CN111517642A - Alkali-resistant glass and preparation method and application thereof - Google Patents

Alkali-resistant glass and preparation method and application thereof Download PDF

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CN111517642A
CN111517642A CN202010360866.9A CN202010360866A CN111517642A CN 111517642 A CN111517642 A CN 111517642A CN 202010360866 A CN202010360866 A CN 202010360866A CN 111517642 A CN111517642 A CN 111517642A
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alkali
resistant glass
glass
resistant
weight
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CN111517642B (en
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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
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China Building Materials Academy CBMA
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/20—Compositions for glass with special properties for chemical resistant glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C03C1/004—Refining agents
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths

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  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Geochemistry & Mineralogy (AREA)
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Abstract

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 2247‑69％；B2O32.6‑4.5％；Al2O30.5-2.5%; 9-13% of a first component; 9-20.5% of a second component; ZrO (ZrO)27.6‑12％；HfO20 to 1 percent; also comprises a clarifying agent; the clarifying agent is CeO2(ii) a The CeO2The 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 mixture2Obtaining 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.

Description

Alkali-resistant glass and preparation method and application thereof
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) × t1/2(t is reaction time/h, the same applies hereinafter), while the rubidium consumption (. mu.g) of Schott8436 glass was (0.9. + -. 0.15) × t1/2And 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:
Figure BDA0002475027410000021
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) × t1/2。
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 TwNot less than 1085 ℃ and the softening point temperature is TsAt most 830 deg.C, material property (T)w-Ts)≥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-Ts) 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) × t1/2) 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:
Figure BDA0002475027410000041
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.
In specific practice, the Na is2The content of O is greater than or equal to 91% by weight of the total weight of the first component. 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. The alkali resistant glass may also comprise HfO2Said HfO2Is less than 1% of the total weight of the alkali-resistant glass.
SiO2Is an oxide of glass forming body, is a basic skeleton of glass structure, and is a main component of alkali-resistant glass. The invention uses SiO2Is limited to 47-69 wt% in order to maintain the mechanical strength properties, chemical stability, and viscosity and thermal expansion coefficient of the glass.
B2O3Is glassGlass-forming oxides, with appropriate SiO replacement2However, when the content of the glass component of the present invention exceeds 5% by weight, the glass contains a large amount of [ BO ]3]3-The plane structure is not beneficial to the chemical stability of the glass, and also reduces the viscosity of the glass and increases the thermal expansion coefficient, so that the glass material property is reduced.
Al2O3The glass structure regulating oxide with high or low content affects the thermal expansion coefficient and chemical and thermal stability of the glass, and Al is used2O3Substituted moiety B2O3The machinability of the glass can be increased, but too much reduces the material properties, at the same time as ZrO2When present in relatively large amounts, increase Al2O3The amount of (C) is not preferable to increase the alkali resistance of the glass (more than 3 wt%), so that it is only incorporated in a small amount.
Na2O and Li2O is a network exo-oxide of the glass, alkali metal ions are easy to move and diffuse in a glass body, the viscosity of the glass produced by high-temperature melting can be reduced, the glass is easy to melt, the glass is a good fluxing agent, the thermal expansion coefficient of the glass can be increased, the chemical stability and the mechanical strength of the glass are reduced, the alkali resistance of the glass is greatly reduced, and the introduction amount is not more than 13 wt%;
because the ionic radius of K, Rb and Cs is similar to that of rubidium atoms, in the reaction process of rubidium metal atoms and glass components, large-radius ions such as K, Rb and the like are easily replaced, the loss of rubidium metals is increased, meanwhile, the Na ionic radius is small, the atom stacking density is large, the structural compactness of glass is favorably improved, and the corrosion of rubidium metal atoms is reduced, so that Na in alkali-resistant glass components2O is compared with K2The rubidium atom erosion resistance of O and other components is stronger, and Na is introduced into the invention2O without introducing K2O、Rb2O、Cs2O as a monovalent vitreous outer body. While introducing a small amount of Li2O, and Na2O together increases the structural stability of the glass, but Li2The introduction of O will reduce the material properties, so the invention will use Na2O and Li2The ratio of O is defined as (10-20) to (0-1), i.e. the Na2The weight of O is the weight of Na2O and Li251-66.7 percent of the total weight of O.
MgO, CaO, SrO and BaO are extranet oxides of the glass, are alkaline earth metal oxides, have the function of adjusting the physical and chemical properties of the glass and have important function on the material properties of the glass. The introduction of MgO can improve the alkali resistance of the glass, but can reduce the material property; the CaO is introduced to reduce the medium temperature viscosity of the glass, thereby not only improving the processing performance of the glass, but also prolonging the material performance; the high-temperature viscosity of the glass can be reduced and the material property can be reduced by introducing SrO and BaO as cosolvents, so the invention considers the balance of alkali resistance and material property of the glass comprehensively, and limits the ratio of the sum of CaO and sigma (MgO + SrO + BaO) to 1: 1, namely the weight of the CaO accounts for 51-66.7% of the total weight of the second component.
ZrO2And HfO2Is a structurally regulating oxide of glass, the content of which affects the thermal expansion coefficient and the chemical and thermal stability of the glass, ZrO2Is the most main alkali-resistant component of glass, and is accompanied by ZrO2The content is increased, the alkali resistance of the glass is enhanced, but the melting temperature is also greatly increased, the glass material property is sharply reduced, and CeO is used2On the premise of being used as a clarifying agent, ZrO is treated by the method2The mass percentage content of (b) is limited to 7.6-12 wt%, and at the same time, increasing the content of Zr and Hf, which is an element of the same main group, has a more obvious effect on material elongation, but HfO2The introduction of (2) reduces the alkali resistance of the glass, so that only a small amount of substitution is made, and is limited to 1 wt%.
The working point temperature of the alkali-resistant glass is TwNot less than 1085 ℃ and the softening point temperature is TsAt most 830 deg.C, material property (T)w-Ts)≥255℃。
The working point temperature of the glass refers to the temperature of the glass suitable for mechanical processing and manual processing, and is defined as follows: the viscosity of the glass is 104Temperature at dPa · s, denoted Tw(ii) a The softening point temperature of the glass is defined as: the viscosity of the glass is 107.6Temperature at dPa · s, denoted Ts(ii) a The glass material property is a physical property of the glass in a high-temperature melting state, and is distinguished by length and lengthCan be accurately detected by an assistant instrument. Simple recognition is to see: under the same temperature reduction range, the material property is short when the hardening is fast and long when the hardening is slow; glass frit passage (T)w-Ts) And (4) showing.
The invention controls Na2O、Li2O、CaO、BaO、Al2O3The content of the compounds which have influence on the thermodynamic property of the glass, and the like, the alkali-resistant glass with the working point temperature of more than or equal to 1085 ℃ and the softening point temperature of less than or equal to 830 ℃ is prepared, the hot processing performance of the glass is improved, and the material property of the glass is improved.
The thermal expansion coefficient of the alkali-resistant glass at 20-300 ℃ is (60-70) × 10-7/℃。
The invention controls SiO2、ZrO2、Na2O and the like which have influence on the thermal expansion coefficient of the glass, and the thermal expansion coefficient of (60-70) × 10 at 20-300 ℃ is prepared-7Alkali resistant glass at/° c.
The alkali-resistant glass can be repeatedly processed and the times of the unchanged performance are more than or equal to 10 times.
The invention reduces the proportion of carbonate by increasing the proportion of nitrate in the raw materials, thereby reducing CO separated out from the glass after multiple processing2And O2The raw materials added are quartz sand, boric acid, sodium nitrate, lithium nitrate, barium nitrate, basic magnesium carbonate, calcium nitrate, strontium carbonate, aluminum hydroxide, zirconium dioxide and hafnium dioxide, wherein the amount of the nitrate raw materials accounts for more than 90 percent of the total amount of the nitrate and the carbonate, and the nitrate raw materials are calculated by mass percentage. At the same time, CeO is compounded2The use of the clarifying agent prepares the alkali-resistant glass which can be repeatedly processed and has the performance unchanged for more than or equal to 10 times.
The preparation method of the alkali-resistant glass 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 the second mixture (at 1450 and 1550 ℃), mechanically stirring (at the rotating speed of 5-30r/min,preferably 10-20r/min, which is helpful for removing glass micro-bubbles), assisting bubbling clarification, leakage or press forming, and obtaining the alkali-resistant glass finished product, wherein the finished product can be a glass tube, a glass rod, a glass plate and the like; 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 raw materials comprise quartz sand, boric acid, aluminum hydroxide, sodium nitrate, barium nitrate, calcium nitrate and zirconium dioxide. The raw materials also can comprise 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. The thermal decomposition temperature of the carbonate is about 700-1200 ℃, the decomposition temperature of the nitrate is generally 300-600 ℃, the proportion of the nitrate decomposed at relatively low temperature is increased, and the residual CO in the glass after multiple processing is reduced2And O2Generation of microbubbles (mainly carbonate decomposition products). In specific implementation, the clarifying agent is CeO2(ii) a The CeO2The content of (A) is 0.10-0.30% of the alkali-resistant glass in percentage by weight.
During specific implementation, the melting temperature is 1450-1550 ℃, and the melting time is 10-48h, so that the micro-bubble removal is facilitated; the forming temperature is 1080-1200 ℃, and the forming time is 2-30min, so that the rapid forming of the glass is facilitated, and unexpected results such as secondary bubbles, crystallization impurities and the like generated in the cooling process of the glass are prevented.
In the specific implementation, in the raw materials, silicon dioxide is introduced in the form of quartz sand, diboron trioxide is introduced in the form of boric acid, alkali metal oxide is introduced in the form of carbonate and/or nitrate, alkaline earth metal oxide is introduced in the form of carbonate and/or nitrate, and the rest is introduced in the form of oxide or hydroxide.
Example 1
The embodiment provides alkali-resistant glass and a preparation method thereof.
The components and weight percentages of the components of the alkali-resistant glass of this example and the physical properties of the glass produced are shown in Table 1.
The preparation method of the alkali-resistant glass in the embodiment comprises the following steps: quartz sand, boric acid, aluminum hydroxide, sodium nitrate, barium nitrate, calcium nitrate, basic magnesium carbonate, strontium carbonate, zirconium dioxide and hafnium dioxide are used as raw materials, wherein the nitrate accounts for 92 wt% of the total weight of the nitrate and the carbonate, and a clarifying agent CeO accounting for 0.1% of the total weight of the alkali-resistant glass is added2After fully mixing, melting at 1550 ℃ for 15h, mechanically stirring (10r/min, 15h), carrying out auxiliary bubbling clarification (nitrogen is introduced to the bottom of molten glass under the pressure of 0.15MPa, the gas introduction time is 10h), and carrying out leakage molding or press molding at 1080 ℃ for 5min to obtain a glass blank; in this embodiment, the glass blank frit may be a tube-shaped frit (glass tube). In addition, the material can be formed into a strip material, a plate material, a round bar material and the like according to actual requirements.
Example 2
The embodiment provides alkali-resistant glass and a preparation method thereof.
The components and weight percentages of the components of the alkali-resistant glass and the physical properties of the glass produced in this example are shown in Table 1.
In the method for preparing alkali-resistant glass in this embodiment, the refining agent is CeO2The adding amount of the alkali-resistant glass is 0.2 percent of the total weight of the alkali-resistant glass; the melting temperature is 1500 ℃; the molding temperature is 1150 ℃, and other preparation steps and parameters are the same as those of the example 1; in this embodiment, the glass blank frit may be a plate-shaped frit (glass plate). In addition, the material can be formed into a strip material, a tubular material, a round bar material and the like according to actual requirements.
Example 3
The embodiment provides alkali-resistant glass and a preparation method thereof.
The components and weight percentages of the components of the alkali-resistant glass and the physical properties of the glass produced in this example are shown in Table 1.
In the method for preparing alkali-resistant glass in this embodiment, the refining agent is CeO2The adding amount of the alkali-resistant glass is 0.3 percent of the total weight of the alkali-resistant glass; the melting temperature is 1450 ℃; the molding temperature was 1200 ℃ and the other preparation steps and parameters were the same as in example 1; in this embodiment, the glass woolThe blank may be a round bar stock (glass rod). In addition, the material can be formed into a strip material, a pipe material, a plate material and the like according to actual requirements.
Comparative examples 1 and 2
The components and weight percentages of the components of the alkali-resistant glasses of comparative examples 1 and 2 and the physical properties of the glasses produced are shown in table 1.
The preparation steps and parameters of the alkali-resistant glass in comparative example 1 and comparative example 2 are the same as those in example 1.
TABLE 1 composition, content and physical Properties of alkali-resistant glasses according to examples 1 to 3 of the invention and comparative examples and two commercial glass grades (Corning 1720, Schott8436)
Figure BDA0002475027410000091
Figure BDA0002475027410000101
As can be seen from Table 1, the alkali-resistant glasses prepared from the alkali-resistant glass components of examples 1-3 of the invention have a glass quality of more than 255 ℃, and rubidium consumption of less than (0.9 +/-0.15) × t1/2The repeatable processing times are more than 10 times, and the comprehensive performance is better than that of the alkali-resistant glass Corning 1720 and Schott8436 sold in the market and the glass related to the comparative examples 1 and 2. The glass provided in comparative examples 1 and 2 is repeatedly processed for 1-3 times to form flaky micro bubbles which are black and white, and the comprehensive performances of transmittance, material property, alkali resistance (alkali metal) and the like are obviously inferior to those of the alkali-resistant glass in the examples.
As can be seen from the above, the alkali-resistant glass provided in embodiments 1 to 3 of the present invention has a longer material property, an excellent alkali-resistant metal corrosion resistance, an excellent optical transmittance, and an excellent repeated processability, can be applied to various fields requiring alkali-resistant glass materials, and has an advantage of unchanged processability after many times. This is probably due to the fact that the refining agents CeO are added in specific proportions in the preparation of the alkali-resistant glass in examples 1 to 3 of the invention2The ratio of nitrate in the raw material is increasedAnd a specific stirring rotation speed is set. Therefore, the alkali-resistant glass has the advantages of excellent repeated processability, high optical transmittance and low rubidium consumption, and has wide application prospect in the field of alkali-resistant glass.
The recitation of numerical ranges herein includes all numbers subsumed within that range and includes any two numbers subsumed within that range. For example, "SiO2Is 47-69 w% ", which includes all values between 47-69, and includes any two values (e.g., 50, 60) within the range (50-60); different values of the same index appearing in all embodiments of the invention can be combined arbitrarily to form a range value.
In the description of the present invention, numerous specific details are set forth. It is understood, however, that embodiments of the invention may be practiced without these specific details. In some embodiments, well-known methods, structures and techniques have not been shown in detail in order not to obscure an understanding of this description.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent change and modification made to the above embodiment according to the technical spirit of the present invention are still within the scope of the technical solution of the present invention.

Claims (10)

1. The alkali-resistant glass is characterized by comprising the following components in percentage by weight:
Figure FDA0002475027400000011
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) × t1/2(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 TwNot less than 1085 ℃ and the softening point temperature is TsAt most 830 deg.C, material property (T)w-Ts) 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.
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