阅读说明：本技术 一种耐碱玻璃及其制备方法和应用 (Alkali-resistant glass and preparation method and application thereof ) 是由 曹振博 贾金升 李自金 李开宇 吕学良 孙勇 那天一 张敬 洪升 郑京明 于 2020-04-30 设计创作，主要内容包括：本发明涉及一种耐碱玻璃及其制备方法和应用。所述的耐碱玻璃按重量百分比计,包含以下组分：SiO<Sub>2</Sub> 47-69％；B<Sub>2</Sub>O<Sub>3</Sub> 2.6-4.5％；Al<Sub>2</Sub>O<Sub>3</Sub> 0.5-2.5％；第一组分9-13％；第二组分9-20.5％；ZrO<Sub>2</Sub> 7.6-12％；HfO<Sub>2</Sub> 0-1％；还包含澄清剂；所述澄清剂为CeO<Sub>2</Sub>；所述CeO<Sub>2</Sub>的重量占所述耐碱玻璃重量的0.10％-0.30％；所述的玻璃的制备包括以下步骤：按玻璃组分的配方量将原料混合,得到第一混合物；在所述的第一混合物中加入澄清剂CeO<Sub>2</Sub>,得到第二混合物；将所述的第二混合物经熔制、机械搅拌、辅助鼓泡澄清、漏制或压制成型。本发明所述的耐碱玻璃同时具有优异的耐碱金属侵蚀性能和光学透过性能,并具有较长的料性,可应用在需多次反复加工领域,玻璃加工性能优异。(The invention relates to alkali-resistant glass and a preparation method and application thereof. The alkali-resistant glass comprises the following components in percentage by weight: SiO 2 2 47‑69％；B 2 O 3 2.6‑4.5％；Al 2 O 3 0.5-2.5%; 9-13% of a first component; 9-20.5% of a second component; ZrO (ZrO) 2 7.6‑12％；HfO 2 0 to 1 percent; also comprises a clarifying agent; the clarifying agent is CeO 2 (ii) a The CeO 2 The weight of the alkali-resistant glass accounts for 0.10 to 0.30 percent of the weight of the alkali-resistant glass; the preparation of the glass comprises the following steps: mixing the raw materials according to the formula amount of the glass components to obtain a first mixture; adding a clarifying agent CeO into the first mixture 2 Obtaining a second mixture; and melting, mechanically stirring, carrying out auxiliary bubbling clarification, and carrying out leakage or compression molding on the second mixture. The alkali-resistant glass provided by the invention has excellent alkali-resistant metal corrosion resistance and optical transmission performance, has longer material property, can be applied to the field needing repeated processing, and has excellent glass processing performance.)

1. The alkali-resistant glass is characterized by comprising the following components in percentage by weight:

the first component is Na₂O, or Na₂O and Li₂O; the second component comprises CaO and BaO;

also comprises a clarifying agent; the clarifying agent is CeO₂(ii) a The CeO₂The weight of the alkali-resistant glass accounts for 0.10-0.30% of the weight of the alkali-resistant glass.

2. Alkali resistant glass according to claim 1, wherein said Na₂The content of O is more than or equal to the Na in percentage by weight₂O and Li₂91% of the total weight of O.

3. The alkali-resistant glass of claim 1, wherein the second component further comprises MgO and SrO; the weight of the CaO accounts for 51 to 66.7 percent of the total weight of the second component.

4. The alkali-resistant glass of claim 1, wherein the alkali-resistant glass further comprises HfO₂Said HfO₂Is less than 1% of the total weight of the alkali-resistant glass.

5. The alkali-resistant glass of claim 1, wherein the optical properties of the alkali-resistant glass are: in rubidium atomic clock spectral luminescent bubble⁸⁷The optical transmittance at characteristic spectral lines of D1(795nm) and D2(780nm) emitted by Rb atoms is more than or equal to 90 percent, and the alkali-resistant metal property of the alkali-resistant glass is that the consumption of rubidium interacting with metal rubidium is less than or equal to (0.9 +/-0.15) × t^1/2(ii) a The alkali-resistant solution property of the alkali-resistant glass is as follows: reaching grade A1 according to DIN ISO 695 standard of SCHOTT company; the working point temperature of the alkali-resistant glass is T_wNot less than 1085 ℃ and the softening point temperature is T_sAt most 830 deg.C, material property (T)_w-T_s) Not less than 255 ℃, and the thermal expansion coefficient of the alkali-resistant glass at 20-300 ℃ is (60-70) × 10^-7/° c; the times of the alkali-resistant glass which can be repeatedly processed and has unchanged performance are more than or equal to10 times.

6. A method of making alkali-resistant glass as claimed in any one of claims 1 to 5, comprising the steps of:

mixing the raw materials according to the formula of the glass component to obtain a first mixture; adding a clarifying agent into the first mixture, and mixing to obtain a second mixture; melting, mechanically stirring, bubbling and clarifying in an auxiliary way, and performing leakage or compression molding on the second mixture to obtain the alkali-resistant glass;

the clarifying agent is CeO₂(ii) a The CeO₂The weight of the alkali-resistant glass accounts for 0.10-0.30% of the weight of the alkali-resistant glass.

7. The method according to claim 6, wherein the raw materials comprise quartz sand, boric acid, aluminum hydroxide, sodium nitrate, barium nitrate, calcium nitrate and zirconium dioxide.

8. The method of claim 7, wherein the feedstock further comprises basic magnesium carbonate, strontium carbonate, lithium nitrate, and hafnium oxide; the weight of the barium nitrate, the calcium nitrate, the sodium nitrate and the lithium nitrate accounts for more than 90 percent of the total weight of the nitrate and the carbonate.

9. The method of claim 6, wherein the mechanical agitation is performed at a speed of 5 to 30 r/min; the melting temperature is 1450-1550 ℃; the molding temperature is 1080-1200 ℃.

10. A spectrally luminescent glass bubble, characterized in that it is composed of an alkali-resistant glass tube, said alkali-resistant glass tube being composed of the alkali-resistant glass according to any one of claims 1 to 5.

Technical Field

The invention relates to a special glass material, in particular to alkali-resistant glass and a preparation method and application thereof.

Background

Alkali-resistant (metallic) glass is used as one of special glass materials, is usually applied to high-precision alkali-resistant glass devices, and is widely applied under extreme conditions of aviation, aerospace, nuclear detection and the like. Because alkali metal atoms (such as sodium vapor, rubidium atoms and the like) have extremely strong reducibility, the alkali metal atoms can reduce the elements which are easy to change valence in the glass, and even can deprive the oxygen atom position in the Si-O framework of the glass to form a complex structure of Si-R (R is the alkali metal element), so that the alkali metal atoms and the glass are consumed after chemical action. Therefore, the alkali (metal) resistant environment is completely different from the alkali (solution) resistant environment, the application conditions are severe, and the alkali (metal) resistant environment is generally evaluated by the consumption of alkali metal elements.

One of typical application environments is a spectrum luminescent glass bubble of a rubidium atomic clock, a key index for measuring alkali resistance of glass is consumption of rubidium metal atoms, and the consumption of rubidium is small, which shows that the alkali resistance of glass is excellent. The rubidium luminescent bubble is made of an alkali-resistant glass tube, and the chemical reaction between glass and metal rubidium can be effectively prevented and weakened due to the excellent alkali-resistant characteristic. Meanwhile, the luminous bulb is made of alkali-resistant glass through multiple processing (mechanical drawing, lamp blowing and the like), the thickness of the luminous bulb is usually below 0.1mm, even below 0.01mm, and the basic performance of the alkali-resistant glass is required to be unchanged under the repeated processing for multiple times so as to ensure the application stability in a high-strength alkali environment.

The special alkali-resistant (metal) glass at home and abroad mainly comprises alkali-resistant glass reported by Corning 1720, Schott8436 and patent CN 201811044926. Corning 1720 glass is CaO-Al₂O₃-SiO₂High alumina silicon system, while Schott8436 glass is CaO-ZrO₂-SiO₂Corning 1720 glass has excellent processability and longer material properties (Tw-Ts ═ 373 ℃) compared to Schott8436 glass, but the rubidium consumption (μ g) of Corning 1720 glass is (1.4 ± 0.4) × t^1/2(t is reaction time/h, the same applies hereinafter), while the rubidium consumption (. mu.g) of Schott8436 glass was (0.9. + -. 0.15) × t^1/2And the rubidium consumption of Corning 1720 glass is obviously lower. There is a report in the prior art that an alkali-resistant glass belongs to CaO-ZrO₂-SiO₂The alkali resistance of the high-zirconium system is equivalent to that of Schott8436 glass, and the light transmittance of the high-zirconium system is reported, so that the high-zirconium system can be applied to the alkali resistance field in a certain range. However, the three types of alkali-resistant glass have small defects on the surface after being repeatedly processed by a lamp, the images of the three types of alkali-resistant glass are determined to be tiny bubbles after being amplified by an electron microscope, the main components of the gas are analyzed by mass spectrometry, and CO is used₂And O₂Mainly, the micro bubbles are densely appeared after lamp processing, and the glass surface macroscopically shows whitish and blackish, reduces the light transmittance and even completely loses transparency.

Disclosure of Invention

In view of the above, the main objective of the present invention is to provide an alkali-resistant glass, and a preparation method and an application thereof, and to solve the technical problem that the alkali-resistant glass has excellent alkali-resistant metal corrosion resistance, excellent optical transmittance, and long material property, and more importantly, the glass has excellent multiple processing property, is beneficial to use in extreme environments, and is more suitable for practical applications.

The purpose of the invention and the technical problem to be solved are realized by adopting the following technical scheme.

The alkali-resistant glass provided by the invention comprises the following components in percentage by weight:

the first component is Na₂O, or Na₂O and Li₂O; the second component comprises CaO and BaO;

also comprises a clarifying agent; the clarifying agent is CeO₂(ii) a The CeO₂The weight of the alkali-resistant glass accounts for 0.10-0.30% of the weight of the alkali-resistant glass.

The object of the present invention and the technical problems solved thereby can be further achieved by the following technical measures.

Preferably, in the alkali-resistant glass, wherein the Na is₂The content of O is more than or equal to the Na in percentage by weight₂O and Li₂91% of the total weight of O.

Preferably, in the alkali-resistant glass of the above, the second component further comprises MgO and SrO; the weight of the CaO accounts for 51 to 66.7 percent of the total weight of the second component.

Preferably, in the alkali-resistant glass, the alkali-resistant glass further comprises HfO₂Said HfO₂Is less than 1% of the total weight of the alkali-resistant glass.

Preferably, in the alkali-resistant glass, the optical properties of the alkali-resistant glass are as follows: in rubidium atomic clock spectral luminescent bubble⁸⁷The optical transmittance of the Rb atom at two characteristic spectral lines of D1(795nm) and D2(780nm) is more than or equal to 90 percent.

Preferably, in the alkali-resistant glass, the alkali-resistant metal property of the alkali-resistant glass is that the consumption of rubidium interacting with metallic rubidium is not more than (0.9 +/-0.15) × t^1/2。

Preferably, in the alkali-resistant glass, the alkali-resistant solubility of the alkali-resistant glass is: the grade A1 can be achieved according to DIN ISO 695 standard from SCHOTT company.

Preferably, in the alkali-resistant glass, the operating point temperature of the alkali-resistant glass is T_wNot less than 1085 ℃ and the softening point temperature is T_sAt most 830 deg.C, material property (T)_w-T_s)≥255℃。

Preferably, in the alkali-resistant glass, the coefficient of thermal expansion of the alkali-resistant glass at 20-300 ℃ is (60-70) × 10^-7/℃。

Preferably, in the alkali-resistant glass, the number of times of repeated processing and unchanged performance of the alkali-resistant glass is greater than or equal to 10 times.

The purpose of the invention and the technical problem to be solved can be realized by adopting the following technical scheme.

According to the preparation method of the alkali-resistant glass, the method comprises the following steps:

mixing the raw materials according to the formula of the glass component to obtain a first mixture; adding a clarifying agent into the first mixture, and mixing to obtain a second mixture; melting, mechanically stirring, bubbling and clarifying in an auxiliary way, and performing leakage or compression molding on the second mixture to obtain the alkali-resistant glass;

the clarifying agent is CeO₂(ii) a The CeO₂The weight of the alkali-resistant glass accounts for 0.10-0.30% of the weight of the alkali-resistant glass.

Preferably, in the above method for preparing alkali-resistant glass, the raw materials include quartz sand, boric acid, aluminum hydroxide, sodium nitrate, barium nitrate, calcium nitrate and zirconium dioxide.

Preferably, in the above method for preparing alkali-resistant glass, the raw materials further include basic magnesium carbonate, strontium carbonate, hafnium oxide and lithium nitrate; the weight of the barium nitrate, the calcium nitrate, the sodium nitrate and the lithium nitrate accounts for more than 90 percent of the total weight of the nitrate and the carbonate.

Preferably, in the above method for preparing alkali-resistant glass, the rotation speed of the mechanical stirring is 5-30 r/min; the melting temperature is 1450-1550 ℃; the molding temperature is 1080-1200 ℃.

The purpose of the invention and the technical problem to be solved can be realized by adopting the following technical scheme.

According to the spectral luminous glass bulb provided by the invention, the spectral luminous glass bulb is composed of an alkali-resistant glass tube, and the alkali-resistant glass tube is composed of the alkali-resistant glass.

By the technical scheme, the alkali-resistant glass and the preparation method thereof at least have the following advantages:

1. the alkali-resistant glass provided by the invention has moderate melting temperature (1450-_w-T_s) Not less than 255 ℃) and is easy to be processed into practical glass devices, and is applied to the alkali-resistant field.

2. The alkali-resistant glass provided by the invention can be repeatedly processed for more than 10 times, and the performance of the glass is kept unchanged, so that the alkali-resistant glass is more suitable for application in the fields of high precision, high strength and alkali resistance.

3. The alkali-resistant glass provided by the invention has low rubidium consumption (the rubidium consumption interacted with metal rubidium is less than or equal to (0.9 +/-0.15) × t^1/2) High transmission rate of characteristic spectral line (in rubidium atomic clock spectral luminescent bubble)⁸⁷The optical transmittance at two characteristic spectral lines of D1(795nm) and D2(780nm) emitted by Rb atoms is more than or equal to 90 percent, and the method is suitable for the use requirements of long service life and high precision of an atomic clock.

The conventional alkali-resistant glass does not have the performance of repeated processing, and the alkali-resistant glass is prepared by selecting and adjusting the proportion of raw materials and a clarifying agent, has the advantages of excellent repeated processing performance, high optical transmittance and low rubidium consumption, and provides a reliable and practical glass material for the alkali-resistant field.

The foregoing is a summary of the present invention, and in order to provide a clear understanding of the technical means of the present invention and to be implemented in accordance with the present specification, the following is a detailed description of the preferred embodiments of the present invention.

Detailed Description

To further illustrate the technical means and effects of the present invention for achieving the predetermined objects, the following detailed description of the embodiments, structures, characteristics and effects of the alkali-resistant glass, the preparation method and applications thereof according to the present invention will be made with reference to the preferred embodiments.

The invention provides alkali-resistant glass which comprises the following components in percentage by weight:

the first component is Na₂O, or Na₂O and Li₂O; the second component comprises CaO and BaO;

also comprises a clarifying agent; the glass clarifying agent is an auxiliary chemical raw material commonly used in glass production. The raw material which can be decomposed (gasified) at high temperature to generate gas or reduce the viscosity of the glass liquid in the glass melting process to promote the elimination of bubbles in the glass liquid is called as a clarifying agent. The fining agent does not contain conventional variable valence As, oxides of Sb elements, and NaCl. The clarifying agent is preferably CeO₂(ii) a The CeO₂The weight of the alkali-resistant glass accounts for 0.10-0.30% of the weight of the alkali-resistant glass. CeO (CeO)₂Too much glass is introduced to reduce the alkali resistance of the glass, and too little glass cannot play a good clarification role, so that microbubbles in the glass cannot be completely discharged, and the processability of the glass is reduced.