CN114507010B - Medium borosilicate glass composition, and preparation method and application thereof - Google Patents
Medium borosilicate glass composition, and preparation method and application thereof Download PDFInfo
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- CN114507010B CN114507010B CN202210122375.XA CN202210122375A CN114507010B CN 114507010 B CN114507010 B CN 114507010B CN 202210122375 A CN202210122375 A CN 202210122375A CN 114507010 B CN114507010 B CN 114507010B
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61J—CONTAINERS SPECIALLY ADAPTED FOR MEDICAL OR PHARMACEUTICAL PURPOSES; DEVICES OR METHODS SPECIALLY ADAPTED FOR BRINGING PHARMACEUTICAL PRODUCTS INTO PARTICULAR PHYSICAL OR ADMINISTERING FORMS; DEVICES FOR ADMINISTERING FOOD OR MEDICINES ORALLY; BABY COMFORTERS; DEVICES FOR RECEIVING SPITTLE
- A61J1/00—Containers specially adapted for medical or pharmaceutical purposes
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61J—CONTAINERS SPECIALLY ADAPTED FOR MEDICAL OR PHARMACEUTICAL PURPOSES; DEVICES OR METHODS SPECIALLY ADAPTED FOR BRINGING PHARMACEUTICAL PRODUCTS INTO PARTICULAR PHYSICAL OR ADMINISTERING FORMS; DEVICES FOR ADMINISTERING FOOD OR MEDICINES ORALLY; BABY COMFORTERS; DEVICES FOR RECEIVING SPITTLE
- A61J1/00—Containers specially adapted for medical or pharmaceutical purposes
- A61J1/05—Containers specially adapted for medical or pharmaceutical purposes for collecting, storing or administering blood, plasma or medical fluids ; Infusion or perfusion containers
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B25/00—Annealing glass products
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Abstract
The invention relates to a medical glass manufacturing technology, and discloses a mesoborosilicate glass composition, a preparation method and application thereof. The medium borosilicate glass composition comprises the following components in percentage by weight: siO (SiO) 2 68-76 wt% of Al 2 O 3 5-7 wt%, B 2 O 3 9.9 to 11.8 wt% of Na 2 O5.8-6.8 wt%, K 2 0 to 2.5 weight percent of O, 0.4 to 1.2 weight percent of CaO, 0.1 to 3 weight percent of BaO and La 2 O 3 0.1 to 0.4% by weight. The preparation method of the medium borosilicate glass comprises the following steps: siO is made of 2 、Al 2 O 3 、B 2 O 3 、Na 2 O、K 2 O, caO, baO and La 2 O 3 After mixing, melting, clarifying, shaping and annealing are performed. The medium borosilicate glass provided by the invention has high chemical stability, good hydrolysis resistance, low crystallization tendency and low melting and softening temperatures.
Description
Technical Field
The invention relates to a medical glass manufacturing technology, in particular to a mesoborosilicate glass composition, a preparation method and application thereof.
Background
Glass has been widely used in the medical field as a packaging material, and in particular, its special material properties such as high transparency, mechanical resistance, low permeability and high chemical stability are critical to maintaining the quality of the medicinal substance and even its efficacy.
The pharmaceutical glass container or primary package is usually in direct contact with the pharmaceutical substance contained, and therefore it is necessary to follow strict requirements that they are able to remove the content in a suitable manner, while minimizing loss and alteration of the content, preferably without physical or chemical changes of the content; i.e. the quality of the content should not change due to direct contact with the container or primary package, so that the required limit value is exceeded. In any case it is ensured that the glass material does not release a certain amount of substances which would affect the stability of the pharmaceutical substance or even be toxic to the user.
In the case of packaging an aqueous pharmaceutical substance, the most important property of the glass package is the stability of its inner surface, which comes into contact with and is eroded by the aqueous pharmaceutical substance, and may be dissolved to release various ions from the glass surface, for example, a pH change of the aqueous medium, which may be caused by alkali metal ions or alkaline earth metal ions, may reduce the efficacy of the pharmaceutical substance. In addition, aluminum in glass compositions is also a concern, for example, in humans with specific genetic characteristics, excessive aluminum intake in the metabolic system may cause damage to health. Therefore, in order to avoid health risks, glass should generally be dissolved to release as few ions as possible.
In a conventional medical container such as a penicillin bottle or an ampoule formed by borosilicate glass processing, it was found that the filled medical liquid was checked for the presence of foreign matter by an image checking device at the time of shipment inspection.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide a medium borosilicate glass composition, a preparation method and application thereof, wherein the medium borosilicate glass has high chemical stability, good hydrolysis resistance, low crystallization tendency and low melting and softening temperatures.
In order to achieve the above object, the first aspect of the present invention provides a medium borosilicate glass composition, which is composed of the following components in weight percent: siO (SiO) 2 68-76 wt% of Al 2 O 3 5-7 wt%, B 2 O 3 9.9 to 11.8 wt% of Na 2 O5.8-6.8 wt%, K 2 0 to 2.5 weight percent of O, 0.4 to 1.2 weight percent of CaO, 0.1 to 3 weight percent of BaO and La 2 O 3 0.1 to 0.4% by weight.
Preferably, the medium borosilicate glass composition consists of the following components in weight percent: siO (SiO) 2 70-74 wt% of Al 2 O 3 5.5 to 6.8 wt% of B 2 O 3 10-11.5 wt% Na 2 O6-6.5 wt%, K 2 0.5 to 2 weight percent of O, 0.5 to 1 weight percent of CaO, 1 to 2.5 weight percent of BaO and La 2 O 3 0.1-0.2 wt%.
Preferably, the SiO 2 With said B 2 O 3 The weight ratio of (2) is 5-9, preferably 6-7.5.
Preferably, the SiO 2 With the Al 2 O 3 The sum of the contents of (2) is 75-82 wt%, preferably 76-80 wt%.
Preferably, the Na 2 O and the K 2 The sum of the O contents is 6 to 9.3% by weight, preferably 7.5 to 9% by weight.
Preferably, the sum of the CaO and BaO content is 1.5 to 4 wt%, preferably 2.2 to 3.5 wt%.
The second aspect of the invention provides a method for preparing medium borosilicate glass, comprising the following steps: siO is made of 2 、Al 2 O 3 、B 2 O 3 、Na 2 O、K 2 O, caO, baO and La 2 O 3 After mixing, melting, clarifying, forming and annealing are carried out;
wherein the weight percentages of the raw material components are as follows: siO (SiO) 2 68-76 wt% of Al 2 O 3 5-7 wt%, B 2 O 3 9.9 to 11.8 wt% of Na 2 O5.8-6.8 wt%, K 2 0 to 2.5 weight percent of O, 0.4 to 1.2 weight percent of CaO, 0.1 to 3 weight percent of BaO and La 2 O 3 0.1 to 0.4% by weight.
Preferably, the raw material components are used in the following weight percent: siO (SiO) 2 70-74 wt% of Al 2 O 3 5.5 to 6.8 wt% of B 2 O 3 10-11.5 wt% Na 2 O6-6.5 wt%, K 2 0.5 to 2 weight percent of O, 0.5 to 1 weight percent of CaO, 1 to 2.5 weight percent of BaO and La 2 O 3 0.1-0.2 wt%.
Preferably, the conditions of mixing include: the stirring speed is 10-20rpm, the temperature is 1450-1500 ℃, and the time is 20-30min.
Preferably, the conditions of melting include: the temperature is 1500-1650 ℃ and the time is 300-480min.
Preferably, the clarification conditions include: the temperature is 1580-1630 ℃ and the time is 30-60min.
Preferably, the molding conditions include: the temperature is 1250-1280 ℃.
Preferably, the annealing conditions include: the temperature is 560-595 ℃ and the time is 10-20min.
The third aspect of the invention provides the medium borosilicate glass prepared by the preparation method.
Preferably, the ion elution amount of the medium borosilicate glass is 1.0ppm or less.
Preferably, the mesoborosilicate glass has a liquid phase viscosity of greater than 10 4.5 dpa·s。
Preferably, the medium borosilicate glass has a linear thermal expansion coefficient of less than 58×10 in the temperature range of 30-380 DEG C -7 Preferably 48X 10 at a temperature of °C -7 -55×10 -7 /℃。
The fourth aspect of the invention provides the use of the mesoborosilicate glass composition described above for the preparation of a medical glass tube.
Through the technical scheme, the invention has the beneficial effects that:
the medium borosilicate glass composition provided by the invention forms a mutual synergistic effect through the components and the specific dosage proportion thereof, can obviously reduce the total ion release of the glass, ensures that the glass has excellent hydrolysis resistance and high chemical stability, and simultaneously has lower crystallization tendency and lower melting and softening temperatures, so that the glass meets the requirements applied to the medicine field to a higher degree, and is especially suitable for packaging water-based or water-containing medicinal substances; the medium borosilicate glass provided by the invention has high appearance quality, good preparation performance and processing performance, and is easy to process into medical containers such as penicillin bottles, ampoules and the like.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The invention provides a medium borosilicate glass composition, which consists of the following components in percentage by weight: siO (SiO) 2 68-76 wt% of Al 2 O 3 5-7 wt%, B 2 O 3 9.9 to 11.8 wt% of Na 2 O5.8-6.8 wt%, K 2 0 to 2.5 weight percent of O, 0.4 to 1.2 weight percent of CaO, 0.1 to 3 weight percent of BaO and La 2 O 3 0.1 to 0.4% by weight.
The inventors of the present invention have unexpectedly found that, during the production and development, a conventional borosilicate glass-molded penicillin bottle or ampoule is filled with a chemical liquid, and the filled chemical liquid is checked for the presence of foreign matter by an image checking device at the time of shipment inspection, but SiO is used as a material for the production and development of a borosilicate glass-molded penicillin bottle or ampoule 2 、Al 2 O 3 、B 2 O 3 、Na 2 O、K 2 O, caO, baO and La 2 O 3 As the components of the medium borosilicate glass, and combined with the specific dosage proportion of each component, the mutual synergistic effect is formed, so that the glass has excellent hydrolysis resistance and high chemical stability, and also has lower crystallization tendency and lower melting and softening temperatures, so that the glass meets the requirements of being applied to the field of medicine to a higher degree, is particularly suitable for packaging water-based or water-containing medicinal substances, and has no foreign matters after being filled with liquid medicine.
According to the invention, the medium borosilicate glass composition preferably consists of the following components in wt.%: siO (SiO) 2 70-74 wt% of Al 2 O 3 5.5 to 6.8 wt% of B 2 O 3 10-11.5 wt% Na 2 O6-6.5 wt%, K 2 0.5 to 2 weight percent of O, 0.5 to 1 weight percent of CaO, 1 to 2.5 weight percent of BaO and La 2 O 3 0.1-0.2 wt%.The inventor finds that under the preferred embodiment, the medium borosilicate glass has good defoaming performance and lower viscosity, is beneficial to further improving the hydrolytic resistance and chemical stability of the medium borosilicate glass, can meet the acid resistance required by the borosilicate glass for a medical container, can reduce the processing temperature of the glass, and improves the solubility of the glass.
According to the present invention, preferably, the SiO 2 With said B 2 O 3 The weight ratio of (2) is 5-9, preferably 6-7.5. The inventors have found that in this preferred embodiment it is advantageous to further improve the hydrolytic resistance and chemical durability of the glass.
According to the present invention, preferably, the SiO 2 With the Al 2 O 3 The sum of the contents of (2) is 75-82 wt%, preferably 76-80 wt%. The inventors found that in this preferred embodiment, it is advantageous to improve the defoaming property of the glass, and the viscosity is low.
According to the present invention, preferably, the Na 2 O and the K 2 The sum of the O contents is 6 to 9.3% by weight, preferably 7.5 to 9% by weight. The inventors have found that in this preferred embodiment it is advantageous to improve the coefficient of thermal expansion and the meltability of the glass.
According to the invention, the sum of the CaO and BaO content is preferably 1.5 to 4 wt%, preferably 2.2 to 3.5 wt%. The inventors have found that in this preferred embodiment, it is advantageous to improve the processability of the glass.
The second aspect of the invention provides a method for preparing medium borosilicate glass, comprising the following steps: siO is made of 2 、Al 2 O 3 、B 2 O 3 、Na 2 O、K 2 O, caO, baO and La 2 O 3 After mixing, melting, clarifying, forming and annealing are carried out;
wherein the weight percentages of the raw material components are as follows: siO (SiO) 2 68-76 wt% of Al 2 O 3 5-7 wt%, B 2 O 3 9.9 to 11.8 wt% of Na 2 O5.8-6.8 wt%, K 2 0 to 2.5 weight percent of O, 0.4 to 1.2 weight percent of CaO, 0.1 to 3 weight percent of BaO and La 2 O 3 0.1 to 0.4% by weight.
According to the invention, the preparation process of the medium borosilicate glass is simple, the processing performance is good, and the raw material components do not need to use As 2 O 3 、Sb 2 O 3 The heavy metal oxide can greatly reduce the environmental load during glass manufacturing and discarding.
The preparation method of the medium borosilicate glass provided by the invention can be carried out by adopting conventional glass production equipment, for example, the forming process can use the device of the Dana process or the device of the Virro process. Illustratively, the process of forming using the Dana method is specifically: adding the glass batch obtained by melting and clarifying into a kiln through a feeding system, melting into glass liquid at high temperature, regulating the temperature of the glass liquid through a feeding channel to enable the viscosity to be about 102.5Pa.s, enabling the glass liquid to flow out in a strip shape from a material flowing groove at the end part of the feeding channel, and falling on a forming rotary pipe made of refractory materials coated with platinum, wherein the glass gradually flows downwards due to the gravity of the glass and the rotation of the forming pipe and is wound on the rotating forming pipe; the forming tube forms an inclination angle of 15-20 degrees with the horizontal, and is placed in a muffle furnace, and the glass viscosity is gradually increased to about 104Pa.s because the temperature of the muffle furnace is lower than the glass temperature, and a uniform glass layer is gradually formed on the surface of the rotary cylinder; the upper feeding machine of the muffle furnace is used for stirring and further homogenizing the glass liquid, adjusting the discharge amount, conveying the glass liquid to a rotating pipe of the muffle furnace, providing stable rotating speed and air source by a Danner machine, enabling the glass liquid to be stably and uniformly wound and distributed on the rotating pipe at a proper temperature, and enabling a shaft to be connected with a rotating sleeve driving system and rotate at a certain downward inclination angle; the glass ribbon wound on the forming tube is rugged, similar to rope winding, but forms a smooth plane before leaving the end of the forming tube, and as the glass layer is pulled and compressed air with certain pressure is blown into the hollow shaft, the glass liquid is blown into a hollow shape to form a tube root, and is led out from the tail of the tube drawing machine, and the glass leaving the forming tube is formed into a glass tube.
According to the invention, the outer diameter and thickness of the glass tube can be controlled by changing the pressure of compressed air and the drawing speed when the Danna method is used for molding; the glass tube passes through the runway, the laser diameter measurement is carried out by the tube drawing machine, rough cutting is carried out, and the glass tube is cut into the required length.
According to the invention, the raw material components are preferably used in amounts of weight-%: siO (SiO) 2 70-74 wt% of Al 2 O 3 5.5 to 6.8 wt% of B 2 O 3 10-11.5 wt% Na 2 O6-6.5 wt%, K 2 0.5 to 2 weight percent of O, 0.5 to 1 weight percent of CaO, 1 to 2.5 weight percent of BaO and La 2 O 3 0.1-0.2 wt%.
According to the present invention, preferably, the conditions of mixing include: the stirring speed is 10-20rpm, and specifically may be 10rpm, 12rpm, 14rpm, 16rpm, 18rpm, 20rpm or any value between the foregoing values; the temperature is 1450-1500deg.C, specifically 1450 deg.C, 1460 deg.C, 1470 deg.C, 1480 deg.C, 1490 deg.C, 1500 deg.C or any value between the above values; the time is 20-30min, and can be specifically 20min, 22min, 24min, 26min, 28min, 30min or any value between the above values.
According to the present invention, stirring may be performed 1 to 4 times during the melting process in order to remove bubbles from the melt. Preferably, the conditions of melting include: the temperature is 1500-1650deg.C, specifically 1500 deg.C, 1530 deg.C, 1560 deg.C, 1590 deg.C, 1620 deg.C, 1650 deg.C or any value between the above values; the time is 300-480min, and can be 300min, 360min, 420min, 480min or any value between the above values.
According to the present invention, preferably, the clarifying conditions include: the temperature is 1580-1630 deg.C, specifically 1580 deg.C, 1590 deg.C, 1600 deg.C, 1610 deg.C, 1620 deg.C, 1630 deg.C or any value between the above values; the time is 30-60min, and can be 30min, 40min, 50min, 60min or any value between the above values.
According to the present invention, preferably, the molding conditions include: the temperature is 1250-1280deg.C, and can be 1250 deg.C, 1260 deg.C, 1270 deg.C, 1280deg.C or any value between the above values.
According to the present invention, preferably, the annealing conditions include: the temperature is 560-595 ℃, specifically 560 ℃, 565 ℃, 570 ℃, 575 ℃, 580 ℃, 585 ℃, 590 ℃, 595 ℃ or any value between the above values; the time is 10-20min, and can be specifically 10min, 12min, 14min, 16min, 18min, 20min or any value between the above values.
The third aspect of the invention provides the medium borosilicate glass prepared by the preparation method.
In the present invention, the consumption of 0.02mol/L hydrochloric acid per unit (1 g) of glass mass in the powder test of the hydrolysis resistance test according to European pharmacopoeia 7.0 was 0.03mL or less. If the consumption of hydrochloric acid increases, the dissolution of glass components, particularly alkali components, increases considerably when a bottle container such as an ampoule or a penicillin is produced and the liquid medicine is filled and stored, and there is a possibility that the liquid medicine component may deteriorate. In the invention, the operating temperature of the medium borosilicate glass prepared by the preparation method is lower than 1180 ℃.
According to the present invention, the ion elution amount of the mesoborosilicate glass is preferably 1.0ppm or less.
According to the invention, preferably, the mesoborosilicate glass has a liquid phase viscosity of greater than 10 4.5 dpa·s。
According to the present invention, preferably, the medium borosilicate glass has a linear thermal expansion coefficient of less than 58×10 in a temperature range of 30 to 380 DEG C -7 Preferably 48X 10 at a temperature of °C -7 -55×10 -7 /℃。
The medium borosilicate glass provided by the invention has high appearance quality, good preparation performance and processing performance, and is easy to process into medical containers such as penicillin bottles, ampoules and the like, so the fourth aspect of the invention provides the application of the medium borosilicate glass composition in preparing medical glass tubes.
The present invention will be described in detail by examples.
In the following examples, densities were measured by the archimedes method;
the linear thermal expansion coefficient was measured using a glass sample having a size of about phi 5mm by 50mm and formed into a rod shape using an dilatometer at a temperature range of 30 to 380 ℃;
the strain point Ps, the annealing point Ta, and the softening point Ts are measured by a glass fiber elongation method;
the operating temperature Tw is 10 based on the equation of the glass high temperature viscosity Fulecher 4 dPa.s temperature;
measurement of liquidus temperature: filling a platinum boat of about 120 x 20 x 10mm with a crushed glass sample, putting the glass sample into an electric furnace with a linear temperature gradient for 24 hours, then, observing the glass sample by a microscope to determine a crystal precipitation position, and calculating the temperature corresponding to the crystal precipitation position according to a temperature gradient diagram of the electric furnace, wherein the temperature is taken as a liquid phase temperature;
the hydrolysis resistance test was carried out using Al 2 O 3 The prepared mortar and the prepared milk stick are used for crushing the sample, and the powder test method is carried out according to European pharmacopoeia 7.0;
the acid resistance test was carried out by setting the surface area of the sample to 50cm 2 The amount of hydrochloric acid of 6mol/L as the dissolution liquid was set to 800ml and measured in accordance with DIN 2116;
bubble quality measurement of glass: a sample having a thickness of 3mm was cut out from the central portion of the ingot to be produced, and both sides thereof were ground, and then observed with a microscope to give a sample having a thickness of 1cm 2 The number of bubbles having a size of 100 μm or more is 1 or less, and the number exceeding 1 is determined as "X";
transmittance measurement of glass: a sample having a thickness of 1mm was cut out from the center of the glass, and both sides thereof were polished, and then the transmittance at 300 to 800nm was measured by a spectrophotometer. If the transmittance at 400nm is 90% or more, it is determined as o, and if it is less than 90%, it is determined as x.
Unless otherwise specified, the raw materials and reagents in the following examples and comparative examples are all conventional commercial products.
Example 1 to example 5
The SiO was weighed in the ratio of the amounts of the respective components shown in Table 1 based on 500g of the total amount of the medium borosilicate glass composition 2 、Al 2 O 3 、B 2 O 3 、Na 2 O、K 2 O, caO, baO and La 2 O 3 At a stirring speed of 15rpm and a temperature of 1480 DEG CMixing for 25min, melting at 1650deg.C for 360min, stirring for 2 times during melting, clarifying at 1600 deg.C for 45min, shaping at 1260 deg.C, and annealing at 570 deg.C for 15min to obtain mesoborosilicate glass.
TABLE 1
Example 6
Borosilicate glass was prepared according to the composition and method of example 3, except that the melting temperature was 1700℃and the time was 250min.
Example 7
Borosilicate glass was prepared according to the composition and method of example 3, except that the fining temperature was 1500℃for 50 minutes.
Example 8
Borosilicate glass was prepared according to the composition and method of example 3, except that the annealing temperature was 500℃for 10min.
Comparative example 1
Borosilicate glass was prepared as in example 3, except that the amounts of the raw materials of the respective components were used in the ratios shown in Table 1.
Comparative example 2
Borosilicate glass was prepared as in example 3, except that the mass ratios of the raw material components were: siO (SiO) 2 79.9 wt.% of Al 2 O 3 3.6 wt%, B 2 O 3 5 wt% of Na 2 O4 wt%, K 2 O5 wt%, caO 2 Wt%, baO 0.5 wt%.
Test case
The glasses obtained in examples 1 to 8 and comparative examples 1 to 2 were measured for density, linear thermal expansion coefficient, liquidus temperature, strain point Ps, annealing point Ta, softening point Ts, operating temperature Tw, liquid phase viscosity, hydrolysis resistance, acid resistance, ion elution amount, bubble quality and transmittance, respectively, and the results are shown in tables 2 and 3.
TABLE 2
TABLE 3 Table 3
The sample having an ion elution amount of n.d. in table 3 shows that the lower limit of detection of the ICP emission analysis apparatus was lower.
As can be seen from the results of tables 2 and 3, the medium borosilicate glass compositions provided in examples 1 to 8 have better hydrolysis resistance, better chemical durability and better transmittance than the glasses prepared in comparative examples 1 to 2.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (11)
1. A medium borosilicate glass composition, which is characterized by comprising the following components in percentage by weight: siO (SiO) 2 70-74 wt% of Al 2 O 3 5.5 to 6.8 wt% of B 2 O 3 10-11.5 wt% Na 2 O6-6.5 wt%, K 2 0.5 to 2 weight percent of O, 0.5 to 1 weight percent of CaO, 1 to 2.5 weight percent of BaO and La 2 O 3 0.1 to 0.2 wt%;
the consumption of 0.02mol/L hydrochloric acid per 1g of glass by powder test method of European pharmacopoeia 7.0 is below 0.03 mL.
2. The mesoborosilicate glass composition according to claim 1, wherein said SiO 2 With said B 2 O 3 The weight ratio of (2) is 6-7.5.
3. The mesoborosilicate glass composition according to claim 1, wherein said SiO 2 With the Al 2 O 3 The sum of the contents of (2) being 76-80% by weight.
4. The mesoborosilicate glass composition according to claim 1, wherein said Na 2 O and the K 2 The sum of the O content is 7.5 to 9 wt.%.
5. The mesoborosilicate glass composition according to claim 1, wherein the sum of the CaO and BaO content is 2.2-3.5 wt%.
6. The preparation method of the medium borosilicate glass is characterized by comprising the following steps of: siO is made of 2 、Al 2 O 3 、B 2 O 3 、Na 2 O、K 2 O, caO, baO and La 2 O 3 After mixing, melting, clarifying, forming and annealing are carried out;
wherein the weight percentages of the raw material components are as follows: siO (SiO) 2 70-74 wt% of Al 2 O 3 5.5 to 6.8 wt% of B 2 O 3 10-11.5 wt% Na 2 O6-6.5 wt%, K 2 0.5 to 2 weight percent of O, 0.5 to 1 weight percent of CaO, 1 to 2.5 weight percent of BaO and La 2 O 3 0.1 to 0.2 wt%;
the consumption of 0.02mol/L hydrochloric acid per 1g of glass is below 0.03mL as measured by a powder test method according to European pharmacopoeia 7.0.
7. The method of claim 6, wherein the mixing conditions include: stirring at 10-20rpm at 1450-1500deg.C for 20-30min;
the conditions of melting include: the temperature is 1500-1650 ℃ and the time is 300-480min;
the clarification conditions include: the temperature is 1580-1630 ℃ and the time is 30-60min;
the molding conditions include: the temperature is 1250-1280 ℃;
the annealing conditions include: the temperature is 560-595 ℃ and the time is 10-20min.
8. A mesoborosilicate glass produced by the production method according to claim 6 or 7.
9. The medium borosilicate glass according to claim 8, wherein said medium borosilicate glass has an ion elution amount of 1.0ppm or less;
the liquid phase viscosity of the medium borosilicate glass is more than 10 4.5 dpa·s；
The linear thermal expansion coefficient of the medium borosilicate glass is less than 58 multiplied by 10 in the temperature range of 30-380 DEG C -7 /℃。
10. The medium borosilicate glass according to claim 9, wherein said medium borosilicate glass has a linear thermal expansion coefficient of 48 x 10 in a temperature range of 30-380 °c -7 -55×10 -7 /℃。
11. Use of a mesoborosilicate glass composition according to any of claims 1 to 5 for the preparation of medical glass tubing.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003018498A1 (en) * | 2001-08-22 | 2003-03-06 | Schott Glas | Antimicrobial, anti-inflammatory, wound-healing and disinfecting glass and use thereof |
| JP2015093820A (en) * | 2013-11-14 | 2015-05-18 | 日本電気硝子株式会社 | Glass for medical container |
| CN110128011A (en) * | 2013-04-26 | 2019-08-16 | 肖特股份有限公司 | It is preferred for the Pyrex of the hydrolytic resistance with improvement of field of medicaments |
| CN112694254A (en) * | 2021-01-04 | 2021-04-23 | 河北光兴半导体技术有限公司 | Medium borosilicate glass composition, medium borosilicate glass, and preparation method and application thereof |
| CN113831013A (en) * | 2021-08-31 | 2021-12-24 | 甘肃旭康材料科技有限公司 | Neutral borosilicate glass composition, neutral borosilicate glass, and preparation method and application thereof |
-
2022
- 2022-02-09 CN CN202210122375.XA patent/CN114507010B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003018498A1 (en) * | 2001-08-22 | 2003-03-06 | Schott Glas | Antimicrobial, anti-inflammatory, wound-healing and disinfecting glass and use thereof |
| CN110128011A (en) * | 2013-04-26 | 2019-08-16 | 肖特股份有限公司 | It is preferred for the Pyrex of the hydrolytic resistance with improvement of field of medicaments |
| JP2015093820A (en) * | 2013-11-14 | 2015-05-18 | 日本電気硝子株式会社 | Glass for medical container |
| CN112694254A (en) * | 2021-01-04 | 2021-04-23 | 河北光兴半导体技术有限公司 | Medium borosilicate glass composition, medium borosilicate glass, and preparation method and application thereof |
| CN113831013A (en) * | 2021-08-31 | 2021-12-24 | 甘肃旭康材料科技有限公司 | Neutral borosilicate glass composition, neutral borosilicate glass, and preparation method and application thereof |
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| CN114507010A (en) | 2022-05-17 |
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