Glass compositions and glass articles

Abstract

The embodiments described herein relate to glass compositions and glass articles formed from the same. An exemplary glass composition may include: greater than or equal to 70 mol.% and less than or equal to 80 mol.% SiO2; greater than or equal to 4 mol.% and less than or equal to 10 mol.% Al2O3; less than or equal to 2.5 mol.% B2O3; alkali oxide; and greater than or equal to 0.2 mol.% and less than or equal to 5 mol.% cerium oxide CeOx, wherein x is greater than or equal to 1.5 and less than or equal to 2. The alkali oxide may include greater than or equal to 5 mol.% and less than or equal to 12 mol.% of Na2O; and Li2O in an amount that is less than or equal to the amount of Al2O3.

Description

GLASS COMPOSITIONS AND GLASS ARTICLESCROSS REFERENCE TO RELATED APPLICATION

[0001] This application claims the benefit of priority of U.S. Provisional Application Serial No. 63 / 592317 filed on October 23, 2023, the content of which is relied upon and incorporated herein by reference in its entirety.FIELD

[0002] The present specification generally relates to glass compositions and, more specifically, to low-coloring and / or anti-coloring glass compositions suitable for use in pharmaceutical packaging.BACKGROUND

[0003] Pharmaceutical companies use optical inspection when filling pharmaceutical products. Amber (colored) glass is used in the pharmaceutical industry for optically sensitive drug products but poses challenges for optical inspection. Optical qualities, e.g., colorless, are desirable traits for glass used in pharmaceutical packages. Accordingly, a need exists for low- coloring and / or anti -coloring glass compositions for use in glass pharmaceutical packages and other applications.SUMMARY

[0004] Various embodiments of glass compositions described herein exhibit low level coloring upon manufacturing of the glass, and minimal color change and / or accelerated transmission recovery / color fading after high levels of irradiation. The glass compositions described herein may be suitable for use in various applications including, without limitation, pharmaceutical packaging applications.

[0005] In some embodiments, a glass composition may include: greater than or equal to 70 mol.% and less than or equal to 80 mol.% SiCh; greater than or equal to 4 mol.% and less than or equal to 10 mol.% AI2O3; less than or equal to 2.5 mol.% B2O3; alkali oxide; and greater than or equal to 0.2 mol.% and less than or equal to 5 mol.% cerium oxide CeOx, wherein x is greater than or equal to 1.5 and less than or equal to 2. The alkali oxide may include: greater than or equal to 5 mol.% and less than or equal to 12 mol.% of Na2O; and Li2O in an amount that is less than or equal to the amount of AI2O3.

[0006] In some embodiments, a glass composition may include: greater than or equal to 65 mol.% and less than or equal to 82 mol.% SiC ; greater than or equal to 2 mol.% and less than or equal to 12 mol.% AI2O3; B2O3 in an amount that is less than or equal to the amount of AI2O3; alkali oxide; greater than or equal to 0.2 mol.% and less than or equal to 0.8 mol.% cerium oxide CeOx, wherein x is greater than or equal to 1.5 and less than or equal to 2; less than or equal to 8 mol.% ZrCh. wherein a combined amount of AI2O3 and ZrO? is greater than or equal to 3.5 mol.% and less than or equal to 14 mol.%; and less than or equal to 1 mol.% BaO. The alkali oxide may include: greater than or equal to 6 mol.% and less than or equal to 12 mol.% ofNa2O; and less than or equal to 0.5 mol.% Li2O.

[0007] In some embodiments, a glass article may include: a glass composition, wherein the glass composition may include: AI2O3, B2O3 in an amount less than or equal to the amount of AI2O3, and cerium oxide CeOx, wherein x is greater than or equal to 1.5 and less than or equal to 2. After radiation, a color of the glass article may change, and a change in the color of the glass article, when compared to the color of the glass article prior to radiation, may be less than or equal to 6, as calculated with CIE 76 formula for CIELAB AE* a b.

[0008] In some embodiments, a glass article may include a glass composition, wherein the glass composition may include: AI2O3, B2O3 in an amount less than or equal to the amount of AI2O3, and cerium oxide CeOx, wherein x is greater than or equal to 1.5 and less than or equal to 2. After exposure to radiation, a loss in transmission through at least one portion of the glass article at wavelengths from 400 nm to 700 nm may be less than 50% when compared to transmission through the portion of the glass article prior to radiation.

[0009] In some embodiments, a method of processing a glass article may include: exposing a glass article to radiation. The glass article may include a glass composition including cerium oxide CeOx, wherein x is greater than or equal to 1.5 and less than or equal to 2. A color difference between a first color of the glass article measured prior to exposing the glass article to radiation and a second color of the glass article measured after exposing the glass article to radiation may be less than or equal to 6, as calculated with CIE 76 formula for CIELAB AE* a b.

[0010] In some embodiments, a method of processing a glass article may include: exposing a glass article to radiation. The glass article may include a glass composition including cerium oxide CeOx, wherein x is greater than or equal to 1.5 and less than or equal to 2. After exposure to radiation, a loss in transmission through at least one portion of the glass article atwavelengths from 400 nm to 700 nm may be less than 50% as compared to transmission through the at least one portion of the glass article prior to radiation.

[0011] Additional features and advantages will be 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.

[0012] 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 into and constitute a part of this specification. The drawings illustrate the various embodiments described herein, and together with the description serve to explain the principles and operations of the claimed subject matter.BRIEF DESCRIPTION OF THE DRAWINGS

[0013] FIG. 1. schematically depicted in cross section a glass container, according to some embodiments.

[0014] FIG. 2A shows images of 1 mm aluminosilicate glass samples prior to exposure to high energy radiation.

[0015] FIG. 2B shows images of 1 mm borosilicate glass samples prior to exposure to high energy radiation.

[0016] FIG. 2C shows images of additional 1 mm aluminosilicate and borosilicate glass samples prior to high energy radiation.

[0017] FIG. 3 shows additional images of 1 mm aluminosilicate glass samples prior to high energy radiation.

[0018] FIG. 4 shows 5 mm aluminosilicate glass samples prior to high energy radiation.

[0019] FIG. 5 shows transmission spectra through 1 mm aluminosilicate and borosilicate glass samples prior to high energy radiation.

[0020] FIG. 6 shows images of 1 mm aluminosilicate glass samples prior to high energy radiation and 76 hours after high energy radiation.

[0021] FIG. 7 shows images of 1 mm borosilicate glass samples prior to high energy radiation and 76 hours after high energy radiation.

[0022] FIG. 8 shows images of 1 mm aluminosilicate and borosilicate glass samples side by side 76 hours after high energy radiation.

[0023] FIG. 9 shows transmission spectra through 1 mm aluminosilicate and borosilicate glass samples 76 hours after high energy radiation.

[0024] FIG. 10 shows images of 1 mm aluminosilicate glass samples 10 minutes, 24 hours, 7 days, and 7 weeks after high energy radiation.

[0025] FIG. 11 shows images of 1 mm borosilicate glass samples 10 minutes, 24 hours, 48 hours, 7 days, and 7 weeks post X-ray radiation.DETAILED DESCRIPTION

[0026] Irradiation of pharmaceutical glass is of interest as a sterilization technique for pharmaceutical articles, especially in ready to use (RTU) applications which is gaining popularity for the ease and flexibility of filling lines. RTU applications prefer high energy irradiation due to the low temperature sterility requirements of the additional packaging required in the RTU process. However, upon high intensity radiation, such as gamma, X-ray or electron beam (E-Beam) radiation, discoloration / coloring tends to occur in conventional pharmaceutical glass. Color induced by irradiation may be thermally treated, or “bleached” with a heating step at as low as about 200 °C for about 1 hour, which is relatively fast, convenient, and well below the temperature used to depyrogenate glass pharmaceutical products. However, the pharmaceutical industry generally would not use high energy irradiation before depyrogenation or use depyrogenation at all if an irradiation technique is used. Therefore, the ability to thermally bleach or remove color after irradiation would have limited applications.

[0027] Cerium oxide (CeCh and / or CeOi.s) is known as a mild colorant in glasses and it does not significantly limit glass coloring after high energy irradiation. Thus, the levels of cerium oxide (CeCh and / or CeOi.s) are kept relatively low, such as below 0.2 mol.%, in conventional pharmaceutical glasses to limit discoloration of the glass as increased cerium oxide (CeCh and / or CeOi.s) content results in more prominent coloring due to a red shift in the UV cutoff.

[0028] The inventors have unexpectedly discovered that when added to aluminosilicate glass compositions as described herein at various levels, including at levels significantly greater thanor equal to 0.2 mol.%, cerium oxide (CeCh and / or CeOi.s) does not cause pronounced coloring / discoloration in the pharmaceutical glasses made from the compositions described herein. Further, when exposed to high energy radiation, such as gamma, X-Ray, E-beam, etc., for sterilization applications, glasses made from the compositions described herein exhibit minimal color change, demonstrating superior anti -coloring performance and accelerated color fading / transmission recovery after high levels of irradiation / sterilization. Accordingly, glass articles, such as pharmaceutical packages, made from the compositions described herein can be sterilized using a single radiation technique and supplied to consumers as ready to use (RTU) articles that have minimal coloring without requiring multiple and / or subsequent thermal treatments and / or sterilization techniques.

[0029] Various embodiments of the glass compositions will be described herein and further illustrated with reference to specific examples. In the embodiments of the glass compositions described herein, the concentrations of constituent components are specified in mole percent (mol.%) on an oxide basis, unless otherwise specified.

[0030] The terms “free” and “substantially free,” when used to describe the concentration and / or absence of a particular constituent component in a glass composition, means that the constituent component is not intentionally added to the glass composition. However, the glass composition may contain traces of the constituent component as a contaminant or tramp in amounts of less than or equal to 0.01 mol.%.

[0031] Reference will now be made in detail to various embodiments of glass compositions which exhibit low level coloring upon manufacturing of the glass, minimal color change after high levels of irradiation, and / or accelerated transmission recovery / color fading after high levels of irradiation. The glass compositions described herein may generally include silica (SiCh), alumina (AI2O3), and cerium oxide (CeCh and / or CeOi.s) in amounts which impart anticoloring properties to the glass compositions. The glass compositions described herein may further include one or more alkali oxides and / or one or more alkaline earth oxides.

[0032] SiCh may be the largest constituent of the aluminosilicate glass composition described herein, and thus the primary constituent of the resulting glass network. In some embodiments, the amount of SiCh in the aluminosilicate glass composition may be greater than or equal to 65 mol.%. For example, in some embodiments, the amount of SiCh in the aluminosilicate glass composition described herein may be greater than or equal to 68 mol.%, greater than or equal to 71.5 mol.%, greater than or equal to 73 mol.%, or greater than or equalto 76 mol.%. In some embodiments, the amount of SiC>2 in the aluminosilicate glass composition may be less than or equal to 82 mol.% to maintain desired formability of the glass. For example, in some embodiments, the amount of SiC>2 in the aluminosilicate glass composition described herein may be less than or equal to 80 mol.%, less than or equal to 79 mol.%, or less than or equal to 77 mol.%.

[0033] In some embodiments, the amount of SiCh in the aluminosilicate glass composition described herein may be greater than or equal to 65 mol.% and less than or equal to 82 mol.% - including all sub-ranges and values there-between. For example, in some embodiments, the amount of SiC>2 in the aluminosilicate glass composition described herein may be greater than or equal to 65 mol.% and less than or equal to 80 mol.%, greater than or equal to 70 mol.% and less than or equal to 82 mol.%, greater than or equal to 70 mol.% and less than or equal to 80 mol.%, greater than or equal to 72 mol.% and less than or equal to 80 mol.%, or greater than or equal to 74 mol.% and less than or equal to 78 mol.%.

[0034] The aluminosilicate glass compositions described herein may further include AI2O3. In some embodiments, the amount of AI2O3 in the aluminosilicate glass composition described herein may be less than or equal to 12 mol.%. For example, in some embodiments, the amount of AI2O3 may be less than or equal to 11 mol.%, less than or equal to 10 mol.%, less than or equal to 9 mol.%, less than or equal to 8 mol.%, less than or equal to 7 mol.%, or less than or equal to 6.5 mol.%. Additionally, in some embodiments, the amount of AI2O3 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 greater than or equal to 5.5 mol.%.

[0035] In some embodiments, the amount of AI2O3 in the aluminosilicate glass composition described herein may be greater than or equal to 2 mol.% and less than or equal to 12 mol.% - including all sub-ranges and values there-between. For example, in some embodiments, the amount of AI2O3 in the aluminosilicate glass composition may be greater than or equal to 4 mol.% and less than or equal to 10 mol.%, greater than or equal to 4 mol.% and less than or equal to 8 mol.%, greater than or equal to 5 mol.% and less than or equal to 7 mol.%, or greater than or equal to 5.5 mol.% and less than or equal to 6.5 mol.%.

[0036] The aluminosilicate glass compositions described herein may further include cerium oxide, which may include cerium(IV) oxide CeC>2 and / or cerium(III) oxide CeOi.5. Accordingly, the cerium oxide in the aluminosilicate glass composition described herein maybe represented by CeOx, where x may be greater than or equal to 1 .5 and less than or equal to 2.

[0037] Conventionally, glass compositions containing cerium oxide may include cerium in only one oxidation state or mostly one oxidation state (Ce3+or Ce4+) because the presence of a mixed oxidation states, such as in the case of a mixture of cerium(IV) oxide CcCh and cerium(III) oxide CeOi.s, tends to result in more pronounced coloring in the as-manufactured glass. The inventors have found that in the aluminosilicate glass composition described herein, cerium can be in either oxidation state, including a mixed oxidation states at any ratios, while still exhibiting minimal discoloration in the as-manufactured glass prior to high energy radiation, as well as superior anti-coloring and / or color fading performance post high energy radiation.

[0038] The inventors have found that when the combined amount of alkali oxide, select alkaline earth oxide (excluding MgO), and cerium oxide is greater than or equal to the amount of AI2O3 in the glass composition, cerium may be in any oxidation state without adversely affecting the anti-color and / or color fading performance of the glass formed from such composition. The select alkaline earth oxide may include one or more of CaO, SrO, and / or BaO, but may not include MgO. The relationship between the combined amount of alkali oxide, select alkaline earth oxide, and cerium oxide, and the amount of AI2O3 may be represented by the following:(R2O + CaO + SrO + BaO + CeOx) mol.% > AI2O3 mol.% where R2O represents the sum of the alkali oxide, which may include one or more of Li2O, Na2O, K2O, Rb2O, CS2O, and / or Fr2O.

[0039] Since in some embodiments, the cerium oxide may be either cerium(IV) oxide CeO2 or cerium(III) oxide CeOi.s, or a combination thereof at any ratio, the composition, as well as the glass formed therefrom, may be prepared and / or manufactured more easily without implementing oxidation state control measures that may be otherwise required.

[0040] In some embodiments, the aluminosilicate glass composition described herein may include cerium(IV) oxide CeC>2 while being substantially free from cerium(III) oxide CeOi.s. In some embodiments, the aluminosilicate glass composition described herein may include cerium(III) oxide CeOi.s while being substantially free from cerium(IV) oxide CeO2. In some embodiments, a mixture of cerium(IV) oxide CeO2 and cerium(III) oxide CeOi.s may be present in the aluminosilicate glass composition described herein, and a ratio of cerium(IV)oxide CeCh to cerium(III) oxide CeOi.s may range from about 0.01: 1 to about 100: 1 - including all sub-ranges and values there-between. In some embodiments, the ratio of cerium(IV) oxide CeCh to cerium(III) oxide CeOi.s may range from about 0.1 : 1 to about 10: 1, from about 0.25: 1 to about 7: 1, from about 0.5: 1 to about 3: 1, or from about 0.75: 1 to about 1.5: 1, or from about 0.9: 1 to about 1.1: 1. In some embodiments, the ratio of cerium(IV) oxide CeCh to cerium (III) oxide CeOi.s may be greater than or equal to 0.01: 1, greater than or equal to 0.1: 1, greater than or equal to 0.5: 1, greater than or equal to 1: 1, greater than or equal to 2: 1, greater than or equal to 5: 1, greater than or equal to 10: 1, greater than or equal to 50: 1, or greater than or equal to 80: 1. In some embodiments, the ratio of cerium(IV) oxide CeCh to cerium(III) oxide CeOi.s may be less than or equal to 100: 1, less than or equal to 75: 1, less than or equal to 30: 1, less than or equal to 15: 1, less than or equal to 5: 1, less than or equal to 1: 1, less than or equal to 0.8: 1, less than or equal to 0.3: 1, less than or equal to 0.08: 1, less than or equal to 0.05: 1, or less than or equal to 0.02: 1.

[0041] In some embodiments, the total amount of cerium oxide CeOx, regardless of the oxidation state of cerium, in the aluminosilicate glass composition described herein may be greater than or equal to 0.2 mol.% so as to achieve desired post radiation anti -color and / or color fading performance in the glass formed from the composition described herein. In some embodiments, the total amount of cerium oxide CeOxin the aluminosilicate glass composition described herein may be greater than or equal to 0.25 mol.%, greater than or equal to 0.3 mol.%, greater than or equal to 0.4 mol.%, greater than or equal to 0.5 mol.%, greater than or equal to 0.6 mol.%, greaterthan or equal to 0.7 mol.%, greater than or equal to 0.8 mol.%, greater than or equal to 0.9 mol.%, greater than or equal to 1 mol.%, greater than or equal to 1.2 mol.%, greater than or equal to 1.5 mol.%, greater than or equal to 1.8 mol.%, greater than or equal to 2 mol.%, greater than or equal to 2.5 mol.%, greater than or equal to 3 mol.%, greater than or equal to 4 mol.%, or greater than or equal to 4.5 mol.%.

[0042] In some embodiments, the total amount of cerium oxide CeOxin the aluminosilicate glass composition described herein may be less than or equal to 5 mol.% so as to limit coloring / discoloring in the as-manufactured glass. In some embodiments, the total amount of cerium oxide CeOxmay be less than or equal to 4 mol.%, less than or equal to 2 mol.%, less than or equal to 1.7 mol.%, less than or equal to 1.4 mol.%, less than or equal to 1.1 mol.%, less than or equal to 1 mol.%, less than or equal to 0.9 mol.%, less than or equal to 0.8 mol.%, less than or equal to 0.7 mol.%, less than or equal to 0.6 mol.%, less than or equal to 0.5 mol.%,less than or equal to 0.4 mol.%, less than or equal to 0.3 mol.%, or less than or equal to 0.25 mol.%.

[0043] In some embodiments, the total amount of cerium oxide CeOxin the aluminosilicate glass composition described herein may be greater than or equal to 0.2 mol.% and less than or equal to 5 mol.% - including all sub-ranges and values there-between. For example, in some embodiments, the total amount of cerium oxide CeOxin the aluminosilicate glass composition described herein may be greater than or equal to 0.2 mol.% and less than or equal to 3 mol.%, greater than or equal to 0.2 mol.% and less than or equal to 1 mol.%, greater than or equal to 0.2 mol.% and less than or equal to 0.9 mol.%, greater than or equal to 0.2 mol.% and less than or equal to 0.8 mol.%, greater than or equal to 0.25 mol.% and less than or equal to 0.7 mol.%, greater than or equal to 0.3 mol.% and less than or equal to 0.8 mol.%, greater than or equal to 0.4 mol.% and less than or equal to 0.8 mol.%, greater than or equal to 0.5 mol.% and less than or equal to 0.8 mol.%, greater than or equal to 0.6 mol.% and less than or equal to 0.8 mol.%, greater than or equal to 0.3 mol.% and less than or equal to 0.7 mol.%, or greater than or equal to 0.3 mol.% and less than or equal to 0.6 mol.%.

[0044] Boron oxide (B2O3) is a flux which may be added to glass compositions to improve the formability of the glass. However, it has been found that when the amount of B2O3 is relatively high, such as greater than the amount of AI2O3 in borosilicate glass compositions, the addition of cerium oxide CeOxcan cause significantly discoloring, especially upon exposure to high energy radiation as will be discussed in more detail below. Accordingly, in some embodiments, the amount of B2O3 in the aluminosilicate glass composition described herein may not exceed the amount AI2O3. In some embodiments, the aluminosilicate glass composition described herein may preferably not include B2O3 or other boron-containing compound to limit discoloring of the glass both before and after irradiation.

[0045] In some embodiments, the amount of B2O3 in the aluminosilicate glass composition described herein may be less than or equal to 2.5 mol.%, less than or equal to 2 mol.%, less than or equal to 1 mol.%, less than or equal to 0.5 mol.%, less than or equal to 0. 1 mol.%, or less than or equal to 0.01 mol.% to limit discoloring of the glass. In some embodiments, a ratio of B2O3 to AI2O3 in the aluminosilicate glass composition described herein may be less than or equal to 1: 1, less than or equal to 1:5, less than or equal to 1: 10, less than or equal to 1 : 50, less than or equal to 1 : 100, or less than or equal to 1 : 1000.

[0046] In some embodiments, the aluminosilicate glass composition described herein may also include one or more alkali oxides. In some embodiments, the alkali oxide may include Na2O, K2O, Li2O, Rb2O, CS2O, FnO. or combinations thereof. In some embodiments, the total amount of the one or more alkali oxides may be greater than or equal to 0 mol.% and less than or equal to 20 mol.% - including all sub-ranges and values there-between. For example, in some embodiments, the amount of alkaline earth oxide may be greater than or equal to 0 mol.% and less than or equal to 18 mol.%, greater than or equal to 0 mol.% and less than or equal to 16 mol.%, greater than or equal to 0 mol.% and less than or equal to 14 mol.%, or greater than or equal to 0 mol.% and less than or equal to 12 mol.%.

[0047] In some embodiments, the aluminosilicate glass composition described herein may include Na2O. In some embodiments, the amount of Na2O in the aluminosilicate glass composition described herein may be greater than or equal to 5 mol.% and less than or equal to 12 mol.% of Na2O - including all sub-ranges and values there-between. For example, in some embodiments, the amount of Na2O in the aluminosilicate glass composition described herein may be greater than or equal to 6 mol.% and less than or equal to 12 mol.%, greater than or equal to 7 mol.% and less than or equal to 12 mol.%, greater than or equal to 8 mol.% and less than or equal to 12 mol.%, greater than or equal to 9 mol.% and less than or equal to 12 mol.%, greater than or equal to 10 mol.% and less than or equal to 12 mol.%, greater than or equal to 11 mol.% and less than or equal to 12 mol.%. In some embodiments, the amount of Na2O in the aluminosilicate glass composition described herein may be greater than or equal to 5 mol.%, greater than or equal to 6 mol.%, greater than or equal to 7 mol.%, greater than or equal to 8 mol.%, greater than or equal to 9 mol.%, greater than or equal to 10 mol.%, greater than or equal to 10.5 mol.%, greater than or equal to 11 mol.%, or greater than or equal to 11.5 mol.%.

[0048] In some embodiments, the aluminosilicate glass composition described herein may include K2O. In some embodiments, the amount of K2O in the aluminosilicate glass composition described herein may be greater than or equal to 0 mol.% and less than or equal to 7 mol.% - including all sub-ranges and values there-between. For example, in some embodiments, the amount of K2O in the aluminosilicate glass composition described herein may be greater than or equal to 0 mol.% and less than or equal to 5 mol.%, greater than or equal to 0 mol.% and less than or equal to 3 mol.%, greater than or equal to 0 mol.% and less than or equal to 2 mol.%, greater than or equal to 0 mol.% and less than or equal to 1 mol.%, greater than or equal to 0 mol.% and less than or equal to 0.8 mol.%, greater than or equal to 0 mol.%and less than or equal to 0.6 mol.%, greater than or equal to 0 mol.% and less than or equal to 0.5 mol.%, greater than or equal to 0 mol.% and less than or equal to 0.4 mol.%, greater than or equal to 0 mol.% and less than or equal to 0.3 mol.%, greater than or equal to 0 mol.% and less than or equal to 0.2 mol.%, greater than or equal to 0 mol.% and less than or equal to 0.15 mol.%, greater than or equal to 0 mol.% and less than or equal to 0.1 mol.%, or greater than or equal to 0 mol.% and less than or equal to 0.05 mol.%. In some embodiments, the aluminosilicate glass composition described herein may not include K2O or may be free from or substantially free from K2O.

[0049] In some embodiments, the aluminosilicate glass composition described herein may include Li2O in an amount that may be less than the amount of AI2O3. In some embodiments, the aluminosilicate glass composition described herein may include less than or equal to 3 mol.% or less than or equal to 0.5 mol.% Li2O. In some embodiments, the aluminosilicate glass composition described herein may not include Li2O or may be free from or substantially free from Li2O. The amount of Li2O in the aluminosilicate glass composition described herein may be limited because Li2O in a greater amount may interact with the content contained in the pharmaceutical package.

[0050] In some embodiments, the aluminosilicate glass composition described herein may include one or more alkaline earth oxides. The alkaline earth oxide in the glass composition may include MgO, CaO, SrO, BaO, BeO, RaO, or combinations thereof. In some embodiments, the total amount of total alkaline earth oxides may be greater than or equal to 0 mol.% and less than or equal to 20 mol.% - including all sub-ranges and values there -between. For example, in some embodiments, the amount of alkaline earth oxide may be greater than or equal to 0 mol.% and less than or equal to 15 mol.%, greater than or equal to 0 mol.% and less than or equal to 12 mol.%, greater than or equal to 0 mol.% and less than or equal to 8 mol.%, or greater than or equal to 0 mol.% and less than or equal to 6 mol.%.

[0051] In some embodiments, the aluminosilicate glass composition described herein may include MgO. In some embodiments, the amount of MgO may be greater than or equal to 0 mol.% and less than or equal to 10 mol.% - including all sub-ranges and values there-between. For example, in some embodiments, the amount of MgO may be greater than or equal to 0 mol.% and less than or equal to 8 mol.%, greater than or equal to 2 mol.% and less than or equal to 8 mol.%, greater than or equal to 0 mol.% and less than or equal to 6 mol.%, greater than or equal to 2 mol.% and less than or equal to 6 mol.%, greater than or equal to 0 mol.% and less than or equal to 5 mol.%, greater than or equal to 2 mol.% and less than or equal to 5mol.%, greater than or equal to 4 mol.% and less than or equal to 6 mol.%, greater than or equal to 4 mol.% and less than or equal to 5 mol.%, or greater than or equal to 5 mol.% and less than or equal to 6 mol.%.

[0052] In some embodiments, the aluminosilicate glass composition described herein may include CaO. In some embodiments, the amount of CaO may be greater than or equal to 0 mol.% and less than or equal to 10 mol.% - including all sub-ranges and values there-between. For example, in some embodiments, the amount of CaO may be greater than or equal to 0 mol.% and less than or equal to 6 mol.%, greater than or equal to 0 mol.% and less than or equal to 3 mol.%, greater than or equal to 0 mol.% and less than or equal to 2 mol.%, greater than or equal to 0 mol.% and less than or equal to 1 mol.%, greater than or equal to 0 mol.% and less than or equal to 0.6 mol.%, greater than or equal to 0 mol.% and less than or equal to 0.3 mol.%, greater than or equal to 0 mol.% and less than or equal to 0.2 mol.%, greater than or equal to 0.2 mol.% and less than or equal to 0.7 mol.%, or greater than or equal to 0.3 mol.% and less than or equal to 0.6 mol.%.

[0053] In some embodiments, the aluminosilicate glass composition described herein may include less than or equal to 1 mol.% BaO to limit further discoloring that may be caused by BaO. In some embodiments, the amount of BaO in the aluminosilicate glass composition described herein may be less than or equal to 0.5 mol.%, less than or equal to 0.1 mol.%, less than or equal to 0.05 mol.%, or less than or equal to 0.01 mol.%. In some embodiments, the aluminosilicate glass composition described herein may not include BaO or Ba-containing compound or may be free from or substantially from BaO or Ba-containing compound.

[0054] In some embodiments, the aluminosilicate glass composition described herein may include less than or equal to 4 mol.% Bi2Os to limit further discoloring that may be caused by Bi2O3. In some embodiments, the amount of Bi2Os in the aluminosilicate glass composition described herein may be less than or equal to 2 mol.%, less than or equal to 1 mol.%, less than or equal to 0.5 mol.%, less than or equal to 0.1 mol.%, less than or equal to 0.05 mol.%, or less than or equal to 0.01 mol.%. In some embodiments, the aluminosilicate glass composition described herein may not include Bi2Os or may be free from or substantially from Bi2C>3.

[0055] In some embodiments, the aluminosilicate glass composition described herein may include less than or equal to 1 mol.% TiCh to limit further discoloring that may be caused by TiCh as the combination of TiCh and cerium oxide CeOxmay cause significant yellowing of the glass. In some embodiments, the amount of TiCh in the aluminosilicate glass compositiondescribed herein may be less than or equal to 0.5 mol.%, less than or equal to 0.1 mol.%, less than or equal to 0.05 mol.%, or less than or equal to 0.01 mol.%. In some embodiments, the aluminosilicate glass composition described herein may not include TiCh or may be free from or substantially from TiCh.

[0056] In some embodiments, the aluminosilicate glass composition described herein may include less than or equal to 8 mol.% ZrCh. In some embodiments, the amount of ZrCh in the aluminosilicate glass composition described herein may be less than or equal to 6 mol.%, less than or equal to 4 mol.%, less than or equal to 2 mol.%, less than or equal to 1 mol.%, less than or equal to 0.5 mol.%, less than or equal to 0.1 mol.%, less than or equal to 0.05 mol.%, or less than or equal to 0.01 mol.%. In some embodiments, the aluminosilicate glass composition described herein may not include ZrCh or may be free from or substantially from ZrCh.

[0057] In some embodiments, the combined amount of AI2O3 and ZrCh in the aluminosilicate glass composition described herein may be greater than or equal to 3.5 mol.% and less than or equal to 14 mol.% - including all sub-ranges and values there-between. For example, in some embodiments, the combined amount of AI2O3 and ZrCh may be greater than or equal to 4 mol.% and less than or equal to 12 mol.%, greater than or equal to 4 mol.% and less than or equal to 10 mol.%, or greater than or equal to 4 mol.% and less than or equal to 8 mol.%.

[0058] The glass compositions described herein are formed by mixing a batch of glass raw materials (e.g., powders of SiCh, AI2O3, cerium oxide CeOx, alkali oxides, alkaline earth oxides and the like) such that the batch of glass raw materials has the desired composition. Thereafter, the batch of glass raw materials is heated to form a molten glass composition which is subsequently cooled and solidified to form the glass composition. During solidification (i.e., when the glass composition is plastically deformable) the glass composition may be shaped using various forming techniques to shape the glass composition into a desired final form. Alternatively, the glass article may be shaped into a stock form, such as a sheet, tube or the like, and subsequently reheated and formed into the desired final form. The glass compositions described herein may be particularly well suited for use in the formation of glass articles used as pharmaceutical packages or pharmaceutical containers for containing pharmaceutical compositions, such as liquids, powders and the like.

[0059] One embodiment of a glass container 100, specifically a glass pharmaceutical vial, is shown in FIG. 1. The glass container 100 for storing a pharmaceutical formulation isschematically depicted in cross section. The glass container 100 may include abody 112 having a central axis A, an inner surface 114, and an outer surface 116. The body 112 may generally enclose an interior volume 118. The body 112 may generally include a sidewall 120 and a floor portion 122. The sidewall 120 may transition into the floor portion 122 through a heel portion 124. The glass container 100 may further include a flange 126, a neck 128 extending from the flange 126, and a shoulder 130 extending between the neck 128 and the sidewall 120. In some embodiments, the glass container 100 may be symmetrical about the central axis A, with each of the sidewall 120, neck 128, and flange 126 being substantially cylindrical-shaped.

[0060] The body 112 may have an average wall thickness Ti extending from the inner surface 114 to the outer surface 116, as depicted in FIG. 1. In some embodiments, the average wall thickness Ti of the sidewall 120 and the neck 128 may be similar or the same.

[0061] In some embodiments, the average wall thickness Ti of the body 112 may be greater than or equal to 0.1 mm, greater than or equal to 0.3 mm, greater than or equal to 0.5 mm, greater than or equal to 0.7 mm, greater than or equal to 0.9 mm, greater than or equal to 1 mm, greater than or equal to 1.2 mm, greater than or equal to 1.4 mm, greater than or equal to 1.6 mm, greater than or equal to 1.8 mm, greater than or equal to 2 mm, greater than or equal to 3 mm, greater than or equal to 5 mm, greater than or equal to 7 mm, greater than or equal to 9 mm, greater than or equal to 10 mm, greater than or equal to 15 mm, greater than or equal to 25 mm, greater than or equal to 50 mm, greater than or equal to 75 mm, greater than or equal to 100 mm, greater than or equal to 250 mm, greater than or equal to 500 mm, greater than or equal to 750 mm, or greater than or equal to 1,000 mm.

[0062] In some embodiments, the average wall thickness Ti of the body 112 may be less than or equal to 1,000 mm, less than or equal to 800 mm, less than or equal to 600 mm, less than or equal to 400 mm, less than or equal to 200 mm, less than or equal to 100 mm, less than or equal to 90 mm, less than or equal to 80 mm, less than or equal to 60 mm, less than or equal to 40 mm, less than or equal to 20 mm, less than or equal to 10 mm, less than or equal to 8 mm, less than or equal to 6 mm, less than or equal to 4 mm, less than or equal to 2 mm, less than or equal to 1.7 mm, less than or equal to 1.5 mm, less than or equal to 1.1 mm, less than or equal to 1 mm, less than or equal to 0.8 mm, less than or equal to 0.6 mm, less than or equal to 0.4 mm, less than or equal to 0.2 mm, or less than or equal to 0.1 mm.

[0063] In some embodiments, the average wall thickness Ti of the body 112 may be greater than or equal to 0.1 mm and less than or equal to 1,000 mm - including all sub-ranges andvalues there-between. For example, in some embodiments, the average wall thickness Ti of the body 112 may be greater than or equal to 0. 1 mm and less than or equal to 500 mm, greater than or equal to 0. 1 mm and less than or equal to 100 mm, greater than or equal to 0. 15 mm and less than or equal to 75 mm, greater than or equal to 0.25 mm and less than or equal to 50 mm, greater than or equal to 0.35 mm and less than or equal to 25 mm, greater than or equal to 0.45 mm and less than or equal to 10 mm, greater than or equal to 0.55 mm and less than or equal to 5 mm, greater than or equal to 0.65 mm and less than or equal to 2 mm, greater than or equal to 0.75 mm and less than or equal to 1.75 mm, greater than or equal to 0.8 mm and less than or equal to 1.5 mm, greater than or equal to 0.85 mm and less than or equal to 1.25 mm, or greater than or equal to 0.95 mm and less than or equal to 1.05 mm.

[0064] While the glass container 100 is depicted in FIG. 1 as having a specific form -factor (i.e., a vial), it should be understood that the glass container 100 may have other form factors, including, without limitation, Vacutainers®, cartridges, syringes, ampoules, bottles, flasks, phials, tubes, beakers, or the like. Further, it should be understood that the glass containers described herein may be used for a variety of applications including, without limitation, as pharmaceutical packages, beverage containers, or the like.

[0065] As noted above, the CeOx-doped aluminosilicate glass compositions described herein and glass samples or articles made therefrom exhibit surprisingly minimal coloring upon manufacturing of the glass article. In some embodiments, glass samples (including but not limited to glass samples having a thickness ranging from about 0. 1 mm to about 1,000 mm) or portions of the glass articles (including but not limited to wall portions of the glass articles, such as wall portions of the glass container 100 described herein) made from the CeOx-doped aluminosilicate glass compositions descried herein may exhibit color change or difference AE* a b values (as calculated with CIE 76 formula for CIELAB AE* a b) of less than or equal to 6, less than or equal to 5, less than or equal to 4, less than or equal to 3, less than or equal to 2, less than or equal to 1, less than or equal to 0.75, less than or equal to 0.5, less than or equal to 0.25, less than or equal to 0.2, less than or equal to 0.15, less than or equal to 0.1, less than or equal to 0.05, or less, when referenced to glass samples made from a base aluminosilicate glass composition containing no CeOx.

[0066] In some embodiments, the glass samples or the portions of the glass articles may have a transmission greater than or equal to 80%, greater than or equal to 85%, greater than or equal to 87%, greater than or equal to 89%, greater than or equal to 90%, greater than or equal to 91%, greater than or equal to 92%, greater than or equal to 93%, greater than or equal to 94%,greater than or equal to 95%, greater than or equal to 96%, greater than or equal to 97%, or greater than or equal to 98%, in the wavelength range between 375 nm and 700 nm.

[0067] Transmission through the glass samples or portions of the glass articles may be measured using a spectrophotometer with a light beam directed normal to the surfaces of the glass samples or glass articles. When the glass article is a glass container, such as the glass container 100 shown in FIG. 1, the measurements are performed to measure transmission through two wall portions of the glass container. Specifically, the light beam is directed normal to the container wall such that the beam passes through two opposing wall portions, with the beam passing through a first wall portion when entering the glass container and then passing through a second, opposing wall portion when exiting the glass container. As described herein, the light transmission can be measured prior to radiation or post radiation. When the light transmission is measured prior to radiation, athermal treatment can be performed (e.g., heating the glass sample or the glass article at 300 °C for 0.5 hour) so as to remove existing color.

[0068] In addition to high transmission in the wavelength range between 375 nm and 700 nm, the CeOx-doped aluminosilicate glass compositions described herein, as well as the glass samples and the portions of the glass articles made therefrom, further exhibit superior anticoloring and / or color fading / transmission recovery behavior after high energy radiation. The high energy radiation may include gamma, X-Ray, E-beam, etc., for sterilization applications, such as radiation sterilization conducted in accordance with ANSI / AAMI / ISO 11137 1-3. In some instances, the high energy radiation utilized may include gamma radiation at 35 kGy. In some instances, the high energy radiation utilized may include X-ray radiation of 60 kV, 66 mA for 15 minutes.

[0069] In some embodiments, upon radiation, a color change or AE* a b value in the glass samples or the portions of the glass articles may be less than or equal to 6, less than or equal to 5, less than or equal to 4, less than or equal to 3, less than or equal to 2, less than or equal to 1, less than or equal to 0.75, less than or equal to 0.5, less than or equal to 0.25, less than or equal to 0.2, less than or equal to 0. 15, less than or equal to 0.1, less than or equal to 0.05, or less, when referenced to the same glass samples or portions of the glass articles prior to radiation.

[0070] A loss in transmission through the glass samples or the portions of the glass articles upon radiation may be less than or equal to 25%, less than or equal to 20%, less than or equal to 15%, less than or equal to 10%, less than or equal to 9%, less than or equal to 8%, less than or equal to 7%, less than or equal to 6%, less than or equal to 5%, less than or equal to 4%, less than or equal to 3%, less than or equal to 2%, or less than or equal to 1%, at wavelengths from400 nm to 700 nm, when referenced to transmission through the same glass samples or portions of the glass articles prior to radiation. The loss in transmission is the difference between the transmission prior to radiation and the transmission after radiation. As a non-limiting example, a loss in transmission through a glass sample or a portion of a glass article upon radiation may be less than or equal to 25%, less than or equal to 20%, less than or equal to 15%, less than or equal to 10%, less than or equal to 9%, less than or equal to 8%, less than or equal to 7%, less than or equal to 6%, less than or equal to 5%, less than or equal to 4%, less than or equal to 3%, less than or equal to 2%, or less than or equal to 1%, at wavelengths from 400 nm to 700 nm, when referenced to transmission through the same glass sample or the same portion of the glass article prior to radiation. As another non-limiting example, in the case of a glass container, such as the glass container 100 shown in FIG. 1, a loss in transmission through two opposing wall portions of the glass container may be less than or equal to 50 %, less than or equal to 25%, less than or equal to 20%, less than or equal to 15%, less than or equal to 10%, less than or equal to 9%, less than or equal to 8%, less than or equal to 7%, less than or equal to 6%, less than or equal to 5%, less than or equal to 4%, less than or equal to 3%, less than or equal to 2%, or less than or equal to 1%, at wavelengths from 400 nm to 700 nm, when referenced to transmission through the same two opposing wall portions of the glass container prior to radiation.

[0071] Recovery in transmission over predetermined time periods through the glass samples or the portions of the glass articles may be greater than or equal to 75%, greater than or equal to 80%, greater than or equal to 85%, greater than or equal to 86%, greater than or equal to 87%, greater than or equal to 88%, greater than or equal to 89%, greater than or equal to 90%, greater than or equal to 91%, greater than or equal to 92%, greater than or equal to 93%, greater than or equal to 94%, greater than or equal to 95%, greater than or equal to 96%, greater than or equal to 97%, greater than or equal to 98%, greater than or equal to 99%, greater than or equal to 99.3%, greater than or equal to 99.5%, greater than or equal to 99.7%, or may be 100%, when referenced to transmission through the same glass samples or portions of the glass articles prior to radiation. In some embodiments, the predetermined time periods may be 10 minutes from the high energy radiation, 24 hours from the high energy radiation, 48 hours from the high energy radiation, 76 hours from the high energy radiation, 7 days from the high energy radiation, 7 weeks from the high energy radiation, etc.

[0072] Due to the minimal color change / transmission loss upon radiation and accelerated color fading / transmission recovery post high energy radiation, glass articles, such aspharmaceutical packages, made from the CeOx-doped aluminosilicate glass compositions described herein can be sterilized via high energy radiation and supplied to consumers as ready to use (RTU) articles without subsequent thermal treatments and / or other sterilization techniques.

[0073] While the color properties of various glasses, including glass samples or glass articles (or portions thereof), are provided herein by referencing exemplary sample thicknesses or exemplary portions of glass articles having a range of thicknesses described herein, it is contemplated that color differences and / or transmission properties for glasses of greater or less thicknesses would increase or decrease in a predictable manner (e.g., color differences increase with glass thicknesses, transmissions decrease with glass thicknesses, etc.). Accordingly, the color differences and / or transmission properties of glasses of greater or less thicknesses could be compared to those described herein by extrapolation. Alternatively, the color differences and / or transmission properties of glasses of greater or less thicknesses could be compared to those described herein by creating samples from the glasses to be evaluated. For example, samples may be created by stacking thinner glasses or machining / polishing down thicker glasses to the thicknesses referenced herein and the created samples may be measured and directly compared to the glass samples described herein.EXAMPLES

[0074] The embodiments of the glass compositions described herein will be further clarified by the following examples.

[0075] It should be noted that although CcO? is referenced in the various examples for describing / calculating the cerium oxide amount in mol.%, cerium may be present in either oxidation state. In other words, the various examples discussed below may included cerium (IV) oxide CeCh, cerium(III) oxide CeOi.s, or a combination thereof that exhibit superior anticoloring and / or color fading performance as described herein.Pre Radiation PerformanceAnti-Color Performance

[0076] Aluminosilicate glass compositions doped with varying levels of CcO? (composition A1-A8) and borosilicate glass compositions doped with varying levels of CcO? (composition B1-B4) were prepared according to some embodiments. A reference aluminosilicate glass composition without CcO? doping (reference composition Ref. I) and a reference borosilicate glass composition without CcO? doping (reference composition Ref. II) were also prepared.The specific compositions of each aluminosilicate glass composition are reported below in Table 1. The specific compositions of each borosilicate glass composition are reported below in Table 2.Table 1Table 2

[0077] Tables 1 and 2 also contain color change or AE* a b values of glass samples made from the various glass compositions prior to being exposed to high energy radiation (pre radiation). Pre-radiation or non-irradiated glass samples may refer to glass samples as manufactured without being exposed to any high energy radiation, or glass samples that may have been exposed to radiation but have been subsequently treated to remove coloring due to such radiation. Treatment to remove coloring due to radiation may include heating the radiated glass at about 300 °C for about 0.5 hour.

[0078] The color change or AE* a b values are calculated with CIE 76 formula for CIELAB AE* ab. Specifically, given two colors in CIELAB color space, (L*i, ai, bi) and (L*2, a2, b2), the CIE 76 formula for calculating the color difference or AE* a b values is defined as follows:

[0079] Unless stated otherwise, the color measurements as described herein were taken in accordance with standard operating procedure for X-Rite Color i7 unit. Specifically, using the X-Rite Color i7 unit, the values of *L, a, b were measured in reflectance using D65-10 illumination and aperture setting of 10 mm with specular excluded condition and D65 selected for UV control.

[0080] The color change or AE* a b values of glass samples made from CeCh-doped aluminosilicate glass compositions are referenced to a glass sample made from the reference aluminosilicate glass composition without CeCh doping (Ref. I), and the color change or AE* a b values of glass samples made from CeCh-doped borosilicate glass compositions are referenced to a glass sample made from the reference borosilicate glass composition without CeCh doping (Ref. II). The glass samples made from various compositions were polished glass pieces having a thickness of 1 mm and a roughness low enough for sufficiently accurate measurements to be obtained.

[0081] Table 3 further contains L* a b color coordinates, in addition to A E* a b values, for select glass samples made from aluminosilicate glass compositions of Table 1 prior to being exposed to high energy radiation, and Table 4 further contains L* a b color coordinates, in addition to A E* a b values, for the glass samples made from borosilicate glass compositions of Table 2 prior to being exposed to high energy radiation.Table 3Table 4

[0082] The inventors have discovered that all aluminosilicate glass samples have demonstrated surprisingly low coloring. Conventionally, CeCh contents are kept low, such as below 0.2 mol.%, in order to limit coloring in glass articles made from such CcCh-containing glass compositions. Unexpectedly, all the aluminosilicate glass samples, even with added CeCh amounts of as high as 1 mol.%, have exhibited very low coloring. As shown in Tables 1 and 3, all aluminosilicate glass samples have a AE* a b value of less than or equal to 3, which is considered not detectable by the average human eye. In contrast, as shown in Tables 2 and 4, only glass samples made from borosilicate glass compositions having 0.4 mol.% or less CeCh have a AE* a b value of less than or equal to 3, and the glass sample made from the borosilicate glass composition containing 0.6 mol.% CeCh already has a AE* a b value greater than or equal to 3.

[0083] Further, when compared to the borosilicate glass samples, the aluminosilicate glass samples having the same or comparable amounts of CeCh exhibit much less color change. Even with greater amounts of CeCh (e.g., up to 1 mol.% CeCh), the aluminosilicate glass samples still exhibit less coloring when compared to the borosilicate glass samples with a lesser amount of CeCh. For example, the aluminosilicate glass sample having 1.0 mol.% CeCh still demonstrates a lower AE* a b value of 1.79 as compared to the borosilicate glass sample having only 0.4 mol.% CeCh and a AE* a b value of 2.95. Overall, coloring due to the addition of CeO2 is much less pronounced in glass samples made from the aluminosilicate glass compositions than the borosilicate glass compositions, as also shown in FIGS. 2A, 2B, and 2C.

[0084] FIG. 3 shows four 1 mm thick aluminosilicate glass samples made from aluminosilicate glass compositions having varying amounts of CeCh (0 mol.% CeCh, 0.2 mol.% CeCh, 0.3 mol.% CeCh, and 0.4 mol.% CeCh). FIG. 4 shows four 5 mm thick aluminosilicate glass samples made from aluminosilicate glass compositions having similar amounts of CeCh (0 mol.% CeCh, 0.2 mol.% CeCh, 0.3 mol.% CeCh, and 0.4 mol.% CeCh).Due to increased pathlength, the 5 mm thick samples display more color than the 1 mm thick samples but still exhibit very low coloring.Transmission Performance

[0085] FIG. 5 shows transmission spectra through 1 mm thick aluminosilicate and borosilicate glass samples with varying CeCh contents (0 mol.% CeCh, 0.2 mol.% CeCh, 0.3 mol.% CeCh, 0.4 mol.% CeCh, and 0.6 mol.% CeCh). Consistent with the coloring results discussed above, with the same or comparable CeCh content, the aluminosilicate glass samples have greater transmission in the wavelength range between 375 nm and 500 nm than the borosilicate glass samples. The superior anti-coloring and transmission performance exhibited by the aluminosilicate glass over borosilicate glass is more evident after exposure to high energy radiation as discussed below.Post Gamma Radiation PerformanceAnti-Color Performance

[0086] Table 5 contains L* a b color coordinates and AE* a b values for various CeCh doped 1 mm thick aluminosilicate glass samples measured 76 hours and 7 days after high intensity gamma radiation (35 kGy). The CeCh doped aluminosilicate glass samples were made from select aluminosilicate glass compositions of Table 1. The AE* a b values are referenced to (i) non-irradiated 1 mm thick aluminosilicate glass sample made from the reference aluminosilicate glass composition without CeCh doping (Ref. I, 0 mol.% CeCh), and (ii) nonirradiated 1 mm sister sample with same CeCh doping for each dopant level. The various nonirradiated and irradiated aluminosilicate glass samples are also shown in FIG. 6. As discussed above, non-irradiated samples may refer to glass samples as manufactured without being exposed to any high energy radiation, or glass samples that may have been exposed to radiation but have been subsequently treated to remove coloring due to such radiation by, e.g., heating the radiated glass at about 300 °C for about 0.5 hour. After color measurements of the nonirradiated samples are taken, the non-irradiated samples are then exposed to radiation and color measurements are taken again post radiation, and color change or AE* a b values are then calculated based on the pre- and post-radiation measurements.Table 5

[0087] Table 6 contains L* a b color coordinates and AE* a b values for various CeCh doped 1 mm thick borosilicate glass samples measured 76 hours and 7 days after high intensity gamma radiation (35 kGy). The CeCh doped borosilicate glass samples were made from select borosilicate glass compositions of Table 2. The AE* a b values are referenced to (i) nonirradiated 1 mm thick borosilicate glass sample made from the reference borosilicate glass composition without CeCh doping (Ref. II, 0 mol.% CeCh), and (ii) non-irradiated 1 mm sister sample with same CeCh doping for each dopant level. The various non-irradiated and irradiated borosilicate glass samples are also shown in FIG. 7.Table 6

[0088] As shown by Tables 5 and 6 and FIGS. 6 and 7, although increasing CcCE content decreased the amount of color change upon gamma irradiation for both aluminosilicate and borosilicate glass samples, the CeCh-doped aluminosilicate glass samples experienced significantly less color change (as demonstrated by the significantly smaller AE* a b values) than the CeCh-doped borosilicate glass samples when doped with comparable amount of CeCh. FIG. 8 shows side by side gamma irradiated aluminosilicate and borosilicate glass samples. Compared to the borosilicate glass samples, the CeCh-doped aluminosilicate glass samples exhibit minimal color change caused by the high energy radiation. Even when doped with as low as 0.3 mol.% CeCh, the aluminosilicate glass samples had AE* a b values of less than or equal to 3 when measured 76 hours after gamma irradiation. In contrast, even after 7 days, a AE* a b value of less than or equal to 3 was not achieved by any irradiated, CeCh-dopd borosilicate glass samples. This further demonstrate the superior anti-coloring property of the CeCh-doped aluminosilicate glass compositions over CeCh-doped borosilicate glass compositions.Transmission Performance

[0089] FIG. 9 shows transmission spectra through 1 mm thick aluminosilicate and borosilicate glass samples with varying CeCh doping levels (0 mol.% CeCh, 0.2 mol.% CeCh, 0.3 mol.% CeCh, 0.4 mol.% CeCh, and 0.6 mol.% CeCh) 76 hours after gamma radiation. As shown, when compared to the irradiated aluminosilicate glass samples, the irradiated borosilicate glass samples had significantly lower transmission over the wavelength range between 375 nm and 500 nm due to the more pronounced yellow / brown coloring caused by gamma radiation. In contrast, the aluminosilicate glass samples exhibit almost no transmission loss (e.g., less than or equal to 6%) in the visible light wavelength range between 400 nm and 700 nm when doped with greater than or equal to 0.3 mol.% CeCh, and exhibit almost notransmission loss in the visible light wavelength range between 450 nm and 700 nm when doped with greater than or equal to 0.2 mol.% CeCh.

[0090] Table 7 shows transmission loss (%T loss) (through 1 mm glass) for aluminosilicate and borosilicate glass samples with varying CeCh dopant levels (0 mol.% CeCh, 0.2 mol.% CeCh, 0.3 mol.% CeCh, 0.4 mol.% CeCh, and 0.6 mol.% CeCh) at 76 hours post gamma radiation, referenced to non-irradiated, CeCh-doped sister samples.Table 7

[0091] Table 8 shows transmission (through 1 mm glass) recovery from fading for aluminosilicate and borosilicate glass samples with varying CeCh dopant levels (0 mol.% CeCh, 0.2 mol.% CeCh, 0.3 mol.% CeCh, 0.4 mol.% CeCh, and 0.6 mol.% CeCh) at 76 hours post gamma radiation, referenced to non-irradiated, CeCh-doped sister samples.Table 8

[0092] Table 9 shows transmission loss (through 1 mm glass) for aluminosilicate and borosilicate glass samples with varying CeCh dopant levels (0 mol.% CeCh, 0.2 mol.% CeCh, 0.3 mol.% CeCh, 0.4 mol.% CeCh, and 0.6 mol.% CeCh) at 76 hours post gamma radiation, referenced to non-irradiated, non-CcCh-dopcd samples.Table 9

[0093] Table 10 shows transmission (through 1 mm glass) recovery from fading for aluminosilicate and borosilicate glass samples with varying CeCh dopant levels (0 mol.% CeCh, 0.2 mol.% CeCh, 0.3 mol.% CeCh, 0.4 mol.% CeCh, and 0.6 mol.% CeCh) at 76 hours post gamma radiation, referenced to non-irradiated, non-CeCh-doped samples.Table 10

[0094] As shown by the transmission loss data in Tables 7 and 9, when doped with greater than or equal to 0.2 mol.% CeCh. the aluminosilicate glass samples exhibit almost no transmission loss (e.g., less than or equal to 6 %) in the visible light wavelength range between 450 nm and 700 nm. When doped with greater than or equal to 0.3 mol.% CeCh, the aluminosilicate glass samples exhibit almost no transmission loss in the visible light wavelength range between 400 nm and 700 nm. In contrast, the borosilicate glass samples had over 10%, and in some instances, over 25% or even over 35% transmission loss in the visible light wavelength range between 400 nm and 700 nm.

[0095] Additionally, as shown by the recovery data in Tables 8 and 10, when doped with greater than or equal to 0.2 mol.% CeCh, the aluminosilicate glass samples achieved over 93% transmission recovery in the visible light wavelength range between 450 nm and 700 nm. When doped with greater than or equal to 0.3 mol.% CeCh, the aluminosilicate glass samples achieved over 94% transmission recovery in the visible light wavelength range between 400 nm and 700 nm. In contrast, the borosilicate glass samples had significantly lower transmission recovery in the visible light wavelength range between 400 nm and 700 nm, e.g., less than 84% even when doped with 0.6 mol.% CeCh and in some instances, less than 75% or less than 65% when doped with lower amounts of CeCh.

[0096] In view of the above, when compared to CeCh-doped borosilicate glass samples, glass samples made from CeCh-doped aluminosilicate glass compositions not only possess greater anti-coloring capability, but also exhibit superior transmission recovery within the same time frame, i.e., losing color caused by high energy radiation at a faster rate.Post X-ray Radiation Performance

[0097] Table 11 contains L* a b color coordinates and AE* a b values, measured 9 days and 7 weeks after high intensity X-ray radiation (60 kV, 66 mA for 15 minutes), for 1 mm thick aluminosilicate glass samples doped with 0.4 mol.% CeCh (composition A8 of Table 1). The AE* a b values are referenced to (i) non-irradiated 1 mm thick aluminosilicate glass sample made from the reference aluminosilicate glass composition without CeCh doping (Ref. I, 0 mol.% CeCh), and (ii) non-irradiated 1 mm sister sample with 0.4 mol.% CeCh doping (A8, 0.4 mol.% CeCh). FIG. 10 further shows images of the 0.4 mol.% CeCh doped aluminosilicate glass samples 10 minutes, 24 hours, 7 days, and 7 weeks post X-ray radiation.Table 11

[0098] As shown by Table 11 and FIG. 10, color fading can be observed within 24 hours, and by 9 days post X-ray radiation, color difference between the irradiated and non-irradiated samples is no longer detectable by the average human eye.

[0099] Table 12 contains L* a b color coordinates and AE* a b values, measured 10 days and 7 weeks after high intensity X-ray radiation (60 kV, 66 mA for 15 minutes), for 1 mm thick borosilicate glass samples doped with 0.4 mol.% CeCh (composition B3 of Table 2). The AE* a b values are referenced to (i) non-irradiated 1 mm thick borosilicate glass sample made from the reference aluminosilicate glass composition without CeCh doping (Ref. II, 0 mol.% CeCh). and (ii) non-irradiated 1 mm sister sample with 0.4 mol.% CeCh doping (B3, 0.4 mol.% CeCh). FIG. 11 further shows the coloring of the 0.4 mol.% CeCh doped borosilicate glass samples 10 minutes, 24 hours, 48 hours, 7 days, and 7 weeks post X-ray radiation.Table 12

[0100] Unlike the CeCh-doped aluminosilicate glass samples, strong color in the CeCh- doped borosilicate glass samples can still be easily observed by 7 days post X-ray radiation. As shown in Table 12 and FIG. 11, even after 7 weeks from X-ray radiation, pronounced coloring can still be observed.

[0101] Table 13 contains AE* a b values for additional 1 mm glass samples made from select aluminosilicate glass compositions of Table 1 with varying CeCh doping levels (0.2 mol.% CeCh, 0.3 mol.% CeCh, 0.4 mol.% CeCh, and 0.6 mol.% CeCh). The AE* a b values are referenced to non-irradiated 1 mm aluminosilicate glass sample made from the reference aluminosilicate glass composition without CeCh doping (Ref. I, 0 mol.% CeCh).Table 13

[0102] Table 14 contains AE* a b values for additional glass samples (1 mm) made from borosilicate glass compositions of Table 2 with varying CeCh doping levels (0.2 mol.% CeCh, 0.3 mol.% CeCh, 0.4 mol.% CeCh, and 0.6 mol.% CeCh). The AE* a b values are referenced to non-irradiated 1 mm thick borosilicate glass sample made from the reference borosilicate glass composition without CeCh doping (Ref. II, 0 mol.% CeCh).Table 14

[0103] As shown by Tables 13 and 14, the CcCh-dopcd aluminosilicate glass compositions exhibit superior anti-coloring and / or color fading performance over the CcCf-dopcd borosilicate glass compositions. With CeCh doping level greater than or equal to 0.3 mol.%, AE* a b values of the aluminosilicate glass samples were reduced to less than or equal to 3, less than or equal to 2, or even less than or equal to 1 within 1 week, 76 hours, 48 hours, or 24 hours from radiation, depending on the CcCE content. Even with low level of CcCf doping (e.g., 0.2 wt. %), much lower levels of AE* a b values were achieved by the aluminosilicate glass sample than any of the borosilicate glass samples. None of the borosilicate glass samples achieved a AE* a b value of less than or equal to 3 with 7 days of radiation.

[0104] Overall, addition of CeOxto aluminosilicate base glass compositions reduces coloring more effectively both prior to and after high energy radiation, in comparison to borosilicate glass compositions doped with the same or comparable levels of CeOx. In addition, the CeOx-doped aluminosilicate glasses demonstrate surprisingly fast transmission recovery and / or accelerated color fading after high energy radiation. Accordingly, pharmaceutical articles made from the CeCh-doped aluminosilicate glass compositions described herein can be sterilized using one radiation technique without requiring further thermal treatment and supplied to customers in a RTU configuration. In contrast, to reduce or limit coloring in glasses made from CeOx-doped borosilicate compositions, lower doses of radiation may be required, which can lead to lower kill rate for sterilization, or more involved thermal techniques may be needed to remove color that may be incompatible with all RTU configurations.

[0105] 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 specification cover the modifications and variations of the various embodiments described herein provided such modification and variations come within the scope of the appended claims and their equivalents.EXEMPLARY CLAIM SET

[0106] Exemplary Claim 1. A glass composition, comprising: greater than or equal to 70 mol.% and less than or equal to 80 mol.% SiC ; greater than or equal to 4 mol.% and less than or equal to 10 mol.% AI2O3; less than or equal to 2.5 mol.% B2O3; alkali oxide; and greater than or equal to 0.2 mol.% and less than or equal to 5 mol.% cerium oxide CeOx, wherein x is greater than or equal to 1.5 and less than or equal to 2; and wherein the alkali oxide comprises: greater than or equal to 5 mol.% and less than or equal to 12 mol.% of Na20; and Li2O in an amount that is less than or equal to the amount of AI2O3.

[0107] Exemplary Claim 2. The glass composition of Exemplary Claim 1, wherein Li2O is present in an amount that is less than or equal to 3 mol.%.

[0108] Exemplary Claim 3. A glass composition, comprising: greater than or equal to 65 mol.% and less than or equal to 82 mol.% SiC ; greater than or equal to 2 mol.% and less than or equal to 12 mol.% AI2O3; B2O3 in an amount that is less than or equal to the amount of AI2O3; alkali oxide; greater than or equal to 0.2 mol.% and less than or equal to 0.8 mol.% cerium oxide CeOx, wherein x is greater than or equal to 1.5 and less than or equal to 2; less than or equal to 8 mol.% ZrCE. wherein a combined amount of AI2O3 and ZrCL is greater than or equal to 3.5 mol.% and less than or equal to 14 mol.%; and less than or equal to 1 mol.% BaO; wherein the alkali oxide comprises: greater than or equal to 6 mol.% and less than or equal to 12 mol.% of Na20; and less than or equal to 0.5 mol.% Li2O.

[0109] Exemplary Claim 4. The glass composition of any of Exemplary Claim 1 to Exemplary Claim 3, wherein the cerium oxide CeOxcomprises present in an amount greater than or equal to 0.2 mol.%.

[0110] Exemplary Claim 5. The glass composition of any of Exemplary Claim 1 to Exemplary Claim 4, wherein the amount of cerium oxide CeOxis greater than or equal to 0.25 mol.% and less than or equal to 0.7 mol.%.

[0111] Exemplary Claim 6. The glass composition of any of Exemplary Claim 1 to Exemplary Claim 5, wherein the cerium oxide CeOxcomprises at least one of cerium (III) oxide CeOi.5 or cerium(IV) oxide CeC>2.

[0112] Exemplary Claim 7. The glass composition of any of Exemplary Claim 1 to Exemplary Claim 6, further comprising: less than or equal to 4 mol.% Bi2C>3.

[0113] Exemplary Claim 8. The glass composition of any of Exemplary Claim 1 to Exemplary Claim 7, wherein the glass composition is substantially free from boron or boron compound.

[0114] Exemplary Claim 9. The glass composition of any of Exemplary Claim 1 to Exemplary Claim 8, wherein the glass composition is substantially free from lithium or lithium compound.

[0115] Exemplary Claim 10. The glass composition of any of Exemplary Claim 1 to Exemplary Claim 9, further comprising: alkaline earth oxide.

[0116] Exemplary Claim 11. The glass composition of Exemplary Claim 10, wherein the alkaline earth oxide is present in an amount greater than or equal to 0 mol.% and less than or equal to 20 mol.% alkaline earth oxide.

[0117] Exemplary Claim 12. The glass composition of any of Exemplary Claim 10 to Exemplary Claim 11, further comprising: greater than or equal to 0 mol.% and less than or equal to 12 mol.% alkaline earth oxide.

[0118] Exemplary Claim 13. The glass composition of any of Exemplary Claim 10 to Exemplary Claim 12, wherein the alkaline earth oxide comprises at least one of MgO or CaO.

[0119] Exemplary Claim 14. The glass composition of Exemplary Claim 13, MgO is present in an amount that is greater than or equal to 0 mol.% and less than or equal to 10 mol.%.

[0120] Exemplary Claim 15. The glass composition of any of Exemplary Claim 13 to Exemplary Claim 14, MgO is present in an amount that is greater than or equal to 0 mol.% and less than or equal to 6 mol.%.

[0121] Exemplary Claim 16. The glass composition of any of Exemplary Claim 13 to Exemplary Claim 15, CaO is present in an amount that is greater than or equal to 0 mol.% and less than or equal to 10 mol.%.

[0122] Exemplary Claim 17. The glass composition of any of Exemplary Claim 13 to Exemplary Claim 16, CaO is present in an amount that is greater than or equal to 0 mol.% and less than or equal to 6 mol.%.

[0123] Exemplary Claim 18. The glass composition of any of Exemplary Claim 1 to Exemplary Claim 17, wherein the alkali oxide further comprises K2O.

[0124] Exemplary Claim 19. The glass composition of Exemplary Claim 18, wherein K2O is present in an amount that is greater than or equal to 0 mol.% and less than or equal to 7 mol.%.

[0125] Exemplary Claim 20. The glass composition of any of Exemplary Claim 18 to Exemplary Claim 19, wherein K2O is present in an amount that is greater than or equal to 0 mol.% and less than or equal to 2 mol.%.

[0126] Exemplary Claim 21. The glass composition of any of Exemplary Claim 10 to Exemplary Claim 20, wherein a combined amount of the alkali oxide, the alkaline earth oxide excluding MgO, and the cerium oxide CeOxin mol.% is greater than or equal to the amount of AI2O3 in mol.%.

[0127] Exemplary Claim 22. A glass article formed from the glass composition of any of Exemplary Claim 1 to Exemplary Claim 21.

[0128] Exemplary Claim 23. A glass article, the glass article comprising: a glass composition; wherein the glass composition comprises: AI2O3, B2O3 in an amount less than or equal to the amount of AI2O3, and cerium oxide CeOx, wherein x is greater than or equal to 1.5 and less than or equal to 2; wherein after exposure to radiation, a color of the glass article changes, and wherein a change in the color of the glass article, when compared to the color of the glass article prior to radiation, is less than or equal to 6, as determined in accordance with CIE 76 formula for CIELAB AE* a b.

[0129] Exemplary Claim 24. A glass article, the glass article comprising: a glass composition comprising: AI2O3; B2O3 in an amount less than or equal to the amount of AI2O3; and cerium oxide CeOx, wherein x is greater than or equal to 1.5 and less than or equal to 2; wherein after exposure to radiation, a loss in transmission through at least one portion of the glass article at wavelengths from 400 nm to 700 nm is less than 50% when compared to transmission through the at least one portion of the glass article prior to radiation.

[0130] Exemplary Claim 25. The glass article of any of Exemplary Claims 23 to 24, wherein the radiation comprises one of gamma, X-ray, or electron beam.

[0131] Exemplary Claim 26. The glass article of any of Exemplary Claims 23 to 25, wherein the radiation is conducted in accordance with ANSI / AAMI / ISO 11137 1-3.

[0132] Exemplary Claim 27. The glass article of any of Exemplary Claim 23 to Exemplary Claim 25, wherein the radiation comprises gamma radiation at 35 kGy.

[0133] Exemplary Claim 28. The glass article of any of Exemplary Claim 23 to Exemplary Claim 25, wherein the radiation X-ray radiation of 60 kV, 66 mA for 15 minutes.

[0134] Exemplary Claim 29. The glass article of any of Exemplary Claim 23 to Exemplary Claim 28, wherein determining the change in the color of the glass article comprises: determining the color of the glass article prior to the radiation; determining the color of the glass article after the radiation by measuring the color of the glass article 10 minutes after theradiation, 24 hours after the radiation, 48 hours after the radiation, 76 hours after the radiation, 7 days after the radiation, or 7 weeks after the radiation; and calculating the change in the color of the glass article based on the determined color of the glass article prior to the radiation and the determined color of the glass article after the radiation.

[0135] Exemplary Claim 30. The glass article of Exemplary Claim 29, wherein determining the change in the color of the glass article further comprises: heating the glass article at 300 °C for 0.5 hour prior to the radiation.

[0136] Exemplary Claim 31. The glass article of any of Exemplary Claim 23 to Exemplary Claim 28, wherein determining the change in the color of the glass article further comprises: obtaining a glass sample from the glass article, wherein the glass sample has a thickness of 1 mm; and exposing the glass sample to the radiation; wherein the color of the glass article prior to the radiation is represented by the color of the glass sample prior to the radiation; and wherein the change in the color of the glass article is represented by the difference between the color of the glass sample prior to the radiation and the color of the glass sample after the radiation.

[0137] Exemplary Claim 32. The glass article of Exemplary Claim 31, wherein determining the change in the color of the glass article further comprises: heating the glass sample at 300 °C for 0.5 hour prior to exposing the glass sample to the radiation.

[0138] Exemplary Claim 33. The glass article of any of Exemplary Claim 23 to Exemplary Claim 32, wherein after radiation, the change in the color of the glass article, when compared to the color of the glass article prior to radiation, is less than or equal to 3.

[0139] Exemplary Claim 34. The glass article of any of Exemplary Claim 23 to Exemplary Claim 33, wherein immediately after radiation, transmission through the at least one portion of the glass article reduces at wavelengths from 400 nm to 700 nm as compared to transmission through the at least one portion of the glass article prior to radiation.

[0140] Exemplary Claim 35. The glass article of any of Exemplary Claim 23 to Exemplary Claim 34, wherein after irradiation, transmission through the at least one portion of the glass article gradually increases for all wavelengths from 400 nm to 700 nm.

[0141] Exemplary Claim 36. The glass article of any of Exemplary Claim 23 to Exemplary Claim 35, wherein a loss in transmission through the at least one portion of the glass article is less than 25% at wavelengths from 400 nm to 700 nm as compared to transmission through the at least one portion of the glass article prior to radiation.

[0142] Exemplary Claim 37. The glass article of any of Exemplary Claim 23 to Exemplary Claim 36, wherein the at least one portion of the glass article comprises a wall portion of the glass article.

[0143] Exemplary Claim 38. The glass article of any of Exemplary Claim 23 to Exemplary Claim 36, wherein the at least one portion of the glass article comprises two opposing wall portions of the glass article.

[0144] Exemplary Claim 39. The glass article of any of Exemplary Claim 23 to Exemplary Claim 36, wherein the at least one portion of the glass article comprises a glass sample obtained from the glass article.

[0145] Exemplary Claim 40. The glass article of any of Exemplary Claim 23 to Exemplary Claim 30, wherein a thickness of the at least one portion of the glass article is greater than or equal to 0.1 mm and less than or equal to 1,000 mm.

[0146] Exemplary Claim 41. The glass article of any of Exemplary Claim 23 to Exemplary Claim 40, wherein the glass article is a pharmaceutical package.

[0147] Exemplary Claim 42. The glass article of any of Exemplary Claim 23 to Exemplary Claim 41, wherein the glass composition comprising a glass composition of any of Exemplary Claim 1 to Exemplary Claim 21.

[0148] Exemplary Claim 43. A method of processing a glass article, comprising: exposing a glass article to radiation; wherein the glass article comprises a glass composition comprising cerium oxide CeOx, wherein x is greater than or equal to 1.5 and less than or equal to 2; and wherein a color difference between a first color of the glass article measured prior to exposing the glass article to the radiation and a second color of the glass article measured after exposing the glass article to the radiation is less than or equal to 6, as calculated with CIE 76 formula for CIELAB AE* a b.

[0149] Exemplary Claim 44. A method of processing a glass article, comprising: exposing a glass article to radiation; wherein: the glass article comprises a glass composition comprising cerium oxide CeOx, wherein x is greater than or equal to 1.5 and less than or equal to 2; and wherein after exposure to radiation, a loss in transmission through at least one portion of the glass article at wavelengths from 400 nm to 700 nm is less than 50% as compared to transmission through the at least one portion of the glass article prior to radiation.

[0150] Exemplary Claim 45. The method of any of Exemplary Claims 43 to 44, wherein the radiation comprises one of gamma, X-ray, or electron beam.

[0151] Exemplary Claim 46. The method of any of Exemplary Claims 43 to 45, wherein exposing the glass article to radiation is performed in accordance with ANSI / AAMI / ISO 11137 1-3.

[0152] Exemplary Claim 47. The method of any of Exemplary Claim 43 to Exemplary Claim 46, wherein the radiation comprises gamma radiation at 35 kGy.

[0153] Exemplary Claim 48. The method of any of Exemplary Claim 43 to Exemplary Claim 46, wherein the radiation comprises X-ray radiation of 60 kV, 66 mA for 15 minutes.

[0154] Exemplary Claim 49. The method of any of Exemplary Claim 43 to Exemplary Claim48, wherein after exposure to the radiation, a loss in transmission through the at least one portion of the glass article is less than or equal to 25% for all wavelengths from 400 nm to 700 nm.

[0155] Exemplary Claim 50. The method of any of Exemplary Claim 43 to Exemplary Claim49, wherein after exposure to the radiation, a loss in transmission through the at least one portion of the glass article is less than or equal to 6% for all wavelengths from 400 nm to 700 nm.

[0156] Exemplary Claim 51. The method of any of Exemplary Claim 43 to Exemplary Claim50, wherein the at least one portion of the glass article comprises a wall portion of the glass article.

[0157] Exemplary Claim 52. The method of any of Exemplary Claim 43 to Exemplary Claim 50, wherein the at least one portion of the glass article comprises two opposing wall portions of the glass article.

[0158] Exemplary Claim 53. The method of any of Exemplary Claim 43 to Exemplary Claim 52, wherein a thickness of the at least one portion of the glass article is greater than or equal to 0. 1 mm and less than or equal to 1,000 mm.

[0159] Exemplary Claim 54. The method of any of Exemplary Claim 43 to Exemplary Claim 53, wherein the glass composition comprising a glass composition of any of Exemplary Claim 1 to Exemplary Claim 21.

Claims

CLAIMSWhat is claimed is:1 . A glass composition, comprising: greater than or equal to 70 mol.% and less than or equal to 80 mol.% SiCh; greater than or equal to 4 mol.% and less than or equal to 10 mol.% AI2O3; less than or equal to 2.5 mol.% B2O3; alkali oxide comprising: greater than or equal to 5 mol.% and less than or equal to 12 mol.% of Na2O; andLi2O in an amount that is less than or equal to the amount of AI2O3; and greater than or equal to 0.2 mol.% and less than or equal to 5 mol.% cerium oxide CeOx, wherein x is greater than or equal to 1.5 and less than or equal to 2.

2. The glass composition of claim 1, wherein Li2O is present in an amount that is less than or equal to 3 mol.%.

3. A glass composition, comprising: greater than or equal to 65 mol.% and less than or equal to 82 mol.% SiCh; greater than or equal to 2 mol.% and less than or equal to 12 mol.% AI2O3; B2O3 in an amount that is less than or equal to the amount of AI2O3; alkali oxide comprising: greater than or equal to 6 mol.% and less than or equal to 12 mol.% of Na2O; and less than or equal to 0.5 mol.% Li2O; greater than or equal to 0.2 mol.% and less than or equal to 0.8 mol.% cerium oxide CeOx, wherein x is greater than or equal to 1.5 and less than or equal to 2; less than or equal to 8 mol.% ZrCh. wherein a combined amount of AI2O3 and ZrCh is greater than or equal to 3.5 mol.% and less than or equal to 14 mol.%; and less than or equal to 1 mol.% BaO.

4. The glass composition of any of claims 1 to 3, wherein the cerium oxide CeOxcomprises present in an amount greater than 0.2 mol.%.

5. The glass composition of any of claims 1 to 4, wherein the amount of cerium oxide CeOxis greater than or equal to 0.25 mol.% and less than or equal to 0.7 mol.%.

6. The glass composition of any of claims 1 to 5, wherein the cerium oxide CeOx comprises at least one of cerium(III) oxide CeOi.s or cerium(IV) oxide CeCh.

7. The glass composition of any of claims 1 to 6, further comprising: less than or equal to 4 mol.% EfeOs.

8. The glass composition of any of claims 1 to 7, wherein the glass composition is substantially free from boron or boron compound.

9. The glass composition of any of claims 1 to 8, wherein the glass composition is substantially free from lithium or lithium compound.

10. The glass composition of any of claims 1 to 9, further comprising: alkaline earth oxide.

11. The glass composition of claim 10, wherein the alkaline earth oxide is present in an amount greater than or equal to 0 mol.% and less than or equal to 20 mol.% alkaline earth oxide.

12. The glass composition of any of claims 10 to 11, further comprising: greater than or equal to 0 mol.% and less than or equal to 12 mol.% alkaline earth oxide.

13. The glass composition of any of claims 10 to 12, wherein the alkaline earth oxide comprises at least one of MgO or CaO.

14. The glass composition of claim 13, MgO is present in an amount that is greater than or equal to 0 mol.% and less than or equal to 10 mol.%.

15. The glass composition of any of claims 13 to 14, MgO is present in an amount that is greater than or equal to 0 mol.% and less than or equal to 6 mol.%.

16. The glass composition of any of claims 13 to 15, CaO is present in an amount that is greater than or equal to 0 mol.% and less than or equal to 10 mol.%.

17. The glass composition of any of claims 13 to 16, CaO is present in an amount that is greater than or equal to 0 mol.% and less than or equal to 6 mol.%.

18. The glass composition of any of claims 1 to 17, wherein the alkali oxide further comprises K2O.

19. The glass composition of claim 18, wherein K2O is present in an amount that is greater than or equal to 0 mol.% and less than or equal to 7 mol.%.

20. The glass composition of any of claims 18 to 19, wherein K2O is present in an amount that is greater than or equal to 0 mol.% and less than or equal to 2 mol.%.

21. The glass composition of any of claims 10 to 20, wherein a combined amount of the alkali oxide, the alkaline earth oxide excluding MgO, and the cerium oxide CeOxin mol.% is greater than or equal to the amount of AI2O3 in mol.%.

22. A glass article formed from the glass composition of any of claims 1 to 21.

23. A glass article, the glass article comprising: a glass composition comprising:AI2O3;B2O3 in an amount less than or equal to the amount of AI2O3; and cerium oxide CeOx, wherein x is greater than or equal to 1.5 and less than or equal to 2; wherein after exposure to radiation, a color of the glass article changes, and wherein a change in the color of the glass article, when compared to the color of the glass article prior to radiation, is less than or equal to 6, as determined in accordance with CIE 76 formula for CIELAB AE* a b.

24. A glass article, the glass article comprising: a glass composition comprising:AI2O3;B2O3 in an amount less than or equal to the amount of AI2O3; and cerium oxide CeOx, wherein x is greater than or equal to 1.5 and less than or equal to 2; wherein after exposure to radiation, a loss in transmission through at least one portion of the glass article at wavelengths from 400 nm to 700 nm is less than 50% when compared to transmission through the at least one portion of the glass article prior to radiation.

25. The glass article of any of claims 23 to 24, wherein the radiation comprises one of gamma, X-ray, or electron beam.

26. The glass article of any of claims 23 to 25, wherein the radiation is conducted in accordance with ANSI / AAMI / ISO 11137 1-3.

27. The glass article of any of claims 23 to 25, wherein the radiation comprises gamma radiation at 35 kGy.

28. The glass article of any of claims 23 to 25, wherein the radiation comprises X-ray radiation of 60 kV, 66 mA for 15 minutes.

29. The glass article of any of claims 23 to 28, wherein determining the change in the color of the glass article comprises: determining the color of the glass article prior to the radiation; determining the color of the glass article after the radiation by measuring the color of the glass article 10 minutes after the radiation, 24 hours after the radiation, 48 hours after the radiation, 76 hours after the radiation, 7 days after the radiation, or 7 weeks after the radiation; and calculating the change in the color of the glass article based on the determined color of the glass article prior to the radiation and the determined color of the glass article after the radiation.

30. The glass article of claims 29, wherein determining the change in the color of the glass article further comprises: heating the glass article at 300 °C for 0.5 hour prior to the radiation.

31. The glass article of any of claims 23 to 28, wherein determining the change in the color of the glass article further comprises: obtaining a glass sample from the glass article, wherein the glass sample has a thickness of 1 mm; and exposing the glass sample to the radiation; wherein the color of the glass article prior to the radiation is represented by the color of the glass sample prior to the radiation; and wherein the change in the color of the glass article is represented by the difference between the color of the glass sample prior to the radiation and the color of the glass sample after the radiation.

32. The glass article of claim 31, wherein determining the change in the color of the glass article further comprises: heating the glass sample at 300 °C for 0.5 hour prior to exposing the glass sample to the radiation.

33. The glass article of any of claims 23 to 32, wherein after radiation, the change in the color of the glass article, when compared to the color of the glass article prior to radiation, is less than or equal to 3.

34. The glass article of any of claims 23 to 33, wherein immediately after radiation, transmission through the at least one portion of the glass article reduces at wavelengths from 400 nm to 700 nm as compared to transmission through the at least one portion of the glass article prior to radiation.

35. The glass article of any of claims 23 to 34, wherein after irradiation, transmission through the at least one portion of the glass article gradually increases for all wavelengths from 400 nm to 700 nm.

36. The glass article of any of claims 23 to 35, wherein the loss in transmission through the at least one portion of the glass article is less than 25% at wavelengths from 400 nm to 700 nm when compared to transmission through the at least one portion of the glass article prior to radiation.

37. The glass article of any of claims 23 to 36, wherein the at least one portion of the glass article comprises a wall portion of the glass article.

38. The glass article of any of claims 23 to 36, wherein the at least one portion of the glass article comprises two opposing wall portions of the glass article.

39. The glass article of any of claims 23 to 36, wherein the at least one portion of the glass article comprises a glass sample obtained from the glass article.

40. The glass article of any of claims 23 to 39, wherein a thickness of the at least one portion of the glass article is greater than or equal to 0.1 mm and less than or equal to 1,000 mm.

41. The glass article of any of claims 23 to 40, wherein the glass article is a pharmaceutical package.

42. The glass article of any of claims 23 to 41, wherein the glass composition comprising a glass composition of any of claims 1 to 21.

43. A method of processing a glass article, comprising: exposing a glass article to radiation; wherein: the glass article comprises a glass composition comprising cerium oxide CeOx, wherein x is greater than or equal to 1.5 and less than or equal to 2; and a color difference between a first color of the glass article measured prior to exposing the glass article to the radiation and a second color of the glass article measured after exposing the glass article to the radiation is less than or equal to 6, as calculated with CIE 76 formula for CIELAB AE* a b.

44. A method of processing a glass article, comprising: exposing a glass article to radiation; wherein: the glass article comprises a glass composition comprising cerium oxide CeOx, wherein x is greater than or equal to 1.5 and less than or equal to 2; and wherein after exposure to radiation, a loss in transmission through at least one portion of the glass article at wavelengths from 400 nm to 700 nm is less than 50% as compared to transmission through the at least one portion of the glass article prior to radiation.

45. The method of any of claims 43 to 44, wherein the radiation comprises one of gamma, X-ray, or electron beam.

46. The method of any of claims 43 to 45, wherein exposing the glass article to radiation is performed in accordance with ANSI / AAMI / ISO 11137 1-3.

47. The method of any of claims 43 to 45, wherein the radiation comprises gamma radiation at 35 kGy.

48. The method of any of claims 43 to 45, wherein the radiation comprises X-ray radiation of 60 kV, 66 mA for 15 minutes.

49. The method of any of claims 43to 48, wherein after exposure to the radiation, a loss in transmission through the at least one portion of the glass article is less than or equal to 25% for all wavelengths from 400 nm to 700 nm.

50. The method of any of claims 43, to 49, wherein after exposure to the radiation, a loss in transmission through the at least one portion of the glass article is less than or equal to 6% for all wavelengths from 400 nm to 700 nm.

51. The method of any of claims 43 to 50, wherein the at least one portion of the glass article comprises a wall portion of the glass article.

52. The method of any of claims 43 to 50, wherein the at least one portion of the glass article comprises two opposing wall portions of the glass article.

53. The method of any of claims 43 to 52, wherein a thickness of the portion of the glass article is greater than or equal to 0.1 mm and less than or equal to 1,000 mm.

54. The method of any of claims 43 to 53, wherein the glass composition comprising a glass composition of any of claims 1 to 21.

Images