Clarifying package for glass compositions

Abstract

A fining package for a glass composition may contain a sulfate or sulfide in an amount from about 0.001 to about 1 mol% of the glass composition. The fining package may contain a polyvalent compound, such as CeO 2、 SnO2, or Fe2O3 in an amount from about 0.001 to about 1 mol% of the glass composition. The fining package may not contain a sulfide. The fining package may not contain a reducing agent for reducing the sulfate to a sulfide. The fining package may not contain at least one of Cl, F, Sn, Ce, and As. The glass composition can be used to form a glass tube. The glass tube can be used to form a pharmaceutical package.

Description

Cross - Reference to Related Applications

[0001] This application claims the benefit of priority under 35 U.S.C. § 119 to U.S. Provisional Patent Application No. 63 / 393,067, filed on July 28, 2022, the content of which is relied upon and incorporated herein by reference in its entirety.

Technical Field

[0002] The present disclosure generally relates to the clarification of glass, and more particularly to a clarification package for glass compositions for use in glass tubes and pharmaceutical packaging.

Background Art

[0003] Due to safety concerns, regulatory agencies analyze packaging materials for storing or administering pharmaceuticals. For example, regulatory agencies limit the types and amounts of materials present in pharmaceutical packaging such as sealed ampoules. Such pharmaceutical packaging is made of glass and, due to the types of materials and the industrial manufacturing processes used, typically is not washed before filling each ampoule with the respective pharmaceutical composition. Some processes for manufacturing glass on an industrial scale include materials that are considered toxic or that may be present in amounts that would not be considered safe. For example, fining is a process in which glass that may contain regulated materials is formed. Fining agents are introduced into the glass composition to remove gases or bubbles from the glass composition, thereby reducing the bubbles in the formed glass and improving the transparency of the glass.

[0004] For example, a common fining agent for borosilicate glass is sodium chloride (NaCl), which is particularly effective for borosilicate glass. In such conventional fining, NaCl re-condenses on the inner wall of the glass tube during conversion. The sealed ampoule is opened by flame or cutting just before filling, and therefore, it usually cannot be washed in advance. Since the sealed ampoule is usually not washed before filling and NaCl remains on the inner wall of the ampoule, there is a possibility that NaCl mixes with the filling liquid when the ampoule is filled. However, in order to use such a glass tube as a sealed ampoule for pharmaceutical packaging, it is necessary to contain chloride (Cl) in the glass composition at a sufficiently low level to meet the requirements of the European Pharmacopoeia (EP). According to the European Pharmacopoeia, 10th Edition, the chloride test for sterile water for injection is a maximum of 0.5 ppm in containers with a nominal volume of 100 mL or less.

[0005] In some cases, borosilicate glass with a low Cl content may be used in an attempt to achieve a chloride level low enough to meet the requirements of EP. To address the clarification of glass with a low chloride content, clarifying agents such as As2O3, Sb2O3, F, CeO2, or SnO2 are typically used. However, certain clarifying agents such as As have high toxicity. Even if the levels of such poisons in the final glass are kept low within the allowable range, their toxicity can be dangerous to the people involved in glass manufacturing. When clarifying glass for pharmaceutical use, the use of clarifying agents As2O3 and Sb2O3 may be avoided due to their toxicity. As a result, the clarification package becomes complex, includes multiple clarifying agents, and the amount and variety of raw materials increase, making it expensive. Despite being complex, such a clarification package typically has a lower clarification quality than when using NaCl as a clarifying agent. Agents such as Cl and / or F are less dangerous than more toxic agents, but are corrosive to pollution reduction systems or are undesirable for certain users in certain applications. For example, using Sn as a clarifying agent can cause evaporation / condensation problems, which can lead to appearance defects. In addition, since Sn is a new element for the pharmaceutical industry, it may cause hesitation in adoption and is an expensive material.

Summary of the Invention

Problems to be Solved by the Invention

[0006] There is a need for low-cost alternatives to conventional clarifying agents. Similarly, a clarifying agent that can achieve an effective clarification effect with a smaller amount can reduce the batch cost because the amount of clarifying agent required per batch is reduced. In addition, some glass compositions require a high clarification temperature to reach an appropriate clarification viscosity, so a clarification package suitable for such a temperature is also needed.

[0007] Therefore, there is a need for a simple and low-cost fining package for use in glass pharmaceutical packaging that maintains the fining performance as well as the properties of the glass and the product and can be used even at the high fining temperatures of some glass compositions. **Means for Solving the Problems**

[0008] According to aspect 1 of the present disclosure, there is provided a fining package for a glass composition, comprising a sulfate or sulfide in an amount of from about 0.001 to about 0.1 mol% of the glass composition.

[0009] According to aspect 2, there is provided a fining package according to aspect 1, wherein the fining package contains a sulfate and does not contain a sulfide.

[0010] According to aspect 3, there is provided a fining package according to aspect 1 or aspect 2, wherein the sulfate contains at least one of an alkali sulfate and an alkaline earth sulfate.

[0011] According to aspect 4, there is provided a fining package according to any of the preceding aspects, wherein the fining package further comprises a polyvalent compound in an amount of from about 0.001 to about 1 mol% of the glass composition.

[0012] According to aspect 5, there is provided a fining package according to aspect 4, wherein the polyvalent compound contains Sn or Ce.

[0013] According to aspect 6, there is provided a fining package according to aspect 5, wherein the polyvalent compound contains CeO2, SnO2, or Fe2O3.

[0014] According to aspect 7, there is provided a fining package according to any of the preceding aspects, wherein the fining package further comprises a nitrate in an amount of from about 0.01% to about 0.1 mol% of the glass composition.

[0015] According to aspect 8, there is provided a fining package according to any of the preceding aspects, wherein the sulfate contains a heavy alkaline earth sulfate.

[0016] According to Aspect 9, there is provided a clarified package according to Aspect 8, further comprising a redox modifier.

[0017] According to Aspect 10, there is provided a clarified package according to Aspect 9, wherein the redox modifier is carbon, sugar, or nitrate.

[0018] According to Aspect 11, there is provided a clarified package according to any of the foregoing aspects, wherein the clarified package does not contain a reducing agent for reducing sulfate to sulfide.

[0019] According to Aspect 12, there is provided a clarified package according to any of the foregoing aspects, wherein the glass composition comprises a borosilicate glass composition.

[0020] According to Aspect 13, there is provided a clarified package according to any of the foregoing aspects, wherein the glass composition comprises an aluminosilicate glass composition.

[0021] According to Aspect 14, there is provided a clarified package according to any of the foregoing aspects, wherein the glass composition is used for forming a glass tube.

[0022] According to Aspect 15, there is provided a clarified package according to Aspect 14, wherein the glass tube is used for forming a pharmaceutical package.

[0023] According to Aspect 16, there is provided a clarified package according to Aspect 15, wherein the pharmaceutical package comprises at least one of a vial, an ampoule, a syringe, and a cartridge.

[0024] According to Aspect 17, there is provided a clarified package according to any of the foregoing aspects, wherein the clarified package does not contain at least one of Cl, F, Sn, Ce, and As.

[0025] According to aspect 18, the glass composition comprises SiO2 in an amount of 70 to 76% by mass of the glass composition; B2O3 in an amount of 9 to 13.5% by mass of the glass composition; Al2O3 in an amount of 4 to 8% by mass of the glass composition; TiO2 in an amount of 0 to 0.1% by mass of the glass composition; Fe2O3 in an amount of 0 to 0.1% by mass of the glass composition; BaO in an amount of 0 to 0.1% by mass of the glass composition; CaO in an amount of 0 to 3% by mass of the glass composition; Na2O in an amount of 5 to 8.5% by mass of the glass composition; K2O in an amount of 0.5 to 3% by mass of the glass composition; MgO in an amount of 0 to 1% by mass of the glass composition; Cl in an amount of 0 to 0.03% by mass of the glass composition; F in an amount of 0 to 0.02% by mass of the glass composition; CeO2 in an amount of 0.08 to 0.5% by mass of the glass composition; SnO2 in an amount of 0.02 to 0.23% by mass of the glass composition; and ZrO2 in an amount of 0 to 0.08% by mass of the glass composition, and a fining package according to any of the foregoing aspects is provided.

[0026] According to aspect 19, the glass composition comprises SiO2 in an amount of 70 to 74% by mass of the glass composition; B2O3 in an amount of 10 to 13.5% by mass of the glass composition; Al2O3 in an amount of 5 to 7% by mass of the glass composition; TiO2 in an amount of 0 to 0.03% by mass of the glass composition; Fe2O3 in an amount of 0 to 0.04% by mass of the glass composition; BaO in an amount of 0 to 0.04% by mass of the glass composition; CaO in an amount of 0.5 to 2.3% by mass of the glass composition; Na2O in an amount of 6.5 to 7.5% by mass of the glass composition; K2O in an amount of 1.0 to 1.8% by mass of the glass composition; MgO in an amount of 0 to 0.1% by mass of the glass composition; Cl in an amount of 0.01 to 0.03% by mass of the glass composition; ~ in an amount of 0 to 0.02% by mass of the glass composition; CeO2 in an amount of 0.08 to 0.2% by mass of the glass composition; SnO2 in an amount of 0.02 to 0.12% by mass of the glass composition; and ZrO2 in an amount of 0 to 0.08% by mass of the glass composition, and a fining package according to aspect 18 is provided.

[0027] According to embodiment 20, a glass composition comprises SiO2 in an amount of 70 to 73% by mass of the glass composition; B2O3 in an amount of 10.5 to 13.2% by mass of the glass composition; Al2O3 in an amount of 5 to 7% by mass of the glass composition; TiO2 in an amount of 0 to 0.03% by mass of the glass composition; Fe2O3 in an amount of 0 to 0.04% by mass of the glass composition; BaO in an amount of 0 to 0.04% by mass of the glass composition; CaO in an amount of 1 to 2.3% by mass of the glass composition; Na2O in an amount of 6.5 to 7.3% by mass of the glass composition; K2O in an amount of 1.0 to 1.5% by mass of the glass composition; MgO in an amount of 0 to 0.1% by mass of the glass composition; Cl in an amount of 0.01 to 0.02% by mass of the glass composition; F in an amount of 0 to 0.02% by mass of the glass composition; CeO2 in an amount of 0.08 to 0.2% by mass of the glass composition; SnO2 in an amount of 0.02 to 0.12% by mass of the glass composition; and ZrO2 in an amount of 0 to 0.08% by mass of the glass composition, and a fining package according to embodiment 19 is provided.

[0028] According to embodiment 21, a glass composition comprises SiO2 in an amount of 75 to 85% by mass of the glass composition; B2O3 in an amount of 9.5 to 14.5% by mass of the glass composition; Al2O3 in an amount of 0.5 to 5% by mass of the glass composition; TiO2 in an amount of 0 to 0.1% by mass of the glass composition; Fe2O3 in an amount of 0 to 0.1% by mass of the glass composition; BaO in an amount of 0 to 0.1% by mass of the glass composition; Na2O in an amount of 2 to 8% by mass of the glass composition; K2O in an amount of 0 to 3% by mass of the glass composition; CaO and MgO in a total amount of 0 to 1.0% by mass of the glass composition; Cl in an amount of 0 to 0.10% by mass of the glass composition; and SnO2 in an amount of 0 to 0.2% by mass of the glass composition, and a fining package according to any one of embodiments 1 to 17 is provided.

[0029] According to aspect 22, there is provided a fining package according to any of aspects 1 to 17, wherein the glass composition comprises SiO2 in an amount of 74 to 80% by mass of the glass composition; Al2O3 in an amount of 4 to 8% by mass of the glass composition; CaO in an amount of 0 to 0.5% by mass of the glass composition; Na2O in an amount of 8 to 14% by mass of the glass composition; MgO in an amount of 3 to 7% by mass of the glass composition; and SnO2 in an amount of 0 to 0.23% by mass of the glass composition.

[0030] According to aspect 23, there is provided a method of fining glass to form a pharmaceutical package, comprising the step of fining the glass composition by adding a fining package according to any of aspects 1 to 22 to the glass composition to remove bubbles; and the step of forming a glass tube from the fined glass composition.

[0031] According to aspect 24, there is provided a method according to aspect 23, further comprising the step of forming a pharmaceutical package from the glass tube.

[0032] According to aspect 25, there is provided a method according to aspect 24, wherein the pharmaceutical package comprises a pharmaceutical ampoule.

[0033] According to aspect 26, there is provided a method according to any of aspects 23 to 25, wherein the fining is carried out at a fining temperature of at least 1400 °C.

[0034] According to aspect 27, there is provided a method according to aspect 26, wherein the fining temperature is at least 1500 °C.

[0035] According to aspect 28, there is provided a method according to aspect 27, wherein the fining 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.

[0036] According to aspect 29, there is provided a method according to aspect 24, further comprising the step of melting a batch of materials for the glass composition, wherein the batch of materials comprises sand having a D50 average particle size of more than 200 μm or more than 300 μm.

[0037] Additional aspects of the present disclosure are, in part, described in the following detailed description, the drawings, and the claims, and in part, are derived from the detailed description or can be learned by the practice of the present disclosure. It should be understood that both the foregoing summary and the following detailed description are merely exemplary and explanatory and are not restrictive of the present disclosure as disclosed.

Brief Description of the Drawings

[0038]

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Mode for Carrying Out the Invention

[0039] Various aspects of the present disclosure are described in detail with reference to the drawings, if any. References to various aspects do not limit the scope of the invention, which is limited only by the appended claims. In addition, the examples described herein are not limiting and merely describe some of the many possible aspects of the claimed invention.

[0040] The embodiments described herein provide a simple and low-cost fining package that replaces or significantly reduces the amount of halides and / or other commonly used polyvalent elements such as Sn and Ce present in the fining package, compared to conventional fining packages for glass tubes compounded for pharmaceutical packaging, using the addition of sulfates or sulfides. The methods described herein relate to the fining of borosilicate glass and aluminosilicate glass for use in glass tube applications for primary packaging of pharmaceuticals. Embodiments of the disclosure include fining packages that use sulfates and / or sulfides as low-cost alternatives to Sn and Ce fining agents, and further, the use of small amounts of sulfates and / or sulfides in the fining package can effectively fine the glass. The retention amount of sulfate in the glass is very small, and thus, using sulfate as a fining agent should be relatively easy for the end user to understand. The fining package disclosed herein can be used for glass compositions that require high fining temperatures. As used herein, "fining temperature" refers to the temperature of the glass composition required for the glass to reach a fining viscosity or the viscosity at which the glass is fined.

[0041] The problem associated with glass compositions having a relatively high clarification temperature is to find a fining agent suitable for removing bubbles from the glass, which is acceptable to a wide range of end-users and / or acceptable for a wide range of applications, and is also low-cost and melt-resource friendly. For example, in some cases, the toxic element arsenic (As) may be used as a fining agent. If present in low concentrations in the glass, it may be harmless from the perspective of many end-users, but it is still potentially dangerous for people working in factories that use arsenic. Other agents such as Cl and / or F are not as dangerous, but are corrosive to pollution reduction systems, and in some end-users or applications such as sealed ampoules, it is not possible to tolerate Cl in the glass container. Furthermore, Sn is also commonly used as a fining agent, but has problems with evaporation and / or condensation, causing appearance defects. Sn is also a relatively new element for the pharmaceutical industry, which may cause hesitation in its adoption, and is also an expensive raw material.

[0042] One common fining agent for such borosilicate glasses is sodium chloride (NaCl), which is particularly effective for borosilicate glasses. However, in certain applications such as glass tubes used for pharmaceutical packaging in sealed ampoules, the glass needs to contain a sufficiently low chloride (Cl) level to meet the requirements of the European Pharmacopoeia (EP). According to the European Pharmacopoeia, 10th Edition, the chloride test for 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, according to the EP requirements, for containers with a nominal volume of less than 100 mL, a maximum of 0.5 ppm of Cl is allowed. Therefore, when NaCl is used as a fining agent for borosilicate glasses such as Corning 51-D borosilicate glass tubes (Corning Incorporated, Corning, New York, USA), the Cl level in the batch process is limited to 0.03 mass%.

[0043] To address the clarification of borosilicate glass with low chloride (Cl) content, conventional clarification techniques use clarifying agents such as As2O3, Sb2O3, F, CeO2, or SnO2. However, when clarifying glass for pharmaceutical applications, As2O3 and Sb2O3 are typically avoided. Therefore, conventional clarification packages used for borosilicate glass used in pharmaceutical applications, such as Corning 51-D borosilicate glass tubing (Corning Incorporated, Corning, New York, USA), are complex and contain four clarifying agents. The four clarifying agents in the conventional clarification package can include SnO2, CeO2, F, and Cl. Despite being complex, the clarification quality is significantly lower compared to borosilicate glass clarified with NaCl.

[0044] However, such clarification packages are complex and require multiple raw materials, leading to increased costs compared to NaCl as a clarifying agent. For example, SnO2 is obtained from expensive raw materials. Therefore, there is a need for a simpler and lower-cost clarification package for use in pharmaceutical applications that maintains the clarification performance achieved by the conventional clarification package and also achieves the glass and product characteristics required for pharmaceutical applications.

[0045] In embodiments of the present disclosure, a simple and low-cost clarification package is provided. The clarification package can be used for clarifying glass. The embodiments 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.

[0046] In an embodiment, a glass composition using the fining package described herein can be used to form a glass tube. In an embodiment, a glass tube formed from a glass composition using the fining package described herein can be used for pharmaceutical packaging. In an embodiment, the pharmaceutical packaging can include vials, ampoules, cartridges, or syringes. Non-limiting examples of transparent borosilicate glass tubes include Corning 33 and 51-D borosilicate glass tubes (Corning Incorporated, Corning, New York, USA). A non-limiting example of a transparent aluminosilicate glass vial is a Corning Valor® glass vial (Corning Incorporated, Corning, New York, USA).

[0047] Non-limiting examples of glass compositions are described in the specifications of U.S. Patent Application Publication Nos. 2014 / 0001076, 2014 / 0001143, 2014 / 0151320, 2014 / 0151321, 2014 / 0151370, U.S. Patent Nos. 9,034,442, and 9,428,302, each of which is hereby incorporated by reference in its entirety.

[0048] The embodiments described herein include a fining package that contains sulfur element (S), specifically a fining package that contains sulfur in the form of alkali and alkaline earth sulfates. Fining with sulfates is used in the soda lime glass industry. For example, by using Na2SO4 in combination with a reducing agent such as sugar or graphite, the sulfate is decomposed to release a gas that helps in the fining of the glass. In a batch pile, most or all of the Na2SO4 is converted to Na2S + 2O2. This conversion process makes the gas escape easily at a low temperature (e.g., less than 1000 °C), causes the batch to swell, and reduces the number of bubbles in the final glass. Na2S decomposes between 1200 °C and 1400 °C and clarifies soda lime glass at a relatively low temperature. However, other glass compositions are clarified at much higher temperatures. These higher fining temperatures can be 1550 °C or higher, including about 1400 °C, for example 1650 °C or higher.

[0049] The embodiments described herein provide a fining package in which one or more of the typical fining agents (e.g., F, Cl, Sn, Ce, etc.) are removed and replaced with only S-containing compounds, or a mixture of S-containing compounds and polyvalent compounds (e.g., including Sn, Ce, Fe, etc.) and / or one or more oxidizing agents (e.g., nitrates). The fining package containing sulfates and optionally oxides has the following advantages: (1) it fines with an efficiency equal to or greater than that of conventional polyvalent elements; (2) it significantly reduces the amount and cost of fining agents by, for example, eliminating the use of Sn; (3) it produces Cl-free glass required by some end users and applications; (4) it reduces the outflow of volatile metals (e.g., Sn) from the glass; and, (5) it reduces or eliminates a decrease in color and / or transmittance.

[0050] Embodiments of the present disclosure include a fining package having at least one S-containing compound. The S-containing compound can be a sulfate or a sulfide. In embodiments, the fining package contains sulfate and no sulfide. The sulfate can be an alkali sulfate or an alkaline earth sulfate. Non-limiting examples include sodium sulfate (Na2SO4), potassium sulfate (KSO4), calcium sulfate (CaSO4), barium sulfate (BaSO4), and strontium sulfate (SrSO4). Embodiments can include additional compounds in the form of a polyvalent compound in an amount from about 0.001 to about 1.0 mol%. Non-limiting examples include Sn, Ce, and Fe compounds, including CeO2, SnO2, and Fe2O3.

[0051] Embodiments described herein provide a fining package that contains a low amount of SnO2 compared to conventional fining packages. For example, a low amount of SnO2 can be considered to be an amount less than about 0.3 mass%. In one embodiment, a large amount of SnO2 can be considered to be less than about 0.1 mass%.

[0052] Embodiments described herein also include a fining package that contains sulfate together with nitrate as described above. The nitrate can be used in an amount from about 0.01% to about 0.1 mol% of the glass composition. It is thought that the nitrate can add oxygen that diffuses into the bubbles, grow the size of the bubbles to increase the rising rate, and clarify the melt more quickly, which is similar to the advantage of adding a polyvalent compound. However, according to embodiments, the fining package can enhance fining without including a redox modifier such as nitrate (oxidizing agent) or carbon (reducing agent).

[0053] Embodiments include a clarification package that contains sulfates but does not contain a reducing agent for reducing the sulfates to sulfides. The clarification package can be free of at least one of Cl, F, Sn, Ce, and As; or can be free of at least two or at least three of Cl, F, Sn, Ce, and As. In embodiments of the clarification package using heavy alkaline earth sulfates, by adding a reducing agent such as carbon or sugar, similar or better performance can be observed, which is thought to cause a reaction from sulfate (sulfur oxide) to sulfide (reduced sulfur), changing the decomposition temperature and reaction rate of the compound.

[0054] Sulfates are significantly less expensive than tin, and according to the embodiments herein, the level of sulfates required for clarification is lower than the levels used for tin and halide clarification, so especially in binland factories, costs are saved and pollution prevention problems are reduced. Sulfates can be batch processed in various forms including sodium, calcium, or potassium depending on the glass composition, providing flexibility and potentially further cost savings. Additionally, since the retention of sulfates is at low ppm levels, it results in a clear clarification package for the customer.

[0055] The decomposition reaction of sulfate (where "M" represents an alkali or alkaline earth element) is MSO4(s) → MO(s) + SO2(g) + 1 / 2O2(g) It becomes like (M = Na, K, Ca, Sr, Ba), and both sulfur and oxygen form dissolved gases in the glass melt (this reaction occurs at temperatures higher than 1400 °C, and at lower temperatures, carbon is used to promote the decomposition of sulfates). Then, these gases diffuse into the existing bubbles, and when these bubbles enter the clarification region of the glass melt tank, bubble growth and Stokes clarification occur. The temperature in the clarification region is typically 50 - 100 °C higher than that in the melting zone, which further promotes the growth and upward movement of the bubbles, and Stokes clarification occurs. Therefore, the entire clarification process consists of the following three phases: (1) the chemical component, decomposing sulfates into gas compounds of sulfur and oxygen; (2) the transport component, the diffusion of gas into the existing bubbles; and (3) the physical component, the growth and upward movement of bubbles, generally called Stokes clarification.

[0056] CeO 2、 Adding polyvalent compounds such as SnO2 or Fe2O3 to provide additional oxygen to the melt can further enhance the clarification process. For example, CeO2 is decomposed into Ce2O3 and O2 by the following reaction: 2CeO2 → Ce2O3 + 1 / 2O2 This supplies additional oxygen that can diffuse into the bubbles to assist in clarification. The range of batch-processed CeO2 is from 0.01 to 0.1 mol%, typically less than 0.06 mol%. The clarification of SnO2 is a similar reaction: SnO2 → SnO + 1 / 2O2 Neither tin nor cerium is a particularly powerful clarifying agent by itself. The decision of which to use to assist in clarification mainly depends on temperature. Cerium is more effective at low temperatures (less than 1550 °C), and tin is more effective at high temperatures (above 1550 °C).

[0057] A simple clarification package containing fewer components is beneficial for batch mixing. For example, it is advantageous to have fewer raw materials to store and meter before mixing, preparation, and introduction into the industrial production tank. Such glass compositions can save on the cost of raw materials. Simplifying the clarification package also enables further development of the remaining clarifying agents and understanding of the mechanism.

[0058] As an example, various glass compositions and fining packages are shown in Tables 1 to 5 as examples of embodiments of the present disclosure. Tables 1 and 2 show aluminosilicate glass compositions including various fining packages according to embodiments of the present disclosure. Tables 3, 4, and 5 show borosilicate glass compositions including 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, and are provided only as examples for explaining aspects of the embodiments disclosed herein.

[0059]

Table 1

[0060] As shown in Table 1, Samples C1 and C2 are aluminosilicate glass compositions fined with a combination of NaNO2 and SnO2. Sample C3 is a glass composition without a fining agent. Samples C4 to C11 show glass compositions including fining packages according to embodiments of the present disclosure. In particular, Samples C4 to C11 each use a sulfate (e.g., 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 fined with NaSO4, Sample C7 is fined with K2SO4, Sample C8 is fined with CaSO4, Sample C9 is fined with SrSO4, Sample C10 is fined with SrSO4 and C, and C11 is fined with BaSO4. All fining packages do not contain Cl, F, Sn, Ce, and As.

[0061]

Table 2

[0062] As shown in Table 2, Samples C12 to C21 are aluminosilicate glass compositions containing a clarifying package containing one or more S-containing compounds. In particular, the clarifying package contains one or more sulfates and / or sulfides. Specifically, in the sulfate-containing clarifying package, Samples C17 to C21 contain NaSO4, Sample C13 contains SrSO4, and Samples C12 and C14 contain BaSO4. Sample C12 further contains a reducing agent (i.e., C). Samples C17 and C19 to C21 further contain the polyvalent compound SnO2, and Sample C18 further contains the polyvalent compound CeO2. Samples C15 and C16 are clarified with sulfides BaS and SrS, respectively. The clarifying packages of Samples C12 to C16 do not contain Cl, F, Sn, Ce, and As, and the remaining Samples C17 to C21 contain only a small amount of Cn and Ce as part of the polyvalent compounds in the clarifying package.

[0063]

Table 3

[0064] Table 3 shows examples of borosilicate glass compositions and clarifying packages. As comparative examples for the embodiments of the present disclosure, Sample C22 is a composition without a clarifying agent, and Sample C23 uses a conventional NaCl clarifying package. Samples C24 and C25 use Na2SO4, and Sample C25 further contains SnO2. Samples C28 and C29 also use sulfates in the form of BaSO4 and SrSO4, respectively. As a comparative example, Sample C26 uses SnO2, a typical clarifying agent. Sample C27 uses BaS.

[0065]

Table 4

[0066] Table 4 shows examples of borosilicate glass compositions and fining packages. Samples C30, C31, and C32 were each clarified with sulfates using Na2SO4, CaSO4, and K2SO4, respectively, and do not contain Sn, Cl, F, or Ce. As a comparative example against the embodiments of the present disclosure, sample C33 is a composition using a conventional fining package containing Sn, Cl, F, and Ce.

[0067]

Table 5

[0068] As shown in Table 5 above, sample C35 was clarified with sodium sulfate, similar to sample C30 above, sample C36 was clarified with sodium sulfate and sodium nitrate, and samples C34 and C37 are comparative examples showing conventional fining packages using chlorine, fluorine, cerium, and tin.

[0069] The fining package according to the embodiments of the present disclosure can completely eliminate all fining agents currently used in the intended glass composition, except for Ce in some embodiments, and replace them with variations of sulfates commonly used in the float glass and container glass industries, optionally with a redox modifier package, but is modified for borosilicate glass compositions and for melting and fining at higher temperatures.

Examples

[0070] Experimental results Preparation of glass, counting of seed numbers, and solids analysis The glass samples were prepared using both static forming and continuous forming methods. For static forming, a precious metal crucible capable of containing molten glass between approximately 0.5 kg and 1.5 kg was used. The temperatures used were in the range of 1350 - 1500 °C at filling, 1450 - 1600 °C during melting, and 1500 - 1650 °C during fining. Thereafter, the melt was annealed in the crucible, cored out, or poured onto a steel table. The number of defects in the cored samples was counted, and the quenched melt was examined optically and chemically. The selected compositions were studied on a continuous melting platform to investigate the scale-up feasibility of these alternative fining packages. The continuous melting experiments helped ensure the success of the evaluation of the fining package performance according to the embodiments of the present disclosure. The continuous experiments were carried out over 6 days on a precious metal melting platform equipped with a continuous feed system that produced glass strips at a rate of 10 - 15 pounds per hour (about 4.55 - 6.80 kg per hour). The temperatures in the continuous forming experiments were in the range of 1500 °C to 1600 °C during melting and 1550 °C to 1650 °C during fining. The number of defects in the glass strip samples collected periodically throughout each continuous experiment was counted.

[0071] For the borosilicate glass compositions such as the examples shown in Tables 4 and 5 above, observations of melting, fining, and glass quality from two continuous forming experiments that sampled the melting and fining performance throughout the process and after the melt was quenched, by strategic sampling / measurement, indicate that the results of the sulfate solution scale up to the continuous process and are less aggressive or harmful to glass tank refractories.

[0072] In the boron-free aluminosilicate glass such as the examples shown in Tables 1 to 3 above, from the melting, clarification, and observation and sampling of glass quality from a single continuous forming experiment, the results of the sulfate solution have been shown to be improved in a continuous process. According to the embodiment, the sulfate is effective as a substitute for tin for several reasons: (i) when Sn evaporates and condenses during the conversion from a tube to a container (e.g., a vial or other pharmaceutical packaging), there may be appearance defects; (ii) Sn may be the most expensive batch material or one of them in these glass compositions; and (iii) some users or fillers of pharmaceutical packaging hesitate to include Sn as part of the pharmaceutical packaging.

[0073] Characterization and properties of glass compositions Figure 1 shows a comparison table of four images of the core slice at the center of the crucible melt of the borosilicate glass composition. The melting temperature and time for all samples were 1500 °C for 1 hour, respectively, and the clarification temperature was 1550 °C for 30 minutes. Sample D1 did not contain a clarification package, 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% of nitrate. The visual comparison of samples D2 - D4 with sample D1 shows that the glass clarified with sulfate shows far fewer seed numbers compared to the glass without a clarifying agent.

[0074] Figure 2 shows a bar graph comparing the number of defects per 1 cm 3 at three positions (top, center, and bottom) in each of samples D1 - D4 of Figure 1. The number of blisters or defects per 1 cm 3 is plotted on a logarithmic scale. The melt composition without a clarifying agent (D1) contains a large number of bubbles throughout the glass core slice, while the glass clarified with sodium sulfate had blisters in the upper part of the melt, but far fewer blisters in the central and lower sections of the melt, indicating the clarifying effect of the sulfate. Note should be taken of this.

[0075] Figure 3 shows a comparison table of four images of the center core slice of the crucible melt of a borosilicate glass composition (Sample D5) containing 0.1 mol% nitrate but no fining agent, compared with 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, respectively, and the fining temperature was 1550 °C for 30 minutes. As shown in Figure 1, Figure 3 shows more visible seeds in Sample D5, which contains no fining agent, compared to the glasses fined with sulfates in Samples D6 - D8.

[0076] Figure 4 shows a bar graph comparing the number of defects per 1 cm 3 at three positions (top, center, and bottom) in each of Samples D5 - D8 of Figure 3. The number of blisters or defects per 1 cm 3 is plotted on a logarithmic scale. It should be noted that the melt composition without fining agent (D5) contains numerous bubbles throughout the glass core slice, while the glass fined with sulfate contained fewer blisters.

[0077] Figure 5 shows a comparison table of four images of the center core slices of the crucible melts of borosilicate glass compositions (Samples D9 - D12) without nitrates. The melting temperature and time for all samples were 1450 °C for 90 minutes respectively, the fining temperature was 1550 °C for 120 minutes, and then it was cooled to 1400 °C for 1 hour. Samples D9, D10, and D11 were fined with sulfates, while D12 was fined with a conventional fining package for 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. The comparative sample D12 used a fining package containing Cl, F, Ce, and Sn. Note that blisters are present throughout the core of Sample D12. This indicates that fining was very slight when using a fining package containing 0.04 mol% Cl, 0.79 mol% F, 0.06 mol% Ce, and 0.05 mol% Sn. In the two ceria-containing melts, it is thought that ceria promotes Stokes fining by supplying additional O2 to assist in bubble growth and accelerating bubble rise.

[0078] Figure 6 shows a bar graph comparing the number of defects per 1 cm 3 at three positions (upper, central, and bottom) in each of Samples D9 - D12 of Figure 5. The number of blisters or defects per 1 cm 3 is plotted on a logarithmic scale. Note that the melt composition (D12) containing the Sn-Ce-F-Cl fining package contained a large number of bubbles throughout the glass core slice, while the glass fined with sulfates contained far fewer blisters.

[0079] Figure 7 shows a comparison table of four images of the central core slices of the crucible melts of borosilicate glass compositions (Samples D13 - D16) without nitrates. The melting temperature and time for all samples were 1450 °C for 90 minutes, the fining temperature was 1550 °C for 120 minutes, and then it was cooled to 1400 °C over 1 hour. Samples D13, D14, and D15 were fined with sulfates, while D16 was fined with a conventional fining package for 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. The comparative sample D16 used a fining package containing Cl, F, Ce, and Sn. Note that blisters are present throughout the core of Sample D16. This indicates that fining was very slight 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 demonstrated that doubling the sulfate from 0.05 mol% (see, for example, the images in Figures 1, 3, and 5; and the images in Figures 2, 4, and 6) to 0.1 mol% decreased the number of blisters in the melt, as shown in the graphs of Figures 7 and 8.

[0080] Figure 8 shows a bar graph comparing the number of defects per 1 cm 3 at three positions (top, center, and bottom) in each of Samples D13 - D16 of Figure 7. The number of blisters or defects per 1 cm 3 is plotted on a logarithmic scale. Note that the melt composition (D16) containing the Sn - Ce - F - Cl fining package contains a large number of bubbles throughout the glass core slice, while the glasses fined with sulfates (D13 - D15) contained far fewer blisters at all positions. These defect count numbers demonstrate that doubling the sulfate from 0.05 mol% to 0.1 mol% actually decreased the number of blisters in the melt.

[0081] Figure 9 shows a comparison table of four images of the central core slices of the crucible melts of borosilicate glass compositions (Samples D17 - D20) without nitrates. The melting temperature and time for all samples were 1450 °C for 90 minutes respectively, the fining temperature was 1550 °C for 120 minutes, and then it was cooled to 1400 °C for 1 hour. Samples D17, D18, and D19 were fined with sulfates, while D20 was fined with a conventional fining package for 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. The comparative sample D20 used a fining package containing 0.04 mol% Cl, 0.79 mol% F, 0.06 mol% Ce, and 0.05 mol% Sn. Note that blisters are present throughout the core of Sample D20. This indicates that fining was very slight when using a fining package containing Cl, F, Ce, and Sn. This melt also shows the effect of doubling the sulfate from 0.05 mol% to 0.1 mol%. In addition, the above samples used fine sand with a D50 particle size of 154 μm, while the samples in Figure 9 used coarse sand with an average particle size larger than 200 μm and a D50 particle size of 352 μm (e.g., Crystal sand from Sibelco). The coarseness of the sand improved the fining property with the sulfate fining package. Unless otherwise specified, in the examples shown in this specification, fine sand (e.g., with a D50 particle size of 154 μm) is used. This advantage was not observed in the crucible melts using the Sn - Ce - F - Cl fining package. This improvement can delay the melting of silica, thereby reducing the bubble generation rate, enabling the removal of bubbles without burdening the fining package, and resulting in less foaming of the batch due to the surfactant effect of sulfates that cover the sand grains and prevent the sand grains from sticking together. Sulfates can act as surfactants in the melt, preventing the aggregation of sand grains and assisting in melting.

[0082] Figure 10 shows 1 cm at three positions (upper, central, and bottom) in each of Samples D17 - D20 of Figure 93 A bar graph comparing the number of defects per centimeter is shown. 1 cm 3 The number of blisters or defects per centimeter is plotted on a logarithmic scale. Note that the molten composition (D20) containing the Sn-Ce-F-Cl clarifying package contains numerous bubbles throughout the glass core slice, while the sulfated clarified glasses (D17 - D19) contained far fewer blisters at all positions. These melts demonstrate the effect of sulfate clarification using coarse sand. In fact, D19 was completely clarified with no remaining blisters. Even with the sodium sulfate clarifying package of D17, few blisters occurred.

[0083] Figure 11 shows a comparison table of five images of the center core slice of the crucible melts of the boron-free aluminosilicate glass compositions (Samples D21 - D25). Sample D25 was clarified with Na2SO4, Sample D21 was clarified with Na2SO4 and Ce, and Sample D22 was clarified with Na2SO4 and Sn. Each of D21, D22, and D25 shows fewer residual bubbles than D23 using the conventional SnO2 clarifying package. When counted, the number of defects per centimeter 3 also shows that all of the Na2SO4, Na2SO4 + Ce, and Na2SO4 + Sn clarifying packages have fewer defect numbers than the conventional SnO2 clarifying package used in D23. For comparison, Sample D24 did not use clarification and had gaps throughout.

[0084] Figure 12 shows a bar graph comparing the number of defects per centimeter at three positions (top, center, and bottom) in each of Samples D21 - D25 of Figure 11. 1 cm 3 A bar graph comparing the number of defects per centimeter is shown. 1 cm 3 The number of blisters or defects per centimeter is plotted on a logarithmic scale. Note that the molten composition (D24) without a clarifying package contains numerous bubbles throughout the glass core slice, and that the conventional SnO2 package also has a greater number of voids throughout compared to the sulfated clarified melts.

[0085] Figure 13 shows a comparison table of five images of the central core slices of crucible melts of boron-free aluminosilicate glass compositions (Samples D26 - D30). Sample D26 was clarified with BaSO4 together with carbon, Sample D27 was clarified with BaSO4 without carbon, Sample D29 was clarified with SrSO4 together with carbon, and Sample D30 was clarified with SrSO4 without carbon. Comparative Sample D28 did not contain a clarification package and was worse than the results of D26, D27, D29, and D30, having many defects.

[0086] Figure 14 shows a comparison table of two images of borosilicate glass strips formed using a continuous melting platform: Samples D31 and D32. Sample D31 was clarified using the Cl-F-Ce-Sn clarification package discussed in the above example. Sample D32 was clarified with 0.1 mol% sodium sulfate together with nitrate. Visual comparison demonstrates the improvement in glass quality of the sulfate clarification package in a continuous melting process. Analysis of the number of defects showed that for the glass clarified with the Cl-F-Ce-Sn package, the number of defects was between 30,000 and 60,000 per pound (about 453.6 g) of glass. The glass clarified with sulfate and nitrate had a number of defects between 0 and 3,000 per pound (about 453.6 g) of glass. This experiment quantifies the improved glass quality of the sulfate clarification package in a continuous process that may not necessarily be captured in static experiments and provides support for using the clarification packages disclosed herein in a continuous process in a large-scale tank. When using coarser sand such as that with a D50 particle size of 352 μm, the number of defects per pound (about 453.6 g) of glass clarified with sulfate decreased to between 0 and 500 per pound (about 453.6 g).

[0087] Figure 15 shows a comparison table of two images of borosilicate glass strips (Samples D33 and D34) formed using a continuous melting platform without boron. Sample D33 was clarified in the field using a conventional 0.2 mol% tin clarification package, while Sample D34 was clarified using 0.03 mol% sodium sulfate together with a 0.1 mol% tin clarification package. The comparison shown demonstrates the improvement in glass quality of the sulfate clarification package in a continuous process with aluminosilicate glass. Analysis of the number of defects showed that the glass clarified with the conventional tin clarification package had between 5,000 and 25,000 defects per pound (about 453.6 g) of glass. The glass clarified with sulfate and tin had between 0 and 1,000 defects per pound (about 453.6 g) of glass. This experiment also quantifies the improved glass quality of the sulfate clarification package in a continuous process that may not necessarily be captured in static experiments, providing support for using the clarification packages disclosed herein in a continuous process in a large-scale tank.

[0088] In the following examples, the results of which are shown in Figures 16 - 22, the following experimental settings were used. An appropriate amount of raw materials to obtain 1000 g of glass was set in four platinum crucibles and melted in ambient air in an electric furnace heated with a Globar® heating element. The glass compositions are shown in Table 5. In the melting cycle, the crucibles were charged into a furnace preheated to 1450°C and held at 1450°C for 1 hour. Next, they were heated from 1450°C to 1550°C over 150 minutes and held at 1550°C for a residence time designated as D. The crucibles were withdrawn at 1550°C. To obtain average results due to thermal non-uniformity in the furnace, each glass composition was measured twice (i.e., two crucibles were labeled with the suffixes "-1" and "-2"). After melting, the glass was annealed at 600°C for 2 hours in the crucible and then cooled slowly. A sample with a diameter of 50 - 60 mm was cored from the glass in the crucible, and one vertical slice with a thickness of 3 mm was taken from the center of each sample and polished. Seeds were counted at three distances from the glass surface, namely 0, 2.5, and 5 mm, and their number was related to the volume of the associated glass (about 0.5 cubic centimeters (cm3 Normalize with ()). Solids are counted at the same three distances from the glass surface, and the size of each solid is measured individually. Using the average diameter and the number of solids, the total volume of the solids is calculated.

[0089] Figure 16 shows a comparison table of four images of core drilled samples of borosilicate glass (samples D35a, D35b, D36a, and D36b) formed in a crucible. The samples of D35 correspond to sample C34 in Table 5 and were clarified with the conventional Cl-F-Ce-Sn package discussed above. The samples of D36 correspond to sample C35 in Table 5 and were clarified with sodium sulfate. Figure 17 shows, for the samples of Figure 16, the 3 bar graph comparing the number of seeds per 1 cm, and Figure 18 shows the bar graph comparing the number of solids per 1 μm 3 for the same samples. As shown, the samples clarified with sulfate (D36a and D36b) have fewer residual bubbles than the samples clarified with the Cl-F-Ce-Sn package (D35a and D35b). The averages of the D35 samples and the D36 samples are also shown.

[0090] Figures 19 and 20 show bar graphs comparing samples D37a and D37b (which also correspond to sample C34 in Table 5) with samples D38a and D38b (corresponding to sample C36 in Table 5). Similar to D35a and D35b, D37a and D37b were clarified with the conventional Cl-F-Ce-Sn package. D38a and D38b were clarified with sodium sulfate and sodium nitrate. Again in this case, the glass samples clarified with sulfate (D38a, D38b) have fewer residual bubbles than the samples clarified with the conventional Cl-F-Ce-Sn package (D37a, D37b).

[0091] Figures 21 and 22 show bar graphs comparing samples D39a and D39b (corresponding to sample C35 in Table 5) with samples D40a and D40b (corresponding to sample C36 in Table 5). D39a and D39b were clarified with a conventional Cl-F-Ce-Sn package. D40a and D40b were clarified with sodium sulfate and sodium nitrate. Also in this case, the glass samples (D40a, D40b) clarified with sulfate have fewer residual bubbles than the samples (D39a, D39b) clarified with the conventional Cl-F-Ce-Sn package.

[0092] Durability experiment Embodiments of the present disclosure were also tested for durability. To test durability, an appropriate amount of raw materials to obtain 1000 g of glass was set in four platinum crucibles and double melted in an electric furnace heated with a Globar® heating element. The double melting was performed to improve the chemical homogeneity of the glass. The glass composition is shown in Table 5. In the melting cycle, the crucibles were placed in a furnace preheated to 1450°C and held at 1450°C for 1 hour. Next, they were heated from 1450°C to 1550°C over 150 minutes, held at 1550°C for 30 minutes, and then drained. In the next melting cycle, the crucibles were placed in a furnace preheated to 1450°C and held at 1450°C for 1 hour. Next, they were heated from 1450°C to 1550°C over 150 minutes and held at 1550°C for a residence time indicated as D. For the glass having the composition of sample C37 in Table 5, D was 2 hours 30 minutes, and for the glass having the composition of sample C35 in Table 5, D was 0 minutes. Next, the crucibles were removed from the furnace and the molten glass was poured onto a preheated steel plate. The glass was rolled to a thickness of about 4 mm on the steel plate. The glass plate was annealed at 600°C for 1 hour and then cooled slowly.

[0093] The durability tests were carried out in accordance with ISO standard 695 for strong base resistance and CETC, and DIN standard 12116 for strong acid resistance. In ISO 695, two glass samples of 25×25 mm and 1 mm thickness were prepared and all surfaces were polished. In ISO 695, two samples of 28 mm diameter and 3 mm thickness were prepared and all surfaces were polished. In DIN 12116, two glass samples of 51 mm×76 mm and 1 mm thickness were prepared and all surfaces were polished by 1 mm.

[0094] The results are reported in Tables 6 and 7 below, and no significant difference is shown between the two glasses: Sample C37 (clarified with Cl, F, Ce, and Sn) and Sample C35 (clarified with sulfate).

[0095]

Table 6

[0096]

Table 7

[0097] Figure 23 shows a comparison table of four images of borosilicate glass compositions (Samples D41 - D44; corresponding to Compositions C22 - C25 in Table 3). As a comparative example, Sample D41 does not contain a clarifying agent, and Sample D42 was clarified with NaCl. Since Cl may not be desirable as a clarifying agent, the disclosure of the embodiments includes clarifying packages that do not contain Cl, such as those used in Samples D43 and D44. Sample D43 was clarified with Na2SO4, and Sample D44 was clarified with Na2SO4 and SnO2.

[0098] Figure 24 shows a bar graph comparing the number of defects per 1 cm 3 at each of four positions (top, center, bottom, and base) of Samples D41 - D44 in Figure 23. In the sulfate composition, the defect density in the lower half of the crucible decreases by one to two orders of magnitude compared to the case without a clarifying agent. In the sulfate and tin composition, the defect density throughout the crucible decreases by one to two orders of magnitude compared to the case without a clarifying agent.

[0099] The terms "include", "includes", or similar terms mean inclusive but not limiting, i.e., inclusive and not exclusive.

[0100] When describing aspects of the present disclosure, values such as, for example, the amounts, concentrations, volumes, process temperatures, process times, yields, flow rates, pressures, viscosities, etc. of components in a composition, and ranges thereof, or dimensions of components and similar values and ranges thereof that vary by "about" are, for example, through general measurement and handling procedures used in the preparation of materials, compositions, composites, concentrates, components, articles of manufacture, or use formulations; through inadvertent errors in these procedures; through differences in the manufacture, source, or purity of starting materials or raw materials used to carry out the methods; and through similar considerations. The term "about" also encompasses amounts that differ due to degradation of a composition or formulation with a particular initial concentration or mixture, and amounts that differ due to mixing or processing of a composition or formulation with a particular initial concentration or mixture.

[0101] "Optional" or "optionally" means that the event or circumstance described thereafter may or may not occur, and that the description includes both the case where the event or circumstance occurs and the case where it does not occur.

[0102] As used herein, the indefinite articles "a" or "an" and their corresponding definite article "the" mean at least one or one or more unless otherwise specified.

[0103] Abbreviations well known to those skilled in the art may be used (e.g., "h" or "hrs" for time, "g" or "gm" for gram, "mL" for milliliter, "rt" for room temperature, "nm" for nanometer, and similar abbreviations).

[0104] The specific preferred values disclosed for ingredients, raw materials, additives, dimensions, conditions, and similar characteristics, as well as ranges thereof, are for illustrative purposes only and do not exclude other defined values or other values within defined ranges. The systems, kits, and / or methods of the present disclosure can include any value or any combination of any of the values, specific values, more specific values, and preferred values described herein.

[0105] Unless otherwise specified, it is never intended that any method described herein be construed as requiring that its steps be performed in a particular order. Thus, no particular order is ever intended to be inferred where a method claim does not actually recite the order to be followed by its steps or where it is not specifically stated in the claims or the specification that the steps are to be limited to a particular order.

[0106] It will be apparent to those skilled in the art that various modifications and changes can be made without departing from the spirit or scope of the disclosed embodiments. Since modifications, combinations, sub-combinations, and variations of the disclosed embodiments incorporating the spirit and essence of the embodiments can be envisioned by those skilled in the art, the embodiments of the present disclosure should be construed to include anything within the scope of the appended claims and their equivalents.

[0107] Hereinafter, preferred embodiments of the present invention will be described item by item.

[0108] Embodiment 1 A fining package for a glass composition, containing sulfate or sulfide in an amount of about 0.001 to about 0.1 mol% of the glass composition A fining package.

[0109] Embodiment 2 The fining package according to Embodiment 1, wherein the fining package contains the sulfate and does not contain sulfide.

[0110] Embodiment 3 The clarified package according to Embodiment 1 or 2, wherein the sulfate contains at least one of an alkali sulfate and an alkaline earth sulfate.

[0111] Embodiment 4 The clarified package according to any one of Embodiments 1 to 3, wherein the clarified package further contains a polyvalent compound in an amount of about 0.001 to about 1 mol% of the glass composition.

[0112] Embodiment 5 The clarified package according to Embodiment 4, wherein the polyvalent compound contains Sn or Ce.

[0113] Embodiment 6 The clarified package according to Embodiment 5, wherein the polyvalent compound contains CeO2, SnO2, or Fe2O3.

[0114] Embodiment 7 The clarified package according to any one of Embodiments 1 to 6, wherein the clarified package further contains a nitrate in an amount of about 0.01% to about 0.1 mol% of the glass composition.

[0115] Embodiment 8 The clarified package according to any one of Embodiments 1 to 7, wherein the sulfate contains a heavy alkaline earth sulfate.

[0116] Embodiment 9 The clarified package according to Embodiment 8, further comprising a redox modifier.

[0117] Embodiment 10 The clarified package according to Embodiment 9, wherein the redox modifier is carbon, sugar, or nitrate.

[0118] Embodiment 11 The clarified package according to any one of Embodiments 1 to 10, wherein the clarified package does not contain a reducing agent for reducing the sulfate to a sulfide.

[0119] Embodiment 12 The clarified package according to any one of Embodiments 1 to 11, wherein the glass composition contains a borosilicate glass composition.

[0120] Embodiment 13 The clarified package according to any one of Embodiments 1 to 12, wherein the glass composition contains an aluminosilicate glass composition.

[0121] Embodiment 14 The clarified package according to any one of Embodiments 1 to 13, wherein the glass composition is used for forming a glass tube.

[0122] Embodiment 15 The clarified package according to Embodiment 14, wherein the glass tube is used for forming pharmaceutical packaging.

[0123] Embodiment 16 The clarified package according to Embodiment 15, wherein the pharmaceutical packaging contains at least one of a vial, an ampoule, a syringe, and a cartridge.

[0124] Embodiment 17 The clarified package according to any one of Embodiments 1 to 16, wherein the clarified package does not contain at least one of Cl, F, Sn, Ce, and As.

[0125] Embodiment 18 The glass composition is SiO2 in an amount of 70 to 76% by mass of the glass composition, B2O3 in an amount of 9 to 13.5% by mass of the glass composition, Al2O3 in an amount of 4 to 8% by mass of the glass composition, TiO2 in an amount of 0 to 0.1% by mass of the glass composition, Fe2O3 in an amount of 0 to 0.1% by mass of the glass composition, BaO in an amount of 0 to 0.1% by mass of the glass composition, CaO in an amount of 0 to 3% by mass of the glass composition, Na2O in an amount of 5 to 8.5% by mass of the glass composition, K2O in an amount of 0.5 to 3% by mass of the glass composition, MgO in an amount of 0 to 1% by mass of the glass composition, Cl in an amount of 0 to 0.03% by mass of the glass composition, F in an amount of 0 to 0.02% by mass of the glass composition, CeO2 in an amount of 0.08 to 0.5% by mass of the glass composition, SnO2 in an amount of 0.02 to 0.23% by mass of the glass composition, and ZrO2 in an amount of 0 to 0.08% by mass of the glass composition A clarification package according to any one of Embodiments 1 to 17, comprising.

[0126] Embodiment 19 The glass composition is SiO2 in an amount of 70 to 74% by mass of the glass composition, B2O3 in an amount of 10 to 13.5% by mass of the glass composition, Al2O3 in an amount of 5 to 7% by mass of the glass composition, TiO2 in an amount of 0 to 0.03% by mass of the glass composition, Fe2O3 in an amount of 0 to 0.04% by mass of the glass composition, BaO in an amount of 0 to 0.04% by mass of the glass composition, CaO in an amount of 0.5 to 2.3% by mass of the glass composition, Na2O in an amount of 6.5 to 7.5% by mass of the glass composition, K2O in an amount of 1.0 to 1.8% by mass of the glass composition, MgO in an amount of 0 to 0.1% by mass of the glass composition, Cl in an amount of 0.01 to 0.03% by mass of the glass composition, F in an amount of 0 to 0.02% by mass of the glass composition, CeO2 in an amount of 0.08 to 0.2% by mass of the glass composition, SnO2 in an amount of 0.02 to 0.12% by mass of the glass composition, and ZrO2 in an amount of 0 to 0.08% by mass of the glass composition The clarified package according to Embodiment 18, including

[0127] Embodiment 20 The glass composition is SiO2 in an amount of 70 to 73% by mass of the glass composition, B2O3 in an amount of 10.5 to 13.2% by mass of the glass composition, Al2O3 in an amount of 5 to 7% by mass of the glass composition, TiO2 in an amount of 0 to 0.03% by mass of the glass composition, Fe2O3 in an amount of 0 to 0.04% by mass of the glass composition, BaO in an amount of 0 to 0.04% by mass of the glass composition, CaO in an amount of 1 to 2.3% by mass of the glass composition, Na2O in an amount of 6.5 to 7.3% by mass of the glass composition, K2O in an amount of 1.0 to 1.5% by mass of the glass composition, MgO in an amount of 0 to 0.1% by mass of the glass composition, Cl in an amount of 0.01 to 0.02% by mass of the glass composition, F in an amount of 0 to 0.02% by mass of the glass composition, CeO2 in an amount of 0.08 to 0.2% by mass of the glass composition, SnO2 in an amount of 0.02 to 0.12% by mass of the glass composition, and ZrO2 in an amount of 0 to 0.08% by mass of the glass composition The clarified package according to Embodiment 19, including

[0128] Embodiment 21 The glass composition is SiO2 in an amount of 75 to 85% by mass of the glass composition, B2O3 in an amount of 9.5 to 14.5% by mass of the glass composition, Al2O3 in an amount of 0.5 to 5% by mass of the glass composition, TiO2 in an amount of 0 to 0.1% by mass of the glass composition, Fe2O3 in an amount of 0 to 0.1% by mass of the glass composition, BaO in an amount of 0 to 0.1% by mass of the glass composition, Na2O in an amount of 2 to 8% by mass of the glass composition, K2O in an amount of 0 to 3% by mass of the glass composition, CaO and MgO in a total amount of 0 to 1.0% by mass of the glass composition, Cl in an amount of 0 to 0.10% by mass of the glass composition, and SnO2 in an amount of 0 to 0.2% by mass of the glass composition A fining package according to any one of Embodiments 1 to 17, comprising the above.

[0129] Embodiment 22 The glass composition is SiO2 in an amount of 74 to 80% by mass of the glass composition, Al2O3 in an amount of 4 to 8% by mass of the glass composition, CaO in an amount of 0 to 0.5% by mass of the glass composition, Na2O in an amount of 8 to 14% by mass of the glass composition, MgO in an amount of 3 to 7% by mass of the glass composition, and SnO2 in an amount of 0 to 0.23% by mass of the glass composition A fining package according to any one of Embodiments 1 to 17, comprising the above.

[0130] Embodiment 23 A method for fining glass to form a pharmaceutical package, comprising: A step of fining the glass composition by adding the fining package according to any one of Embodiments 1 to 22 to the glass composition to remove bubbles, and A step of forming a glass tube from the fined glass composition A method comprising the above.

[0131] Embodiment 24 The method according to Embodiment 23, further comprising a step of forming a pharmaceutical package from the glass tube.

[0132] Embodiment 25 The method according to embodiment 24, wherein the pharmaceutical package includes a pharmaceutical ampoule.

[0133] Embodiment 26 The method according to any one of embodiments 23 to 25, wherein the fining is carried out at a fining temperature of at least 1400 °C.

[0134] Embodiment 27 The method according to embodiment 26, wherein the fining temperature is at least 1500 °C.

[0135] Embodiment 28 The method according to embodiment 27, wherein the fining 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.

[0136] Embodiment 29 A step of melting a batch of materials for the glass composition, wherein the batch of materials includes sand having a D50 average particle size of more than 200 μm or more than 300 μm. The method according to embodiment 24, further comprising the step.

Claims

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

2. The fining package according to claim 1, wherein the fining package contains the sulfate and does not contain a sulfide.

3. The fining package according to claim 1, wherein the sulfate contains at least one of an alkali sulfate and an alkaline earth sulfate.

4. The fining package according to claim 1, wherein the fining package further contains a polyvalent compound in an amount of about 0.001 to about 1 mol% of the glass composition.

5. The fining package according to claim 4, wherein the polyvalent compound contains Sn or Ce.

6. The polyvalent compound is CeO ２ , SnO ２ , or Fe ２ O ３ 6. The clarification package of claim 5, comprising:

7. The fining package according to claim 1, further comprising a nitrate in an amount of about 0.01% to about 0.1 mol% of the glass composition.

8. The fining package according to claim 1, wherein the sulfate contains a heavy alkaline earth sulfate.

9. The fining package according to claim 8, further comprising a redox modifier.

10. The fining package according to claim 1, wherein the fining package does not contain a reducing agent for reducing the sulfate to a sulfide.

11. The fining package according to claim 1, wherein the glass composition contains a borosilicate glass composition or an aluminosilicate glass composition.

12. The fining package according to claim 1, wherein the fining package does not contain at least one of Cl, F, Sn, Ce, and As.

13. The glass composition is SiO in an amount of 70 to 76% by mass of the glass composition ２ , B in an amount of 9 to 13.5 mass % of the glass composition ２ O ３ , Al in an amount of 4 to 8% by mass of the glass composition ２ O ３ , TiO in an amount of from 0 to 0.1% by mass of the glass composition ２ , Fe in an amount of from 0 to 0.1% by mass of the glass composition ２ O ３ , BaO in an amount of 0 to 0.1% by mass of the glass composition, CaO in an amount of 0 to 3% by mass of the glass composition, Na in an amount of 5 to 8.5% by mass of the glass composition ２ O, K in an amount of 0.5 to 3% by mass of the glass composition ２ O MgO in an amount of 0 to 1% by mass of the glass composition, Cl in an amount of 0 to 0.03% by mass of the glass composition, F in an amount of 0 to 0.02% by mass of the glass composition, CeO in an amount of from 0.08 to 0.5% by mass of the glass composition ２ , SnO in an amount of 0.02 to 0.23% by mass of the glass composition ２ , and ZrO in an amount of 0 to 0.08% by mass of the glass composition ２ The fining package according to claim 1.

14. The glass composition is SiO in an amount of 75 to 85% by mass of the glass composition ２ , B in an amount of 9.5 to 14.5% by mass of the glass composition ２ O ３ , Al in an amount of 0.5 to 5% by mass of the glass composition ２ O ３ , TiO in an amount of from 0 to 0.1% by mass of the glass composition ２ , Fe in an amount of 0 to 0.1% by mass of the glass composition ２ O ３ , BaO in an amount of 0 to 0.1% by mass of the glass composition, Na in an amount of 2 to 8% by mass of the glass composition ２ O K in an amount of from 0 to 3% by mass of the glass composition ２ O, CaO and MgO in a total amount of 0 to 1.0% by mass of the glass composition, Cl in an amount of 0 to 0.10% by mass of the glass composition, and SnO in an amount of from 0 to 0.2% by mass of the glass composition ２ The fining package according to claim 1.

15. The glass composition is SiO in an amount of 74 to 80% by mass of the glass composition ２ , Al in an amount of 4 to 8% by mass of the glass composition ２ O ３ , CaO in an amount of 0 to 0.5% by mass of the glass composition, Na in an amount of 8 to 14% by mass of the glass composition ２ O MgO in an amount of 3 to 7% by mass of the glass composition, and SnO in an amount of from 0 to 0.23% by mass of the glass composition ２ The fining package according to claim 1.

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