阅读说明：本技术 一种中硼硅药用玻璃 (Medical glass of medium borosilicate ) 是由 田英良 赵志永 于 2021-10-25 设计创作，主要内容包括：本发明公开了一种中硼硅药用玻璃,以质量百分比计,其化学组成,包括：Al-(2)O-(3)2-4,B-(2)O-(3)8-9,且Al-(2)O-(3)+B-(2)O-(3)11-12；ZnO 2-4,ZrO-(2)1-2,且ZnO+ZrO-(2)3-6；Li-(2)O+Na-(2)O+K-(2)O 6-8,且Li-(2)O:Na-(2)O:K-(2)O＝3:6:1；CaO+SrO 2-4,且CaO:SrO为(6～8):(2～4),其余为SiO-(2)。本发明所制备的中硼硅药用玻璃具有高化学稳定性、低温熔化、低B-(2)O-(3)挥发、低热膨胀系数。(The invention discloses a medium borosilicate medicinal glass, which comprises the following chemical components in percentage by mass: al (Al) 2 O 3 2‑4，B 2 O 3 8-9, and Al 2 O 3 +B 2 O 3 11‑12；ZnO 2‑4，ZrO 2 1-2 and ZnO + ZrO 2 3‑6；Li 2 O+Na 2 O+K 2 O6-8, and Li 2 O:Na 2 O:K 2 O is 3:6: 1; CaO + SrO 2-4, wherein the CaO is (6-8): (2-4), and the rest is SiO 2 . The medium borosilicate medicinal glass prepared by the invention has high chemical stability, low-temperature melting and low B content 2 O 3 Volatilization and low thermal expansion coefficient.)

1. The medium borosilicate medicinal glass is characterized by comprising the following chemical components in percentage by mass:

Al₂O₃，2-4

B₂O₃，8-9

and Al₂O₃+B₂O₃，11-12

ZnO，2-4

ZrO₂，1-2

And ZnO + ZrO₂，3-6

Li₂O+Na₂O+K₂O，6-8

And Li₂O:Na₂O:K₂O＝3:6:1

CaO+SrO，2-4

And CaO SrO is (6 to 8): (2 to 4)

The balance being SiO₂。

2. The medium borosilicate medicinal glass of claim 1 wherein said Al is₂O₃The raw material of the material is aluminum hydroxide.

3. The medium borosilicate medicinal glass of claim 1 wherein B is₂O₃The raw material of the medicament is borax pentahydrate.

4. The medium borosilicate medicinal glass according to claim 1 wherein said ZrO₂The raw material of the zircon powder is zircon powder.

Technical Field

The invention belongs to the technical field of glass, relates to medium borosilicate medicinal glass, and particularly relates to high-chemical-stability, low-temperature-melting and low-B-content medicinal glass₂O₃Volatile, low thermal expansion coefficient medium borosilicate medical glass.

Background

The Chinese borosilicate medicinal glass is the most internationally recognized and safe medicine packaging material and is widely applied globally. China calls the borosilicate glass as neutral borosilicate, neutral glass, 5.0 medical glass, class A material and the like, and the borosilicate glass is called as the medium borosilicate medical glass in a unified way at present under the constraint of academic specifications and 2013 version YYB standard.

In 1901, german schottky (schottky) company invented a medium borosilicate medicinal glass with excellent chemical and thermal stability, which mainly benefits from its own chemical composition, and its typical chemical composition is SiO in percentage by mass after continuous development and many iterative advances₂ 70～75，Al₂O₃ 5～7，B₂O₃ 9.5～10.5，CaO+BaO 1～3.5，Na₂O+K₂O7-9; a coefficient of linear thermal expansion of (4.9 to 5.4) x 10 at 20 to 300 DEG C^-6The water resistance I grade requirement of the inner surface of ASTM E438 and ISO 12775 can be met.

At present, only German Schottky corporation (Schott), Japanese electric glass Nitroson corporation (NEG), American Corning corporation (Corning) and other companies can stably produce medium borosilicate medicinal glass, China is influenced by a plurality of factors such as lack of boron resources, low industrial manufacturing technical level, low consumption level and the like, low borosilicate medicinal glass (commonly called second grade material) is used as a substitute of water-resistant I-grade medicinal glass for 60 years in the 20 th century, and therefore China is not completely and internationally effectively connected in the aspect of medicinal glass packaging materials.

The comprehensive physical and chemical properties of the medium borosilicate medicinal glass are superior to those of low borosilicate medicinal glass, but the medium borosilicate medicinal glass faces the problems of high production cost, difficult melting and forming and the like, enterprises carry out multiple technical challenges in the 80 s of the 20 th century in China, and the production technology of the medium borosilicate medicinal glass cannot be comprehensively broken through all the time.

In the face of the international market of economic integration and the social background of the high-speed development of the Chinese medical industry, in the face of the emergence of various new medicines and special-effect medicines and the need of guaranteeing the life health of people, the pharmaceutical glass industry of China urgently needs to meet the international orbit and be consistent with the realization of the international medical packaging material standard.

The manufacturing difficulty of the medium borosilicate medicinal glass is mainly caused by the particularity of the chemical composition of the glass, because the glass uses Al in large quantity₂O₃And B₂O₃，Al₂O₃Plays an important role in inhibiting the phase separation of the glass, but the melting temperature of the glass is as high as 2045 ℃, exceeds the melting temperature of a common melting furnace (1580-1620 ℃) and approaches to 500 ℃, and in addition, Al₂O₃The density was 4.0g/cm³Average density of borosilicate medical glass in the ratio of 2.4g/cm³The glass is higher than 60%, which not only causes glass to be infusible, but also induces the glass liquid to generate delamination condition, and is easy to form glass stripe defects. In addition B₂O₃The melting point is only 450 ℃, and under the melting temperature condition of 1580-1620 ℃ of the melting furnace, strong B is generated₂O₃Volatilization, the volatile amount accounts for 15-18% of the use content of the product, even the productHigher due to B₂O₃The volatilization in the high-temperature melting process causes the surface components of the glass to be greatly changed, and silicon-rich glass components are formed on the surface of the molten glass. Al in chemical composition of medium borosilicate medicinal glass₂O₃And B₂O₃Under the combined action, the melting problem of the medium borosilicate medicinal glass is formed, and if the melting temperature is expected to be reduced to reduce B₂O₃Volatile but Al₂O₃But also is not easy to melt, the melting period is prolonged, and the energy saving of glass melting is not facilitated. If the melting temperature is increased, it is desirable to improve the melting quality, but B₂O₃The volatilization becomes so severe that there is a dilemma in melting the borosilicate medical glass.

The chemical stability of the Chinese borosilicate medicinal glass needs to meet the requirements of ISO719 water-resistant performance HGB1, DIN12116 acid-resistant S1 and ISO695 alkali-resistant A2.

Based on the current situation and problems of the prior borosilicate medicinal glass, the expansion coefficient does not exceed 5.4 multiplied by 10 under the premise of achieving chemical stability^-6/° c, the constraint condition of thermal shock stability is satisfied, the chemical composition of the conventional borosilicate medical glass needs to be innovated, and high chemical stability, low-temperature melting and low B content are realized₂O₃Volatile, low thermal expansion coefficient medium borosilicate medical glass.

Disclosure of Invention

In view of the above problems in the prior art, the present invention provides a high chemical stability, low temperature melting, low B₂O₃Volatile, low thermal expansion coefficient medium borosilicate medical glass.

The invention discloses a medium borosilicate medicinal glass, which comprises the following chemical components in percentage by mass:

Al₂O₃，2-4

B₂O₃，8-9

and Al₂O₃+B₂O₃，11-12

ZnO，2-4

ZrO₂，1-2

And ZnO + ZrO₂，3-6

Li₂O+Na₂O+K₂O，6-8

And Li₂O:Na₂O:K₂O＝3:6:1

CaO+SrO，2-4

And CaO SrO is (6 to 8): (2 to 4)

The balance being SiO₂。

As a further improvement of the invention, the Al₂O₃The raw material of the material is aluminum hydroxide.

As a further improvement of the invention, B is₂O₃The raw material of the boron-silicon-boron mixed material is borosilicate.

As a further improvement of the invention, the ZrO₂The raw material of the zircon powder is zircon powder.

Compared with the prior art, the invention has the beneficial effects that:

the medium borosilicate medicinal glass prepared by the invention has high chemical stability, excellent water resistance and acid resistance, and alkali resistance index reaching A1 level standard (less than 75 mg/dm)²)；

The melting temperature of the medium borosilicate medical glass prepared by the invention is low, and the melting temperature (T2) is 1475-1589 ℃;

the thermal expansion coefficient of the medium borosilicate medicinal glass prepared by the invention is (4.5-5.4) multiplied by 10^-6The temperature is lower than the temperature of the traditional Chinese medicine borosilicate medical glass;

b of the borosilicate medical glass prepared by the invention₂O₃The volatilization amount is reduced by 10 to 52 percent.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.

The invention is described in further detail below:

the invention provides a high chemical stability, low temperature melting, low B₂O₃The chemical composition of the volatile and low-thermal expansion coefficient medium borosilicate medicinal glass comprises the following components in percentage by mass: SiO 2₂、Al₂O₃、B₂O₃、ZnO、ZrO₂、Li₂O、Na₂O、K₂O, CaO and SrO, and Al₂O₃And B₂O₃Common, ZnO and ZrO₂In common, Li₂O、Na₂O、K₂O is shared, and CaO and SrO are shared.

The method specifically comprises the following steps:

Al₂O₃，2-4

B₂O₃，8-9

and Al₂O₃+B₂O₃，11-12

ZnO，2-4

ZrO₂，1-2

And ZnO + ZrO₂，3-6

Li₂O+Na₂O+K₂O，6-8

And Li₂O:Na₂O:K₂O＝3:6:1

CaO+SrO，2-4

And the weight ratio of CaO to SrO is (6 to 8) to (2 to 4)

The balance being SiO₂。

The invention provides a preparation method of the medium borosilicate medicinal glass, which comprises the following steps: selecting proper raw materials from the chemical groups, carrying out raw material weighing and mixing according to the formula of the glass which is taken into effective chemical components of the raw materials to form a batch, putting the batch into a glass melting furnace, converting the batch into glass liquid under the energy action of the melting furnace, eliminating solid phase and bubbles, preparing uniform glass liquid, and then carrying out drawing molding or die molding on the glass liquid to prepare a glass tube or a glass bottle.

The medium borosilicate medicinal glass provided by the invention comprises the following oxide components and effects:

Al₂O₃mainly used for inhibiting phase separation of borosilicate glass and promoting partial Al₂O₃The tetrahedron is used for entering the network, which is beneficial to improving the mechanical property and the chemical stability, and the raw material is preferably aluminum hydroxide.

B₂O₃Has the functions of fluxing, reducing the expansion coefficient, improving the thermal stability, strengthening the network structure and blocking the migration of alkali metal ions, and the borax pentahydrate is preferably used as the raw material.

ZnO has fluxing, reduces expansion coefficient, promotes compact network structure, blocks alkali metal ion migration, contributes to improving the chemical stability of glass, and zinc oxide is preferably used as a raw material.

ZrO₂The alkali resistance of the glass is mainly improved, the corrosion of an alkali injection to a glass internal label is solved, and the raw material is preferably zircon powder.

Li₂O、Na₂O、K₂O plays roles of fluxing, oxygen supply and expansion coefficient adjustment, the single construction energy of Li-O is as high as 150.7kJ/mol, and oxygen ions (O)^2-) For lithium ion (Li)⁺) Has strong drag effect, the single construction energy of the material is 2 to 3 times of that of Na-O, K-O respectively, when Li is used₂O+Na₂O+K₂O is 6-8 wt% and Li₂O:Na₂O:K₂When O is 3:6:1, the comprehensive performance can be optimized in all aspects, and Li₂O、Na₂O、K₂The corresponding carbonate species are preferably used for O.

The alkaline earth metal oxide mainly plays a role in high-temperature fluxing, and is particularly mixed with SiO₂、Al₂O₃The combination is not obvious in network fracture, CaO and SrO are preferably used together in the invention, the CaO raw material is preferably calcite, and the SrO raw material is preferably strontium carbonate; the method fully considers that BaO belongs to heavy metal oxide ions with larger radius, and in addition, after the ions of the BaO migrate into the liquid medicine, the solubility of the BaO is relatively low, and the BaO is easy to combine with other anions to form precipitates; SrO completely avoids the defects, the function of SrO in fluxing is equivalent to that of BaO, the weight ratio of CaO + SrO is 2-4, and the weight ratio of CaO to SrO is (6-8) ((S))2-4) is optimal.

Example (b):

the evaluation characterization method and the test result of the physicochemical process performance of the borosilicate medicinal glass in the physicochemical property aspect are shown in the table 1.

Test evaluation characterization methods were as follows:

1. water resistance ISO 719;

2. acid resistance DIN 1211;

3. alkali resistance ISO 695;

4. expansion coefficient GB/T1697;

5. the high-temperature viscosity SJ/T11040 is used for measuring the temperature corresponding to the viscosity of the glass liquid of 100 poise, is called as the melting temperature and is abbreviated as T2; the temperature corresponding to 10000 poise of viscosity of the glass liquid is also measured, which is called as working temperature and is abbreviated as T4;

6. softening point temperature GB/T28195 for measuring glass viscosity of 10^7.6Poise corresponding temperature, called softening point temperature, abbreviated as T7.6;

7. boron volatilizees and measures, adopts simulation experiment device to carry out contrastive analysis to horizontal corundum pipe laboratory furnace, puts into diameter 80mm platinum watch glass with 200 grams of batch mixture, heats according to melting process curve, sends into the mist of simulation flue gas from tube furnace one end: discharging mixed gas of 10% oxygen, 35% carbon dioxide and 55% nitrogen simulating smoke from the other end of the tube furnace, receiving the mixed gas into a collecting tube, sending the mixed gas into a condensation collecting bottle, wherein 5% alkaline solution is contained in the bottle, and the unabsorbed gas is discharged, and recording the weight gain change of the collecting bottle, wherein the weight gain quality mainly comes from boron oxide volatile matters and acid gas. The increased mass absorbed by the boron oxide is reflected by the difference in the gain in g. The melting profile was raised from room temperature to the melting temperature (T2) for 3 hours and then held at the melting temperature (T2) for 5 hours.

TABLE 1

The comparative analysis is carried out by combining 8 examples (1# -8 #) and 1 comparative example (typical representative of international high-quality borosilicate medical glass) shown in the table 1 to prove the innovativeness and good technical effect of the invention. In accordance with the objects of the present invention and the problems of the prior art borosilicate medicinal glass, the subject of the present invention is to achieve a chemical composition of the borosilicate medicinal glass with low expansion, low volatility and high chemical stability, and to develop a multi-dimensional innovation in the glass composition, the invention has fully stated the necessity and effect of using the relevant oxides, and to provide a limited range of the used amount, which has completely different characteristics from the prior art borosilicate medicinal glass chemical composition.

In the aspect of physical and chemical process performance, the expansion coefficient of the medium borosilicate medicinal glass is better controlled to be alpha (4.5-5.4) multiplied by 10^-6The temperature per DEG C provides better technical guarantee for the thermal shock stability of the glass, and the theoretical thermal shock stability delta T is 11500 multiplied by 10^-6A/alpha, expansion coefficient (4.9-5.4) multiplied by 10 of the traditional borosilicate medical glass^-6/° c.

Through systematic innovation and optimization of chemical composition, the melting temperature (T2) of the medium borosilicate medicinal glass is only 1475-1589 ℃, and is reduced by 37-151 ℃ compared with 1626 ℃ of a comparative example, so that the glass melting clarification temperature is reduced, the boron oxide content is reduced by 1-1.5 wt%, and the volatilization amount of a glass batch in the melting process can be effectively reduced under the synergistic action of a system, and the data in the table 1 show that the volatilization mass of the comparative example is 4.8g, the volatilization mass of the invention is 2.3-4.3 g, and the volatilization mass of the invention is reduced by 10-52% compared with that of the comparative example.

In addition, in the aspect of chemical stability, the medium borosilicate medicinal glass also has better effect, has better effect in water resistance and acid resistance, and has the biggest bright point that the alkali resistance index reaches A1-grade standard (less than 75 mg/dm)²) While the alkali resistance index of the comparative example is 100mg/dm²It is A2-grade standard (75 mg/dm)²～175mg/dm²) It is fully demonstrated that the present invention makes a great technical advance.

The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.