CN115231821A - Composition for preparing neutral borosilicate glass, and preparation method and application thereof - Google Patents

Composition for preparing neutral borosilicate glass, and preparation method and application thereof Download PDF

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Publication number
CN115231821A
CN115231821A CN202210727883.0A CN202210727883A CN115231821A CN 115231821 A CN115231821 A CN 115231821A CN 202210727883 A CN202210727883 A CN 202210727883A CN 115231821 A CN115231821 A CN 115231821A
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borosilicate glass
amount
composition
neutral borosilicate
temperature
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CN115231821B (en
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田鹏
严雷
黄志军
杨伽林
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Hunan Hongkang New Material Technology Co ltd
Beijing Yuanda Xinda Technology Co Ltd
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Hunan Hongkang New Material Technology Co ltd
Beijing Yuanda Xinda Technology Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C3/00Glass compositions
    • C03C3/04Glass compositions containing silica
    • C03C3/076Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/095Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03BMANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/16Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00Technologies relating to the processing of minerals
    • Y02P40/50Glass production, e.g. reusing waste heat during processing or shaping
    • Y02P40/57Improving the yield, e-g- reduction of reject rates

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Glass Compositions (AREA)

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, and a preparation method and application of the neutral borosilicate glass. The composition contains the following components which are stored independently or in a mixture of more than two of the components: siO 2 2 、Al 2 O 3 、B 2 O 3 、Na 2 O、K 2 O、CaO、ZrO 2 The rare earth doped oxide is a mixture of 1:0.5-2:0-2:0-2 MoO 3 、Pr 6 O 11 、Ta 2 O 5 And Nb 2 O 5 Combinations of (a) and (b). The neutral borosilicate glass prepared from the composition provided by the invention not only has lower linear expansion coefficient and ion elution amount, but also has good chemical durability and high hydrolytic resistance.

Description

Composition for preparing neutral borosilicate glass, and preparation method and application thereof
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
With the rapid development of the pharmaceutical industry in China, the requirements on the quality of a medicine packaging material are higher and higher, and the corresponding medicinal glass has the requirements on good water resistance, acid resistance, alkali resistance, freezing resistance, thermal stability and the like, and is a main packaging material for controlling the inactivated vaccine for the new coronary pneumonia at present. The phenomenon of serious shortage of glass bottles for putting vaccine injections is reported, the requirement of dosage of the new coronary pneumonia inactivated vaccine cannot be met, and the product qualification rate caused by defects in neutral medical glass tubes is low, mainly caused by calculus and tumor and gas lines.
The medium borosilicate medical glass is an important borosilicate glass variety, and B thereof 2 O 3 The content is 8-12 wt%, and the glass container is used for containing deionized water to keep the pH value unchanged, so that the glass is also called as neutral glass, has excellent performances of good chemical stability, heat-resistant stability, lower linear expansion coefficient and the like, and is widely used for packaging injection biomedical products.
The defects of the neutral medical glass tube are mainly generated in 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, volatility, high loss rate and the like, so that the fused product has the defects of bubbles and nodules, and the product percent of pass is reduced; the volatilized boron oxide corrodes the refractory materials of the kiln, so that the maintenance and replacement cost is improved, and the service life of the kiln is shortened.
Therefore, in the preparation process of the neutral medical glass, an auxiliary agent needs to be introduced into the batch so as to reduce the viscosity of glass liquid, improve the clarification performance, reduce the volatilization loss rate of boron, improve the product quality and the qualification rate and prolong the service life of the kiln.
At present, the medical glass packaging material produced in China mainly comprises soda-lime-silica glass and low borosilicate glass, and only a small amount of medium borosilicate medical glass is used. However, the performance stability and water resistance of the medium borosilicate medical glass have certain difference with those of similar products abroad, the medium borosilicate medical glass has high manufacturing difficulty, the defects of easy occurrence of stones, gas lines and the like in the glass tube forming process exist, the finished product qualification rate is low, and the water resistance and the acid and alkali resistance cannot meet the requirements of the use 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, a first aspect of the present invention provides a composition for producing a neutral borosilicate glass, which contains the following components stored independently of each other or in a mixture of two or more of them: siO 2 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 composition, the SiO 2 In an amount of 74 to 78 wt%, the Al 2 O 3 In an amount of 2 to 5 wt.%, said B 2 O 3 Is contained in an amount of 10.5 to 12wt%, and Na is 2 The content of O is 5-7 wt%, and K is 2 O content of 0.1-1 wt%, caO content of 0-0.3 wt%, and ZrO 2 0.2-1 wt%, and the rare earth doped oxide is 0.4-0.8 wt%;
the rare earth doped oxide comprises the following components in percentage by weight of 1:0.5-2:0-2:0-2 MoO 3 、Pr 6 O 11 、 Ta 2 O 5 And Nb 2 O 5 Combinations of (a) and (b).
Preferably, the SiO is present in an amount based on the total weight of the composition 2 In an amount of 74 to 76 wt%, the Al 2 O 3 In an amount of 2 to 5 wt.%, said B 2 O 3 Is contained in an amount of 10.5 to 12wt%, and Na is 2 The content of O is 5-7 wt%, K 2 O in an amount of 0.1 to 1 wt%, caO in an amount of 0.1 to 0.3 wt%, and ZrO 2 Is 0.2-1 wt%, and the rare earth doped oxide is 0.5-0.7 wt%.
Preferably, the rare earth doped oxide is a rare earth doped oxide with a content weight ratio of 1:0.5-2:0.5-1:0-1 MoO 3 、Pr 6 O 11 、Ta 2 O 5 And Nb 2 O 5 Combinations of (a) and (b).
In a second aspect, the present invention provides a method of making a neutral borosilicate glass, the method comprising: the components of the composition for preparing the neutral borosilicate glass according to the first aspect are sequentially subjected to mixing, melting treatment, clarifying and homogenizing, molding treatment and annealing treatment.
Preferably, the conditions of the mixing include at least: stirring speed is 10-20rpm, temperature is 1450-1500 deg.C, and time is 20-30min.
Preferably, the conditions of the melt processing include at least: the temperature is 1550-1650 deg.C, and the time is 300-480min.
Preferably, the conditions of clarification homogenization comprise at least: the temperature is 1580-1630 deg.C, and the time is 30-60min.
Preferably, the conditions of the forming process include at least: the temperature is 1250-1280 ℃.
Preferably, the annealing conditions include at least: the temperature is 560-595 deg.C, and the time is 10-30min.
The invention provides a neutral borosilicate glass produced by the method according to the second aspect.
Preferably, the ion elution amount of the neutral borosilicate glass is 1.0ppm or less.
Preferably, the linear expansion coefficient of the neutral borosilicate glass in the temperature range of 30-380 ℃ is not more than 55 x 10 -7 /℃。
According to a fourth aspect of the present invention there is provided use of the neutral borosilicate glass of the third aspect in the manufacture of a medical container.
The neutral borosilicate glass prepared from the composition provided by the invention not only has lower linear expansion coefficient and ion release amount, but also has good chemical durability and high hydrolysis resistance, does not release or only releases few ions when being contacted with aqueous or water-containing medicinal substances when being applied to preparation of medical containers, and is not easy to damage caused by thermal shock when a glass tube is manufactured.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For numerical ranges, each range between its endpoints and individual point values, and each individual point value can be combined with each other to give one or more new numerical ranges, and such numerical ranges should be construed as specifically disclosed herein.
In the present invention, unless otherwise specified, the room temperature or the room temperature both represent 25. + -. 2 ℃.
As described above, the first aspect of the present invention provides a composition for producing a neutral borosilicate glass, which contains the following components stored independently of each other or in a mixture of two or more of them: siO 2 2 、 Al 2 O 3 、B 2 O 3 、Na 2 O、K 2 O、CaO、ZrO 2 Rare earth doped oxides;
the SiO is present in an amount based on the total weight of the composition 2 Is 74-78 wt%, the Al 2 O 3 In an amount of 2 to 5 wt.%, said B 2 O 3 Is contained in an amount of 10.5 to 12wt%, and Na is 2 The content of O is 5-7 wt%, and K is 2 O content of 0.1-1 wt%, caO content of 0-0.3 wt%, and ZrO 2 0.2-1 wt%, and the rare earth doped oxide is 0.4-0.8 wt%;
the rare earth doped oxide comprises the following components in percentage by weight of 1:0.5-2:0-2:0-2 MoO 3 、Pr 6 O 11 、 Ta 2 O 5 And Nb 2 O 5 Combinations of (a) and (b).
Preferably, the SiO is present in an amount based on the total weight of the composition 2 In an amount of 74 to 76 wt%, the Al 2 O 3 In an amount of 2 to 5 wt.%, said B 2 O 3 In an amount of 10.5 to 12wt%, the Na 2 The content of O is 5-7 wt%, and K is 2 O in an amount of 0.1 to 1 wt%, caO in an amount of 0.1 to 0.3 wt%, and ZrO 2 Is 0.2-1 wt%, and the rare earth doped oxide is 0.4-0.7 wt%. The inventors have found that, with this preferred embodiment, neutral borosilicate glass with better hydrolytic resistance can be obtained while ensuring chemical stability.
According to a particularly preferred embodiment, the rare earth doped oxide is present in a content by weight ratio of 1:0.5-2:0.5-1:0-1 MoO 3 、Pr 6 O 11 、Ta 2 O 5 And Nb 2 O 5 A combination of (a) and (b). The inventors have found that with this preferred embodiment, neutral borosilicate glasses with a lower linear expansion coefficient can be obtained.
As previously mentioned, a second aspect of the present invention provides a method of making a neutral borosilicate glass, the method comprising: the components of the composition for preparing the neutral borosilicate glass according to the first aspect are subjected to mixing, melting treatment, clarification and homogenization, forming treatment and annealing treatment in sequence.
Preferably, the mixing conditions include at least: stirring speed of 10-20rpm at 1450-1500 deg.C for 20-30min.
Preferably, the conditions of the melt processing include at least: the temperature is 1550-1650 ℃, and the time is 300-480min.
In the present invention, there is no particular limitation in the specific operations of the clarifying homogenization, the forming treatment and the annealing treatment, and known operations in the art may be employed, and the specific operations exemplified hereinafter in the present invention should not be construed as limiting the present invention by those skilled in the art.
Preferably, the conditions of clarification homogenization comprise at least: the temperature is 1580-1630 deg.C, 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 2.3 dPa.s, making bubbles in the molten glassAnd (4) discharging.
Preferably, in the step (3), the method of the molding treatment is selected from at least one of danner method molding process and vero method molding process.
According to a particularly preferred embodiment, in step (3), the method of the forming treatment is a Danner method forming process.
The invention has no special requirements on the specific operation method of the Danna method forming process, and the method can be carried out by adopting the known technical means by the technical personnel in the field.
Preferably, the conditions of the forming process include at least: the temperature is 1250-1280 ℃.
Preferably, the conditions of the annealing treatment at least include: the temperature is 560-595 deg.C, and the time is 10-30min.
As previously mentioned, a third aspect of the present invention provides a 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 linear expansion coefficient of the neutral borosilicate glass in the temperature range of 30-380 ℃ is not more than 55 x 10 -7 /℃。
As mentioned above, the fourth aspect of the present invention provides the use of the neutral borosilicate glass of the third aspect in the preparation of a medical container.
According to a particularly preferred embodiment of the invention, the medical container is selected from at least one vial and ampoule.
The present invention will be described in detail below by way of examples. In the following examples, various raw materials used are commercially available ones unless otherwise specified.
In the following examples, 10g is represented per 1% by weight.
Example 1
This example illustrates the preparation of a neutral borosilicate glass according to the invention according to the formulation and process parameters given in table 1, and according to the method described below.
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 for 30min at 1460 ℃ and 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, adjusting the temperature to 1620 ℃, discharging air bubbles to obtain molten glass, drawing and molding the obtained molten glass by adopting a Danner method molding process to obtain a glass tube substrate to be applied, cutting the glass tube substrate into a preset length (1500 mm), and annealing for 15min at 560 ℃ to obtain a glass sample.
The remaining examples and comparative examples were carried out using the same procedure as in example 1, except that the composition of the neutral borosilicate glass composition used and the process parameters for preparing the neutral borosilicate glass were different, unless otherwise specified, see table 1.
TABLE 1
Example 1 Example 2 Example 3 Example 4
SiO 2 Per weight percent 74.5 76 75.5 77
Al 2 O 3 Per weight percent 5 3.8 4.5 4.2
B 2 O 3 Per weight percent 11.5 11.5 11.5 10.8
Na 2 O/weight% 6.5 6.3 6.5 6.5
K 2 O/weight% 1 0.9 0.8 0.3
CaO/weight% 0.2 0.2 0.2 0.2
ZrO 2 Per weight percent 0.8 0.5 0.6 0.4
MoO 3 Per weight percent 0.1 0.2 0.1 0.2
Pr 6 O 11 Per weight percent 0.2 0.2 0.1 0.2
Ta 2 O 5 Per weight percent 0.1 0.2 0.1 0.1
Nb 2 O 5 Per weight percent 0.1 0.2 0.1 0.1
Mixing of
Stirring speed, rpm 15 15 20 Same as example 1
Temperature, C 1460 1460 1480 Same as example 1
Time, min 30 25 30 Same as example 1
Melt processing
Temperature, C 1580 1550 1620 Same as example 1
Time, min 360 380 450 Same as example 1
Clarification and homogenization
Temperature, C 1620 1620 1630 Same as example 1
Time, min 50 50 40 Same as example 1
Shaping process
Temperature, C 1250 1260 1260 Same as example 1
Annealing treatment
Temperature, C 560 580 590 Same as example 1
Time, min 15 20 30 Same as example 1
Name of
S1 S2 S3 S4
Watch 1 (watch continuation)
Figure BDA0003708577200000071
Figure BDA0003708577200000081
Test example 1
The performance of each of the neutral pharmaceutical borosilicate glass samples prepared in the examples and comparative examples was tested, and the specific test results are shown in table 2.
Wherein, the density: the measurement was carried out by the Archimedes method.
Coefficient of linear expansion: the measurements were carried out on glass samples in a temperature range of 20 ℃ using a dilatometer, the glass samples being rod-shaped glasses having a size phi of 5mm x 50mm.
Strain point P s Annealing point T a And a softening point T s : the measurement was carried out by a glass fiber elongation method.
Operating temperature T w : the viscosity was found to be 10 according to the glass high temperature viscosity Fulecher viscosity equation 4 Temperature at dPa · s.
And (3) hydrolysis resistance: the glass samples were crushed using alumina made mortars and pestles in accordance with the powder test method performed on YBB2015 version.
Water resistance: the measurement was carried out in accordance with the methods of Water resistance measurement at 98 ℃ for YBB00362004 2015 glass particles and Water resistance measurement at 121 ℃ for YBB00252003 2015 glass particles.
Acid resistance: according to YBB00342004-2015 glass boiling hydrochloric acid etching resistance determination method.
Alkali resistance: the measurement was carried out in accordance with "method for measuring the erosiveness of a boiling-resistant mixed alkali aqueous solution for glass" YBB00352004 2015 ".
Ion elution amount: and (4) detecting by using an ICP emission analyzer, wherein N.D. represents that the detection limit is lower than that of the ICP emission analyzer.
TABLE 2
Density, g/cm 3 Coefficient of linear expansion, 10 -7 Ps,℃ Ta,℃ Ts,℃ Tw,℃ Resistance to hydrolysis, 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 (Su Tao)
Water resistance at 98 DEG C Water resistance at 121 DEG C Alkali resistance Acid resistance, mg/dm 2 Amount of ion elution, ppm
Example 1 HGB class 1 Level 1 Stage 2 0.5 N.D.
Example 2 HGB grade 1 Level 1 Stage 2 0.5 N.D.
Example 3 HGB grade 1 Level 1 Stage 2 0.5 N.D.
Example 4 HGB grade 1 Level 1 Stage 2 0.5 N.D.
Example 5 HGB grade 1 Level 1 Stage 2 0.5 N.D.
Example 6 HGB grade 1 Level 1 Stage 2 0.5 N.D.
Comparative example 1 HGB2 stage Stage 2 Grade 3 0.5 0.5
Comparative example 2 HGB class 2 Stage 2 Grade 3 80 50
Comparative example 3 HGB class 2 Stage 2 Grade 3 0.5 100
Comparative example 4 HGB class 2 Stage 2 Grade 3 0.5 95
As can be seen from the results in Table 2, the operating temperature T of the neutral borosilicate glass produced according to the present invention w (viscosity: 10) 4 dPa.S) of not higher than 1180 deg.C, reduced difficulty in melting, softening point of less than 780 deg.C, annealing point of less than 565 deg.C, strain point of more than 515 deg.C, and linear expansion coefficient (20300 deg.C) of glass of 52 × 10 7 /℃54×10 7 Between/° c; the product is transparent and bright, and the glass density is less than 2.4g/cm 3 And meets the requirements of light weight and environmental protection of medicine packaging. In addition, the water resistance of the glass reaches HGB1 grade, and the alkali resistance reaches 2 grade. Thus, it is demonstrated that neutral borosilicate glass prepared from the glass composition of the present invention has good hydrolytic resistance, chemical durability, and low linear expansion coefficient.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (10)

1. A composition for preparing a neutral borosilicate glass, which comprises the following components stored independently of each other or in a mixture of two or more of them: siO 2 2 、Al 2 O 3 、B 2 O 3 、Na 2 O、K 2 O、CaO、ZrO 2 Rare earth doped oxides;
the SiO is present in an amount based on the total weight of the composition 2 In an amount of 74 to 78 wt%, the Al 2 O 3 In an amount of 2 to 5 wt.%, said B 2 O 3 In an amount of 10.5 to 12wt%, the Na 2 The content of O is 5-7 wt%, and K is 2 O in an amount of 0.1 to 1 wt%, caO in an amount of 0 to 0.3 wt%, and ZrO 2 0.2-1 wt%, and the rare earth doped oxide is 0.4-0.8 wt%;
the rare earth doped oxide comprises the following components in percentage by weight of 1:0.5-2:0-2:0-2 MoO 3 、Pr 6 O 11 、Ta 2 O 5 And Nb 2 O 5 A combination of (a) and (b).
2. The composition of claim 1, wherein the SiO is present in an amount based on the total weight of the composition 2 Is 74-76 wt%, the Al 2 O 3 In an amount of 2 to 5 wt.%, said B 2 O 3 In an amount of 10.5 to 12wt%, the Na 2 The content of O is 5-7 wt%, and K is 2 O in an amount of 0.1 to 1 wt%, caO in an amount of 0.1 to 0.3 wt%, and ZrO 2 0.2-1 wt%, and the rare earth doped oxide is 0.4-0.7 wt%.
3. Composition according to claim 1 or 2, characterized in that said rare earth doped oxideThe weight ratio of the contents is 1:0.5-2:0.5-1:0-1 MoO 3 、Pr 6 O 11 、Ta 2 O 5 And Nb 2 O 5 A combination of (a) and (b).
4. A method of making a neutral borosilicate glass, the method comprising: the composition for preparing medical neutral borosilicate glass according to any one of claims 1 to 3, wherein the components are sequentially mixed, melted, clarified and homogenized, formed and annealed.
5. The method according to claim 4, characterized in that the conditions of mixing comprise at least: stirring speed is 10-20rpm, temperature is 1450-1500 deg.C, and time is 20-30min.
6. The method according to claim 4 or 5, characterized in that the conditions of the melt processing comprise at least: the temperature is 1550-1650 ℃, and the time is 300-480min; and/or
The conditions of clarification homogenization include at least: the temperature is 1580-1630 deg.C, and the time is 30-60min.
7. Method according to any one of claims 4 to 6, characterized in that the conditions of the forming process comprise at least: the temperature is 1250-1280 ℃; and/or
The conditions of the annealing treatment at least comprise: the temperature is 560-595 deg.C, and the time is 10-30min.
8. Neutral borosilicate glass produced by the method according to any one of claims 4 to 7.
9. The neutral borosilicate glass according to claim 8, wherein an ion elution amount of the neutral borosilicate glass is 1.0ppm or less; and/or
The linear expansion coefficient of the neutral borosilicate glass in the temperature range of 30-380 ℃ is not more than 55 multiplied by 10 -7 /℃。
10. Use of the neutral borosilicate glass according to claim 8 or 9 for the preparation of a medical container.
CN202210727883.0A 2022-06-22 2022-06-22 Composition for preparing neutral borosilicate glass, preparation method and application thereof Active CN115231821B (en)

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Citations (5)

* Cited by examiner, † Cited by third party
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
US20190084871A1 (en) * 2017-09-15 2019-03-21 Schott Ag High-expansion bonding glass having improved water resistance and uses thereof
US20210047232A1 (en) * 2018-04-24 2021-02-18 Lg Electronics Inc. Antibacterial glass composition and method for preparing same
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

Patent Citations (5)

* Cited by examiner, † Cited by third party
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
US20190084871A1 (en) * 2017-09-15 2019-03-21 Schott Ag High-expansion bonding glass having improved water resistance and uses thereof
US20210047232A1 (en) * 2018-04-24 2021-02-18 Lg Electronics Inc. Antibacterial glass composition and method for preparing same
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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