Clarification bag for glass compositions

Abstract

A clarification package for a glass composition may include a sulfate or sulfide in an amount of from about 0.001 to about 1 mol% of the glass composition. The clarification package may include a multivalent compound, such as CeO2, SnO2, or Fe2O3, in an amount of from about 0.001 to about 1 mol% of the glass composition. The clarification pack may be free of sulfides. The clarification pack may be free of reducing agents for reducing sulfates to sulfides. The clarification package may be free of at least one of Cl, F, Sn, Ce, and As. The glass composition can be used to form glass tubes. The glass tube may be used to form a pharmaceutical package.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of priority under 35 U.S.C. §119 to U.S. Provisional Application Serial No. 63 / 393,067, filed on July 28, 2022, the contents of which are based upon and incorporated herein by reference in their entirety. Field of the Invention

[0003] The present disclosure relates generally to glass fining, and more particularly to fining packages of glass compositions for use in glass tubing and pharmaceutical packaging. Background Art

[0004] For safety reasons, regulatory agencies analyze the packaging materials in which drugs are stored or administered. For example, regulatory agencies limit the type and quantity of materials present in drug packaging (e.g., closed ampoules). Such drug packaging is made of glass, which is usually not cleaned before the corresponding pharmaceutical composition is loaded into the ampoule due to the type of materials used and industrial manufacturing methods. Some methods of industrial-scale production of glass involve being considered to be toxic or not present in an amount that is considered safe. For example, clarification is the process of forming glass, which may involve regulated materials. Clarifiers are introduced into the glass composition to remove gases or bubbles from the composition, thereby reducing the bubbles in the formed glass and increasing the transparency of the glass.

[0005] For example, a typical clarifier for borosilicate glass is sodium chloride (NaCl), which is particularly effective for borosilicate. In such conventional clarification processes, NaCl re-condenses onto the inner wall of the glass tube during the transformation process. The closed ampoule is opened (e.g., by flame or cutting) before filling, so preliminary cleaning is usually not possible. Since the closed ampoule is usually not cleaned before filling, and since NaCl remains on the inner wall of the ampoule, NaCl may mix with the filling fluid when the ampoule is filled. However, for such glass tubes to be used as closed ampoules for drug packaging, the glass composition needs to contain a chloride (Cl) content that is low enough to meet the requirements of the European Pharmacopoeia (EP). According to the 10.4 version of the European Pharmacopoeia, for containers with a nominal volume of 100 ml or less, the test result for chloride in sterile water for injection is required to be a maximum of 0.5 ppm.

[0006] In some cases, borosilicate glass with low Cl content can be used to try to achieve a chloride level low enough to meet EP requirements. In order to solve the clarification problem of glass with low chloride content, clarifiers such as As2O3, Sb2O3, F, CeO2 or SnO2 are usually used. However, some clarifiers are highly toxic, such as As. Even if the content of such toxic agents in the final glass is kept at an acceptable low level, its toxicity is still dangerous for people working in glass manufacturing. When clarifying glass for pharmaceutical applications, due to toxicity, the clarifiers As2O3 and Sb2O3 should be avoided, which make the clarification package very complicated (including multiple clarifiers) and expensive due to the increase in the number and type of raw materials. Despite the complexity, such clarification packages generally have lower clarification quality than using NaCl as a clarifier. Reagents such as Cl and / or F are less dangerous than some more toxic reagents, but they will corrode pollution abatement systems or be unpopular with users in some applications. For example, when Sn is used as a clarifier, evaporation / condensation problems may occur, resulting in appearance defects. Furthermore, Sn is a new element to the pharmaceutical industry, which may lead to hesitancy in adoption, and it is an expensive material.

[0007] There is a need for low-cost alternatives to conventional fining agents. Similarly, fining agents that can achieve effective fining effects with lower amounts of fining agent can reduce batch costs because less fining agent is required per batch. In addition, some glass compositions require high fining temperatures to achieve the appropriate fining viscosity, so there is also a need for fining packages that are suitable for such temperatures.

[0008] Therefore, there is a need for a simple, low-cost fining package for glass pharmaceutical packaging that maintains fining properties while preserving the properties of the glass and product and that can be used at the high fining temperatures of some glass compositions. Summary of the invention

[0009] According to aspect 1 of the present disclosure, there is provided a fining package for a glass composition, comprising: a sulfate or a sulfide in an amount of about 0.001 to about 0.1 mol % of the glass composition.

[0010] According to aspect 2, there is provided the clarification bag according to aspect 1, wherein the clarification bag contains sulfate and does not contain sulfide.

[0011] According to aspect 3, there is provided a clarification bag as described in aspect 1 or aspect 2, wherein the sulfate comprises at least one of an alkali metal sulfate and an alkaline earth metal sulfate.

[0012] According to aspect 4, there is provided a fining bag as described in any of the preceding aspects, wherein the fining bag further comprises a multivalent compound in an amount of about 0.001 to about 1 mol % of the glass composition.

[0013] According to aspect 5, there is provided the clarification package as described in aspect 4, wherein the multivalent compound comprises Sn or Ce.

[0014] According to aspect 6, there is provided a clarification package as described in aspect 5, wherein the multivalent compound comprises CeO 2 , SnO 2 or Fe 2 O 3 .

[0015] According to aspect 7, there is provided a fining package as described in any of the preceding aspects, further comprising a nitrate in an amount of about 0.01 to about 0.1 mol % of the glass composition.

[0016] According to aspect 8, there is provided a clarification packet as described in any of the preceding aspects, wherein the sulfate salt comprises a heavy alkaline earth metal sulfate.

[0017] According to aspect 9, there is provided a clarification package as described in aspect 8, further comprising a redox modifier.

[0018] According to aspect 10, there is provided a clarification packet as described in aspect 9, wherein the redox modifier is carbon, sugar or nitrate.

[0019] According to aspect 11, there is provided a clarification bag as described in any of the preceding aspects, wherein the clarification bag does not contain a reducing agent for reducing sulfate to sulfide.

[0020] According to aspect 12, there is provided a fining bag as described in any of the preceding aspects, wherein the glass composition comprises a borosilicate glass composition.

[0021] According to aspect 13, there is provided a fining bag as described in any of the preceding aspects, wherein the glass composition comprises an aluminosilicate glass composition.

[0022] According to aspect 14, there is provided a fining bag as described in any of the preceding aspects, wherein the glass composition is used to form a glass tube.

[0023] According to aspect 15, there is provided a clear package as described in aspect 14, wherein the glass tube is used to form a pharmaceutical package.

[0024] According to aspect 16, there is provided the clear package of aspect 15, wherein the pharmaceutical packaging comprises at least one of a vial, an ampoule, a syringe, and a cartridge.

[0025] According to aspect 17, there is provided a clarified bag as described in any of the preceding aspects, wherein the clarified bag does not contain at least one of Cl, F, Sn, Ce and As.

[0026] According to aspect 18, a fining package as described in any of the preceding aspects is provided, wherein the glass composition comprises: SiO2 in an amount of 70 to 76 wt% of the glass composition; B2O3 in an amount of 9 to 13.5 wt% of the glass composition; Al2O3 in an amount of 4 to 8 wt% of the glass composition; TiO2 in an amount of 0 to 0.1 wt% of the glass composition; Fe2O3 in an amount of 0 to 0.1 wt% of the glass composition; BaO in an amount of 0 to 0.1 wt% of the glass composition; and CaO in an amount of 0 to 3 wt% of the glass composition. % by weight of the glass composition; Na2O in an amount of 5 to 8.5 wt% of the glass composition; K2O in an amount of 0.5 to 3 wt% of the glass composition; MgO in an amount of 0 to 1 wt% of the glass composition; Cl in an amount of 0 to 0.03 wt% of the glass composition; F in an amount of 0 to 0.02 wt% of the glass composition; CeO2 in an amount of 0.08 to 0.5 wt% of the glass composition; SnO2 in an amount of 0.02 to 0.23 wt% of the glass composition; and ZrO2 in an amount of 0 to 0.08 wt% of the glass composition.

[0027] According to aspect 19, a fining package as described in aspect 18 is provided, wherein the glass composition comprises: SiO2 in an amount of 70 to 74 wt% of the glass composition; B2O3 in an amount of 10 to 13.5 wt% of the glass composition; Al2O3 in an amount of 5 to 7 wt% of the glass composition; TiO2 in an amount of 0 to 0.03 wt% of the glass composition; Fe2O3 in an amount of 0 to 0.04 wt% of the glass composition; BaO in an amount of 0 to 0.04 wt% of the glass composition; and CaO in an amount of 0.5 to 2.3 wt% of the glass composition. % by weight of the glass composition; Na2O in an amount of 6.5 to 7.5 wt% of the glass composition; K2O in an amount of 1.0 to 1.8 wt% of the glass composition; MgO in an amount of 0 to 0.1 wt% of the glass composition; Cl in an amount of 0.01 to 0.03 wt% of the glass composition; F in an amount of 0 to 0.02 wt% of the glass composition; CeO2 in an amount of 0.08 to 0.2 wt% of the glass composition; SnO2 in an amount of 0.02 to 0.12 wt% of the glass composition; and ZrO2 in an amount of 0 to 0.08 wt% of the glass composition.

[0028] According to aspect 20, a fining package as described in aspect 19 is provided, wherein the glass composition comprises: SiO2 in an amount of 70 to 73 wt% of the glass composition; B2O3 in an amount of 10.5 to 13.2 wt% of the glass composition; Al2O3 in an amount of 5 to 7 wt% of the glass composition; TiO2 in an amount of 0 to 0.03 wt% of the glass composition; Fe2O3 in an amount of 0 to 0.04 wt% of the glass composition; BaO in an amount of 0 to 0.04 wt% of the glass composition; and CaO in an amount of 1 to 2.3 wt% of the glass composition. % by weight of the glass composition; Na2O in an amount of 6.5 to 7.3 wt% of the glass composition; K2O in an amount of 1.0 to 1.5 wt% of the glass composition; MgO in an amount of 0 to 0.1 wt% of the glass composition; Cl in an amount of 0.01 to 0.02 wt% of the glass composition; F in an amount of 0 to 0.02 wt% of the glass composition; CeO2 in an amount of 0.08 to 0.2 wt% of the glass composition; SnO2 in an amount of 0.02 to 0.12 wt% of the glass composition; and ZrO2 in an amount of 0 to 0.08 wt% of the glass composition.

[0029] According to aspect 21, a fining package as described in any one of aspects 1-17 is provided, wherein the glass composition comprises: SiO2 in an amount of 75 to 85 weight % of the glass composition; B2O3 in an amount of 9.5 to 14.5 weight % of the glass composition; Al2O3 in an amount of 0.5 to 5 weight % of the glass composition; TiO2 in an amount of 0 to 0.1 weight % of the glass composition; Fe2O3 in an amount of 0 to 0.1 weight % of the glass composition; BaO in an amount of 0 to 0.1 weight % of the glass composition; Na2O in an amount of 2 to 8 weight % of the glass composition; K2O in an amount of 0 to 3 weight % of the glass composition; CaO and MgO in an amount of 0 to 1.0 weight % of the glass composition; Cl in an amount of 0 to 0.10 weight % of the glass composition; and SnO2 in an amount of 0 to 0.2 weight % of the glass composition.

[0030] According to aspect 22, a fining package as described in any one of aspects 1-17 is provided, wherein the glass composition comprises: SiO2 in an amount of 74 to 80 weight % of the glass composition; Al2O3 in an amount of 4 to 8 weight % of the glass composition; CaO in an amount of 0 to 0.5 weight % of the glass composition; Na2O in an amount of 8 to 14 weight % of the glass composition; MgO in an amount of 3 to 7 weight % of the glass composition; and SnO2 in an amount of 0 to 0.23 weight % of the glass composition.

[0031] According to aspect 23, there is provided a method of clarifying glass for forming pharmaceutical packaging, the method comprising: clarifying a glass composition by adding a clarification package as described in any one of claims 1-22 to the glass composition to remove bubbles; and forming a glass tube from the clarified glass composition.

[0032] According to aspect 24, there is provided a method as described in aspect 23, further comprising forming the pharmaceutical package from the glass tube.

[0033] According to aspect 25, there is provided a method as described in aspect 24, wherein the pharmaceutical packaging comprises a pharmaceutical ampoule.

[0034] According to aspect 26, there is provided a method as described in any one of aspects 23-25, wherein the fining process is carried out at a fining temperature of at least 1400°C.

[0035] According to aspect 27, there is provided a method as described in aspect 26, wherein the refining temperature is at least 1500°C.

[0036] According to aspect 28, a method as described in aspect 27 is provided, wherein the refining temperature is from about 1500°C to about 1750°C, from about 1500°C to about 1600°C, from about 1600°C to about 1700°C or from about 1550°C to about 1650°C.

[0037] According to aspect 29, there is provided a method as described in aspect 24, further comprising: melting a batch material for a glass composition, the batch material comprising sand having a D50 average particle size greater than 200 microns or greater than 300 microns.

[0038] Other aspects of the present disclosure will be explained in part in the following detailed description, drawings and any claims, and in part will be derived from the detailed description, or can be learned through the practice of the present disclosure. It should be understood that the above general description and the following detailed description are only exemplary and explanatory, rather than limiting the disclosed invention.

[0039] BRIEF DESCRIPTION OF THE DRAWINGS

[0040] Figure 1 is a comparative photograph of glass samples D1, D2, D3, and D4 formed as described in the present disclosure.

[0041] Figure 2 Yes Display Figure 1 The calculated values ​​per cm in samples D1, D2, D3 and D4 as described in the present disclosure are 3 A histogram of the number of defects.

[0042] Figure 3is a comparative photograph of glass samples D5, D6, D7, and D8 formed as described in the present disclosure.

[0043] Figure 4 Yes Display Figure 3 The calculated values ​​per cm in samples D5, D6, D7 and D8 as described in the present disclosure are 3 A histogram of the number of defects.

[0044] Figure 5 is a comparative photograph of glass samples D9, D10, D11, and D12 formed as described in the present disclosure.

[0045] Figure 6 Yes Display Figure 5 The calculated values ​​per cm in samples D9, D10, D11 and D12 as described in the present disclosure are 3 A histogram of the number of defects.

[0046] Figure 7 are photographic comparisons of glass samples D13, D14, D15, and D16 formed as described in the present disclosure.

[0047] Figure 8 Yes Display Figure 7 The calculated values ​​per cm in samples D13, D14, D15 and D16 as described in the present disclosure are 3 A histogram of the number of defects.

[0048] Fig. 9 are photographic comparisons of glass samples D17, D18, D19, and D20 formed as described in the present disclosure.

[0049] Fig.10 Yes Display Fig. 9 The calculated values ​​per cm in samples D17, D18, D19 and D20 as described in the present disclosure are 3 A histogram of the number of defects.

[0050] Fig.11 is a comparative photograph of glass samples D21, D22, D23, D24, and D25 formed as described in the present disclosure.

[0051] Fig.12 Yes Display Fig.11 The calculated values ​​per cm in samples D21, D22, D23, D24 and D25 as described in the present disclosure are 3 A histogram of the number of defects.

[0052] Fig.13 are photographic comparisons of glass samples D26, D27, D28, D29, and D30 formed as described in the present disclosure.

[0053] Fig.14 is a photographic comparison of glass samples D31 and D32 formed as described in the present disclosure.

[0054] Fig.15 is a photographic comparison of glass samples D33 and D34 formed as described in the present disclosure.

[0055] Fig.16 is a comparison of photographs of glass samples D35a, D35b, D36a, and D36b formed as described in the present disclosure.

[0056] Fig.17 Yes Display Fig.16 The average of samples D35a, D35b, D36a and D36b and samples D35 and D36 as described in the present disclosure is calculated per cm 3 Histogram of seed numbers.

[0057] Fig.18 Yes Display Fig.16 The average of samples D35a, D35b, D36a and D36b and samples D35 and D36 as described in the present disclosure is calculated per μm 3 Histogram of solid numbers.

[0058] Fig.19 is the average number of samples D37a, D37b, D38a and D38b and samples D37 and D38 calculated per cm as described in the present disclosure. 3 Histogram of seed numbers.

[0059] Fig. 20 is the average number of samples D37a, D37b, D38a and D38b and samples D37 and D38 calculated according to the present disclosure. 3 Histogram of solid numbers.

[0060] Fig.21 is the average of the samples D39a, D39b, D40a and D40b and the samples D39 and D40 calculated according to the present disclosure. 3 Histogram of seed numbers.

[0061] Fig. 22 is the average of the samples D39a, D39b, D40a and D40b and the samples D39 and D40 as described in the present disclosure. 3 Histogram of solid numbers.

[0062] Fig.23 is a comparative photograph of glass samples D41, D42, D43, and D44 formed as described in the present disclosure.

[0063] Fig.24 Yes Display Fig.23 The calculated values ​​per cm in samples D41, D42, D43 and D44 as described in the present disclosure are 3 A histogram of the number of defects. DETAILED DESCRIPTION

[0064] The various aspects of the present disclosure are described in detail below with reference to the accompanying drawings (if any). Reference to various aspects does not limit the scope of the present invention, which is limited only by the scope of the appended claims. In addition, any examples listed in this specification are not limiting, but only list some of the many possible aspects of the claimed invention.

[0065] Aspects described herein provide a simple, low-cost clarification package that adds sulfates or sulfides to replace halides and / or other commonly used multivalent elements (such as Sn and Ce) present in the clarification package or significantly reduces their use compared to conventional clarification packages for glass tubes formulated for pharmaceutical packaging. The methods described herein clarify borosilicate and aluminosilicate glasses used as glass tubes for primary pharmaceutical packaging. Embodiments of the present invention include clarification packages that use sulfates and / or sulfides as low-cost alternatives to Sn and Ce clarifiers, and additional use of small amounts of sulfates and / or sulfides in the clarification package can effectively clarify the glass. The retention of sulfates in glass is very low, so the use of sulfates as clarifiers should be relatively transparent to the end user. The clarification packages disclosed herein can be used with glass compositions that require high clarification temperatures. As used herein, "clarification temperature" refers to the temperature of the glass composition required when the glass reaches a clarified viscosity or the viscosity of the glass when it is clarified.

[0066] The problem with glass compositions having relatively high clearing temperatures is finding a suitable fining agent to remove bubbles from the glass that is acceptable to a wide range of end users and / or for a wide range of uses, while also being low cost and gentle on melting resources. For example, some may use the toxic element arsenic (As) as a fining agent, which may be harmless in low levels in glass from the perspective of many end users, but is still potentially dangerous to people working in factories where arsenic is used. Other agents (such as Cl and / or F) are less dangerous, but can corrode the abatement system, and some end users or applications (such as closed ampoules) cannot tolerate the presence of Cl in glass containers. In addition, Sn is also commonly used as a fining agent, but there are evaporation and / or condensation problems, resulting in some cosmetic defects. Sn is also a new element for the pharmaceutical industry, which can lead to hesitation in adoption, and it is also an expensive raw material.

[0067] A typical clarifier for such borosilicate glass is sodium chloride (NaCl), which is particularly effective for borosilicate glass. However, in certain applications, such as glass tubes to be used as closed ampoule drug packaging, the glass needs to contain a chloride (Cl) content low enough to comply with the requirements of the European Pharmacopoeia (EP). According to the 10.4 edition of the European Pharmacopoeia, the test result for chloride in sterile water for injection is a maximum of 0.5 ppm for containers with a nominal volume of 100 ml or less. Therefore, when the ampoule contains water for injection, the EP requirements allow a maximum Cl content of 0.5 ppm for containers with a nominal volume of less than 100 mL. Therefore, if NaCl is used as a clarifier for borosilicate glass [such as Corning 51-D borosilicate glass tubes (Corning Incorporated, Corning, NY)], the batch Cl content must not exceed 0.03 wt%.

[0068] To address the fining problem of borosilicate glass with low chloride (Cl) content, conventional fining techniques use fining agents such as As2O3, Sb2O3, F, CeO2, or SnO2. However, As2O3 and Sb2O3 are generally avoided when fining glass for pharmaceutical applications. Therefore, conventional fining packages for borosilicate glass for pharmaceutical applications [e.g., Corning 51-5 borosilicate glass tubing (Corning Incorporated, Corning, NY)] are complex and contain four fining agents. The four fining agents in the conventional fining package may include SnO2, CeO2, F, and Cl. Despite the complexity, the fining quality is significantly lower than that of borosilicate glass that is clarified using NaCl.

[0069] However, such clarification packages are complex and require multiple raw materials, which results in increased costs compared to when NaCl is used as the fining agent. For example, SnO2 comes from an expensive raw material. Therefore, there is a need for a simpler, lower cost clarification package for pharmaceutical applications that maintains the clarification performance achieved by conventional clarification packages while achieving the glass and product properties necessary for pharmaceutical applications.

[0070] In an embodiment of the present disclosure, a simple, low-cost clarification package is provided. The clarification package can be used to clarify glass. The aspects of the clarification package described herein can be used with a glass composition. In an embodiment, the glass composition includes a borosilicate glass composition. In an embodiment, the glass composition includes an aluminosilicate glass composition.

[0071] In embodiments, glass compositions using the clarification packages described herein can be used to form glass tubes. In embodiments, glass tubes formed from glass compositions using the clarification packages described herein can be used for pharmaceutical packaging. In embodiments, pharmaceutical packaging can include vials, ampoules, cartridges, or syringes. Non-limiting examples of transparent borosilicate glass tubes are Corning 33 and 51-5 borosilicate glass tubes (Corning Incorporated, Corning, NY). Non-limiting examples of transparent aluminosilicate glass bottles are Corning 100-1000. Glass bottles (Corning Incorporated, Corning, NY).

[0072] Non-limiting examples of glass compositions are described in U.S. Patent Application Publication No. 2014 / 0001076, U.S. Patent Application Publication No. 2014 / 0001143, U.S. Patent Application Publication No. 2014 / 0151320, U.S. Patent Application Publication No. 2014 / 0151321, U.S. Patent Application Publication No. 2014 / 0151370, U.S. Patent No. 9,034,442, and U.S. Patent No. 9,428,302, each of which is incorporated herein by reference in its entirety.

[0073] Embodiments described herein include clarification packages containing elemental sulfur (S), specifically in the form of alkali and alkaline earth metal sulfates. Sulfate clarification has been used in the soda-lime glass industry, such as Na2SO4, which is used in combination with a reducing agent (such as sugar or graphite) to decompose the sulfate and release gases that help clarify the glass. In the batch pile, most or all of the Na2SO4 is converted to Na2S+2O2. This conversion process can help the gas escape at low temperatures (e.g., below 1000°C), thereby making the batch fluffy and producing fewer bubbles in the final glass. Na2S decomposes between 1200°C and 1400°C and clarifies relatively low-temperature soda-lime glass. However, other glass compositions are clarified at significantly higher temperatures. These higher clarification temperatures may be about 1400°C, such as 1550°C or higher, including 1650°C or higher.

[0074] Embodiments described herein provide fining packages in which one or more typical fining agents (e.g., F, Cl, Sn, Ce, etc.) are removed and replaced with only S-containing compounds, or with a mixture of S-containing compounds and multivalent compounds (including, for example, Sn, Ce, Fe, etc.) and / or one or more oxidizing agents (e.g., nitrates). Fining packages containing sulfates and optional oxides have the following advantages: (1) they are as effective or more effective at fining as conventional multivalent elements; (2) they significantly reduce the amount and cost of fining agents, for example, by eliminating the use of Sn; (3) they produce glass that is free of Cl, as required by certain end users and applications; (4) they reduce the flux of volatile metals (e.g., Sn) in the glass; (5) they reduce or eliminate color and / or transmission losses.

[0075] Embodiments of the present disclosure include a clarification bag having at least one S-containing compound. The S-containing compound may be a sulfate or a sulfide. In an embodiment, the clarification bag contains sulfate and does not contain sulfide. The sulfate may be an alkali metal sulfate or an alkaline earth metal sulfate. Non-limiting examples include sodium sulfate (Na2SO4), potassium sulfate (KSO4), calcium sulfate (CaSO4), barium sulfate (BaSO4), and strontium sulfate (SrSO4). Embodiments may include another compound in the form of a multivalent compound in an amount of about 0.001 to about 1.0 mole. % Non-limiting examples include Sn, Ce, and Fe compounds, including CeO2, SnO2, and Fe2O3.

[0076] Embodiments described herein provide clarified packages that contain a small amount of SnO2 relative to conventional clarified packages. For example, a small amount of SnO2 can be considered to be less than about 0.3 wt%. In one embodiment, a large amount of SnO2 can be considered to be less than about 0.1 wt%.

[0077] Embodiments described herein also include fining packages containing sulfates and nitrates as described above. Nitrates may be used in amounts of about 0.01 to about 0.1 mol% of the glass composition. It is believed that nitrates increase the oxygen available to diffuse into the bubbles, causing them to grow in size, increase their rate of ascent and refine faster from the melt, similar to the benefits of adding multivalent compounds. However, depending on the embodiment, the fining package may not contain redox modifiers such as nitrates (oxidants) or carbon (reducants) to enhance the fining effect.

[0078] Embodiments include clarification packs containing sulfate but without a reducing agent for reducing the sulfate to sulfide. The clarification pack may be free of at least one of Cl, F, Sn, Ce, and As; or free of at least two or at least three of Cl, F, Sn, Ce, and As. Similar or better performance may be observed for clarification pack embodiments using heavy alkaline earth metal sulfates with the addition of a reducing agent such as carbon or sugar, which is believed to induce a sulfate (oxidized S) to sulfide (reduced S) reaction and change the decomposition temperature and kinetics of the compound.

[0079] Sulfate is much cheaper than tin, and according to embodiments herein, the sulfate content required for clarification is lower than that used in tin and halide clarification, thereby saving costs and alleviating pollution control issues, especially at the Vineland plant. Sulfate can be dosed in a variety of forms, including sodium, calcium or potassium, depending on the glass composition, thereby increasing flexibility and potentially further saving costs. In addition, the retention of sulfate is at low ppm levels, resulting in a clear clarification package for the customer.

[0080] The sulfate decomposition reaction, where "M" represents an alkali metal or alkaline earth metal element, is as follows:

[0081] MSO4(s)→MO(s)+SO2(g)+1 / 2O2(g)

[0082] (M = Na, K, Ca, Sr, Ba) Sulfur and oxygen form dissolved gases in the glass melt (this reaction occurs above 1400°C; at lower temperatures, carbon is used to promote the decomposition of sulfates). These gases then diffuse into existing bubbles, causing bubble growth and Stokes fining when these bubbles enter the fining zone of the glass melt. The temperature in the fining zone is higher than that in the melting zone, typically 50-100°C higher, which further promotes bubble growth and rise, thereby promoting Stokes fining. Therefore, the entire fining process consists of three stages: (1) the chemical part, in which sulfates decompose into sulfur and oxygen gas compounds; (2) the transport part, in which gases diffuse into existing bubbles; and (3) the physical part, in which bubbles grow and rise, commonly known as Stokes fining.

[0083] Polyvalent compounds (such as CeO 2、 SnO2 or Fe2O3) to provide additional oxygen to the melt, further enhancing the fining process. For example, CeO2 decomposes into Ce2O3 and O2 by the following reaction:

[0084] 2CeO2→Ce2O3+1 / 2O2

[0085] Provides additional oxygen which can diffuse into the bubbles and aid in clarification. Batch CeO2 ranges from 0.01 to 0.1 mol%, typically less than 0.06 mol%. SnO2 clarification is a similar reaction:

[0086] SnO2→SnO+1 / 2O2

[0087] Neither tin nor cerium are particularly effective fining agents by themselves. Which substance is used to aid fining depends largely on the temperature, with cerium being more effective at lower temperatures (below 1550°C) and tin being more effective at higher temperatures (above 1550°C).

[0088] Simple fining packages with fewer components are advantageous for batch mixing. For example, it is advantageous to store and weigh fewer raw materials before mixing, preparing and introducing into industrial production tanks. Such glass compositions allow cost savings on raw materials. The simplification of the fining package also allows for further development and understanding of the mechanism of the remaining fining agent.

[0089] For example, various glass compositions and fining packages are shown in Tables 1-5 as examples of embodiments of the present disclosure. Tables 1 and 2 show aluminosilicate glass compositions with various fining packages according to embodiments of the present disclosure. Tables 3, 4, and 5 show borosilicate glass compositions with various fining packages according to embodiments of the present disclosure. These examples are in no way intended to limit the embodiments of the present disclosure, but are merely provided as working examples to illustrate some aspects of the embodiments of the present disclosure.

[0090]

[0091] Table 1. Glass compositions and fining packages.

[0092] As shown in Table 1, samples C1 and C2 are aluminosilicate glass compositions clarified with NaNO2 and SnO2. Sample C3 is a glass composition without a clarifier. Samples C4-C11 show glass compositions with clarifiers according to embodiments of the present disclosure. Specifically, samples C4-C11 each use a sulfate (e.g., a sulfate of Na, K, Ca, Sr, or Ba) alone, or in the case of sample C10, together with a reducing agent (e.g., C). Specifically, samples C4, C5, and C6 are clarified with NaSO4; sample C7 is clarified with K2SO4; sample C8 is clarified with CaSO4; sample C9 is clarified with SrSO4; sample C10 is clarified with SrSO4 and C; and sample C11 is clarified with BaSO4. None of the clarification packages contain Cl, F, Sn, Ce, and As.

[0093]

[0094] Table 2. Glass compositions and fining packages.

[0095] As shown in Table 2, samples C12 to C21 are aluminosilicate glass compositions having a clarification package containing one or more S-containing compounds. Specifically, the clarification package contains one or more sulfates and / or sulfides. Specifically, for the clarification package containing sulfates, samples C17-C21 contain NaSO4; sample C13 contains SrSO4; and samples C12 and C14 contain BaSO4. Sample C12 also contains a reducing agent (i.e., C). Samples C17 and C19-C21 also contain a multivalent compound SnO2, and sample C18 also contains a multivalent compound CeO2. Samples C15 and C16 are clarified with sulfides BaS and SrS, respectively. The clarification packages of samples C12-C16 do not contain Cl, F, Sn, Ce, and As, and the remaining samples C17-C21 contain only a small amount of Cn and Ce as part of the multivalent compounds of the clarification package.

[0096]

[0097] Table 3. Glass compositions and fining packages.

[0098] Table 3 shows examples of borosilicate glass compositions and fining packages. As a comparative example of an embodiment of the present disclosure, sample C22 is a composition without any fining agent, and sample C23 uses a conventional NaCl fining package. Samples C24 and C25 use Na2SO4, and sample C25 also contains SnO2. Samples C28 and C29 also use sulfate in the form of BaSO4 and SrSO4, respectively. As a comparative example, sample C26 uses a typical fining agent, SnO2. Sample C27 uses BaS.

[0099]

[0100] Table 4. Glass compositions and fining packages.

[0101] Table 4 shows examples of borosilicate glass compositions and fining packages. Samples C30, C31, and C32 are sulfate-fined with Na2SO4, CaSO4, and K2SO4, respectively, and do not contain Sn, Cl, F, or Ce. As a comparative example of an embodiment of the present disclosure, sample C33 is a composition using a conventional fining package (containing Sn, Cl, F, and Ce).

[0102]

[0103]

[0104] Table 5. Glass compositions and fining packages.

[0105] As shown in Table 5 above, sample C35 was clarified with sodium sulfate as described above for sample C30; sample C36 was sodium sulfate clarified with sodium nitrate; and samples C34 and C38 were comparative examples showing conventional clarification packages using chlorine, fluorine, cerium, and tin.

[0106] The fining packages according to embodiments of the present disclosure can completely eliminate all existing fining agents used in the intended glass compositions, with the possible exception of Ce in some embodiments, and replace them with a variation of sulfates and an optional redox modifier package commonly used in the float and container glass industries, but modified for borosilicate glass compositions and higher melting and fining temperatures.

[0107] Experimental Results

[0108] Glass preparation, seed counting and solids analysis

[0109] Glass samples were prepared using static and continuous forming techniques. For static forming, a precious metal crucible capable of holding approximately 0.5 kg to 1.5 kg of molten glass was used. The loading temperature range was 1350-1500°C, the melting temperature range was 1450-1600°C, and the clarification temperature range was 1500-1650°C. The melt was then placed in a crucible for annealing and core drilling, or poured onto a steel table. Defects on the core drilling samples were counted, and optical and chemical inspections were performed on the quenched melt pours. Selected components were studied on a continuous melting platform to investigate the feasibility of scaling up these alternative clarification packages. Continuous melting experiments help ensure successful evaluation of the performance of clarification packages according to embodiments of the present disclosure. This continuous experiment was conducted for 6 days on a precious metal melting platform equipped with a continuous feeding system to produce glass ribbons at a rate of 10-15 pounds per hour. The melting temperature in this continuous forming experiment ranged from 1500°C to 1600°C, and the clarification temperature ranged from 1550°C to 1650°C. Defect counts were performed on glass strip samples collected periodically during each consecutive experiment.

[0110] For borosilicate glass compositions (e.g., the examples shown in Table 4 above and Table 5 above), observations of melting, fining, and glass quality from two continuous forming experiments, where melting and fining properties were sampled throughout the process (through strategic sampling / measurements) as well as after the melt was quenched, indicated that the sulfate solution results can indeed be scaled up to a continuous process and are less aggressive and detrimental to the glass tank refractory materials.

[0111] For aluminosilicate glasses that do not contain boron (e.g., the examples shown in Tables 1-3 above), observations and sampling of melting, fining, and glass quality from a continuous forming experiment indicate that sulfate solutions result in improved continuous processes. According to embodiments, sulfates are viable tin replacements for several reasons: (i) evaporation and condensation of Sn during the conversion process from tubes to containers (e.g., vials or other pharmaceutical packaging) can cause cosmetic defects, (ii) tin can be the most expensive batch material or one of the most expensive batch materials in these glass compositions, and (iii) some users or fillers of pharmaceutical packaging are hesitant to include tin as part of their pharmaceutical packaging.

[0112] Characterization of glass composition and properties

[0113] Figure 1 A comparison chart showing four images of a center core slice of a crucible melt of a borosilicate glass composition. The melting temperature and time for all samples were 1500°C for 1 hour, and the fining temperature was 1550°C for 30 minutes. Sample D1 contained no fining bag, while samples D2, D3, and D4 used Na2SO4 in amounts of 0.05, 0.1, and 0.2 mol%, respectively. All samples also used 0.1 mol% nitrate. Visual comparison of samples D2-D4 with sample D1 shows that there are significantly fewer seeds in the sulfate-fined glass compared to the glass without fining agent.

[0114] Figure 2 Shows a comparison Figure 1 Three locations (top, middle and bottom) of each sample in samples D1-D4 are measured per cm 3 Histogram of the number of defects per cm 3 The number of bubbles or defects is plotted on a logarithmic scale. Note that the melt composition without a fining agent (D1) contains a large number of bubbles throughout the glass core slice, while the glass refined with sodium sulfate contains bubbles at the top of the melt, but far fewer bubbles in the center and lower portions of the melt, indicating the fining effect of the sulfate.

[0115] Figure 3 A comparison chart showing four images of center core slices of crucible melts of borosilicate glass compositions containing 0.1 mol % nitrates and no fining agent (sample D5) compared to 0.05 mol % sodium sulfate (Na2SO4) (sample D6), 0.05 mol % potassium sulfate (K2SO4) (sample D7) and 0.05 mol % calcium sulfate (CaSO4) (sample D8). The melting temperature and time for all samples were 1500°C for 1 hour, and the fining temperature was 1550°C for 30 minutes. Figure 1 As shown, Figure 3It is shown that more seeds are visible in the sample D5 without fining agent than in the sulfate-fined glasses in samples D6-D8.

[0116] Figure 4 Shows a comparison Figure 3 Three locations (top, middle and bottom) of each sample in samples D5-D8 are measured per cm 3 Histogram of the number of defects per cm 3 The number of bubbles or defects is plotted on a logarithmic scale. Note that the melt composition without a fining agent (D5) contains a large number of bubbles throughout the glass core slice, while the glass refined with sulfate contains fewer bubbles.

[0117] Figure 5 A comparison chart of four images of center core slices of crucible melts of nitrate-free borosilicate glass compositions (Samples D9-D12) is shown. The melting temperature and time for all samples were 1450°C for 90 minutes, and the fining temperature was 1550°C for 120 minutes, and then cooled to 1400°C for 1 hour. Samples D9, D10, and D11 were clarified with sulfate, while D12 was clarified with a conventional fining package as a comparison. Specifically, sample D9 used 0.05 mol% sodium sulfate; sample D10 used 0.05 mol% sodium sulfate and 0.03% cerium oxide; and D11 used 0.05 mol% sodium sulfate and 0.06 mol% cerium oxide. Comparative sample D12 used a fining package containing Cl, F, Ce, and Sn. Note that there are bubbles throughout the core of sample D12, indicating very poor fining when using the fining package containing 0.04mol% Cl, 0.79mol% F, 0.06mol% Ce, and 0.05mol% Sn. It is believed that in both ceria-containing melts, ceria aids Stokes fining by providing additional O2 to assist sulfates to aid bubble growth, thereby accelerating bubble rise.

[0118] Figure 6 Shows a comparison Figure 5 Three locations (top, middle and bottom) of each sample in samples D9-D12 are measured per cm 3 Histogram of the number of defects per cm 3 The number of bubbles or defects is plotted on a logarithmic scale. Note that the melt composition containing the Sn-Ce-F-Cl fining package (D12) contains a large number of bubbles throughout the glass core slice, while the glass refined with sulfate contains fewer bubbles.

[0119] Figure 7A comparison chart of four images of center core slices of crucible melts of nitrate-free borosilicate glass compositions (Samples D13-D16) is shown. The melting temperature and time for all samples were 1450°C for 90 minutes, and the refining temperature was 1550°C for 120 minutes, and then cooled to 1400°C for 1 hour. Samples D13, D14, and D15 were refined with sulfate, while D16 was refined with a conventional refining package as a comparison. Specifically, sample D13 used 0.1 mol% sodium sulfate; sample D14 used 0.1 mol% sodium sulfate and 0.03% cerium oxide; and D15 used 0.1 mol% sodium sulfate and 0.06 mol% cerium oxide. Comparative sample D16 used a refining package containing Cl, F, Ce, and Sn. Note that there are bubbles throughout the core of sample D16, indicating very poor fining when using a fining package containing 0.04 mol% Cl, 0.79 mol% F, 0.06 mol% Ce, and 0.05 mol% Sn. This melt shows that increasing sulfate from 0.05 mol% (see e.g. Figure 1 , 3 and 5; and Figure 2 , 4 and 6 ) doubled to 0.1 mol % reduces the number of bubbles in the melt, as Figure 7 and Figure 8 As shown in the diagram.

[0120] Figure 8 Shows a comparison Figure 7 Three locations (top, middle and bottom) of each sample in samples D13-D16 are measured per cm 3 Histogram of the number of defects per cm 3 The number of bubbles or defects is plotted on a logarithmic scale. Note that the melt composition containing the Sn-Ce-F-Cl fining package (D16) contains a large number of bubbles throughout the glass core slice, while the glasses refined with sulfate (D13-D15) contain fewer bubbles at all locations. These defect counts show that doubling the sulfate from 0.05 mol% to 0.1 mol% does reduce the number of bubbles in the melt.

[0121] Fig. 9A comparison chart of four images of crucible melt center core slices of nitrate-free borosilicate glass compositions (samples D17-D20) is shown. The melting temperature and time for all samples were 1450°C for 90 minutes, and the refining temperature was 1550°C for 120 minutes, and then cooled to 1400°C for 1 hour. Samples D17, D18, and D19 were refined with sulfates, while D20 was refined with a conventional refining package as a comparison. Specifically, sample D17 used 0.1 mol% sodium sulfate; sample D18 used 0.1 mol% calcium sulfate; and D19 used 0.1 mol% potassium sulfate. Comparative sample D20 used a refining package containing 0.04 mol% Cl, 0.79 mol% F, 0.06 mol% Ce, and 0.05 mol% Sn. Note that there are bubbles throughout the core of sample D20, indicating that the refining effect is very poor when using a refining package containing Cl, F, Ce, and Sn. This melt again demonstrates the effect of doubling the sulfate from 0.05 mol% to 0.1 mol%. Furthermore, although the above samples used fine sand with a D50 particle size of 154 microns, Fig. 9 The samples in used a coarser sand [e.g., crystal sand from Sibelco] with a D50 particle size of 352 microns, which increased the average particle size by more than 200 microns. Coarser sand can improve the clarification effect with sulfate clarification packs. Unless otherwise stated, the examples shown in this article used fine sand (e.g., D50 particle size of 154 microns). This benefit was not observed in the crucible melt containing Sn-Ce-F-Cl clarification packs. The improvement may be due to slower melting of silica, resulting in a slower rate of bubble generation, allowing bubbles to be removed without flooding the clarification pack, and less foaming of the batch, combined with the surfactant effect of sulfate, coating the sand particles and preventing them from sticking together. Sulfate can act as a surfactant in the melt, preventing sand particles from agglomerating, thereby facilitating melting.

[0122] Fig.10 Shows a comparison Fig. 9 Three locations (top, middle and bottom) of each sample in samples D17-D20 are measured per cm 3 Histogram of the number of defects per cm 3 The number of bubbles or defects is plotted on a logarithmic scale. Note that the melt composition containing the Sn-Ce-F-Cl fining package (D20) contains a large number of bubbles throughout the glass core slice, while the glasses refined with sulfate (D17-D19) contain fewer bubbles at all locations. These melts show the impact of sulfate fining with coarser sand. In fact, D19 is completely refined with no residual bubbles. The sodium sulfate fining package in D17 also produced very few bubbles.

[0123] Fig.11A comparison chart showing five images of crucible melt center core slices of boron-free aluminosilicate glass compositions (samples D21-D25). Sample D25 was refined with Na2SO4, sample D21 was refined with Na2SO4 and Ce, and sample D22 was refined with Na2SO4 and Sn. Each of D21, D22, and D25 showed fewer remaining bubbles than D23, which used a conventional SnO2 refining bag. When counted, the number of defects / cm 3 It also shows that the Na2SO4, Na2SO4+Ce and Na2SO4+Sn fining packages all have fewer defects than D23, which uses a conventional SnO2 fining package. In contrast, sample D24 uses no fining agent, resulting in voids throughout the sample.

[0124] Fig.12 Shows a comparison Fig.11 Three locations (top, middle and bottom) of each sample in samples D21-D25 are measured per cm 3 Histogram of the number of defects per cm 3 The number of bubbles or defects is plotted on a logarithmic scale. Note that the melt composition without the fining package (D24) contains a large number of bubbles throughout the glass core slice, and the conventional SnO2 package has more voids throughout the slice compared to the sulfate-fined melt.

[0125] Fig.13 A comparison chart of five images of crucible melt center core slices of aluminosilicate glass compositions containing no boron (samples D26-D30) is shown. Sample D26 was refined with BaSO4 containing carbon, sample D27 was refined with BaSO4 containing no carbon, sample D29 was refined with SrSO4 containing carbon, and sample D30 was refined with SrSO4 containing no carbon. Comparative sample D28 contained no refining package and showed worse results, with more defects than D26, D27, D28, D29, and D30.

[0126] Fig.14A comparison chart showing two images of borosilicate glass ribbons formed using a continuous melting platform: samples D31 and D32. Sample D31 was clarified using the Cl-F-Ce-Sn fining bag discussed in the above examples. Sample D32 was clarified with 0.1 mol% sodium sulfate containing nitrate. Visual comparisons show that the glass quality of the sulfate fining bag in the continuous melting process was improved. Defect analysis showed that the glass using the Cl-F-Ce-Sn fining bag had 30,000 to 60,000 defects per pound of glass. Glass clarified with sulfate and nitrate had 0 to 3,000 defects per pound of glass. This experiment quantified the improvement in glass quality with the sulfate fining bag in the continuous process, which is not necessarily captured in static testing, and provides support for the use of the fining bags disclosed herein in large-scale tanks with continuous processes. When coarser sand (e.g., sand with a D50 particle size of 352 microns) is used, the number of defects per pound of sulfate-fined glass is reduced to 0 to 500 defects per pound.

[0127] Fig.15 A comparison chart showing two images of boron-free aluminosilicate glass ribbons formed using a continuous melting platform: Samples D33 and D34. Sample D33 was refined using a conventional 0.2 mol % tin fining bag, while Sample D34 was refined using a 0.03 mol % sodium sulfate fining bag containing 0.1 mol % tin. The comparison shown shows that the sulfate fining bag improves the glass quality in a continuous process for aluminosilicate glass. Defect analysis showed that the glass refined using the conventional tin fining bag had 5,000 to 25,000 defects per pound of glass. The glass refined with sulfate and tin had 0 to 1,000 defects per pound of glass. This experiment again quantifies the improvement in glass quality with the sulfate fining bag in a continuous process, which is not necessarily captured in a static test, and provides support for the use of the fining bags disclosed herein in large-scale tanks with a continuous process.

[0128] For the following examples, the results are as follows Figure 16-22 As shown in , the following experimental setup was used. Appropriate amounts of raw materials to obtain 1000 g of glass were placed in 4 platinum crucibles and The glass composition is shown in Table 5. For the melting cycle, the crucible is introduced into a furnace preheated to 1450°C and kept at 1450°C for 1 hour. It is then heated from 1450°C to 1550°C in 150 minutes, and then kept at 1550°C during the residence time marked D. The crucible is taken out at 1550°C. Due to the thermal inhomogeneity in the furnace, in order to obtain an average result, each glass composition is tested twice (i.e., two crucibles marked with the suffixes "-1" and "-2"). After melting, the glass is annealed at 600°C for 2 hours in a crucible and then slowly cooled. A sample with a diameter of 50-60 mm is drilled from the glass in the crucible, and a 3 mm thick vertical slice is cut from the center of each sample and polished. The seeds were counted at three distances from the glass surface: 0, 2.5 and 5 mm, and the number of seeds was calculated based on the volume of glass involved (approximately 0.5 cubic centimeters (cm 3 )] to normalize their number. The solids were counted at the same 3 distances from the glass surface and the solid sizes were measured individually. The total volume of the solids was calculated using the average diameter and the number of solids.

[0129] Fig.16 A comparison table showing four images of drill core samples of borosilicate glass formed in a crucible: samples D35a, D35b, D36a, and D36b. The D35 sample corresponds to sample C34 in Table 5 and was refined with the conventional Cl-F-Ce-Sn package described above. The D36 sample corresponds to sample C35 in Table 5 and was refined with sodium sulfate. Fig.17 Shows a comparison Fig.16 Each cm of the sample 3 The histogram of the seed crystal, Fig.18 Shows a comparison Fig.16 Each μm of the sample 3 Bar graph of solid counts. As shown, the sulfate clarified samples (D36a and D36b) had fewer bubbles remaining than the samples clarified with the Cl-F-Ce-Sn bag (D35a and D35b). The average values ​​for the D35 and D36 samples are also shown.

[0130] Fig.19 and 20 The bar graphs for comparative samples D37a and D37b (also corresponding to sample C34 in Table 5) and samples D38a and D38b (corresponding to sample C36 in Table 5) are shown. D37a and D37b were clarified with a conventional Cl-F-Ce-Sn bag, as were D35a and D35b. D38a and D38b were clarified with sodium sulfate and sodium nitrate. Again, the sulfate-clarified glass samples (D38a, D38b) had fewer bubbles remaining than the samples clarified with a conventional Cl-F-Ce-Sn bag (D37a and D37b).

[0131] Fig.21 and 22 The bar graphs of comparative samples D39a and D39b (corresponding to sample C35 in Table 5) and samples D40a and D40b (corresponding to sample C36 in Table 5) are shown. D39a and D39b were clarified with a conventional Cl-F-Ce-Sn bag. D40a and D40b were clarified with sodium sulfate and sodium nitrate. Likewise, the sulfate-clarified glass samples (D40a, D40b) had fewer bubbles remaining than the samples clarified with a conventional Cl-F-Ce-Sn bag (D39a and D39b).

[0132] Tolerance test

[0133] The embodiments of the present disclosure were also tested for resistance. To test resistance, appropriate amounts of raw materials for obtaining 1000 g of glass were placed in 4 platinum crucibles and Double melting is performed in an electric furnace heated by the heating element. Double melting is performed to improve the chemical homogeneity of the glass. The glass composition is shown in Table 5. For the melting cycle, the crucible is placed in a furnace preheated to 1450°C and kept at 1450°C for 1 hour. Then, it is heated from 1450°C to 1550°C in 150 minutes and kept at 1550°C for 30 minutes, followed by water extraction. For the next melting cycle, the crucible is placed in a furnace preheated to 1450°C and kept at 1450°C for 1 hour. Then it is heated from 1450°C to 1550°C in 150 minutes and then kept at 1550°C for a dwell time marked as D. For the glass having the composition of sample C37 in Table 5, D is 2 hours and 30 minutes, and for the glass having the composition of sample C35 in Table 5, D is 0 minutes. The crucible is then removed from the furnace and the molten glass is poured onto a preheated steel plate. This was rolled onto a plate to a thickness of about 4 mm. The glass plate was annealed at 600° C. for 1 hour and then slowly cooled.

[0134] Resistance tests were performed according to ISO 695 for strong alkali resistance and CETC, and according to DIN 12116 for strong acid resistance. For ISO 695, two 25 x 25 mm, 1 mm thick glass samples were prepared and polished on all sides. For ISO 695, two 28 mm diameter, 3 mm thick samples were prepared and polished on all sides. For DIN12116, two 51 mm x 76 mm, 1 mm thick glass samples were prepared and polished 1 mm on all sides.

[0135] The results, reported in Tables 6 and 7 below, show no significant differences between the two glasses: sample C37 (fined with Cl, F, Ce, and Sn) and sample C35 (fined with sulfate).

[0136]

[0137] Table 6. ISO 695 (strong alkali resistance)

[0138]

[0139] Table 7. DIN 12116 (strong acid resistance)

[0140] Fig.23 A comparison chart of four images of borosilicate glass compositions (samples D41-D44; corresponding to compositions C22-C25 in Table 3) is shown. As a comparative example, sample D41 contains no fining agent and sample D42 is refined with NaCl. Because Cl is sometimes undesirable as a fining agent, embodiments of the present disclosure include fining packages that do not contain Cl, such as those used for samples D43 and D44. Sample D43 is refined with Na2SO4 and sample D44 is refined with Na2SO4 and SnO2.

[0141] Fig.24 Shows a comparison Fig.23 Four locations (top, middle, bottom and base) of each sample in samples D41-D44 were measured per cm 3 The sulfate composition reduces the defect density in the lower half of the crucible by 1 to 2 orders of magnitude compared to no fining agent. The sulfate and tin composition reduces the defect density in the entire crucible by 1 to 2 orders of magnitude compared to no fining agent.

[0142] The terms "include", "including" or similar terms mean including but not limited to, ie, being inclusive rather than exclusive.

[0143] "About" used to describe aspects of the present disclosure, for example, to modify the amount, concentration, volume, processing temperature, processing time, yield, flow rate, pressure, viscosity, and the like of an ingredient in a composition and its range, or the size of a component and its range, refers to changes in the numerical amount that may occur, for example, due to: typical measurements and processing procedures used to prepare materials, compositions, compounds, concentrates, component parts, articles, or formulations for use; inadvertent errors in these procedures; differences in the purity, source, or manufacture of raw materials or ingredients used to practice the methods; and similar considerations. The term "about" also includes amounts that vary due to aging of a composition or formulation having a specific initial concentration or mixture, as well as amounts that vary due to mixing or processing a composition or formulation having a specific initial concentration or mixture.

[0144] "Optional" or "optionally" means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where the event or circumstance occurs and instances where it does not.

[0145] As used herein, the indefinite article "a" or "an" and the corresponding definite article "the" mean at least one, or one or more, unless stated otherwise.

[0146] Abbreviations familiar to those of ordinary skill in the art may be used (e.g., "h" or "hrs" for hours; "g" or "gm" for grams; "mL" for milliliters; "rt" for room temperature; "nm" for nanometers, and the like).

[0147] The specific and preferred numerical values ​​and ranges disclosed in components, ingredients, additives, scales, conditions and the like are only for illustration, and they do not exclude other limited numerical values ​​or other numerical values ​​within the limited range. The system, kit and / or method disclosed herein may include any numerical value or any combination of each numerical value, specific numerical value, more specific numerical value and preferred numerical value described herein, including explicit or implicit intermediate numerical values ​​and intermediate ranges.

[0148] Unless expressly stated otherwise, any method set forth herein should not be construed as requiring that its steps be performed in a specific order. Thus, if a method claim does not actually state that the steps follow a certain order, or if it is not otherwise specifically stated in the claims or specification that the steps are to be limited to a specific order, no specific order is intended to be inferred.

[0149] It will be apparent to those skilled in the art that various modifications and variations may be made without departing from the spirit and scope of the disclosed aspects. Because those skilled in the art may combine the spirit and substance of the disclosed aspects to make various improvements, combinations, sub-combinations and variations to the disclosed aspects, the disclosed aspects shall be deemed to include all of the contents within the scope of the appended claims and their equivalents.

Claims

1. A fining bag for a glass composition, the fining bag comprising: Sulfate or sulfide in an amount of about 0.001 to about 0.1 mol % of the glass composition.

2. The clarification bag of claim 1, wherein the clarification bag comprises sulfate and is free of sulfide.

3. The clarification packet of claim 1 or claim 2, wherein the sulfate salt comprises at least one of an alkali metal sulfate salt and an alkaline earth metal sulfate salt.

4. The fining packet as claimed in any one of the preceding claims, wherein the fining packet further comprises a multivalent compound in an amount of about 0.001 to about 1 mol % of the glass composition.

5. The clarification packet of claim 4, wherein the multivalent compound comprises Sn or Ce.

6. The clarification packet of claim 5, wherein the multivalent compound comprises CeO2, SnO2 or Fe2O3.

7. The fining bag of any of the preceding claims, further comprising a nitrate in an amount of about 0.01% to about 0.1 mol% of the glass composition.

8. The clarification packet of any one of the preceding claims, wherein the sulfate salt comprises a heavy alkaline earth metal sulfate salt.

9. The clarification packet of claim 8, further comprising a redox modifier.

10. The clarification packet of claim 9, wherein the redox modifier is carbon, sugar, or nitrate.

11. The clarification bag as claimed in any one of the preceding claims, wherein the clarification bag does not contain a reducing agent for reducing sulfate to sulfide.

12. The fining packet of any one of the preceding claims, wherein the glass composition comprises a borosilicate glass composition.

13. The fining packet of any one of the preceding claims, wherein the glass composition comprises an aluminosilicate glass composition.

14. The fining bag as claimed in any one of the preceding claims, wherein the glass composition is used to form a glass tube.

15. The clear bag of claim 14, wherein the glass tube is used to form a pharmaceutical package.

16. The clear package of claim 15, wherein the pharmaceutical packaging comprises at least one of a vial, an ampoule, a syringe, and a cartridge.

17. The clarified packet of any one of the preceding claims, wherein the clarified packet is free of at least one of Cl, F, Sn, Ce, and As.

18. The fining bag of any one of the preceding claims, wherein the glass composition comprises: SiO2 in an amount of 70 to 76 wt % of the glass composition; B2O3 in an amount of 9 to 13.5 wt. % of the glass composition; Al2O3 in an amount of 4 to 8 wt% of the glass composition; TiO2 in an amount of 0 to 0.1 wt% of the glass composition; Fe2O3 in an amount of 0 to 0.1 wt% of the glass composition; BaO in an amount of 0 to 0.1 wt. % of the glass composition; CaO in an amount of 0 to 3 wt % of the glass composition; Na2O in an amount of 5 to 8.5 wt% of the glass composition; K2O in an amount of 0.5 to 3 wt% of the glass composition; MgO in an amount of 0 to 1 wt % of the glass composition; Cl in an amount of 0 to 0.03 wt % of the glass composition; F, in an amount of 0 to 0.02 wt % of the glass composition; CeO2 in an amount of 0.08 to 0.5 wt % of the glass composition; SnO2 in an amount of 0.02 to 0.23 wt. % of the glass composition; and ZrO2 in an amount of 0 to 0.08 wt. % of the glass composition.

19. The fining bag of claim 18, wherein the glass composition comprises: SiO2 in an amount of 70 to 74 weight percent of the glass composition; B2O3 in an amount of 10 to 13.5 wt. % of the glass composition; Al2O3 in an amount of 5 to 7 wt% of the glass composition; TiO2 in an amount of 0 to 0.03 wt % of the glass composition; Fe2O3 in an amount of 0 to 0.04 wt. % of the glass composition; BaO in an amount of 0 to 0.04 wt. % of the glass composition; CaO in an amount of 0.5 to 2.3 wt. % of the glass composition; Na2O in an amount of 6.5 to 7.5 wt% of the glass composition; K2O in an amount of 1.0 to 1.8 wt. % of the glass composition; MgO in an amount of 0 to 0.1 wt. % of the glass composition; Cl in an amount of 0.01 to 0.03 wt % of the glass composition; F, in an amount of 0 to 0.02 wt % of the glass composition; CeO2 in an amount of 0.08 to 0.2 wt% of the glass composition; SnO2 in an amount of 0.02 to 0.12 wt. % of the glass composition; and ZrO2, in an amount of 0 to 0.08 wt % of the glass composition.

20. The fining bag of claim 19, wherein the glass composition comprises: SiO2 in an amount of 70 to 73 wt% of the glass composition; B2O3 in an amount of 10.5 to 13.2 wt. % of the glass composition; Al2O3 in an amount of 5 to 7 wt% of the glass composition; TiO2 in an amount of 0 to 0.03 wt % of the glass composition; Fe2O3 in an amount of 0 to 0.04 wt. % of the glass composition; BaO in an amount of 0 to 0.04 wt. % of the glass composition; CaO in an amount of 1 to 2.3 wt. % of the glass composition; Na2O in an amount of 6.5 to 7.3 wt% of the glass composition; K2O in an amount of 1.0 to 1.5 wt. % of the glass composition; MgO in an amount of 0 to 0.1 wt. % of the glass composition; Cl in an amount of 0.01 to 0.02 wt % of the glass composition; F, in an amount of 0 to 0.02 wt % of the glass composition; CeO2 in an amount of 0.08 to 0.2 wt% of the glass composition; SnO2 in an amount of 0.02 to 0.12 wt. % of the glass composition; and ZrO2, in an amount of 0 to 0.08 wt % of the glass composition.

21. The fining bag of any one of claims 1 to 17, wherein the glass composition comprises: SiO2 in an amount of 75 to 85 wt % of the glass composition; B2O3 in an amount of 9.5 to 14.5 wt. % of the glass composition; Al2O3 in an amount of 0.5 to 5 wt% of the glass composition; TiO2 in an amount of 0 to 0.1 wt% of the glass composition; Fe2O3 in an amount of 0 to 0.1 wt% of the glass composition; BaO in an amount of 0 to 0.1 wt. % of the glass composition; Na2O in an amount of 2 to 8 wt% of the glass composition; K2O in an amount of 0 to 3 wt% of the glass composition; CaO and MgO, in a total amount of 0 to 1.0 wt. % of the glass composition; Cl in an amount of 0 to 0.10 wt % of the glass composition; and SnO2, in an amount of 0 to 0.2 wt % of the glass composition.

22. The fining bag of any one of claims 1 to 17, wherein the glass composition comprises: SiO2 in an amount of 74 to 80 wt % of the glass composition; Al2O3 in an amount of 4 to 8 wt% of the glass composition; CaO in an amount of 0 to 0.5 wt % of the glass composition; Na2O in an amount of 8 to 14 wt% of the glass composition; MgO in an amount of 3 to 7 wt % of the glass composition; and SnO2, in an amount of 0 to 0.23 wt % of the glass composition.

23. A method of clarifying glass for forming pharmaceutical packaging, the method comprising: clarification of the glass composition by adding a clarification package as described in any one of claims 1 to 22 to the glass composition to remove bubbles; as well as A glass tube is formed from the refined glass composition.

24. The method of claim 23, further comprising forming a pharmaceutical package from the glass tube.

25. The method of claim 24, wherein the pharmaceutical packaging comprises a pharmaceutical ampoule.

26. The method of any one of claims 23 to 25, wherein the fining process is carried out at a fining temperature of at least 1400°C.

27. The method of claim 26, wherein the refining temperature is at least 1500°C.

28. The method of claim 27, wherein the refining temperature is from about 1500°C to about 1750°C, from about 1500°C to about 1600°C, from about 1600°C to about 1700°C or from about 1550°C to about 1650°C.

29. The method of claim 24, further comprising: Batch materials for a glass composition are melted, the batch materials including sand having a D50 average particle size greater than 200 microns or greater than 300 microns.

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