB1 represents up to 31 μg of extracted NaO equivalent, Type HGB2 represents greater than 31 μg and up to 62 μg of extracted NaO equivalent, Type HGB3 represents greater than 62 μg and up to 264 μg of extracted NaO equivalent, Type HGB4 represents greater than 264 μg and up to 620 μg of extracted NaO equivalent, and Type HGB5 represents greater than 620 μg and up to 1085 μg of extracted NaO equivalent. The glass compositions described herein have an ISO 719 hydrolysis resistance of Type HGB2 or greater, with some embodiments having the hydrolysis resistance of Type HGB1.

[0059] The glass compositions described herein have an acid resistance of at least Class S3 according to DIN 12116 both before and after ion-exchange strengthening, with some embodiments having an acid resistance of at least Class S2, or even Class S1, after ion-exchange strengthening. In some other embodiments, the glass compositions may have an acid resistance of at least Class S2 both before and after ion-exchange strengthening, with some embodiments having an acid resistance of Class S1 after ion-exchange strengthening. Additionally, the glass compositions described herein have a base resistance according to ISO 695 of at least Class A2 both before and after ion-exchange strengthening, with some embodiments having a base resistance of at least Class A1 after ion-exchange strengthening. The glass compositions described herein also have a hydrolysis resistance of ISO 720 Type HGA2 both before and after ion-exchange strengthening, with some embodiments having a hydrolysis resistance of Type HGA1 after ion-exchange strengthening, and some other embodiments having a hydrolysis resistance of Type HGA1 both before and after ion-exchange strengthening. The glass compositions described herein have an ISO 719 hydrolysis resistance of Type HGB2 or greater, with some embodiments having a hydrolysis resistance of Type HGB1. When referring to the above classifications according to DIN 12116, ISO 720, and ISO 719, a glass composition or glass article having "at least" the specified classification should be understood to mean that the performance of the glass composition is as good as or better than the specified classification. For example, a glass article having a DIN 12116 acid resistance of "at least Class S2" may have a DIN 12116 classification of either S1 or S2.

[0060] The glass compositions described herein are formed by mixing a batch of glass frits (e.g., powders of SiO, AlO, alkali oxides, alkaline earth oxides, etc.) in a manner such that it has a desired composition. The batch of glass frits is then heated to form a molten glass composition, which is then cooled and solidified to form the glass composition. During solidification (i.e., while the glass composition is plastically deformable), the glass composition may be shaped using standard forming techniques to form it into the desired final shape. Alternatively, the glass article may be formed into a stock form, such as a sheet, tube, etc., and then reheated and formed into the desired final shape.

[0061] The glass compositions described herein may be formed into glass articles having various forms, such as sheets, tubes, etc. However, due to the chemical durability of the glass compositions, the glass compositions described herein are highly suitable for use in forming glass articles used as pharmaceutical packages or containers for containing pharmaceutical compositions, such as liquids and powders. For example, the glass compositions described herein may be used to form glass containers having various shapes and forms, including, but not limited to, Vacutainers®, cartridges, syringes, ampoules, bottles, flasks, phials, test tubes, beakers, vials, etc. Moreover, the ability to chemically strengthen the glass compositions through ion exchange can be utilized to improve the mechanical durability of such pharmaceutical packages or glass articles formed from the glass compositions. Thus, it should be understood that in at least one embodiment, the glass compositions are incorporated into pharmaceutical packaging to improve the chemical and mechanical durability of the pharmaceutical packaging. [Example]

[0062] The embodiments of the glass compositions described herein are more clearly illustrated by the following examples.

[0063] Example 1 Six exemplary glass compositions according to the present invention (Compositions A-F) were prepared. The specific composition of each exemplary glass composition is reported in Table 1 below. Multiple samples were fabricated for each exemplary glass composition. One set of samples of each composition was ion-exchanged in a molten salt bath of 100% KNO at a temperature of 450°C for at least 5 hours to induce a compressive layer within the surface of the sample. The compressive layer had a surface compressive stress of at least 500 MPa and a layer depth of at least 45 μm.

[0064] The chemical durability of each exemplary glass composition was then determined using the aforementioned DIN 12116, ISO 695, and ISO 720 standards. Specifically, non-ion-exchanged test samples of each exemplary glass composition were subjected to testing according to one of the DIN 12116, ISO 695, or ISO 720 standards to determine the sample's acid resistance, base resistance, or hydrolysis resistance, respectively. The hydrolysis resistance of ion-exchanged samples of each exemplary composition was determined according to the ISO 720 standard. To determine the hydrolysis resistance of the ion-exchanged samples, the glasses were crushed to the particle size required in the ISO 720 standard, ion-exchanged in a molten salt bath of 100% KNO at a temperature of 450°C for at least 5 hours to induce a compressive stress layer within the individual glass particles, and then tested according to the ISO 720 standard. The average results for all samples are reported below in Table 1.

[0065] As shown in Table 1, all exemplary glass compositions A-F had a solubility of 1 mg / dm after testing according to DIN 12116. 2 Over 5 mg / dm 2 Exemplary glass composition E exhibits a glass mass loss of less than 1.2 mg / dm 2 The glass compositions had a minimum glass mass loss of 0.01g. Thus, each of the exemplary glass compositions was classified in at least Class S3 of the DIN 12116 standard, with exemplary glass composition E being classified in Class S2. Based on these test results, it is believed that the acid resistance of the glass samples improves with increasing SiO2 content.

[0066] Additionally, all exemplary glass compositions A-F had a viscosity of 80 mg / dm after testing according to ISO 695. 2 Exemplary Glass Composition A exhibits a glass mass loss of less than 60 mg / dm 2 The glass compositions had a minimum glass mass loss of 1000 ppm. Thus, each of the exemplary glass compositions was classified in at least Class A2 of the ISO 695 standard, with exemplary glass compositions A, B, D, and F being classified in Class A1. Generally, compositions with higher silica content exhibited lower base resistance, and compositions with higher alkali / alkaline earth content exhibited greater base resistance.

[0067] Table 1 also shows that all non-ion-exchanged test samples of exemplary glass compositions A-F exhibited hydrolysis resistance of at least Type HGA2 after testing according to ISO 720, and exemplary glass compositions C-F possessed hydrolysis resistance of Type HGA1. The hydrolysis resistance of exemplary glass compositions C-F is believed to be due to the presence of higher amounts of SiO2 and lower amounts of Na2O in the glass compositions compared to exemplary glass compositions A and B.

[0068] Moreover, the ion-exchanged test samples of exemplary glass compositions B-F exhibited lower amounts of extractable NaO per gram of glass after testing according to the ISO 720 standard compared to non-ion-exchanged test samples of the same exemplary glass compositions.

[0069] [Table 1]

[0070] Example 2 Three exemplary glass compositions according to the present invention (Compositions G-I) and three comparative glass compositions (Compositions 1-3) were prepared. The ratio of alkali oxide to alumina (i.e., Y:X) was varied in each composition to assess the effect of this ratio on various properties of the resulting glass melts and glasses. The specific compositions of each of the exemplary glass compositions according to the present invention and comparative glass compositions are reported in Table 2. The strain point, annealing point, and softening point of the melts formed from each glass composition were determined and are reported in Table 2. Additionally, the coefficient of thermal expansion (CTE), density, and stress optical coefficient (SOC) of the resulting glasses were also determined and are reported in Table 2. The hydrolysis resistance of glass samples formed from each exemplary glass composition according to the present invention and each comparative glass composition was determined according to ISO 720 standards both before and after ion exchange in a molten salt bath of 100% KNO at 450°C for 5 hours. For these ion-exchanged samples, compressive stress was determined using a fundamental stress meter (FSM) instrument, with compressive stress values ​​based on the measured stress-optical coefficient (SOC). The FSM instrument couples light into and out of the birefringent glass surface. The measured birefringence is then related to stress through the material constant, the stress-optical coefficient or photoelastic coefficient (SOC or PEC), to obtain two parameters: the maximum surface compressive stress (CS) and the depth of exchanged layer (DOL). The diffusivity of alkali ions in the glass and the stress change per square root of time were also determined. The diffusivity (D) of the glass is calculated from the measured depth of layer (DOL) and the ion-exchange time (t) according to the following relationship: DOL = approx. 1.4 * sqrt(4 * D * t). Diffusivities increase with temperature according to the Arrhenius relation and are therefore reported at specific temperatures.

[0071] [Table 2]

[0072] The data in Table 2 demonstrate that the alkali-to-alumina ratio Y:X affects melting behavior, hydrolysis resistance, and the compressive stress obtainable through ion-exchange strengthening. Specifically, Figure 1 graphically depicts the strain point, annealing point, and softening point as a function of Y:X ratio for the glass compositions in Table 2. Specifically, Figure 1 demonstrates that the strain point, annealing point, and softening point of the glass increase rapidly as the Y:X ratio decreases below 0.9. Therefore, to obtain a glass that is readily meltable and formable, the Y:X ratio must be greater than or equal to 0.9, or even greater than 1.

[0073] Furthermore, the data in Table 2 show that the diffusivity of glass compositions generally decreases with the Y:X ratio. Therefore, to achieve a glass that is rapidly ion-exchangeable for the purpose of reducing process time (and cost), the Y:X ratio must be 0.9 or greater, or even 1 or greater.

[0074] Furthermore, Figure 2 shows that for a given ion-exchange time and ion-exchange temperature, the maximum compressive stress is obtained when the Y:X ratio is about 0.9 or greater, even about 1 or greater and about 2 or less, specifically about 1.3 or greater and about 2.0 or less. Thus, the greatest improvement in the load-bearing strength of the glass can be obtained when the Y:X ratio is greater than about 1 and less than or equal to about 2. It is generally understood that the maximum stress achievable by ion-exchange decreases with increasing ion-exchange duration, as reflected by the stress rate change (i.e., the measured compressive stress divided by the square root of the ion-exchange time). Figure 2 shows that the stress rate change generally decreases as the Y:X ratio decreases.

[0075] Figure 3 graphs hydrolytic resistance (y-axis) as a function of Y:X ratio (x-axis). As shown in Figure 3, the hydrolytic resistance of the glass generally improves as the Y:X ratio decreases.

[0076] Based on the above, it should be appreciated that glasses with good melting behavior, better ion exchange performance, and better hydrolysis resistance can be achieved by maintaining the Y:X ratio of the glass at or above about 0.9, and even at or above about 1 and below about 2.

[0077] Example 3 Three exemplary glass compositions according to the invention (compositions J-L) and three comparative glass compositions (compositions 4-6) were prepared. The concentrations of MgO and CaO in the glass compositions were varied to produce both MgO-rich compositions (e.g., compositions J-L and 4) and CaO-rich compositions (i.e., compositions 5-6). The relative amounts of MgO and CaO were also varied such that the glass compositions had different values ​​for (CaO / (CaO+MgO)). The specific compositions of each exemplary glass composition according to the invention and comparative glass compositions are reported below in Table 3. The properties of each composition were determined as described above with respect to Example 2.

[0078] [Table 3]

[0079] FIG. 4 graphically depicts the diffusivity D of the compositions listed in Table 3 as a function of the (CaO / (CaO+MgO)) ratio. Specifically, FIG. 4 demonstrates that as the (CaO / (CaO+MgO)) ratio increases, the diffusivity of alkali ions in the resulting glass decreases, thus degrading the ion exchange performance of the glass. This trend is supported by the data in FIGS. 3 and 5. FIG. 5 graphically depicts the maximum compressive stress and stress change rate (y-axis) as a function of the (CaO / (CaO+MgO)) ratio. FIG. 5 demonstrates that as the (CaO / (CaO+MgO)) ratio increases, the maximum obtainable compressive stress decreases for a given ion exchange temperature and time. FIG. 5 similarly demonstrates that as the (CaO / (CaO+MgO)) ratio increases, the stress change rate increases (i.e., becomes more adverse and less desirable).

[0080] Therefore, based on the data in Table 3 and Figures 4 and 5, it should be understood that glasses with higher diffusivities can be produced by minimizing the (CaO / (CaO+MgO)) ratio. It has been determined that glasses with suitable diffusivities can be produced when the (CaO / (CaO+MgO)) ratio is less than about 0.5. The diffusivity values ​​of glasses with (CaO / (CaO+MgO)) ratios less than about 0.5 shorten the ion-exchange process time required to achieve a given compressive stress and depth of layer. Alternatively, glasses with higher diffusivities due to their (CaO / (CaO+MgO)) ratio may be used to achieve higher compressive stresses and depths of layer for a given ion-exchange temperature and time.

[0081] Furthermore, the data in Table 3 also show that increasing the MgO concentration and decreasing the (CaO / (CaO+MgO)) ratio generally improves the glass's resistance to hydrolytic degradation as measured by the ISO 720 standard.

[0082] Example 4 Three exemplary glass compositions according to the invention (Compositions M-O) and three comparative glass compositions (Compositions 7-9) were prepared. The concentration of B2O3 in the glass compositions was varied from 0 mol% to about 4.6 mol% so that the resulting glasses had different values ​​for the B2O3 / (RO-Al2O3) ratio. The specific compositions of each of the exemplary glass compositions according to the invention and the comparative glass compositions are reported below in Table 4. The properties of each glass composition were determined as described above for Examples 2 and 3.

[0083] [Table 4]

[0084] Figure 6 graphically depicts the diffusivity (D) (y-axis) of the glass compositions in Table 4 as a function of the B2O3 / (R2O-Al2O3) ratio (x-axis) for the glass compositions in Table 4. As shown in Figure 6, the diffusivity of alkali ions in glass generally decreases as the B2O3 / (R2O-Al2O3) ratio increases.

[0085] Figure 7 graphically depicts the hydrolysis resistance according to ISO 720 (y-axis) as a function of the B2O3 / (R2O-Al2O3) ratio (x-axis) for the glass compositions in Table 4. As shown in Figure 6, the hydrolysis resistance of the glass compositions generally improves as the B2O3 / (R2O-Al2O3) ratio increases.

[0086] Based on Figures 6 and 7, it should be understood that minimizing the B2O3 / (R2O-Al2O3) ratio improves the diffusivity of alkali ions in the glass, thereby improving the ion exchange properties of the glass. Furthermore, increasing the B2O3 / (R2O-Al2O3) ratio also generally improves the glass's resistance to hydrolytic degradation. Furthermore, it has been discovered that the glass's resistance to degradation in acidic solutions (as measured by the DIN 12116 standard) generally improves with decreasing B2O3 concentration. Thus, it has been determined that maintaining a B2O3 / (R2O-Al2O3) ratio of about 0.3 or less provides the glass with improved hydrolytic and acid resistance, while also improving its ion exchange properties.

[0087] It should also be appreciated that the glass compositions described herein exhibit chemical and mechanical durability after ion exchange, properties that make them well suited for use in a variety of applications, including, but not limited to, pharmaceutical packaging.

[0088] Based on the foregoing, it should be understood that various embodiments of glass compositions and glass articles formed therefrom are disclosed herein. According to a first embodiment, the glass composition may include SiO2 at a concentration greater than about 70 mol% and an alkali oxide at Y mol%. The alkali oxide may include Na2O in an amount greater than about 8 mol%. The glass composition may be free of boron and boron compounds.

[0089] In a second embodiment, the glass composition of the first embodiment comprises SiO2 in an amount greater than or equal to about 72 mol%.

[0090] In a third embodiment, the glass composition of the first or second embodiment does not contain phosphorus or phosphorus compounds.

[0091] In a fourth aspect, the glass composition of any one of the first to third aspects further comprises X mol% Al2O3, and the Y:X ratio is greater than 1.

[0092] In a fifth embodiment, the Y:X ratio of the glass composition of the fourth embodiment is 2 or less.

[0093] In a sixth embodiment, the amount of Al2O3 in the glass composition of the fourth or fifth embodiment is about 2 mol% or more and about 10 mol% or less.

[0094] In a seventh aspect, the glass composition of any one of the first to fifth aspects further contains about 3 mol % to about 13 mol % of alkaline earth oxides.

[0095] In an eighth embodiment, the alkaline earth oxide of the seventh embodiment comprises MgO and CaO, wherein CaO is present in an amount greater than or equal to about 0.1 mol % and less than or equal to about 1.0 mol %, and the ratio (CaO(mol %) / (CaO(mol %)+MgO(mol %))) is less than or equal to 0.5.

[0096] In a ninth embodiment, the glass composition may include greater than about 68 mol% SiO, X mol% AlO, Y mol% alkali oxides, and BO. The alkali oxides may include NaO in an amount greater than about 8 mol%. The ratio (BO (mol%) / (Y mol%-X mol%)) may be greater than 0 and less than 0.3.

[0097] In a tenth embodiment, the glass composition of the ninth embodiment comprises SiO2 in an amount of about 72 mol% or greater.

[0098] In an eleventh embodiment, the glass composition of the ninth or tenth embodiment includes B2O3 in an amount of about 0.01 mol% or more and about 4 mol% or less.

[0099] In a twelfth embodiment, the glass composition of any one of the ninth to eleventh embodiments has a Y:X ratio of greater than one.

[0100] In a thirteenth embodiment, the Y:X ratio of the twelfth embodiment is 2 or less.

[0101] A fourteenth aspect comprises the glass composition of any one of the ninth to thirteenth aspects, in which X is not less than about 2 mol % and not more than about 10 mol %.

[0102] A fifteenth aspect comprises the glass composition of any one of the ninth to fourteenth aspects, which does not contain phosphorus or phosphorus compounds.

[0103] A sixteenth aspect includes the glass composition of any of the ninth to fifteenth aspects, further comprising MgO and CaO, wherein the CaO is present in an amount of not less than about 0.1 mol % and not more than about 1.0 mol %, and the ratio (CaO (mol %) / (CaO (mol %)+MgO (mol %))) is not more than 0.5.

[0104] In a seventeenth embodiment, the glass article may have a hydrolysis resistance of Type HGB1 according to ISO 719. The glass article may include greater than about 8 mol% Na2O and less than about 4 mol% B2O3.

[0105] In an eighteenth embodiment, the glass article of the seventeenth embodiment further comprises X mol% Al2O3 and Y mol% alkali oxides, wherein the ratio (B2O3 (mol%) / (Y mol%-X mol%)) is greater than 0 and less than 0.3.

[0106] In a nineteenth embodiment, the glass article of any of the seventeenth and eighteenth embodiments further comprises a compressive stress layer having a surface compressive stress of about 250 MPa or more.

[0107] A twentieth aspect includes the glass article of any one of the seventeenth to nineteenth aspects, which has acid resistance according to DIN12116 of at least class S3.

[0108] A twenty-first aspect includes the glass article of any one of the seventeenth to twentieth aspects, which has a base resistance of at least Class A2 according to ISO695.

[0109] A twenty-second aspect includes the glass article of any one of the seventeenth to twenty-first aspects, which has hydrolysis resistance of type HGA1 in accordance with ISO720.

[0110] In a twenty-third embodiment, the glass pharmaceutical package may comprise SiO in an amount greater than about 70 mol%, AlO in an amount of X mol%, and an alkali oxide in an amount of Y mol%. The alkali oxide may comprise NaO in an amount greater than about 8 mol%. The ratio of the concentration (mol%) of BO in the glass pharmaceutical package to (Y mol% - X mol%) may be less than 0.3. The glass pharmaceutical package may also have a hydrolysis resistance of Type HGB1 according to ISO 719.

[0111] A twenty-fourth embodiment includes the glass pharmaceutical package of the twenty-third embodiment, wherein the amount of SiO2 is greater than or equal to 72 mol % and less than or equal to about 78 mol %.

[0112] A twenty-fifth embodiment includes the glass pharmaceutical package of the twenty-third or twenty-fourth embodiment, wherein X is about 4 mol % or more and about 8 mol % or less.

[0113] A twenty-sixth embodiment includes the glass pharmaceutical package of any one of the twenty-third to twenty-fifth embodiments, wherein the ratio of Y:X is greater than one.

[0114] A twenty-seventh embodiment includes the glass pharmaceutical package of any one of the twenty-third to twenty-sixth embodiments, wherein the ratio of Y:X is less than 2.

[0115] A twenty-eighth embodiment includes the glass pharmaceutical package of any of the twenty-third to twenty-seventh embodiments, further comprising about 4 mol % to about 8 mol % of an alkaline earth oxide.

[0116] A twenty-ninth embodiment includes the glass pharmaceutical package of any of the twenty-third to twenty-eighth embodiments, further comprising MgO and CaO, wherein the CaO is present in an amount of from about 0.2 mol % to about 0.7 mol % and the ratio (CaO (mol %) / (CaO (mol %)+MgO (mol %))) is 0.5 or less.

[0117] A thirtieth aspect includes the glass pharmaceutical package of any one of the twenty-third to twenty-ninth aspects, wherein the pharmaceutical package has hydrolysis resistance of Type HGA1 in accordance with ISO720.

[0118] In a thirty-first embodiment, the glass composition may include about 70 mol% to about 80 mol% SiO, about 3 mol% to about 13 mol% alkaline earth oxides, X mol% AlO, and Y mol% alkali oxides. The alkali oxides may include NaO in an amount greater than about 8 mol%. The Y:X ratio may be greater than 1, and the glass composition may be free of boron and boron compounds.

[0119] In a thirty-second embodiment, the glass composition may include about 72 mol% to about 78 mol% SiO2, about 4 mol% to about 8 mol% alkaline earth oxides, X mol% Al2O3, and Y mol% alkali oxides. The amount of alkaline earth oxides may be about 4 mol% or more and about 8 mol% or less. The alkali oxides may include Na2O in an amount of about 9 mol% or more and about 15 mol% or less. The Y:X ratio may be greater than 1. The glass composition may be free of boron and boron compounds.

[0120] In a thirty-third embodiment, the glass composition may include about 68 mol% to about 80 mol% SiO, about 3 mol% to about 13 mol% alkaline earth oxides, X mol% AlO, and Y mol% alkali oxides. The alkali oxides may include NaO in an amount greater than about 8 mol%. The glass composition may include B0. The ratio (B0 (mol%) / (Y mol%-X mol%)) may be greater than 0 and less than 0.3, and the Y:X ratio may be greater than 1.

[0121] In a thirty-fourth embodiment, the glass composition may include about 70 mol% to about 80 mol% SiO, about 3 mol% to about 13 mol% alkaline earth oxides, X mol% AlO, and Y mol% alkali oxides. The alkaline earth oxides may include CaO in an amount of about 0.1 mol% to about 1.0 mol%. X may be about 2 mol% to about 10 mol%. The alkali oxides may include about 0.01 mol% to about 1.0 mol% KO. The Y:X ratio may be greater than 1. The glass composition may be free of boron and boron compounds.

[0122] In a thirty-fifth embodiment, the glass composition may include SiO in an amount of about 70 mol% or more and about 80 mol% or less, alkaline earth oxides in an amount of about 3 mol% to about 13 mol%, AlO in an amount of X mol%, and alkali oxides in an amount of Y mol%. The alkali oxides may include NaO in an amount greater than about 8 mol%. The ratio of the concentration (mol%) of BO in the glass composition to (Y mol% - X mol%) may be less than 0.3. The Y:X ratio may be greater than 1.

[0123] A thirty-sixth embodiment includes the glass composition of any one of the thirty-first to thirty-fifth embodiments, in which SiO2 is present in an amount of 78 mol % or less.

[0124] A thirty-seventh embodiment includes the glass composition of any one of the thirty-first to thirty-sixth embodiments, in which the amount of alkaline earth oxide is not less than about 4 mol % and not more than about 8 mol %.

[0125] A thirty-eighth aspect includes the glass composition of any one of the thirty-first to thirty-seventh aspects, in which the alkaline earth oxides include MgO and CaO, and the (CaO (mol%) / (CaO (mol%)+MgO (mol%))) ratio is 0.5 or less.

[0126] A thirty-ninth embodiment comprises the glass composition of any one of the thirty-first to thirty-eighth embodiments, in which the alkaline earth oxides comprise about 0.1 mol % to about 1.0 mol % or less of CaO.

[0127] A fortieth aspect comprises the glass composition of any one of the thirty-first to thirty-ninth aspects, in which the alkaline earth oxides include about 3 mol % to about 7 mol % of MgO.

[0128] A forty-first embodiment comprises the glass composition of any of the thirty-first, thirty-second, or thirty-fourth embodiments, wherein X is greater than or equal to about 2 mol % and less than or equal to about 10 mol %.

[0129] A forty-second embodiment comprises the glass composition of any one of the thirty-first to forty-first embodiments, in which the alkali oxide comprises about 9 mol % or more and about 15 mol % or less of Na2O.

[0130] A forty-third aspect comprises the glass composition of any one of the thirty-first to forty-second aspects, in which the Y:X ratio is two or less.

[0131] The 44th aspect comprises the glass composition of any one of the 31st to 43rd aspects, in which the Y:X ratio is 1.3 or more and 2.0 or less.

[0132] A forty-fifth embodiment comprises the glass composition of any one of the thirty-first to forty-fourth embodiments, wherein the alkali oxide further comprises K2O in an amount of about 3 mol % or less.

[0133] A forty-sixth aspect comprises the glass composition of any one of the thirty-first to forty-fifth aspects, which does not contain phosphorus or phosphorus compounds.

[0134] A forty-seventh embodiment includes the glass composition of any one of the thirty-first to forty-sixth embodiments, in which the alkali oxide includes K2O in an amount of not less than about 0.01 mol % and not more than about 1.0 mol %.

[0135] A forty-eighth embodiment comprises the glass composition of either the thirty-second or thirty-fourth embodiment, wherein the amount of SiO2 is greater than or equal to about 70 mol %.

[0136] A forty-ninth embodiment comprises the glass composition of either the thirty-second or thirty-fourth embodiment, wherein the (B2O3 (mol %) / (Y mol %-X mol %)) ratio is less than 0.2.

[0137] A fiftieth embodiment comprises the glass composition of either the thirty-second or thirty-fourth embodiment, wherein the amount of B2O3 is less than or equal to about 4.0 mol%.

[0138] A fifty-first embodiment comprises the glass composition of the fiftyth embodiment, wherein the amount of B2O3 is greater than or equal to about 0.01 mol %.

[0139] A fifty-second embodiment comprises the glass composition of the thirty-fourth embodiment, which is free of boron and boron compounds.

[0140] A fifty-third aspect comprises the glass composition of any one of the thirty-first to thirty-fourth aspects, in which the concentration of SiO2 is equal to or greater than about 72 mol %.

[0141] A fifty-fourth aspect comprises the glass composition of any one of the thirty-first to fifty-third aspects, in which the concentration of SiO2 is equal to or greater than about 73 mol %.

[0142] In a fifty-fifth aspect, a glass article is formed from the glass composition of any one of the thirty-first to fifty-fourth aspects.

[0143] A fifty-sixth embodiment includes the glass article of the fifty-fifth embodiment, having hydrolysis resistance of type HGB1 according to ISO 719.

[0144] A fifty-seventh embodiment comprises the glass article of any one of the fifty-fifth or fifty-sixth embodiment, which has hydrolysis resistance of type HGA1 according to ISO720 after being strengthened by ion exchange.

[0145] A fifty-eighth embodiment includes the glass article of any one of the fifty-fifth to fifty-seventh embodiments, which has hydrolysis resistance of type HGA1 according to ISO720 before and after strengthening by ion exchange.

[0146] A fifty-ninth embodiment comprises the glass article of any one of the fifty-fifth to fifty-eighth embodiments, having acid resistance according to DIN12116 of at least class S3.

[0147] A sixtieth aspect includes the glass article of any one of the fifty-fifth to fifty-ninth aspects, which has a base resistance of at least Class A2 according to ISO695.

[0148] A sixty-first embodiment includes the glass article according to any one of the fifty-fifth to sixtieth embodiments, which is a pharmaceutical package.

[0149] A sixty-second embodiment includes the glass article of any one of the fifty-fifth to sixty-first embodiments, which has been strengthened by ion exchange.

[0150] A sixty-third embodiment includes the glass article of any one of the fifty-fifth to sixty-second embodiments, further including a compressive stress layer having a layer depth of 10 μm or more and a surface compressive stress of 250 MPa or more.

[0151] In a sixty-fourth embodiment, the glass article may have a hydrolysis resistance of type HGB1 according to ISO 719. The glass article may also have a hydrolysis resistance of 16 μm at temperatures of 450° C. or less. 2 They may also have a threshold diffusivity above 1 / hr.

[0152] A sixty-fifth aspect is a method for manufacturing a semiconductor device, the method comprising: forming a semiconductor substrate having a threshold diffusivity of 20 μm at a temperature of 450° C. or less; 2 / hr or more.

[0153] A sixty-sixth embodiment comprises the glass article of any one of the sixty-third or sixty-fourth embodiment, which has hydrolysis resistance of type HGA1 according to ISO720 after being strengthened by ion exchange.

[0154] A sixty-seventh embodiment includes the glass article of any one of the sixty-fourth to sixty-sixth embodiments, further including a compressive stress layer having a layer depth of 25 μm or more.

[0155] A sixty-eighth embodiment comprises the glass article of the sixty-seventh embodiment, wherein the depth of layer is greater than 35 μm.

[0156] A sixty-ninth aspect includes the glass article of any of the sixty-third to sixty-eighth aspects, wherein the glass article has been strengthened by ion exchange, the strengthening by ion exchange comprising treating the glass article in a molten salt bath at a temperature of 450°C or less for a time of 5 hours or less.

[0157] A seventieth embodiment includes the glass article of any one of the sixty-third to sixty-ninth embodiments, further including a surface compressive stress of 350 MPa or more.

[0158] A seventy-first embodiment includes the glass article of any one of the sixty-third to seventieth embodiments, which has a surface compressive stress of 400 MPa or more.

[0159] A 72nd aspect includes the glass article of any of the 63rd to 71st aspects, wherein the glass article has been strengthened by ion exchange, the strengthening by ion exchange comprising treating the glass article in a molten salt bath at a temperature of 450°C or less for a time of 5 hours or less.

[0160] A seventy-second embodiment includes the glass article of any one of the sixty-third to seventy-second embodiments, which is a pharmaceutical package.

[0161] In a seventy-third embodiment, the glass article may have a hydrolysis resistance of Type HGB1 according to ISO 719. The glass article may also have a compressive stress layer having a depth of greater than 25 μm and a surface compressive stress of greater than or equal to 350 MPa. The glass article may be subjected to ion-exchange strengthening, which may include treating the glass article in a molten salt bath at a temperature of less than or equal to 450° C. for a time of less than or equal to 5 hours.

[0162] A seventy-fourth embodiment includes the glass article of the seventy-third embodiment, having a hydrolysis resistance of type HGA1 according to ISO 720 after strengthening by ion exchange.

[0163] The 75th embodiment is a method for manufacturing a thin film having a thickness of 16 μm at a temperature of 450° C. or less. 2 The glass article of any one of the seventy-third to seventy-fourth embodiments has a threshold diffusivity of more than 1 / hr.

[0164] A seventy-sixth aspect is a method for manufacturing a semiconductor device having a threshold diffusivity of 20 μm at temperatures below 450° C. 2 / hr or more.

[0165] A 77th embodiment includes the glass article of any one of the 73rd to 76th embodiments, which is a pharmaceutical package.

[0166] 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 this specification cover modifications and variations of the various embodiments described herein, provided that such modifications and variations come within the scope of the appended claims and their equivalents.

[0167] Preferred embodiments of the present invention will be further described below. Embodiment 1 about 72 mol% or more and about 78 mol% or less of SiO2; X mol% Al2O3, where X is greater than or equal to about 5 mol% and less than or equal to about 7 mol%; Y mole percent alkali oxide, said alkali oxide containing NaO in an amount of about 8 mole percent or greater; 1. A glass container comprising: MgO and CaO, wherein CaO is present in an amount up to about 1.0 mol % and the ratio (CaO(mol %) / (CaO(mol %)+MgO(mol %)) is 0.5 or less; A glass container having a hydrolysis resistance of at least HGB2 according to ISO719, characterized in that the ratio of the concentration (mol %) of B2O3 to (Y mol % - X mol %) in the glass container is 0.3 or less. Embodiment 2 about 72 mol% or more and about 78 mol% or less of SiO2; about 4 mol% or more and about 8 mol% or less alkaline earth oxides, said alkaline earth oxides including both MgO and CaO, wherein the ratio (CaO(mol%) / (CaO(mol%)+MgO(mol%))) is 0.5 or less; X mol% Al2O3, where X is greater than or equal to about 5 mol% and less than or equal to about 7 mol%; Y mole % alkali oxide, said alkali oxide comprising NaO in an amount of about 8 mole % or greater, 16 μm at temperatures below 450°C 2 / hr, and the ratio of the concentration (mol %) of B2O3 in the glass container to (Y mol % - X mol %) is 0.3 or less. Embodiment 3 about 72 mol% or more and about 78 mol% or less of SiO2; alkaline earth oxides including both MgO and CaO, wherein CaO is present in an amount up to about 1.0 mol % and the ratio (CaO(mol %) / (CaO(mol %)+MgO(mol %)) is 0.5 or less; X mol% Al2O3, where X is greater than or equal to about 5 mol% and less than or equal to about 7 mol%; 1. A glass container comprising Y mol% alkali oxide, the alkali oxide containing about 0.01 mol% to about 1.0 mol% K2O, wherein the ratio of the concentration (mol%) of B2O3 in the glass container to (Y mol% - X mol%) is 0.3 or less. Embodiment 4 4. The glass container of any one of embodiments 1 to 3, wherein the ratio of Y:X is greater than 1. Embodiment 5 5. The glass container of embodiment 4, wherein the ratio of Y:X is less than 2. Embodiment 6 4. The glass container according to any one of embodiments 1 to 3, wherein the ratio of Y:X is 0.9 or more and less than 2. Embodiment 7 4. The glass container of embodiment 1 or 3, further comprising about 4 mol % to about 8 mol % of an alkaline earth oxide. Embodiment 8 8. The glass container according to any one of embodiments 1 to 7, wherein the glass container does not contain boron or boron compounds. Embodiment 9 8. The glass container of any one of embodiments 1 to 7, wherein the glass container comprises about 0.01 mol % or more and about 4 mol % or less of B2O3. Embodiment 10 10. The glass container of any one of embodiments 1 to 9, wherein the glass container comprises about 13 mol % or less of Na2O. Embodiment 11 The glass container according to any one of embodiments 1 to 10, further comprising a compressive stress layer having a depth of 10 μm or more. Embodiment 12 12. The glass container according to any one of embodiments 1 to 11, wherein the glass container has a surface compressive stress of 250 MPa or more. Embodiment 13 13. The glass container according to any one of embodiments 1 to 12, wherein the surface compression is a stress of 350 MPa or more. Embodiment 14 14. The glass container according to any one of embodiments 1 to 13, wherein the glass container is strengthened by ion exchange. Embodiment 15 20 μm at temperatures below 450°C 2 15. The glass container of any one of embodiments 1 to 14, having a threshold diffusivity of greater than 1 / hr. Embodiment 16 16. The glass container according to any one of embodiments 1 to 15, wherein the glass container has a hydrolysis resistance of at least HGA2 according to ISO720. Embodiment 17 17. The glass container according to any one of embodiments 1 to 16, wherein the glass container has a hydrolysis resistance of at least HGB2 according to ISO719. Embodiment 18 18. The glass container according to any one of the preceding embodiments, wherein the glass container has an acid resistance of at least class S3 according to DIN 12116. Embodiment 19 19. The glass container according to any one of embodiments 1 to 18, wherein the glass container has a base resistance according to ISO 695 of at least class A2. Embodiment 20 20. The glass container according to any one of embodiments 1 to 19, wherein the glass container is a pharmaceutical package.

Claims

1. 68 mol% or more and 80 mol% or less of SiO ２ and, 3 mol% or more and 13 mol% or less of alkaline earth oxides; X mol% Al ２ O ３ and X is 5 mol% or more and less than 7 mol%. ２ O ３ and, Y mol% alkali oxides containing more than 8 mol% Na ２ an alkali oxide containing O and having a Y:X ratio of greater than 1 and less than or equal to 2; B ２ O ３ (B ２ O ３ B. (mol%) / (Y mol%-X mol%) ratio is greater than 0 and less than 0.3; ２ O ３ and 70×10 over a temperature range from room temperature to 300° C. －７ K －１ A glass composition having a coefficient of thermal expansion less than 1000 .mu.m.

2. SiO ２ The glass composition of claim 1 , wherein the amount of is 72 mol % or more.

3. The glass composition of claim 1 , which is free of phosphorus and phosphorus compounds.

4. SiO ２ The glass composition of claim 1 , wherein the amount of is 70 mol % or more.

5. 10. The glass composition of claim 1, comprising at least 4 mol% and at most 8 mol% alkaline earth oxides.

6. 2. The glass composition according to claim 1, wherein the alkaline earth oxides include MgO and CaO, and the ratio of (CaO (mol%) / (CaO (mol%)+MgO (mol%)) is 0.5 or less.

7. 2. The glass composition of claim 1, wherein the alkaline earth oxides include 0.1 mol% or more and 1.0 mol% or less of CaO.

8. 2. The glass composition of claim 1, wherein the alkaline earth oxides include 3 mol% or more and 7 mol% or less of MgO.

9. The alkali oxide is 9 mol % or more and 15 mol % or less of Na ２ The glass composition of claim 1 , further comprising O.

10. (B ２ O ３ 2. The glass composition according to claim 1, wherein the ratio (mol %) / (Y mol %-X mol %) is less than 0.

2.

11. B ２ O ３ The glass composition of claim 1 , wherein the amount of is less than or equal to 4.0 mol %.

12. 10. The glass composition of claim 1, wherein the ratio of Y:X is greater than 1.

3.

13. The alkali oxide has a concentration of 3 mol % or less. ２ The glass composition of claim 1 further comprising O.

14. The alkali oxide has a concentration of 0.01 mol % or more and 1.0 mol % or less. ２ The glass composition of claim 1 further comprising O.

15. 10. A glass article formed from the glass composition of claim 1, wherein the glass article has a hydrolysis resistance according to ISO 719 of at least HGB1.

16. 16. The glass article of claim 15, having a hydrolysis resistance according to ISO 720 of at least HGA1 before and after ion exchange strengthening.

17. 16. A glass article according to claim 15, having an acid resistance of at least class S3 according to DIN 12116.

18. 16. The glass article of claim 15, having a base resistance according to ISO 695 of at least class A2.

19. 16. The glass article of claim 15, wherein the glass article is a pharmaceutical package.

20. 16. The glass article of claim 15, further comprising a compressive stress layer having a layer depth of 10 μm or more and a surface compressive stress of 250 MPa or more.

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