CN115231821B - Composition for preparing neutral borosilicate glass, preparation method and application thereof - Google Patents
Composition for preparing neutral borosilicate glass, preparation method and application thereof Download PDFInfo
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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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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
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Abstract
The invention relates to the technical field of medical glass packaging materials, and discloses a composition for preparing neutral borosilicate glass, the neutral borosilicate glass, a preparation method and application thereof. The composition contains the following components which are stored independently or stored by mixing more than two of the components: siO (SiO) 2 、Al 2 O 3 、B 2 O 3 、Na 2 O、K 2 O、CaO、ZrO 2 The rare earth doped oxide comprises the following components in percentage by weight: 0.5-2:0-2: moO of 0-2 3 、Pr 6 O 11 、Ta 2 O 5 And Nb (Nb) 2 O 5 Is a combination of (a) and (b). The neutral borosilicate glass prepared by the composition provided by the invention not only has a low linear expansion coefficient and ion leaching amount, but also has good chemical durability and high hydrolytic resistance.
Description
Technical Field
The invention relates to the technical field of medical glass packaging materials, in particular to a composition for preparing neutral borosilicate glass, the neutral borosilicate glass and a preparation method and application thereof.
Background
Along with the rapid development of the pharmaceutical industry in China, the requirements on the quality of the medicine packaging material are higher and higher, and the corresponding medicinal glass has good water resistance, acid and alkali resistance, freezing resistance, thermal stability and the like, so that the glass is the main packaging material of the conventional inactivated vaccine. It is reported that the glass bottle for placing vaccine injection has serious shortage, and the requirement of inactivated vaccine dose cannot be met, so that the product yield is low due to the defect in a neutral medicine glass tube, and the product yield is mainly caused by calculus and air line.
The medium borosilicate medical glass is an important borosilicate glass variety, B 2 O 3 The content is 8-12 wt%, and the deionized water contained in the glass container can keep the pH value unchanged, so the glass container is of the typeThe glass is also called as neutral glass, has excellent performances such as good chemical stability, heat resistance stability, low linear expansion coefficient and the like, and is widely used for packaging injection type biological medicine products.
The defects of neutral medical glass tubes mainly result from the glass melting and clarifying stage. Al in neutral medical glass 2 O 3 And SiO 2 High content, high melting temperature and difficult clarification; the boron oxide has the characteristics of high content, easy volatilization, high loss rate and the like, and can cause bubbles and node defects of the melted product, thereby reducing the qualification rate of the product; the volatilized boron oxide corrodes the kiln refractory material, so that the maintenance and replacement cost is increased, and the service life of the kiln is shortened.
Therefore, in the preparation process of the neutral medical glass, auxiliary agents are required to be introduced into the batch materials so as to reduce the viscosity of glass liquid, improve the clarification performance, reduce the boron volatilization loss rate, improve the product quality and the qualification rate and prolong the service life of the kiln.
At present, medical glass packaging materials produced in China mainly comprise sodium-calcium-silicon glass and low-borosilicate glass, and only a small amount of medium-boron-silicon medical glass exists. However, the performance stability and the water resistance of the medium boron silicon medical glass have a certain gap with the like products abroad, meanwhile, the manufacturing difficulty of the medium boron silicon is high, the defects of easy occurrence of stones, gas lines and the like in glass tube molding exist, the qualification rate of finished products is low, and the water resistance, acid and alkali resistance cannot meet the use requirements of medical packaging materials.
Disclosure of Invention
The invention aims to solve the problems of high linear expansion coefficient, poor hydrolytic resistance and poor chemical stability of borosilicate glass in the prior art.
In order to achieve the above object, the first aspect of the present invention provides a composition for preparing neutral borosilicate glass, comprising the following components stored independently or in a mixture of two or more: siO (SiO) 2 、Al 2 O 3 、B 2 O 3 、Na 2 O、K 2 O、CaO、ZrO 2 Rare earth doped oxides;
based on the total weight of the compositionThe SiO is 2 The content of (C) is 74-78 wt%, the Al 2 O 3 The content of (B) is 2-5 wt% 2 O 3 The content of Na is 10.5-12 wt% 2 O content of 5-7 wt%, said K 2 The content of O is 0.1-1 wt%, the content of CaO is 0-0.3 wt%, and the ZrO 2 The content of the rare earth doped oxide is 0.2 to 1 weight percent, and the content of the rare earth doped oxide is 0.4 to 0.8 weight percent;
the rare earth doped oxide comprises the following components in percentage by weight: 0.5-2:0-2: moO of 0-2 3 、Pr 6 O 11 、Ta 2 O 5 And Nb (Nb) 2 O 5 Is a combination of (a) and (b).
Preferably, the SiO is present in an amount based on the total weight of the composition 2 The content of (C) is 74-76 wt%, the Al 2 O 3 The content of (B) is 2-5 wt% 2 O 3 The content of Na is 10.5-12 wt% 2 O content of 5-7 wt%, said K 2 The content of O is 0.1-1 wt%, the content of CaO is 0.1-0.3 wt%, and the content of ZrO is 0.1-1 wt% 2 The content of the rare earth doped oxide is 0.2-1 wt%, and the content of the rare earth doped oxide is 0.5-0.7 wt%.
Preferably, the rare earth doped oxide is prepared from the following components in percentage by weight: 0.5-2:0.5-1: moO of 0-1 3 、Pr 6 O 11 、Ta 2 O 5 And Nb (Nb) 2 O 5 Is a combination of (a) and (b).
In a second aspect, the invention provides a method of making neutral borosilicate glass, the method comprising: the components in the composition for preparing neutral borosilicate glass according to the first aspect are sequentially subjected to mixing, melting treatment, clarification and homogenization, forming treatment and annealing treatment.
Preferably, the mixing conditions include at least: the stirring speed is 10-20rpm, the temperature is 1450-1500 ℃, and the time is 20-30min.
Preferably, the conditions of the melting treatment include at least: the temperature is 1550-1650 ℃ and the time is 300-480min.
Preferably, the conditions of clarification homogenization include at least: the temperature is 1580-1630 ℃ and the time is 30-60min.
Preferably, the conditions of the molding process include at least: the temperature is 1250-1280 ℃.
Preferably, the annealing conditions include at least: the temperature is 560-595 ℃ and the time is 10-30min.
The present invention provides neutral borosilicate glass produced by the method of the second aspect.
Preferably, the ion elution amount of the neutral borosilicate glass is 1.0ppm or less.
Preferably, the neutral borosilicate glass has a linear expansion coefficient of not more than 55X 10 in a temperature range of 30-380 DEG C -7 /℃。
According to a fourth aspect of the invention, there is provided the use of neutral borosilicate glass according to the third aspect for the preparation of a medical container.
The neutral borosilicate glass prepared by the composition provided by the invention not only has lower linear expansion coefficient and ion leaching amount, but also has good chemical durability and high hydrolytic resistance, when the neutral borosilicate glass is applied to preparing a medical container, the neutral borosilicate glass is contacted with aqueous or water-containing medicinal substances, no ions are released or only little ions are released, and breakage caused by thermal shock is not easy to occur when a glass tube is manufactured.
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.
In the present invention, unless otherwise stated, the room temperature or the normal temperature represents 25.+ -. 2 ℃.
As described above, the first aspect of the present invention provides a composition for preparing neutral borosilicate glass, which comprises the following components stored independently or in a mixture of two or more: siO (SiO) 2 、Al 2 O 3 、B 2 O 3 、Na 2 O、K 2 O、CaO、ZrO 2 Rare earth doped oxides;
the SiO being based on the total weight of the composition 2 The content of (C) is 74-78 wt%, the Al 2 O 3 The content of (B) is 2-5 wt% 2 O 3 The content of Na is 10.5-12 wt% 2 O content of 5-7 wt%, said K 2 The content of O is 0.1-1 wt%, the content of CaO is 0-0.3 wt%, and the ZrO 2 The content of the rare earth doped oxide is 0.2 to 1 weight percent, and the content of the rare earth doped oxide is 0.4 to 0.8 weight percent;
the rare earth doped oxide comprises the following components in percentage by weight: 0.5-2:0-2: moO of 0-2 3 、Pr 6 O 11 、Ta 2 O 5 And Nb (Nb) 2 O 5 Is a combination of (a) and (b).
Preferably, the SiO is present in an amount based on the total weight of the composition 2 The content of (C) is 74-76 wt%, the Al 2 O 3 The content of (B) is 2-5 wt% 2 O 3 The content of Na is 10.5-12 wt% 2 O content of 5-7 wt%, said K 2 The content of O is 0.1-1 wt%, the content of CaO is 0.1-0.3 wt%, and the content of ZrO is 0.1-1 wt% 2 The content of the rare earth doped oxide is 0.2-1 wt%, and the content of the rare earth doped oxide is 0.4-0.7 wt%. The inventors found that, by adopting the preferred embodiment, neutral borosilicate glass with better hydrolysis resistance can be obtained under the premise of ensuring chemical stability.
According to a particularly preferred embodiment, the rare earth doped oxide is present in a content weight ratio of 1:0.5-2:0.5-1: moO of 0-1 3 、Pr 6 O 11 、Ta 2 O 5 And Nb (Nb) 2 O 5 Is a combination of (a) and (b). The inventors have found that with this preferred embodiment, neutral borosilicate glass having a lower linear expansion coefficient can be obtained.
As previously described, a second aspect of the present invention provides a method of preparing neutral borosilicate glass, the method comprising: the components in the composition for preparing neutral borosilicate glass according to the first aspect are sequentially subjected to mixing, melting treatment, clarification and homogenization, forming treatment and annealing treatment.
Preferably, the mixing conditions include at least: the stirring speed is 10-20rpm, the temperature is 1450-1500 ℃, and the time is 20-30min.
Preferably, the conditions of the melting treatment include at least: the temperature is 1550-1650 ℃ and the time is 300-480min.
In the present invention, the specific operations of the clarification and homogenization, the molding treatment, and the annealing treatment are not particularly limited, and the specific operations, which are exemplified in the following of the present invention, may be employed by those skilled in the art, and should not be construed as limiting the present invention.
Preferably, the conditions of clarification homogenization include at least: the temperature is 1580-1630 ℃ and the time is 30-60min.
Preferably, in the step (3), the clarifying and homogenizing method is to adjust the temperature of the molten glass to 10 viscosity of the molten glass 2.3 And d, dPa.s, and discharging bubbles in the molten glass.
Preferably, in step (3), the molding treatment method is at least one selected from the group consisting of a danna molding process and a voronoi molding process.
According to a particularly preferred embodiment, in step (3), the method of the shaping treatment is a danna shaping process.
The invention has no special requirements on the specific operation method of the Dana method forming process, and the technical means known by the person skilled in the art can be adopted.
Preferably, the conditions of the molding process include at least: the temperature is 1250-1280 ℃.
Preferably, the annealing conditions include at least: the temperature is 560-595 ℃ and the time is 10-30min.
As previously described, a third aspect of the present invention provides neutral borosilicate glass produced by the method of the second aspect.
Preferably, the ion elution amount of the neutral borosilicate glass is 1.0ppm or less.
Preferably, the neutral borosilicate glass has a linear expansion coefficient of not more than 55X 10 in a temperature range of 30-380 DEG C -7 /℃。
As previously mentioned, a fourth aspect of the invention provides the use of the neutral borosilicate glass according to the third aspect for the preparation of a medical container.
According to a particularly preferred embodiment of the invention, the medical container is selected from at least one of a penicillin bottle and an ampoule.
The present invention will be described in detail by examples. In the following examples, all of the raw materials used were commercial products unless otherwise specified.
In the examples below, 10g is indicated per 1% by weight.
Example 1
This example illustrates the neutral borosilicate glass according to the invention according to the formulation and process parameters in table 1 and was prepared as follows.
The method for preparing the neutral borosilicate glass comprises the following steps:
weighing the components of the raw material composition shown in table 1, stirring at 1460 ℃ for 30min at 15rpm, uniformly mixing to obtain a mixture, putting the mixture into a melting kiln at 1580 ℃ for melting for 360min to obtain glass liquid, clarifying and homogenizing the glass liquid, regulating the temperature to 1620 ℃, discharging bubbles to obtain molten glass, drawing and molding the obtained molten glass by adopting a Danner molding process to obtain a glass tube matrix to be applied, cutting the glass tube matrix into a preset length (1500 mm), and annealing at 560 ℃ for 15min to obtain a glass sample.
The rest of the examples and comparative examples were carried out, without any particular explanation, using the same procedure as in example 1, except that the neutral borosilicate glass composition used was composed and the process parameters for preparing the neutral borosilicate glass were different, see in particular table 1.
TABLE 1
| Example 1 | Example 2 | Example 3 | Example 4 | |
| SiO 2/wt% | 74.5 | 76 | 75.5 | 77 |
| Al2O 3/wt% | 5 | 3.8 | 4.5 | 4.2 |
| B2O 3/wt% | 11.5 | 11.5 | 11.5 | 10.8 |
| Na 2O/wt% | 6.5 | 6.3 | 6.5 | 6.5 |
| K2O/wt% | 1 | 0.9 | 0.8 | 0.3 |
| CaO/wt.% | 0.2 | 0.2 | 0.2 | 0.2 |
| ZrO 2/wt% | 0.8 | 0.5 | 0.6 | 0.4 |
| MoO 3/wt% | 0.1 | 0.2 | 0.1 | 0.2 |
| Pr6O 11/wt% | 0.2 | 0.2 | 0.1 | 0.2 |
| Ta2O 5/wt% | 0.1 | 0.2 | 0.1 | 0.1 |
| Nb2O5/Weight percent | 0.1 | 0.2 | 0.1 | 0.1 |
| Mixing | ||||
| Stirring speed, rpm | 15 | 15 | 20 | Same as in example 1 |
| Temperature, DEG C | 1460 | 1460 | 1480 | Same as in example 1 |
| Time, min | 30 | 25 | 30 | Same as in example 1 |
| Melt processing | ||||
| Temperature, DEG C | 1580 | 1550 | 1620 | Same as in example 1 |
| Time, min | 360 | 380 | 450 | Same as in example 1 |
| Clarification homogenization | ||||
| Temperature, DEG C | 1620 | 1620 | 1630 | Same as in example 1 |
| Time, min | 50 | 50 | 40 | Same as in example 1 |
| Shaping treatment | ||||
| Temperature, DEG C | 1250 | 1260 | 1260 | Same as in example 1 |
| Annealing treatment | ||||
| Temperature, DEG C | 560 | 580 | 590 | Same as in example 1 |
| Time, min | 15 | 20 | 30 | Same as in example 1 |
| Naming the name | ||||
| S1 | S2 | S3 | S4 |
Table 1 (subsequent table)
| Example 5 | Example 6 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| SiO 2/wt% | 78 | Same as in example 1 | 72 | 80 | Same as in example 1 | Same as in example 1 |
| Al2O 3/wt% | 2 | Same as in example 1 | 7 | 6 | Same as in example 1 | Same as in example 1 |
| B2O 3/wt% | 11.5 | Same as in example 1 | 10 | 9 | Same as in example 1 | Same as in example 1 |
| Na 2O/wt% | 6.3 | Same as in example 1 | 8 | 4 | Same as in example 1 | Same as in example 1 |
| K2O/wt% | 0.9 | Same as in example 1 | 1 | 0.2 | Same as in example 1 | Same as in example 1 |
| CaO/wt.% | 0.2 | Same as in example 1 | 0.3 | 0.1 | Same as in example 1 | Same as in example 1 |
| ZrO 2/wt% | 0.5 | Same as in example 1 | 0.6 | 0.5 | Same as in example 1 | Same as in example 1 |
| MoO 3/wt% | 0.2 | 0.3 | 0.3 | 0.1 | 0.05 | 0.3 |
| Pr6O 11/wt% | 0.2 | 0.2 | 0.3 | 0.1 | 0.15 | 0.1 |
| Ta2O 5/wt% | 0.1 | 0 | 0.3 | 0 | 0.15 | 0.05 |
| Nb2O 5/wt.% | 0.1 | 0 | 0.2 | 0 | 0.15 | 0.05 |
| Mixing | ||||||
| Stirring speed, rpm | Same as in example 1 | Same as in example 1 | Same as in example 1 | Same as in example 1 | Same as in example 1 | Same as in example 1 |
| Temperature, DEG C | Same as in example 1 | Same as in example 1 | Same as in example 1 | Same as in example 1 | Same as in example 1 | Same as in example 1 |
| Time, min | Same as in example 1 | Same as in example 1 | Same as in example 1 | Same as in example 1 | Same as in example 1 | Same as in example 1 |
| Melt processing | ||||||
| Temperature, DEG C | Same as in example 1 | Same as in example 1 | Same as in example 1 | Same as in example 1 | Same as in example 1 | Same as in example 1 |
| Time, min | Same as in example 1 | Same as in example 1 | Same as in example 1 | Same as in example 1 | Same as in example 1 | Same as in example 1 |
| Clarification homogenization | ||||||
| Temperature, DEG C | Same as in example 1 | Same as in example 1 | Same as in example 1 | Same as in example 1 | Same as in example 1 | Same as in example 1 |
| Time, min | Same as in example 1 | Same as in example 1 | Same as in example 1 | Same as in example 1 | Same as the practiceExample 1 | Same as in example 1 |
| Shaping treatment | ||||||
| Temperature, DEG C | Same as in example 1 | Same as in example 1 | Same as in example 1 | Same as in example 1 | Same as in example 1 | Same as in example 1 |
| Annealing treatment | ||||||
| Temperature, DEG C | Same as in example 1 | Same as in example 1 | Same as in example 1 | Same as in example 1 | Same as in example 1 | Same as in example 1 |
| Time, h | Same as in example 1 | Same as in example 1 | Same as in example 1 | Same as in example 1 | Same as in example 1 | Same as in example 1 |
| Naming the name | ||||||
| S5 | S6 | DS1 | DS2 | DS3 | DS4 |
Test example 1
Performance tests are carried out on each neutral medicinal borosilicate glass sample prepared in the examples and the comparative examples, and specific test results are shown in Table 2.
Wherein, density: the measurement was performed by the archimedes method.
Linear expansion coefficient: the glass samples were measured using a dilatometer at a temperature range of 20-380 ℃ and were rod-shaped glasses having dimensions of phi 5mm by 50 mm.
Strain point P s Annealing point T a Softening point T s : the measurement was performed by the glass fiber elongation method.
Operating temperature T w : the viscosity was found to be 10 from the viscosity calculation formula of Fulecher for high temperature viscosity of glass 4 dPa.s.
Hydrolysis resistance: the glass samples were crushed using alumina to make mortar and cream bars according to the method of the powder test method performed by YBB 2015.
Water resistance: the measurement was carried out according to the "Water resistance measurement method of YBB 0036204-2015 glass particles at 98 ℃ and the" Water resistance measurement method of YBB00252003-2015 glass particles at 121 ℃.
Acid resistance: the boiling hydrochloric acid etching resistance test method of YBB00342004-2015 glass is adopted.
Alkali resistance: the determination was carried out according to YBB00352004-2015 glass boiling resistance mixed alkaline aqueous solution aggressiveness determination method.
Ion elution amount: the detection was performed by an ICP emission analysis apparatus, and n.d. indicates that the detection limit was lower than that of the ICP emission analysis apparatus.
TABLE 2
| Density, g/cm3 | Linear expansion coefficient of 10-7deg.C | Ps,℃ | Ta,℃ | Ts,℃ | Tw,℃ | Hydrolysis resistance, mL | |
| Example 1 | 2.34 | 53 | 520 | 565 | 775 | 1170 | 0.025 |
| Example 2 | 2.33 | 52 | 515 | 555 | 775 | 1170 | 0.024 |
| Example 3 | 2.34 | 53 | 525 | 564 | 774 | 1175 | 0.023 |
| Example 4 | 2.35 | 52 | 520 | 564 | 780 | 1175 | 0.025 |
| Example 5 | 2.35 | 53 | 520 | 565 | 775 | 1170 | 0.025 |
| Example 6 | 2.33 | 54 | 523 | 562 | 780 | 1180 | 0.025 |
| Comparative example 1 | 2.34 | 58 | 525 | 570 | 780 | 1190 | 0.035 |
| Comparative example 2 | 2.32 | 58 | 535 | 580 | 795 | 1195 | 0.038 |
| Comparative example 3 | 2.34 | 53 | 525 | 560 | 778 | 1176 | 0.036 |
| Comparative example 4 | 2.34 | 53 | 524 | 561 | 779 | 1178 | 0.037 |
Table 2 (subsequent table)
| Water resistance at 98 °c | Water resistance at 121 DEG C | Alkali resistance | Acid resistance, mg/dm2 | Ion elution amount, ppm | |
| Example 1 | HGB grade 1 | Level 1 | Level 2 | 0.5 | N.D. |
| Example 2 | HGB grade 1 | Level 1 | Level 2 | 0.5 | N.D. |
| Example 3 | HGB grade 1 | Level 1 | Level 2 | 0.5 | N.D. |
| Example 4 | HGB grade 1 | Level 1 | Level 2 | 0.5 | N.D. |
| Example 5 | HGB grade 1 | Level 1 | Level 2 | 0.5 | N.D. |
| Example 6 | HGB grade 1 | Level 1 | Level 2 | 0.5 | N.D. |
| Comparative example 1 | HGB2 grade | Level 2 | 3 grade | 0.5 | 0.5 |
| Comparative example 2 | HGB2 grade | Level 2 | 3 grade | 80 | 50 |
| Comparative example 3 | HGB2 grade | Level 2 | 3 grade | 0.5 | 100 |
| Comparative example 4 | HGB2 grade | Level 2 | 3 grade | 0.5 | 95 |
As can be seen from the results of Table 2, the neutral borosilicate glass prepared according to the present invention has an operating temperature T w (viscosity 10) 4 dPa.S) is not higher than 1180 ℃, the melting difficulty is reduced, the softening point is less than 780 ℃, the annealing point is less than 565 ℃, the strain point is more than 515 ℃, and the linear expansion coefficient (20-300 ℃) of the glass is 52 multiplied by 10 -7 /℃-54×10 -7 between/DEG C; the product is transparent and shiny, and the density of glass is less than 2.4g/cm 3 Meets the requirements of light weight and environmental protection of medicine package. In addition, the water resistance of the glass reaches HGB1 grade, and the alkali resistance reaches HGB2 grade. Thus, it was demonstrated that neutral borosilicate glass prepared from the glass composition of the present invention has good hydrolysis resistance, chemical durability and low linear expansion coefficient.
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 (10)
1. A composition for preparing neutral borosilicate glass, which is characterized by comprising the following components which are stored independently or in a mixed way: siO (SiO) 2 、Al 2 O 3 、B 2 O 3 、Na 2 O、K 2 O、CaO、ZrO 2 Rare earth doped oxides;
the SiO being based on the total weight of the composition 2 The content of (C) is 74-78 wt%, the Al 2 O 3 The content of (B) is 2-5 wt% 2 O 3 The content of Na is 10.5-12 wt% 2 O content of 5-7 wt%, said K 2 The content of O is 0.1-1 wt%, the content of CaO is 0-0.3 wt%, and the ZrO 2 The content of the rare earth doped oxide is 0.2 to 1 weight percent, and the content of the rare earth doped oxide is 0.4 to 0.8 weight percent;
the rare earth doped oxide comprises the following components in percentage by weight: 0.5-2:0.1-2: moO of 0.1-2 3 、Pr 6 O 11 、Ta 2 O 5 And Nb (Nb) 2 O 5 Is a combination of (a) and (b).
2. The composition of claim 1, wherein the SiO is based on the total weight of the composition 2 The content of (C) is 74-76 wt%, the Al 2 O 3 The content of (B) is 2-5 wt% 2 O 3 The content of Na is 10.5-12 wt% 2 O content of 5-7 wt%, said K 2 The content of O is 0.1-1 wt%, the content of CaO is 0.1-0.3 wt%, and the content of ZrO is 0.1-1 wt% 2 The content of the rare earth doped oxide is 0.2-1 wt%, and the content of the rare earth doped oxide is 0.4-0.7 wt%.
3. The composition according to claim 1 or 2, wherein the rare earth doped oxide is present in an amount of 1 by weight: 0.5-2:0.5-1: moO of 0.1-1 3 、Pr 6 O 11 、Ta 2 O 5 And Nb (Nb) 2 O 5 Is a combination of (a) and (b).
4. A method of making neutral borosilicate glass, the method comprising: the composition for producing neutral borosilicate glass according to any of claims 1 to 3, wherein the components are sequentially mixed, melt-processed, clarified homogenized, shaped, and annealed.
5. The method according to claim 4, wherein the mixing conditions include at least: the stirring speed is 10-20rpm, the temperature is 1450-1500 ℃, and the time is 20-30min.
6. The method according to claim 4 or 5, characterized in that the conditions of the melt processing at least comprise: the temperature is 1550-1650 ℃ and the time is 300-480min; and/or
The conditions of clarification and homogenization at least comprise: the temperature is 1580-1630 ℃ and the time is 30-60min.
7. The method according to claim 4 or 5, characterized in that the conditions of the shaping process comprise at least: the temperature is 1250-1280 ℃; and/or
The annealing conditions include at least: the temperature is 560-595 ℃ and the time is 10-30min.
8. Neutral borosilicate glass obtainable by the process according to any of claims 4 to 7.
9. The neutral borosilicate glass according to claim 8, wherein an ion elution amount of said neutral borosilicate glass is 1.0ppm or less; and/or
The neutral borosilicate glass has a linear expansion coefficient of not more than 55×10 in a temperature range of 30-380deg.C -7 /℃。
10. Use of neutral borosilicate glass according to claim 8 or 9 for the preparation of a medical container.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210727883.0A CN115231821B (en) | 2022-06-22 | 2022-06-22 | Composition for preparing neutral borosilicate glass, preparation method and application thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85105990A (en) * | 1985-08-06 | 1987-02-25 | 中国科学院南京土壤研究所 | Sensing glass for ultra-low-resistance electrode |
| 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 |
| CN114180828A (en) * | 2016-12-29 | 2022-03-15 | 广东东阳光药业有限公司 | High chemical resistance borosilicate glass and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE102017216422B3 (en) * | 2017-09-15 | 2019-01-03 | Schott Ag | High-expansion bonded glass with improved water resistance and its applications |
| KR102104318B1 (en) * | 2018-04-24 | 2020-04-24 | 엘지전자 주식회사 | Antibacterial glass composite, manufacturing method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85105990A (en) * | 1985-08-06 | 1987-02-25 | 中国科学院南京土壤研究所 | Sensing glass for ultra-low-resistance electrode |
| CN114180828A (en) * | 2016-12-29 | 2022-03-15 | 广东东阳光药业有限公司 | High chemical resistance borosilicate glass and application thereof |
| 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 |
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