Colorless medium borosilicate medicinal glass tube and preparation method thereof

Abstract

The invention discloses a colorless medium borosilicate medicinal glass tube and a preparation method thereof, and belongs to the technical field of glass products. The medicinal glass tube comprises the following raw materials in parts by weight: 550-650 parts of quartz sand, 60-70 parts of aluminum hydroxide, 100-250 parts of borax pentahydrate, 5-15 parts of sodium nitrate, 15-30 parts of sodium carbonate, 1-5 parts of sodium fluosilicate, 10-15 parts of calcite, 5-10 parts of barium carbonate, 5-10 parts of potassium carbonate, 10-20 parts of a compound clarifying agent and 400-500 parts of medium borosilicate glass slag. The quartz sand and the borax pentahydrate in a high proportion provide a basis for the high borosilicate glass, the chemical stability of the glass is remarkably improved, the glass can resist acid and alkali erosion and is very suitable for storing various medicines, and in addition, substances such as aluminum hydroxide, calcite, sodium nitrate, sodium carbonate and sodium fluosilicate are added, so that the thermal stability and the mechanical property of a glass product are improved.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of glass products, and particularly relates to a colorless neutral borosilicate pharmaceutical glass tube and a preparation method thereof. BACKGROUND

[0002] Pharmaceutical glass tubes are a type of glass product specifically used in the pharmaceutical industry. They are mainly used to produce various pharmaceutical containers, such as ampoule bottles, injection bottles, oral liquid bottles, and pre-filled syringes. Pharmaceutical glass tubes can be divided into sodium-calcium glass tubes, lead glass tubes, and borosilicate glass tubes (including low borosilicate and neutral borosilicate glass tubes) based on their composition.

[0003] Neutral borosilicate glass tubes are widely used as pharmaceutical tubes in the pharmaceutical industry because they have many advantages, especially for storing and transporting sensitive drugs. The main advantages include:

[0004] (1) High transparency:

[0005] High transparency makes it easy to observe the state of the drug inside the pharmaceutical tube, which is important for checking the color, clarity, or presence of precipitates in the drug, which is crucial for quality control of pharmaceutical products.

[0006] (2) High chemical stability:

[0007] Neutral borosilicate glass has very high chemical stability, which can effectively resist the erosion of various chemicals, including strong acids, strong bases, and organic solvents. This means that it can safely store various types of drugs without reacting with them or releasing harmful substances, ensuring the purity and stability of the drugs.

[0008] (3) Excellent sealing performance:

[0009] It can achieve good sealing effect to prevent the invasion of air, moisture or microorganisms, ensuring the long-term preservation and safe transportation of drugs.

[0010] (4) High-temperature sterilization:

[0011] Due to the excellent thermal stability of neutral borosilicate glass tubes, they can withstand high-temperature sterilization processes, which is a crucial step in the pharmaceutical industry to ensure the sterility of drugs.

[0012] Although neutral borosilicate glass tubes have many advantages as pharmaceutical tubes, they also have some disadvantages that may limit their application in certain situations. The following are some of the main disadvantages of neutral borosilicate glass tubes:

[0013] (1) Fragility:

[0014] Although the mechanical strength of neutral borosilicate glass is higher than that of ordinary glass, the glass is still more fragile than plastic materials and is prone to breakage during handling, storage or use, which can result in loss of pharmaceuticals and additional cleaning work.

[0015] (2) Cold and hot shock resistance

[0016] Although the thermal stability of neutral borosilicate glass is high and can withstand high-temperature sterilization, some pharmaceuticals need to be stored in a cycle of low and high temperatures, which causes the temperature resistance of the glass product to deteriorate and even to burst. SUMMARY

[0017] The purpose of the present application is to provide a colorless neutral borosilicate pharmaceutical glass tube and a preparation method thereof to solve the problems of poor mechanical properties and poor cold and hot shock resistance of the above-mentioned neutral borosilicate glass. The present application precisely controls the weight range of each raw material, and high proportions of quartz sand and borax pentahydrate provide the basis for high borosilicate glass. The two components work together to significantly improve the chemical stability of the glass, making it resistant to acid and alkali corrosion, and are very suitable for storing various drugs. In addition, aluminum hydroxide, calcite, sodium nitrate, soda ash, sodium fluorosilicate and other substances are added and mixed with quartz sand and borax pentahydrate to improve the comprehensive performance of the glass product, such as thermal stability and mechanical properties.

[0018] To achieve the above-mentioned purpose, the first aspect of the present application provides a colorless neutral borosilicate pharmaceutical glass tube, which comprises the following raw materials according to weight parts:

[0019]

[0020] The current formula of borosilicate glass usually contains multiple components, and the proportion of each component needs to be accurately controlled to achieve the desired physical and chemical properties, which increases the complexity of formula development and production process, and may also introduce more variables affecting the stability of product quality. In addition, during the melting process, complex chemical reactions may occur between different raw materials, which may also affect the performance of the final product. The present application uses quartz sand, aluminum hydroxide, borax pentahydrate, sodium nitrate, soda ash, sodium fluorosilicate, calcite, barium carbonate, potassium carbonate, composite fining agent, and borosilicate glass slag as raw materials. The formula design is reasonable, which improves the chemical stability and high temperature stability of the glass. Specifically, the quartz sand in the present application is the main component of the glass, providing silicon dioxide, which is the basic structural unit of the glass, determining the hardness and transparency of the glass. Aluminum hydroxide can increase the chemical stability and mechanical strength of the glass, and at high temperature, it can decompose to produce water vapor, which helps to clarify the glass. Borax pentahydrate is a key component of borosilicate glass, which provides boron element, reduces the thermal expansion coefficient of the glass, and improves the thermal stability and chemical stability of the glass. Sodium nitrate as a fluxing agent and fining agent, helps to reduce the melting point of the glass, accelerate the melting process of the glass, and promote the clarification of the glass liquid. Soda ash is another common fluxing agent, which reduces the temperature of glass melting, making the melting process more economical. Sodium fluorosilicate as a fining agent helps to remove bubbles in the glass liquid, improving the transparency of the glass. Calcite provides calcium element, enhances the mechanical strength of the glass, and helps to adjust the melting point and viscosity of the glass. Barium carbonate can improve the refractive index and gloss of the glass, while enhancing its mechanical strength. Potassium carbonate as a fluxing agent, reduces the melting temperature, while can improve the chemical stability and thermal stability of the glass. The composite fining agent contains multiple components, the purpose is to accelerate the escape of bubbles, further improve the transparency and purity of the glass. Borosilicate glass slag can reduce the cost of raw materials, and at the same time, it is helpful for the melting of glass, because the broken glass itself is in a molten state, it is easier to integrate with other raw materials.

[0021] Preferably, the sum of the weight parts of borax pentahydrate, aluminum hydroxide, calcite and barium carbonate accounts for 18-22% of the total weight parts.

[0022] The inventors continue to develop and find that various raw materials are combined in proportion, although the chemical stability and thermal stability of the medium borosilicate glass are improved to a certain extent, the mechanical properties are limited for use in some specific environments (such as alternating cold and hot), prone to burst, and the safety performance also decreases. On this basis, the present application further limits the weight parts and the proportion between the total weight parts of the added borax pentahydrate, aluminum hydroxide, calcite and barium carbonate, wherein the addition of aluminum hydroxide and calcite can further improve the chemical stability of the glass, so that it can better resist acid and alkali corrosion when storing drugs. Borax pentahydrate and barium carbonate also contribute to chemical stability, especially borax, which is a key component of borosilicate glass, helps to enhance the resistance of glass to chemicals. The four substances have a synergistic effect, further improving the chemical stability of the glass. The added aluminum hydroxide and calcite in the present application can increase the mechanical strength of the glass, making the pharmaceutical tube more solid and not easy to break, which is crucial for safety during transportation and use. Controlling the total proportion of these components helps to ensure the uniformity of the glass composition, avoiding inconsistent performance caused by excessive or insufficient local chemical composition, and ensuring the quality consistency of the glass tube. Therefore, by precisely controlling the addition amount and proportion of borax pentahydrate, aluminum hydroxide, calcite and barium carbonate, the present application can manufacture colorless medium borosilicate pharmaceutical glass tubes with high chemical stability, good thermal stability and strong mechanical strength, meeting the high standard requirements of the pharmaceutical industry for drug packaging materials.

[0023] Preferably, the mass ratio of quartz sand to borax pentahydrate is 3-4:1.

[0024] The main components of the medium borosilicate glass in the present application are quartz sand and borax pentahydrate, and the mass ratio of quartz sand to borax pentahydrate is limited to 3-4:1, which helps to manufacture colorless medium borosilicate pharmaceutical glass tubes with excellent thermal stability, chemical stability, mechanical strength and processing performance. In the present application, quartz sand is the main component of glass, providing the basic structural framework, while borax pentahydrate significantly reduces the thermal expansion coefficient of glass by introducing boron elements. Controlling this ratio helps the glass to maintain dimensional stability when the temperature changes, thereby improving the thermal stability. At the same time, a high proportion of quartz sand combined with an appropriate amount of borax pentahydrate can effectively improve the chemical stability of the glass, enabling it to resist the erosion of various chemicals, including acids, bases and solvents, which is crucial for pharmaceutical tubes that store drugs. In the present application, the appropriate ratio of quartz sand to borax pentahydrate helps to improve the mechanical strength and impact resistance of the glass, reducing the risk of breakage during transportation and use, ensuring the integrity and safety of the pharmaceutical tube. For the preparation process of the glass, by controlling the ratio of quartz sand to borax pentahydrate, the melting process of the glass can be optimized to ensure good fluidity of the glass liquid, which helps to form a uniform glass structure, reduces bubbles and impurities, and improves the transparency and purity of the pharmaceutical tube.

[0025] Preferably, the total weight parts of sodium nitrate, soda ash, sodium fluorosilicate and potassium carbonate added accounts for 2.5-4% of the total weight parts.

[0026] The addition of potassium carbonate in the present application helps to improve the chemical stability of the glass, so that it can resist the erosion of chemicals, and the appropriate amount of addition can ensure that the glass maintains good chemical stability when storing and transporting drugs, avoiding reaction with drugs. The addition of sodium nitrate and soda ash in the present application also affects the mechanical strength of the glass to some extent, and the appropriate amount of addition can ensure that the glass has good impact resistance and bending strength, which is crucial for the safety of the pharmaceutical tube during handling and transportation. For the glass preparation process, by controlling the total amount of these additives, the homogeneity of the glass liquid can be promoted, the bubbles and impurities can be reduced, and the transparency and appearance quality of the pharmaceutical tube can be improved, which is crucial for the visual inspection and identification of drugs. Therefore, the total amount of sodium nitrate, soda ash, sodium fluorosilicate and potassium carbonate added in the present application is limited, which not only improves the solvent resistance and high temperature resistance of the glass product, but also improves the mechanical properties of the glass product, and the prepared pharmaceutical tube can maintain its impact resistance in extreme environments, improving the safety of the pharmaceutical tube.

[0027] Preferably, the medium borosilicate glass slag is compounded by medium borosilicate glass slag with particle size of 200-500 nm, particle size of 1.0-3.0 μm and particle size of 10-20 μm in a weight ratio of 0.2-0.4:0.8-1.2:0.05-0.15.

[0028] The present application limits the particle size distribution and ratio of medium borosilicate glass slag, which can significantly optimize the melting efficiency, homogeneity, clarification effect, mechanical properties and chemical stability of colorless medium borosilicate pharmaceutical glass tube. In the present application, the medium borosilicate glass slag with different particle sizes is compounded and used, which can significantly improve the melting efficiency, the small particle size (200-500 nm) can be quickly melted, and the larger particle size (10-20 μm) can help to form a more stable melting environment. Such particle size distribution helps the overall melting process to be more uniform, reducing energy consumption. At the same time, the difference in particle size helps the uniform mixing of raw materials during the melting process, ensuring the homogeneity of the glass liquid, which is crucial for improving the mechanical properties and chemical stability of the finished product. The optimization of particle size distribution helps to promote the removal of bubbles in the glass liquid, the small particle size can act as a bubble nucleation center to help bubbles float out faster, thereby improving the transparency and purity of the glass. Uniform melting and good bubble removal help to form a glass structure without defects, thereby enhancing the mechanical strength of the pharmaceutical tube, improving the impact resistance and pressure resistance, and the homogeneous glass liquid helps to ensure the chemical stability of the final product, which is particularly important for storing drugs with active chemical properties.

[0029] The medium borosilicate glass slag used in the present application is obtained by crushing and grinding the waste produced in the process of preparing medium borosilicate glass by the applicant.

[0030] Preferably, the composite fining agent comprises chlorinated salt, fluorinated salt and sulfate salt, wherein the mass ratio of the chlorinated salt, fluorinated salt and sulfate salt is 6-8:3-5:1-3.

[0031] The present application limits the mass ratio of chlorinated salt, fluorinated salt and sulfate salt in the composite fining agent, which can significantly improve the fining efficiency, optical performance and chemical stability of colorless medium borosilicate pharmaceutical glass tubes. The chlorinated salt in the present application decomposes at high temperatures, releasing chlorine gas, which can act as a bubble nucleation center, helping the gas to quickly escape from the glass liquid, improving the fining speed and efficiency of the glass liquid. The presence of fluorinated salt helps the merging of bubbles, reduces the small bubbles in the glass, and enables the bubbles to more effectively gather and rise to the surface, thereby improving the transparency and purity of the glass. The sulfate salt plays a role in inhibiting the formation of secondary bubbles during the fining process, preventing the generation of bubbles again during the cooling stage, thereby ensuring the uniformity and stability of the glass. The present application uses chlorinated salt, fluorinated salt and sulfate salt in a specific ratio, which can optimize their synergistic effect, improve the fining effect, and at the same time avoid the adverse effects caused by excessive amount of a certain component, such as increased corrosion or negative impact on glass performance. The composite fining agent of the present application can remove bubbles and impurities from the glass liquid, help improve the chemical stability of the finished product, reduce the potential chemical reaction between the drug and the container, and ensure the safety and effectiveness of the drug.

[0032] Preferably, the chlorinated salt is one or more of NaCl, KCl and NH4Cl; the fluorinated salt is one or more of CaF2, Na2SiF6 and NaF; and the sulfate salt is one or more of Na2SO4, CaSO4 and BaSO4.

[0033] Preferably, the colorless medium borosilicate pharmaceutical glass tube has an expansion coefficient of 5.01x10 -6 -5.03x10 -6 K -1 , a bending strength of 90-100 MPa, and a surface hardness of 7-8 GPa.

[0034] The second aspect of the present application provides a preparation method of a colorless medium borosilicate pharmaceutical glass tube, comprising the following steps:

[0035] (1) mixing raw materials according to weight parts to obtain a mixture;

[0036] (2) melting the mixture in a high-temperature melting furnace to form a glass liquid;

[0037] (3) fining and homogenizing the glass liquid;

[0038] (4) forming the glass liquid into a glass tube.(4) homogenized glass liquid is drawn into shape to obtain colorless medium borosilicate pharmaceutical glass tube.

[0039] Preferably, the heating temperature of the high-temperature smelting furnace in step (2) is 1600-1800 DEG C, and the heating time is 5-10h.

[0040] The refining in step (3) includes primary refining and high-temperature refining in sequence, the temperature of the primary refining is 1450-1500 DEG C, and the time is 1-1.5h, the temperature of the high-temperature refining is 1550-1600 DEG C, and the time is 1-1.5h, the homogenization temperature is 1350-1400 DEG C, and the time is 20-30min.

[0041] The drawing temperature in step (4) is 1100-1200 DEG C.

[0042] Therefore, the colorless medium borosilicate pharmaceutical glass tube and the preparation method thereof have the following beneficial effects:

[0043] 1. The weight range of each raw material is accurately controlled, high proportion of quartz sand and borax pentahydrate provide the basis for high borosilicate glass, the two components work together to significantly improve the chemical stability of the glass, making it resistant to acid and alkali corrosion, which is very suitable for storing various drugs, in addition, aluminum hydroxide, calcite, sodium nitrate, soda ash, sodium fluorosilicate and other substances are added and mixed with quartz sand and borax pentahydrate to improve the thermal stability and mechanical properties and other comprehensive properties of the glass product.

[0044] 2. The addition amount of borax pentahydrate, aluminum hydroxide, calcite and barium carbonate is further limited, which helps to further optimize and improve the chemical stability of the glass, so that it can safely store various drugs without reaction.

[0045] 3. The mass ratio of quartz sand and borax pentahydrate is limited, which optimizes the thermal expansion coefficient and ensures the dimensional stability of the glass under temperature change, which is suitable for high-temperature sterilization process.

[0046] 4. By controlling the addition amount of sodium nitrate, soda ash, sodium fluorosilicate and potassium carbonate, the mechanical strength of the glass is optimized, and the bending resistance and surface hardness are improved.

[0047] 5. The particle size of the medium borosilicate glass slag is designed, which helps to improve the melting efficiency, promote the homogeneity and refining of the glass liquid, and reduce the bubbles and defects in the finished product. DETAILED DESCRIPTION

[0048] The present application will be further described below, it should be noted that the present embodiment is based on the technical solution, and detailed implementation and specific operation process are given, but the present application is not limited to the present embodiment.

[0049] Embodiment 1

[0050] The embodiment provides a colorless medium borosilicate pharmaceutical glass tube, which comprises the following raw materials in parts by weight:

[0051]

[0052] The sum of the weight parts of added borax pentahydrate, aluminum hydroxide, calcite and barium carbonate accounts for 18.68% of the total weight parts.

[0053] The mass ratio of quartz sand to borax pentahydrate is 3.4:1.

[0054] The sum of the weight parts of added sodium nitrate, soda ash, sodium fluosilicate and potassium carbonate accounts for 2.99% of the total weight parts.

[0055] The medium borosilicate glass slag is a compound of medium borosilicate glass slag with a particle size of 300 nm, a particle size of 2.0 μm and a particle size of 15 μm at a weight ratio of 0.3:1.0:0.1.

[0056] The composite refining agent comprises chlorinated salts, fluorinated salts and sulfate salts, wherein the mass ratio of the chlorinated salts, the fluorinated salts and the sulfate salts is 7:4:2. The chlorinated salt is NaCl; the fluorinated salt is CaF2; and the sulfate salt is Na2SO4.

[0057] The embodiment further provides a preparation method of the colorless medium borosilicate pharmaceutical glass tube, comprising the following steps:

[0058] (1) mixing raw materials according to weight parts to obtain a mixture;

[0059] (2) melting the mixture in a high-temperature smelting furnace to form a glass liquid; the heating temperature of the high-temperature smelting furnace is 1600 DEG C, and the heating time is 6 h;

[0060] (3) clarifying and homogenizing the glass liquid; the clarification comprises preliminary clarification and high-temperature clarification in sequence, the temperature of the preliminary clarification is 1460 DEG C, the time is 1 h, the temperature of the high-temperature clarification is 1560 DEG C, and the time is 1.5 h; the temperature of the homogenization is 1400 DEG C, and the time is 30 min;

[0061] (4) drawing the homogenized glass liquid into a shape at a drawing temperature of 1150 DEG C to obtain the colorless medium borosilicate pharmaceutical glass tube.

[0062] Embodiment 2

[0063] The difference between the embodiment and Embodiment 1 is that the formula of the colorless medium borosilicate pharmaceutical glass tube is different.

[0064] The embodiment provides a colorless medium borosilicate pharmaceutical glass tube, which comprises the following raw materials in parts by weight:

[0065]

[0066]

[0067] The sum of the weight parts of the added borax pentahydrate, aluminum hydroxide, calcite and barium carbonate accounts for 19.66% of the total weight parts.

[0068] The mass ratio of the quartz sand to the borax pentahydrate is 3:1.

[0069] The sum of the weight parts of the added sodium nitrate, soda ash, sodium fluosilicate and potassium carbonate accounts for 3.89% of the total weight parts.

[0070] The intermediate borosilicate glass slag is a compound of the intermediate borosilicate glass slag with a particle size of 500 nm, a particle size of 3.0 μm and a particle size of 10 μm at a weight ratio of 0.2:0.8:0.15.

[0071] The composite clarifier comprises chloride salt, fluoride salt and sulfate salt, wherein the mass ratio of the chloride salt, the fluoride salt and the sulfate salt is 8:5:1. The chloride salt is KCl; the fluoride salt is NaF; and the sulfate salt is CaSO4.

[0072] Comparative Example 1

[0073] The difference between the present comparative example and Example 1 is that the weight parts of the added borax pentahydrate, aluminum hydroxide, calcite and barium carbonate, in the present comparative example, the borax pentahydrate 150 parts, the aluminum hydroxide 60 parts, the calcite 10 parts and the barium carbonate 5 parts, the sum of the weight parts of the added borax pentahydrate, aluminum hydroxide, calcite and barium carbonate accounts for 16.5% of the total weight parts, the mass ratio of the quartz sand to the borax pentahydrate is 3.97:1, the sum of the weight parts of the added sodium nitrate, soda ash, sodium fluosilicate and potassium carbonate accounts for 3.07% of the total weight parts.

[0074] Comparative Example 2

[0075] The difference between the present comparative example and Example 1 is that the mass ratio of the quartz sand to the borax pentahydrate, in the present comparative example, the quartz sand 600 parts, the borax pentahydrate 230 parts, the sum of the weight parts of the added borax pentahydrate, aluminum hydroxide, calcite and barium carbonate accounts for 21.70% of the total weight parts, the mass ratio of the quartz sand to the borax pentahydrate is 2.61:1, the sum of the weight parts of the added sodium nitrate, soda ash, sodium fluosilicate and potassium carbonate accounts for 2.86% of the total weight parts.

[0076] Comparative Example 3

[0077] The difference between the present comparative example and example 1 is that the weight parts of sodium nitrate, soda ash, sodium fluorosilicate, potassium carbonate added, 5 parts of sodium nitrate, 15 parts of soda ash, 1 part of sodium fluorosilicate, and 5 parts of potassium carbonate are added in the present comparative example, the sum of the weight parts of borax pentahydrate, aluminum hydroxide, calcite, and barium carbonate accounts for 18.90% of the total weight parts, the mass ratio of quartz sand to borax pentahydrate is 3.41:1, and the sum of the weight parts of sodium nitrate, soda ash, sodium fluorosilicate, and potassium carbonate accounts for 1.88% of the total weight parts.

[0078] Comparative Example 4

[0079] The difference between the present comparative example and example 1 is that the addition amount of borax pentahydrate is 400 parts, the sum of the weight parts of borax pentahydrate, aluminum hydroxide, calcite, and barium carbonate accounts for 29.94% of the total weight parts, the mass ratio of quartz sand to borax pentahydrate is 1.49:1, and the sum of the weight parts of sodium nitrate, soda ash, sodium fluorosilicate, and potassium carbonate accounts for 2.57% of the total weight parts.

[0080] Comparative Example 5

[0081] The difference between the present comparative example and example 1 is that the addition amount of quartz sand is 1000 parts, the sum of the weight parts of borax pentahydrate, aluminum hydroxide, calcite, and barium carbonate accounts for 14.4% of the total weight parts, the mass ratio of quartz sand to borax pentahydrate is 5.71:1, and the sum of the weight parts of sodium nitrate, soda ash, sodium fluorosilicate, and potassium carbonate accounts for 2.31% of the total weight parts.

[0082] Comparative Example 6

[0083] The difference between the present comparative example and example 1 is that the addition amount of aluminum hydroxide is 200 parts, the sum of the weight parts of borax pentahydrate, aluminum hydroxide, calcite, and barium carbonate accounts for 25.74% of the total weight parts, the mass ratio of quartz sand to borax pentahydrate is 3.40:1, and the sum of the weight parts of sodium nitrate, soda ash, sodium fluorosilicate, and potassium carbonate accounts for 2.72% of the total weight parts.

[0084] Comparative Example 7

[0085] The difference between the present comparative example and example 1 is that the addition amount of intermediate borosilicate glass slag is 1000 parts, the sum of the weight parts of borax pentahydrate, aluminum hydroxide, calcite, and barium carbonate accounts for 13.69% of the total weight parts, the mass ratio of quartz sand to borax pentahydrate is 3.4:1, and the sum of the weight parts of sodium nitrate, soda ash, sodium fluorosilicate, and potassium carbonate accounts for 2.19% of the total weight parts.

[0086] Comparative Example 8

[0087] The difference between the present comparative example and example 1 is that the intermediate borosilicate glass slag is a mixture of intermediate borosilicate glass slag with a particle size of 300 nm, a particle size of 2.0 μm, and a particle size of 15 μm in a weight ratio of 1:1:1.

[0088] Comparative Example 9

[0089] The difference between the present comparative example and Example 1 is that the intermediate borosilicate glass frit is a mixture of intermediate borosilicate glass frits with particle sizes of 1.0 μm, 10 μm and 50 μm at a weight ratio of 0.3:1.0:0.1.

[0090] Comparative Example 10

[0091] The difference between the present comparative example and Example 1 is that the mass ratio of the chlorinated salt, fluorinated salt and sulfate salt in the composite clarifying agent is 1:1:1.

[0092] Performance test

[0093] (1) The stability test method of the neutral borosilicate glass is as follows:

[0094] Water resistance: refer to standard ISO 719-1985.

[0095] Acid resistance: refer to standard DIN 12116-2011.

[0096] Alkali resistance: refer to standard ISO 695-1991.

[0097] Coefficient of expansion: GB / T 16920-2015.

[0098] Table 1 Stability test results

[0099]

[0100]

[0101] From the above performance test results, it can be seen that the intermediate borosilicate glass prepared in Examples 1-2 has good chemical resistance and thermal stability, and the comprehensive performance of Example 1 is the most outstanding, which is mainly because the addition ratio of each raw material in the present application is reasonable, and the weight range of each raw material is accurately controlled, which significantly improves the temperature resistance, chemical resistance and mechanical properties of the glass product.

[0102] The comparative examples do not adopt the necessary technical solutions, resulting in a significant difference in the corresponding performance test compared with the examples. In Comparative Example 1, the weight parts of the added borax pentahydrate, aluminum hydroxide, calcite and barium carbonate are changed, resulting in a total weight fraction of 16.5% of the sum of the weight parts of the added borax pentahydrate, aluminum hydroxide, calcite and barium carbonate, which is not within the range defined in the application. The high-temperature resistance and chemical resistance of the prepared medium borosilicate glass have a certain decline compared with the examples, proving that the total weight parts of the added borax pentahydrate, aluminum hydroxide, calcite and barium carbonate have an important influence on the chemical resistance and high-temperature resistance of the glass product. In Comparative Example 2, the weight parts of the added quartz sand and borax pentahydrate are changed, and the mass ratio of quartz sand to borax pentahydrate is 2.61:1, which is not within the range defined in the application. The high-temperature resistance and chemical resistance of the prepared medium borosilicate glass have a certain decline compared with the examples, proving that the mass ratio of quartz sand to borax pentahydrate has an important influence on the chemical resistance and high-temperature resistance of the glass product. In Comparative Example 3, the weight parts of the added sodium nitrate, soda ash, sodium fluorosilicate and potassium carbonate are changed, resulting in a total weight fraction of 1.88% of the sum of the weight parts of the added sodium nitrate, soda ash, sodium fluorosilicate and potassium carbonate, which is not within the range defined in the application. The high-temperature resistance and chemical resistance of the prepared medium borosilicate glass have a certain decline compared with the examples, proving that the sum of the weight parts of the added sodium nitrate, soda ash, sodium fluorosilicate and potassium carbonate has an important influence on the chemical resistance and high-temperature resistance of the glass product.

[0103] In Comparative Example 4, the amount of added borax pentahydrate is changed, and the weight parts added are far beyond the range of 100-250 parts defined in the application. The proportion of the sum of the weight parts of the added borax pentahydrate, aluminum hydroxide, calcite and barium carbonate to the total weight fraction and the mass ratio of quartz sand to borax pentahydrate also change greatly. The high-temperature resistance and chemical resistance of the prepared medium borosilicate glass have a significant decline compared with the examples, which shows that the addition of borax pentahydrate in the application has a very important influence on the performance of the glass product. Similarly, Comparative Examples 5-7 change the amounts of added quartz sand, aluminum hydroxide and medium borosilicate glass slag, respectively, resulting in different changes in the proportion of the sum of the weight parts of the added borax pentahydrate, aluminum hydroxide, calcite and barium carbonate to the total weight fraction, the mass ratio of quartz sand to borax pentahydrate, and the proportion of the sum of the weight parts of the added sodium nitrate, soda ash, sodium fluorosilicate and potassium carbonate to the total weight fraction. The high-temperature resistance and chemical resistance of the prepared medium borosilicate glass have a significant decline compared with the examples, which shows that the amounts of added quartz sand, aluminum hydroxide and medium borosilicate glass slag in the application have a very important influence on the performance of the glass product.

[0104] The high temperature resistance and chemical resistance of the glass product prepared in Comparative Example 8 are both decreased, which indicates that the particle size distribution ratio of the medium borosilicate glass slag has an effect on the performance of the product. The high temperature resistance and chemical resistance of the glass product prepared in Comparative Example 9 are both decreased, which indicates that the particle size of the medium borosilicate glass slag has an effect on the performance of the product. The mass ratio of the chlorinated salt, fluorinated salt and sulfate salt in the composite clarifying agent in Comparative Example 10 is changed, which affects the clarifying process in the preparation process of the glass product, and causes the performance of the glass product to decrease, which indicates that the ratio of the various types of salt substances in the composite clarifying agent also has an effect on the performance of the glass. The above experimental results further prove the importance of the technical solutions defined in the present application to the technical effects.

[0105] (2) The mechanical property test method of the neutral borosilicate glass is as follows:

[0106] The bending strength parameter is measured by the method of GB / T6569-86;

[0107] The hardness parameter is measured by the method of GB / T6739-1996;

[0108] Cold and hot impact performance: placed at 260℃ for 1h, then placed at 0℃ for 1h, alternately for 3 times, no cracking is determined as "good", cracking is determined as "poor";

[0109] The impact resistance of the glass is determined by using a falling ball impact tester according to GB15763.2-2005, a steel ball with a diameter of 63.5mm (mass about 1040g) and a smooth surface is freely dropped from a certain height, and the lowest height at the time of breaking is tested, unit: m.

[0110] Table 2: Mechanical property test results

[0111]

[0112] In the preparation of the intermediate borosilicate glass into the medical tube, not only the high temperature resistance and chemical resistance are required, but also the mechanical properties are required based on the characteristics of the drug itself, and the mechanical properties are required to be almost unchanged in the cold and hot alternating environment. As can be seen from Table 2, the intermediate borosilicate glass prepared in Examples 1-2 has high bending strength and surface hardness, excellent mechanical properties, and no cracking occurs after cold and hot alternating treatment, which not only ensures that the drug is not wasted, but also ensures the safety of the medical tube. In addition, the intermediate borosilicate glass prepared in Examples 1-2 also has good impact resistance and is not easily broken when dropped from a high place, which is convenient for transportation and storage of drugs. The comparative examples 1-10 do not use the technical solution defined in the present application, and the intermediate borosilicate glass prepared has different degrees of decline in bending strength, surface hardness and impact resistance, and some of the comparative examples prepared have cracking after cold and hot alternating treatment, which seriously affects the safety of the intermediate borosilicate glass tube.

[0113] Therefore, the present application adopts the above structure of a colorless intermediate borosilicate medical glass tube and its preparation method, the weight range of each raw material is accurately controlled, and high proportion of quartz sand and borax pentahydrate provides the basis for high borosilicate glass. The two components work together to significantly improve the chemical stability of the glass, making it resistant to acid and alkali corrosion, and are very suitable for storing various drugs. In addition, aluminum hydroxide, calcite, sodium nitrate, soda ash, sodium fluorosilicate and other substances are added and mixed with quartz sand and borax pentahydrate to improve the thermal stability and mechanical properties of the glass product.

[0114] Finally, it should be noted that: the above examples are only used to illustrate the technical solutions of the present application and not to limit it, although the present application has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present application can still be modified or replaced by equivalents, and these modifications or equivalent replacements cannot make the modified technical solutions deviate from the spirit and scope of the technical solutions of the present application.

Claims

1. A colorless, intermediate borosilicate pharmaceutical glass tubing characterized in that, The raw materials include the following by weight parts:

2. A colorless, intermediate borosilicate pharmaceutical glass tubing according to claim 1, characterized in that, The sum of the weight parts of borax pentahydrate, aluminum hydroxide, calcite and barium carbonate added accounts for 18-22% of the total weight parts.

3. A colorless, intermediate borosilicate pharmaceutical glass tubing according to claim 1, wherein, The mass ratio of quartz sand to borax pentahydrate is 3-4:

1.

4. The colorless, intermediate borosilicate pharmaceutical glass tubing of claim 1, wherein, The sum of the weight parts of sodium nitrate, soda ash, sodium fluosilicate and potassium carbonate added accounts for 2.5-4% of the total weight parts.

5. A colorless, intermediate borosilicate pharmaceutical glass tubing according to claim 1, wherein, The medium borosilicate glass slag is a mixture of medium borosilicate glass slag with a particle size of 200-500 nm, a particle size of 1.0-3.0 μm and a particle size of 10-20 μm in a weight ratio of 0.2-0.4:0.8-1.2:0.05-0.

15.

6. A colorless, intermediate borosilicate pharmaceutical glass tubing according to claim 1, wherein, The composite clarifier includes chlorinated salt, fluorinated salt and sulfate salt, wherein the mass ratio of chlorinated salt, fluorinated salt and sulfate salt is 6-8:3-5:1-3.

7. A colorless, intermediate borosilicate pharmaceutical glass tubing according to claim 6, characterized in that, The chlorinated salt is one or more of NaCl, KCl and NH4Cl; the fluorinated salt is one or more of CaF2, Na2SiF6 and NaF; and the sulfate salt is one or more of Na2SO4, CaSO4 and BaSO4.

8. A colorless, intermediate borosilicate pharmaceutical glass tubing according to claim 1, wherein The expansion coefficient of the colorless medium borosilicate pharmaceutical glass tube is 5.01 x 10 -6 ~ 5.03 x 10 -6 K -1 The bending strength is 90 ~ 100 MPa, and the surface hardness is 7 ~ 8 GPa.

9. A method of making a colorless, intermediate borosilicate pharmaceutical glass tubing according to any one of claims 1 to 8, characterized in that, The method includes the following steps: (1) mixing the raw materials according to the weight parts to obtain a mixture; (2) adding the mixture into a high-temperature smelting furnace to melt and form a glass liquid; (3) clarifying and homogenizing the glass liquid; (4) drawing and forming the homogenized glass liquid to obtain colorless medium borosilicate pharmaceutical glass tubes.

10. The method for preparing a colorless borosilicate pharmaceutical glass tube according to claim 9, characterized in that, The heating temperature of the high-temperature smelting furnace in step (2) is 1600-1800℃, and the heating time is 5-10 h; The clarification in step (3) includes preliminary clarification and high-temperature clarification in sequence, the temperature of the preliminary clarification is 1450-1500℃, and the time is 1-1.5 h, the temperature of the high-temperature clarification is 1550-1600℃, and the time is 1-1.5 h; the homogenization temperature is 1350-1400℃, and the time is 20-30 min; The drawing temperature in step (4) is 1100-1200℃.

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