阅读说明：本技术 一种硼硅玻璃组合物、硼硅玻璃及其制备方法和应用 (Borosilicate glass composition, borosilicate glass, and preparation method and application thereof ) 是由 李青 李赫然 李志勇 胡恒广 史伟华 闫冬成 王博 于 2021-01-15 设计创作，主要内容包括：本公开涉及一种硼硅玻璃组合物,以组合物的总摩尔数为基准,该硼硅玻璃组合物包含：75-79摩尔％的SiO-2、2-6摩尔％的Al-2O-3、8-12摩尔％的B-2O-3、0-2摩尔％的K-2O、5-7.5摩尔％的Na-2O、0.5-2摩尔％的CaO、0-2摩尔％的MgO、0-1摩尔％的BaO、0-1摩尔％的ZrO-2、0-2摩尔％的ZnO、0-0.05摩尔％的Se-2O-3、0-0.05摩尔％的MoO-3、0-0.001摩尔％的CeO-2、0-0.015摩尔％的Fe-2O-3、0-0.002摩尔％的CuO和0-0.002摩尔％的La-2O-3。本公开的硼硅玻璃组合物可以获得具有良好理化性能和较低电阻率的硼硅玻璃,制备出的硼硅玻璃具有化学稳定性良好、电阻率低、热膨胀系数低、晶体稳定性良好等优点,同时易熔融和拉伸、结晶化足够稳定,能够用于医药领域、尤其适用于药物的初级包装。(The present disclosure relates to a borosilicate glass composition comprising, based on the total moles of the composition: 75-79 mol% SiO 2 2-6 mol% of Al 2 O 3 8-12 mol% of B 2 O 3 0-2 mol% of K 2 O, 5-7.5 mol% Na 2 O, CaO 0.5-2 mol%, MgO 0-2 mol%, BaO 0-1 mol%, ZrO 0-1 mol% 2 0 to 2 mol percent of ZnO and 0 to 0.05 mol percent of Se 2 O 3 0-0.05 mol% of MoO 3 0 to 0.001 mol% of CeO 2 0-0.015 mol% Fe 2 O 3 0 to 0.002 mol% of CuO and 0 to 0.002 mol% of La 2 O 3 . The borosilicate glass composition of the present disclosure mayThe borosilicate glass with good physical and chemical properties and lower resistivity is obtained, and the prepared borosilicate glass has the advantages of good chemical stability, low resistivity, low thermal expansion coefficient, good crystal stability and the like, is easy to melt, stretch and crystallize, is stable enough, can be used in the field of medicines, and is particularly suitable for primary packaging of medicines.)

1. A borosilicate glass composition, wherein the borosilicate glass composition comprises, based on the total moles of the composition: 75-79 mol% SiO₂2-6 mol% of Al₂O₃8-12 mol% of B₂O₃0-2 mol% of K₂O, 5-7.5 mol% Na₂O, CaO 0.5-2 mol%, MgO 0-2 mol%, BaO 0-1 mol%, ZrO 0-1 mol%₂0 to 2 mol percent of ZnO and 0 to 0.05 mol percent of Se₂O₃0-0.05 mol% of MoO₃0 to 0.001 mol% of CeO₂0-0.015 mol% Fe₂O₃0 to 0.002 mol% of CuO and 0 to 0.002 mol% of La₂O₃。

2. The borosilicate glass composition according to claim 1, wherein the borosilicate glass composition comprises, based on the total moles of the composition: 76-78 mol% SiO₂3-6 mol% of Al₂O₃9.5-10.5 mol% of B₂O₃0.001-0.8 mol% of K₂O, 5-7 mol% Na₂O, CaO 0.5-2 mol%, MgO 0.001-1 mol%, BaO 0.001-0.6 mol%, ZrO 0-0.03 mol%₂0.001-1.5 mol% of ZnO, 0.0001-0.05 mol% of Se₂O₃0.0001-0.05 mol% of MoO₃0 to 0.001 mol% of CeO₂0 to 0.012 mol% Fe₂O₃0-0.0015 mol% of CuO and 0-0.0015 mol% of La₂O₃。

3. The borosilicate glass composition according to claim 1, wherein, in mole percent:

calculated according to formula (1) A is 0.5-1.901 mol%;

a ═ MgO + CaO + BaO + ZnO formula (1);

b is obtained in a proportion of 5 to 9.3 mol% calculated according to formula (2);

B＝K₂O+Na₂o formula (2);

c is 0 to 0.615 as calculated according to formula (3);

C＝K₂O/(K₂O+Na₂o) formula (3);

d is 0 to 0.98 as calculated according to formula (4);

d is MgO/(CaO + ZnO + MgO + BaO) formula (4);

e is 0 to 0.998 as calculated according to formula (5);

e ═ CaO/(CaO + ZnO + MgO + BaO) formula (5);

f is 0 to 0.5 as calculated according to formula (6);

f ═ ZnO/(CaO + ZnO + MgO + BaO) formula (6);

wherein each component represents a mole percentage of that component in the borosilicate glass composition.

4. The borosilicate glass composition according to claim 1, wherein the borosilicate glass composition comprises 0 to 1.28 mole percent of a fluorine-containing compound selected from the group consisting of Na and Na, based on the total moles of the composition₂SiF₆、CaF₂NaF and MgF₂One or more of the above;

optionally, the borosilicate glass composition contains 0 to 0.5 mole percent of a chlorine-containing compound selected from the group consisting of NaCl and NaClO, based on the total moles of the composition₃And NaClO₄One or more ofSeed growing;

optionally, the borosilicate glass composition contains 0 to 0.003 mole percent of an inorganic sulfate selected from the group consisting of CaSO, based on the total moles of the composition₄、Na₂SO₄、K₂SO₄And MgSO₄One or more of the above;

optionally, the borosilicate glass composition contains 0.5 to 0.8 mole percent of K, based on the total moles of the composition₂O。

5. A method of making a borosilicate glass, the method comprising: the borosilicate glass composition according to any of claims 1 to 4, which is subjected to a melting treatment, a refining homogenization, a forming treatment and an annealing treatment in this order.

6. The method of claim 5, wherein the melt processing conditions comprise: the melting temperature is more than 1500 ℃, and the melting time is more than 1 h;

the clarifying homogenization conditions include: the clarifying temperature is 1630-₂、NaCl、CaCl₂、CaF₂、NaF、Na₂SiF₆、Na₂One or more of S, CaS, MgS and ZnS; the content of the clarifying agent is 0.002-0.5 mol% based on the total moles of the composition.

7. A borosilicate glass produced by the method of claim 5 or 6.

8. The borosilicate glass according to claim 7, wherein the borosilicate glass contains 0 to 0.5 mol% of chlorine and 0 to 1.5 mol% of fluorine, based on the total moles of the borosilicate glass₃The content of sulfur element is 0-0.006 mol%;

preferably, the chlorine content is 0.003-0.5 mol%, the fluorine content is 0.001-0.8 mol%, and SO is used₃The content of the sulfur element is 0 to 0.005 mol percent.

9. The borosilicate glass according to claim 7 or 8, wherein the borosilicate glass has a resistivity of the glass melt of 0 to 15 Ω -cm, preferably 0 to 10 Ω -cm, at 1500 ℃.

10. Use of the borosilicate glass according to any of claims 7 to 9 in the medical field.

Technical Field

The disclosure relates to the field of materials, in particular to a borosilicate glass composition, borosilicate glass, and a preparation method and application thereof.

Background

With the development of the medical glass technology, the demand of the borosilicate glass is more and more increased. Under such a trend, the requirements on water resistance, acid resistance and alkali resistance of glass performance are very strict, and the available glass electric melting technology includes two technologies of full melting and partial melting (also called electric melting), and the electric melting technology has many advantages, such as reducing energy consumption, increasing yield, reducing environmental pollution, and the like. When the molten glass is at a high temperature of more than 1200 ℃, the resistivity is an important index for melting and clarifying the glass and is reduced along with the rise of the temperature. Therefore, the control of the high-temperature resistivity of the glass has important significance on the production of medicinal glass.

For industrial electric heating, a mode of small voltage and large current is generally adopted, and when the voltage is constant, P ═ U is adopted²and/R, therefore, under the condition that the heating voltage is not changed, the resistivity is reduced, which is beneficial to improving the heating power. The conventional glass composition has a high specific resistance when it is melted into a molten glass at a high temperature.

Disclosure of Invention

The invention aims to provide a borosilicate glass composition, borosilicate glass, and a preparation method and application thereof.

In order to achieve the above object, a first aspect of the present disclosure provides a borosilicate glass composition comprising, based on the total moles of the composition: 75-79 mol% SiO₂2-6 mol% of Al₂O₃8-12 mol% of B₂O₃0-2 mol% of K₂O, 5-7.5 mol% Na₂O, CaO 0.5-2 mol%, MgO 0-2 mol%, BaO 0-1 mol%, ZrO 0-1 mol%₂0 to 2 mol percent of ZnO and 0 to 0.05 mol percent of Se₂O₃0-0.05 mol% of MoO₃0 to 0.001 mol% of CeO₂0-0.015 mol% Fe₂O₃0 to 0.002 mol% of CuO and 0 to 0.002 mol% of La₂O₃。

Optionally, the borosilicate glass composition comprises, based on the total moles of the composition: 76-78 mol% SiO₂3-6 mol% of Al₂O₃9.5-10.5 mol% of B₂O₃0.001-0.8 mol% of K₂O, 5-7 mol% Na₂O, CaO 0.5-2 mol%, MgO 0.001-1 mol%, BaO 0.001-0.6 mol%, ZrO 0-0.03 mol%₂0.001-1.5 mol% of ZnO, 0.0001-0.05 mol% of Se₂O₃0.0001-0.05 mol% of MoO₃0 to 0.001 mol% of CeO₂0 to 0.012 mol% Fe₂O₃0-0.0015 mol% of CuO and 0-0.0015 mol% of La₂O₃。

Alternatively, the composition comprises, in mole percent:

calculated according to formula (1) A is 0.5-1.901 mol%;

a ═ MgO + CaO + BaO + ZnO formula (1);

b is obtained in a proportion of 5 to 9.3 mol% calculated according to formula (2);

B＝K₂O+Na₂o formula (2);

c is 0 to 0.615 as calculated according to formula (3);

C＝K₂O/(K₂O+Na₂o) formula (3);

d is 0 to 0.98 as calculated according to formula (4);

d is MgO/(CaO + ZnO + MgO + BaO) formula (4);

e is 0 to 0.998 as calculated according to formula (5);

e ═ CaO/(CaO + ZnO + MgO + BaO) formula (5);

f is 0 to 0.5 as calculated according to formula (6);

f ═ ZnO/(CaO + ZnO + MgO + BaO) formula (6);

wherein each component represents a mole percentage of that component in the borosilicate glass composition.

Optionally, the borosilicate glass composition contains 0 to 1.28 mole percent of a fluorine-containing compound selected from Na based on the total moles of the composition₂SiF₆、CaF₂NaF and MgF₂One or more of the above;

optionally, the borosilicate glass composition contains 0 to 0.5 mole percent of a chlorine-containing compound selected from the group consisting of NaCl and NaClO, based on the total moles of the composition₃And NaClO₄One or more of them.

Optionally, the borosilicate glass composition contains 0 to 0.003 mole percent of an inorganic sulfate selected from the group consisting of CaSO, based on the total moles of the composition₄、Na₂SO₄、K₂SO₄And MgSO₄One or more of them.

Optionally, the borosilicate glass composition contains 0.5 to 0.8 mole percent of K, based on the total moles of the composition₂O。

A second aspect of the present disclosure provides a method of making a borosilicate glass comprising: the borosilicate glass composition according to the first aspect of the present disclosure is subjected to melting treatment, clarification homogenization, molding treatment, and annealing treatment in this order.

Optionally, the conditions of the melt processing include: the melting temperature is more than 1500 ℃, and the melting time is more than 1 h;

the clarifying homogenization conditions include: the clarifying temperature is 1630-₂、NaCl、CaCl₂、CaF₂、NaF、Na₂SiF₆、Na₂One or more of S, CaS, MgS and ZnS; the content of the clarifying agent is 0.002-0.5 mol% based on the total moles of the composition.

A third aspect of the present disclosure provides a borosilicate glass produced by the method of the second aspect of the present disclosure.

Optionally, the borosilicate glass contains 0-0.5 mol% of chlorine and 0-1.5 mol% of fluorine, based on the total moles of the borosilicate glass₃The content of sulfur element is 0-0.006 mol%;

preferably, the chlorine content is 0.003-0.5 mol%, the fluorine content is 0.001-0.8 mol%, and SO is used₃The content of the sulfur element is 0 to 0.005 mol percent.

Optionally, the borosilicate glass has a resistivity of the glass melt at 1500 ℃ of 0 to 15 Ω -cm, preferably 0 to 10 Ω -cm.

The fourth aspect of the present disclosure provides the use of the borosilicate glass of the third aspect of the present disclosure in the medical field.

Through the technical scheme, the borosilicate glass composition can obtain the borosilicate glass with good physical and chemical properties and lower resistivity, can reduce energy loss in melting, improves the utilization rate of resources, and reduces the production cost of glass production enterprises. The borosilicate glass prepared by the method has the advantages of good chemical stability, low resistivity, low thermal expansion coefficient, good crystal stability and the like, is easy to melt and stretch, has less total alkali metal ion release, obviously reduces aluminum ion release, obviously reduces total ion release, and has excellent hydrolysis resistance. Can be used in the field of medicine, in particular for primary packaging of medicaments. Can also reduce production cost and CO₂The emission of greenhouse gases is equal, and the environment-friendly effect is achievedIn principle, large-scale pharmaceutical industrial production can be carried out.

Additional features and advantages of the disclosure will be set forth in the detailed description which follows.

Detailed Description

It should be understood that the detailed description and specific examples, while indicating the present disclosure, are given by way of illustration and explanation only, not limitation.

The present disclosure provides, in a first aspect, a borosilicate glass composition comprising, based on the total moles of the composition: 75-79 mol% SiO₂2-6 mol% of Al₂O₃8-12 mol% of B₂O₃0-2 mol% of K₂O, 5-7.5 mol% Na₂O, CaO 0.5-2 mol%, MgO 0-2 mol%, BaO 0-1 mol%, ZrO 0-1 mol%₂0 to 2 mol percent of ZnO and 0 to 0.05 mol percent of Se₂O₃0-0.05 mol% of MoO₃0 to 0.001 mol% of CeO₂0-0.015 mol% Fe₂O₃0 to 0.002 mol% of CuO and 0 to 0.002 mol% of La₂O₃。

The borosilicate glass composition provided by the present disclosure can result in borosilicate glass with good physicochemical properties and lower resistivity. The inventors have adjusted K in borosilicate glass compositions₂The content of O can obviously reduce the release amount of total alkali metal ions, so that the glass prepared by the borosilicate glass composition disclosed by the invention has good hydrolytic resistance. The amount of aluminium ions released is also significantly reduced compared to the prior art, thereby minimizing the health risks associated therewith.

In one embodiment, the borosilicate glass composition comprises, based on the total moles of the composition: 76-78 mol% SiO₂3-6 mol% of Al₂O₃9.5-10.5 mol% of B₂O₃0.001-0.8 mol% of K₂O, 5-7 mol% Na₂O, CaO 0.5-2 mol%, MgO 0.001-1 mol%, BaO 0.001-0.6 mol%, ZrO 0-0.03 mol%₂0.001 to 1.5 mol% ofZnO, 0.0001-0.05 mol% Se₂O₃0.0001-0.05 mol% of MoO₃0 to 0.001 mol% of CeO₂0 to 0.012 mol% Fe₂O₃0-0.0015 mol% of CuO and 0-0.0015 mol% of La₂O₃。

In one embodiment, K is present in the borosilicate glass composition based on the total moles of the composition₂The O content may be 0.001 to 1.8 mol%, preferably 0.001 to 1.5 mol%, more preferably 0.001 to 1 mol%, particularly preferably 0.001 to 0.8 mol%, most preferably 0.5 to 0.8 mol%. The inventors have found that K is useful in the present disclosure₂The content range of O not only can reduce the total release amount of alkali metal, but also can obviously reduce the release amount of other ions, such as aluminum ions. K of 0.5 mol% or more₂The O content can improve the hydrolysis resistance of the borosilicate glass. After the glass container is manufactured, the alkali metal borate therein is devitrified in a subsequent cooling process to destroy the glass structure, resulting in that the inner glass surface of the damaged container is exuded by reaction with the contained medicinal substance during the sterilization process, thereby causing the exuded glass portion to be decomposed in a scaly form. K of the disclosure₂The content range of O can effectively improve the crystallization of glass and reduce the damage of a glass container.

In one embodiment, the SiO in the borosilicate glass composition is based on the total moles of the composition₂The amount of (b) may range from 75 to 78 mole%, preferably from 75 to 77 mole%, or from 76 to 78 mole%, or from 75 to 76 mole%. The borosilicate glass composition provided by the present disclosure avoids SiO₂The melting temperature and the processing temperature are increased due to the over-high content, and the energy consumption is effectively reduced.

In one embodiment, the Al in the borosilicate glass composition is based on the total moles of the composition₂O₃The content of (b) may be 2 to 5 mol%, or 3 to 6 mol%, preferably 2 to 4 mol%, and more preferably 3 to 4 mol%. Al (Al)₂O₃The addition of (A) results in a relatively compact structure of the glass, which is capable of considerably reducing the release of alkali metals when it is attacked by aqueous solutions, andAl₂O₃the devitrification stability of the glass can be improved.

In one embodiment, B is present in the borosilicate glass composition based on the total moles of the composition₂O₃The amount of (b) may be 8 to 10 mole%, or 10.5 to 11.5 mole%, or 8 to 9 mole%, or 9.5 to 10.5 mole%. B in the composition₂O₃The hydrolytic resistance of the glass is improved, so that alkali metal ions can be firmly connected in the glass structure, and meanwhile, evaporation in the container molding process caused by overhigh boron content can be avoided.

In one embodiment, Na is present in the borosilicate glass composition based on the total moles of the composition₂The content of O is preferably 6.5 to 7.5 mol%, or 5 to 7 mol%.

In one embodiment, the amount of CaO in the borosilicate glass composition may be in the range of 0.5 to 1.84 mole percent, preferably 0.8 to 1.84 mole percent, based on the total moles of the composition. The addition of calcium lowers the processing temperature and can improve the acid resistance of borosilicate glass.

In one embodiment, the content of BaO in the borosilicate glass composition is preferably 0.001 to 0.6 mol%, and more preferably 0.001 to 0.5 mol%, based on the total number of moles of the composition.

In one embodiment, the ZrO in the borosilicate glass composition is based on the total moles of the composition₂The content of (b) is preferably 0.001 to 0.05 mol%, or 0 to 0.03 mol%. ZrO (ZrO)₂The hydrolysis resistance can be improved to a large extent.

In one embodiment, the amount of ZnO in the borosilicate glass composition is in the range of 0.001 to 1.5 mole percent, preferably 0.001 to 1 mole percent, based on the total moles of the composition. The content range of ZnO in the borosilicate glass composition of the present disclosure helps to improve crystal stability, while also reducing the resistivity of the glass under high temperature conditions.

According to one embodiment of the present disclosure, the borosilicate glass composition contains CeO in an amount of 0 to 0.001 mol% based on the total number of moles of the composition₂(ii) a In a preferred embodiment, CeO₂Of (1) containsThe amount was 0.001 mol%. Glass containers in the medical field are generally required to be sterilized before filling, and are also required to be sterilized by high-energy rays (e.g., β rays, γ rays, strong ultraviolet rays) in addition to heat sterilization at a temperature of about 250 to 300 ℃ or ultra-high-temperature steam sterilization. Glass containers may appear yellow or even brown due to the radiation dose used. CeO (CeO)₂The addition of (2) can avoid such a situation, so that the prepared glass product is stable to radiation and does not change color in the disinfection process carried out by high-energy radiation.

According to one embodiment of the present disclosure, the composition comprises, in mole percent:

calculated according to formula (1) A is 0.5-4.05 mol%;

a ═ MgO + CaO + BaO + ZnO formula (1);

b is obtained in a proportion of 5 to 9.3 mol% calculated according to formula (2);

B＝K₂O+Na₂o formula (2);

c is 0 to 0.615 as calculated according to formula (3);

C＝K₂O/(K₂O+Na₂o) formula (3);

d is 0 to 0.999 calculated according to the formula (4);

d is MgO/(CaO + ZnO + MgO + BaO) formula (4);

e is 0 to 0.999 calculated according to formula (5);

e ═ CaO/(CaO + ZnO + MgO + BaO) formula (5);

f is 0 to 0.6 as calculated according to formula (6);

f ═ ZnO/(CaO + ZnO + MgO + BaO) formula (6);

wherein each component represents a mole percentage of that component in the borosilicate glass composition. Preferably, A is 0.5 to 1.901 mole%, B is 5 to 7.3 mole%, D is 0 to 0.98, E is 0 to 0.998, and F is 0 to 0.5.

The inventors of the present disclosure have unexpectedly found that, in the case where the content of each component in the borosilicate glass composition satisfies the range of A, B, C, D, E and F defined by formula (1) -formula (6), a synergistic effect between the components of the glass composition can be achieved, the electrical conductivity of the prepared borosilicate glass is further reduced, the physicochemical properties are further improved, and the temperature variation stability of the borosilicate glass is further improved.

In accordance with the present disclosure, the borosilicate glass composition contains 0 to 1.28 mole percent, preferably 0.5 to 1.28 mole percent, of a fluorine-containing compound, based on the total moles of the composition; the fluorine-containing compound is selected from Na₂SiF₆、CaF₂NaF and MgF₂One or more of the above; specifically, the fluorine-containing compound is Na₂SiF₆And/or CaF₂The mixture needs to be subjected to high-temperature melting treatment for preparing the glass, and the addition of the fluorine-containing compound can effectively reduce the viscosity, the high-temperature surface tension and the high-temperature volume resistivity of the glass melt. The amount of fluorochemical in the compositions of the present disclosure avoids opacification and devitrification due to excess fluoride.

According to the present disclosure, the borosilicate glass composition contains 0 to 0.5 mole percent of a chlorine-containing compound, based on the total moles of the composition; preferably, 0.003-0.5 mol% of chlorine-containing compound; the chlorine-containing compound is selected from NaCl and NaClO₃And NaClO₄One or more of the above; preferably NaCl.

According to the disclosure, the content of fluorine-containing compounds and chlorine-containing compounds in the borosilicate glass composition is not particularly required, and the prepared borosilicate glass can meet the requirements that the content of chlorine is 0-0.5 mol% and the content of fluorine is 0-1.5 mol%.

According to the present disclosure, the borosilicate glass composition contains 0 to 0.003 mole percent of an inorganic sulfate selected from the group consisting of CaSO, based on the total moles of the composition₄、Na₂SO₄、K₂SO₄And MgSO₄Preferably CaSO₄And/or Na₂SO₄The addition of the inorganic sulfate can eliminate gaseous inclusions contained in the composition.

A second aspect of the present disclosure provides a method of making a borosilicate glass comprising: the borosilicate glass composition according to the first aspect of the present disclosure is subjected to melting treatment, clarification homogenization, molding treatment, and annealing treatment in this order.

According to the present disclosure, the conditions of the melt processing include: the melting temperature is more than 1500 ℃, the melting time is more than 1h, preferably, the melting temperature is 1580 ℃ and the melting time is 1-8 h; the melting treatment mode of the borosilicate glass composition is selected from one or more of a continuous melting tank, electric heating and gas heating; preferably, electric heating and/or gas heating are used, wherein the electric heating refers to heating the mixture directly through a plurality of groups of paired electrodes to promote the completion of the processes of reaction, clarification homogenization and the like, and the electrodes can be molybdenum oxide electrodes or platinum electrodes. The specific melting temperature and melting time can be determined by those skilled in the art according to practical situations, which are well known to those skilled in the art and will not be described herein.

The clarifying homogenization conditions include: the clarifying temperature is 1630-₂、NaCl、CaCl₂、CaF₂、NaF、Na₂SiF₆、Na₂One or more of S, CaS, MgS and ZnS; the content of the clarifying agent is 0.002-0.5 mol% based on the total moles of the composition; preferably, the clarifying agent is selected from NaCl, CaF₂And Na₂SiF₆One or more of them. The disclosed solution uses a composite fining agent, i.e., fining homogenization with two or more fining agents, each of which performs bubble removal in the glass at a different temperature, e.g., CeO₂Removing bubbles from clarifier at 1300-1450 deg.C, removing bubbles from NaCl clarifier at above 1400 deg.C, and removing CaF₂And Na₂SiF₆Bubble removal was performed above 1500 ℃. Other steps for preparing borosilicate glass are conventional in the art and will not be described in detail herein.

A third aspect of the present disclosure provides a borosilicate glass produced by the method of the second aspect of the present disclosure.

According to the present disclosure, the borosilicate glass contains 0 to 0.5 mol% of chlorine and 0 to 1.5 mol% of fluorine, based on the total number of moles of the borosilicate glass₃The sulfur content is 0-0.006 mol%(ii) a Preferably, the chlorine content is 0.003-0.5 mol%, the fluorine content is 0.001-0.8 mol%, and SO is used₃The content of the sulfur element is 0 to 0.005 mol percent.

According to the present disclosure, the borosilicate glass has a resistivity of the glass melt of 0 to 15 Ω · cm, preferably 0 to 10 Ω · cm, at 1500 ℃. The coefficient of thermal expansion CTE (50-380 ℃ C.) is in the range of 52X 10^-7-55.1×10^-7/K。

The borosilicate glass prepared by the method has the advantages of good chemical stability, low resistivity, good crystal stability and the like, and can reduce the production cost and reduce CO₂The emission of greenhouse gases is equal, the environment-friendly principle is met, and the prepared borosilicate glass is more suitable for the production of medicinal glass.

The fourth aspect of the present disclosure provides the use of the borosilicate glass of the third aspect of the present disclosure in the medical field.

The borosilicate glass of the present disclosure can be relatively easily melted and drawn, for example, into a tube by the Danner-tube drawing process. While pharmaceutical containers and primary packages made of glass are generally made by thermoforming, the borosilicate glass of the present disclosure is very suitable for primary packaging of pharmaceuticals, while pharmaceutical substances stored in the container, especially aqueous or water-containing pharmaceutical substances, such as aqueous solutions, injections, do not significantly intrude into the borosilicate glass, so that the glass does not release or rarely releases ions.

The applications of the borosilicate glass of the present disclosure in the medical field include all broad meanings of the type, size and shape of the glass container. This means a glass hollow body of all shapes that can be closed and used in the medical field, such as bottles (tubes), ampoules, syringes, etc.

The present disclosure is further illustrated by the following examples, but is not limited thereto.

In the examples and comparative examples, various reagents used were commercially available.

The physicochemical properties were tested according to the following methods:

(1) the acid resistance test method comprises the following steps: see GB/T15728-1995.

(2) Alkali resistance test method: reference is made to the method of GB/T6580-1997.

(3) Water resistance test method: see GB/T15728-1995.

(4) Annealing point temperature and strain point temperature: the annealing point and strain point of the glass were measured in degrees Celsius using an annealing strain point tester according to ASTM C-336.

(5) Softening point temperature: the softening point of the glass was determined using a softening point tester, using the reference ASTM C-338, in degrees Celsius.

(6) Young's modulus: the Young's modulus of the glass was measured in GPa using a mechanical testing machine in accordance with ASTM C-623.

(7) Vickers hardness: measured using a Vickers hardness tester in MPa.

(8) Density: the method of GB/T7962.20-2010 is adopted.

(9) Poisson ratio: the method of GB/T31544-2015 is adopted.

(10) Coefficient of expansion CTE (50-380 ℃): the method of GB/T169920-.

(11) Resistivity (1500 ℃): the bridge method is adopted.

(12) Test method of Cl and F element content: the method of GB/T15549-2008 is adopted.

(13)SO₃The test method (2): an inductively coupled plasma atomic emission spectroscopy (ICP) method is used.

Examples 1-19 are illustrative of borosilicate glass compositions and borosilicate glasses of the present disclosure and methods of making the same.

The borosilicate glass is prepared by the following method:

the raw materials of examples 1 to 19 shown in tables 1 to 5 were weighed, mixed, and melt-processed at 1630 ℃ for 2.5 to 4.5 hours in a platinum crucible. Then, the melted glass liquid is clarified and homogenized at the temperature of 1636-₂、Na₂SiF₆The total amount of fining agent was 0.1 mol%, and then the glass was shaped on a steel plate to form a bulk glass. Then annealing the glass product for 1-2 hours at an annealing temperatureAt 553-575 ℃. And cooling and cutting to obtain 50 × 20 × 25mm block borosilicate glass product. Various performance tests are carried out on the prepared borosilicate glass, and the contents of F element and Cl element in the finished product glass are tested by adopting the method of GB/T15549-2008, and the results are listed in tables 1-5.

TABLE 1

TABLE 2

TABLE 3

TABLE 4

TABLE 5

As can be seen from the data in tables 1 to 5, the borosilicate glass composition of the present disclosure can obtain a borosilicate glass having good physicochemical properties and a relatively low resistivity, and the prepared borosilicate glass has the advantages of good chemical stability, low resistivity, low thermal expansion coefficient, good crystal stability, etc., and is also sufficiently stable in melting, stretching and crystallization, and can be used in the field of medicine, particularly in primary packaging of drugs. As can be seen by comparing the data of examples 1-4 with those of examples 5-19, in a preferred embodiment of the present invention, the borosilicate glass composition comprises, based on the total moles of the composition: 76-78 mol% SiO₂3-6 mol% of Al₂O₃9.5-10.5 mol% of B₂O₃0.001-0.8 mol% of K₂O, 5-7 mol% Na₂O, CaO 0.5-2 mol%, MgO 0.001-1 mol%, BaO 0.001-0.6 mol%, ZrO 0-0.03 mol%₂0.001-1.5 mol% of ZnO, 0.0001-0.05 mol% of Se₂O₃0.0001-0.05 mol% of MoO₃0 to 0.001 mol% of CeO₂0 to 0.012 mol% Fe₂O₃0-0.0015 mol% of CuO and 0-0.0015 mol% of La₂O₃(ii) a And according to the mole percentage, A is 0.5-1.901 mole percent, B is 5-9.3 mole percent, C is 0-0.615, D is 0-0.98, E is 0-0.998, F is 0-0.5, the borosilicate glass composition disclosed by the invention has lower resistivity, and has good acid and alkali resistance and stable property.

The preferred embodiments of the present disclosure have been described in detail above, however, the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all fall within the protection scope of the present disclosure.

It should be noted that, in the foregoing embodiments, various features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various combinations that are possible in the present disclosure are not described again.

In addition, any combination of various embodiments of the present disclosure may be made, and the same should be considered as the disclosure of the present disclosure, as long as it does not depart from the spirit of the present disclosure.