阅读说明：本技术 一种玻璃粉及其制备方法 (Glass powder and preparation method thereof ) 是由 郑文彬 秦国斌 卢克军 张宁 于 2021-09-30 设计创作，主要内容包括：本申请提供了一种玻璃粉及其制备方法,所述玻璃粉包括基质玻璃粉和填料；基于基质玻璃粉的总重量,所述基质玻璃粉包括：Bi-(2)O-(3) 55-65wt％,B-(2)O-(3) 25-30wt％,ZnO 5-15wt％,SiO-(2) 2-6wt％,Al-(2)O-(3) 3-5wt％和调节料0-3wt％；所述基质玻璃粉与所述填料的重量比为(60-90)：(10-40)。本申请提供的玻璃粉及其制备方法,采用本申请的基质玻璃粉和填料,通过本申请的制备方法,获得对环境无污染、耐温性好、强度高、不易吸水、理化性能稳定、热膨胀系数与阀片相匹配的玻璃粉。(The application provides a glass powder and a preparation method thereof, wherein the glass powder comprises matrix glass powder and a filler; the matrix glass frit comprises, based on the total weight of the matrix glass frit: bi 2 O 3 55‑65wt％，B 2 O 3 25‑30wt％，ZnO 5‑15wt％，SiO 2 2‑6wt％，Al 2 O 3 3-5 wt% and 0-3 wt% of regulating material; the weight ratio of the matrix glass powder to the filler is (60-90): (10-40). According to the glass powder and the preparation method thereof, the matrix glass powder and the filler are adopted, and the glass powder which is free of pollution to the environment, good in temperature resistance, high in strength, not easy to absorb water, stable in physical and chemical properties and matched in thermal expansion coefficient with the valve sheet is obtained through the preparation method.)

1. A glass frit comprising a matrix glass frit and a filler;

the matrix glass frit comprises, based on the total weight of the matrix glass frit: bi₂O₃ 55-65wt％，B₂O₃ 25-30wt％，ZnO 5-15wt％，SiO₂ 2-6wt％，Al₂O₃3-5 wt% and 0-3 wt% of regulating material;

the weight ratio of the matrix glass powder to the filler is (60-90): (10-40).

2. The glass frit of claim 1, wherein the frit comprises La₂O₃NiO and TiO₂Said La₂O₃NiO and TiO₂The weight ratio of (1): (0.5-1.5): (0.5-1.5).

3. The glass frit of claim 1, wherein the filler comprises at least one of aluminum titanate, beta-eucryptite, cordierite, and zircon.

4. A method for producing a glass frit according to any one of claims 1 to 3, which comprises the steps of:

(1) weighing raw materials of matrix glass powder, and mixing to obtain a mixture;

(2) melting the mixture at 1100-1300 ℃ for 1-3h to obtain a melt, quenching and grinding to obtain matrix glass powder;

(3) weighing a filler, and mixing the matrix glass powder with the filler to obtain glass powder;

wherein the matrix glass frit comprises, based on the total weight of the matrix glass frit: bi₂O₃ 55-65wt％，B₂O₃ 25-30wt％，ZnO 5-15wt％，SiO₂ 2-6wt％，Al₂O₃3-5 wt% and 0-3 wt% of regulating material;

the weight ratio of the matrix glass powder to the filler is (60-90): (10-40).

5. The production method according to claim 4, wherein the conditioning material comprises La₂O₃NiO and TiO₂Said La₂O₃NiO and TiO₂The weight ratio of (1): (0.5-1.5): (0.5-1.5).

6. The method of manufacturing of claim 4, wherein the filler comprises at least one of aluminum titanate, beta-eucryptite, cordierite, and zircon.

Technical Field

The application relates to the technical field of glass materials, in particular to glass powder and a preparation method thereof.

Background

The metallic oxide lightning arrester consists of a zinc oxide valve plate, an insulating resin sleeve and the like, and the core part of the metallic oxide lightning arrester is the zinc oxide valve plate. The zinc oxide valve plate has the defects of easy reaction with moisture in the air, no oil stain resistance and the like, after the valve plate is affected with damp or when the valve plate receives high voltage in thunderstorm weather, flashover can occur on the side surface of the valve plate to cause the failure of the lightning arrester, the normal work of the lightning arrester is seriously influenced, and in order to ensure the normal work of the lightning arrester, the side surface of the valve plate needs to be protected. At present, three protection methods are commonly used, one is organic glaze protection, one is inorganic glass glaze protection, and organic-inorganic composite protection is also provided. However, the valve plates are required to be connected in series in the packaging process of the lightning arrester, then the gaps around the valve plates are filled through injection molding at about 280 ℃, the effects of fixing, preventing moisture and protecting the valve plates are achieved, but the organic glaze cannot bear the injection molding process exceeding 200 ℃, organic substances can be decomposed, and meanwhile, due to the fact that the organic glaze is low in strength and difficult to match with the valve plates in thermal expansion coefficient, cracks can be generated due to heating, the organic glaze is aged, the insulation effect is poor, and the service life is influenced. Inorganic glass glazes are widely used for their high temperature resistance, excellent chemical stability and high mechanical strength.

The sealing glass for the prior metal oxide lightning arrester is mainly PbO-B₂O₃-ZnO series, doped with SiO₂、Al₂O₃When the additives are used for adjusting the glass performance, the lower sintering temperature can be obtained only when the PbO content in the glass is higher, which is contrary to the current required environment-friendly standard, and the European Union proposes to gradually take the glass as early as 2003The provision of products containing lead. Although the lead-free glass glaze is made at home and abroad, like phosphate and vanadate lead-free glass, the bismuth-based sealing glass has stable performance, has water resistance which is not possessed by phosphate and non-toxicity which is not possessed by vanadate, but has the defects of higher cost of bismuth oxide raw materials, higher thermal expansion coefficient and difficulty in matching with zinc oxide valve plates.

Disclosure of Invention

The application aims to provide glass powder and a preparation method thereof, so as to obtain the glass powder which has no pollution to the environment, good temperature resistance, high strength, difficult water absorption, stable physical and chemical properties and matched thermal expansion coefficient with a valve plate. The specific technical scheme is as follows:

a first aspect of the present application provides a glass frit comprising a matrix glass frit and a filler;

the matrix glass frit comprises, based on the total weight of the matrix glass frit: bi₂O₃ 55-65wt％，B₂O₃ 25-30wt％，ZnO 5-15wt％，SiO₂ 2-6wt％，Al₂O₃3-5 wt% and 0-3 wt% of regulating material;

the weight ratio of the matrix glass powder to the filler is (60-90): (10-40).

A second aspect of the present application provides a method for preparing a glass frit according to the first aspect of the present application, comprising the steps of:

(1) weighing raw materials of matrix glass powder, and mixing to obtain a mixture;

(2) melting the mixture at 1100-1300 ℃ for 1-3h to obtain a melt, quenching and grinding to obtain matrix glass powder;

(3) weighing a filler, and mixing the matrix glass powder with the filler to obtain glass powder;

wherein the matrix glass frit comprises, based on the total weight of the matrix glass frit: bi₂O₃ 55-65wt％，B₂O₃25-30wt％，ZnO 5-15wt％，SiO₂ 2-6wt％，Al₂O₃3-5 wt% and 0-3 wt% of regulating material;

the weight ratio of the matrix glass powder to the filler is (60-90): (10-40).

According to the glass powder and the preparation method thereof, the matrix glass powder and the filler are adopted, and the glass powder which is free of pollution to the environment, good in temperature resistance, high in strength, not easy to absorb water, stable in physical and chemical properties and matched in thermal expansion coefficient with the valve sheet is obtained through the preparation method. The glass powder has the advantages that the performance is good, the glass powder does not contain lead, the environment is not polluted, the temperature resistance is good, the strength is high, water is not easy to absorb, when the glass powder is used for the valve block, the wettability of the valve block is good, the difference between the thermal expansion coefficient of the glass powder and the valve block is small, the problem of stability deterioration caused by thermal shock can be avoided, the performance is stable, the valve block is protected, and due to the fact that the glass powder contains the components of the valve block in the components, a good transition layer is easily formed between the glass powder and the valve block, and the glass powder glaze layer is well combined with the valve block.

Of course, not all advantages described above need to be achieved at the same time in the practice of any one product or method of the present application.

Detailed Description

The technical solutions in the embodiments of the present application will be described clearly and completely below, and it should be understood that the described embodiments are only a part of the embodiments of the present application, and not all embodiments. All other embodiments that can be derived by one of ordinary skill in the art from the description herein are intended to be within the scope of the present disclosure.

A first aspect of the present application provides a glass frit comprising a matrix glass frit and a filler;

the matrix glass frit comprises, based on the total weight of the matrix glass frit: bi₂O₃ 55-65wt％，B₂O₃ 25-30wt％，ZnO 5-15wt％，SiO₂ 2-6wt％，Al₂O₃3-5 wt% and 0-3 wt% of regulating material;

the weight ratio of the matrix glass powder to the filler is (60-90): (10-40).

The matrix glass powder has a glass transition temperature of 400-430 ℃, a softening temperature of 450-480 ℃, and a thermal expansion coefficient of 25-300 DEG C60×10^-7-90×10^-7V. C. The glass powder is obtained by adding the filler into the matrix glass powder and mixing, and different requirements on the thermal expansion coefficient of the glass powder can be met.

The adjusting material can be selectively added according to actual needs, and the color of the glass powder can be adjusted by adding different adjusting materials.

The glass powder has good performance, does not contain lead, does not pollute the environment, has good temperature resistance and high strength, is not easy to absorb water, has good wettability to the valve plate when being used for the valve plate, has small difference between the thermal expansion coefficient and the valve plate, can avoid the problem of poor stability when being subjected to thermal shock, has stable performance and plays a role in protecting the valve plate; when the glass powder is applied to the zinc oxide valve plate, the component ZnO of the valve plate is contained in the component of the glass powder, so that a good transition layer is easily formed between the glass powder and the valve plate, and the glass powder glaze layer is well combined with the valve plate.

In some embodiments of the first aspect of the present application, the conditioning compound comprises La₂O₃NiO and TiO₂La as described in the present application₂O₃NiO and TiO₂Is not particularly limited as long as the object of the present application can be achieved, for example, the La₂O₃NiO and TiO₂The weight ratio of (A) may be 1: (0.5-1.5): (0.5-1.5).

In certain embodiments of the first aspect of the present application, the filler comprises at least one of aluminum titanate, beta-eucryptite, cordierite, and zircon. In the present application, the coefficient of thermal expansion of the glass frit can be adjusted by adjusting the added filler, which may have a coefficient of thermal expansion of-70 x 10^-7～20×10^-7/° c; when the glass powder is used for the valve plate, different fillers can be selectively added into the matrix glass powder according to the difference between the thermal expansion coefficient of the valve plate and the sintering temperature so as to meet the requirement of matching and sealing the thermal expansion coefficients of the valve plates with different formulas; the glass powder obtained by adding the filler can match the thermal expansion coefficient of sealing and is 0-150 multiplied by 10^-7The material between/° c provides a sealed sample.

A second aspect of the present application provides a method for preparing a glass frit according to the first aspect of the present application, comprising the steps of:

(1) weighing raw materials of matrix glass powder, and mixing to obtain a mixture;

(2) melting the mixture at 1100-1300 ℃ for 1-3h to obtain a melt, quenching and grinding to obtain matrix glass powder;

(3) weighing a filler, and mixing the matrix glass powder with the filler to obtain glass powder;

wherein the matrix glass frit comprises, based on the total weight of the matrix glass frit: bi₂O₃ 55-65wt％，B₂O₃25-30wt％，ZnO 5-15wt％，SiO₂ 2-6wt％，Al₂O₃3-5 wt% and 0-3 wt% of regulating material;

the weight ratio of the matrix glass powder to the filler is (60-90): (10-40).

In the application, the mixing in the step (1) is uniform mixing, the mixing mode is not limited in the application, as long as the purpose of the application can be achieved, and illustratively, the weighed raw materials are put into a zirconia bottle and ball-milled by using zirconia balls, and are ball-milled for 1-2 hours by a planetary ball mill, and then are fully mixed to obtain a mixture; the rapid cooling in step (2), which is rapid cooling, is not limited in the present application as long as the object of the present application can be achieved, and for example, rolling mill rapid cooling or water quenching rapid cooling, etc. may be adopted; the melting and grinding are not limited in the present application as long as the purpose of the present application can be achieved, and for example, a silicon carbide rod resistance furnace can be used for melting operation, the obtained melt is poured on a stainless steel rolling mill and rolled into a glass sheet for quenching, the glass sheet is put into an alumina porcelain bottle filled with alumina balls after cooling, the alumina porcelain bottle is put on a bottle rolling machine for ball milling for 22-26h, the glass sheet is ground to obtain matrix glass powder, and the matrix glass powder can be ground to a particle size D50 of 10 μm.

In the present application, the raw material component content of the matrix glass frit is the same as the component content of the matrix glass frit.

In some embodiments of the second aspect of the present applicationWherein the regulating material comprises La₂O₃NiO and TiO₂Said La₂O₃NiO and TiO₂The weight ratio of (1): (0.5-1.5): (0.5-1.5).

In some embodiments of the second aspect of the present application, the filler comprises at least one of aluminum titanate, beta-eucryptite, cordierite, and zircon.

When the glass powder is used for the valve plate, the glass powder is coated on the side surface of the valve plate and then sintered to obtain the valve plate structure with the glass powder glaze layer, so that the side surface of the valve plate can be well protected, the glass powder glaze layer is good in temperature resistance, high in strength and good in wettability to the valve plate, can be matched with the thermal expansion coefficient of the valve plate, and is good in moisture-proof effect; when the glass powder glaze layer is used for the zinc oxide valve plate, the component ZnO of the valve plate is contained in the components, so that a good transition layer is easily formed between the glass powder glaze layer and the valve plate, and the glass powder glaze layer and the valve plate can be well combined; the color of the glass powder glaze layer can be adjusted by adding different adjusting materials during preparation of the used glass powder, so that the inorganic glass powder glaze layer with a smooth surface, such as grey yellow, grey green or black, can be obtained.

The embodiments of the present application will be described in more detail below with reference to examples and comparative examples.

Example 1

Weighing raw material Bi₂O₃ 58g、B₂O₃ 25g、ZnO 12g、SiO₂ 2g、Al₂O₃3g, putting the raw materials into a zirconia bottle, ball-milling the raw materials for 1 hour by using zirconia balls in a planetary ball mill, and fully mixing to obtain a mixture; placing the mixture in a silicon-carbon rod resistance furnace to melt for 3 hours at 1250 ℃ to obtain a melt; pouring the melt on a stainless steel rolling mill, rolling into glass sheets, quenching, cooling, putting the glass sheets into an alumina porcelain bottle filled with alumina balls, and ball-milling for 24 hours on a bottle rolling machine to obtain matrix glass powder; weighing a filler, wherein the weight ratio of the matrix glass powder to the filler is 90:10, the filler is cordierite and zircon with the weight ratio of 25:1, and mixing the matrix glass powder with the filler to obtain the glass powder.

Taking the dispersion liquid as weightMixing glass powder and the dispersion liquid according to the ratio of 36:59:5 of diethylene glycol butyl ether, butyl acetate and ethyl cellulose, and then putting the mixture into an automatic stirrer for 1 hour to obtain uniform slurry, wherein the content of the glass powder in the slurry is 50 percent; spraying the slurry on the side surface of unannealed valve plate blank which is a zinc oxide material (D30 type zinc oxide valve plate with thermal expansion coefficient of 62-65 × 10)^-7/° c); heating the sprayed valve element blank to 550 ℃ after 2 hours, and preserving heat for 1 hour for sintering; and then cooling to 320 ℃ after 3 hours, and then cooling to room temperature along with the furnace to obtain the valve plate structure with the glass powder glaze layer.

Examples 2 to 3

The preparation steps of the glass powder and the valve plate structure are the same as those of the example 1, and the change of relevant preparation parameters is shown in the table 1, wherein the adjusting material is La with the weight ratio of 1:1:1₂O₃NiO and TiO₂。

Comparative examples 1 to 2

The preparation steps of the glass frit and the valve plate structure are the same as those of example 1, and the changes of the relevant preparation parameters are shown in table 1.

The glass frits of examples 1-3 and comparative examples 1-2 were tested by a conventional thermal expansion coefficient test method, and the results are shown in table 1.

After polishing the valve plate structures of the embodiments 1-3 and the comparative examples 1-2, respectively spraying aluminum layers on the upper surface and the lower surface of the valve plate to obtain a sample to be tested with a smooth surface, and carrying out a 65kA heavy current test of 4/10 mu s of national standard on the sample to be tested; and carrying out continuous three times of high-current tests without cooling on the sample to be tested, wherein the test standard is 70kA, and the test results are shown in table 1.

The test method and the test equipment are as follows:

testing the thermal expansion coefficient:

taking 4.5g of glass powder, pressing into a round bar with the length of about 22mm and the diameter of about 9mm by using a cylindrical die with the diameter of 9mm, sintering at the temperature of 520-550 ℃, and reading the expansion coefficient to be the average expansion coefficient value of 50-300 ℃ by using a German relaxation-resistant DIL 402Classic horizontal thermal expansion instrument.

And (3) testing large current:

according to the method specified in the national standard GB/T11032-2010.

The performance parameters of the glass frit and valve sheet structures prepared in the examples and comparative examples are shown in table 1.

TABLE 1

The valve plate structures obtained in the embodiments 1 to 3 are opposite to each other by using two coated and sintered valve plate structures, and no obvious mark exists, which indicates that the glass powder has high strength; the valve plate structures obtained in the embodiments 1 to 3 have smooth surfaces and good glossiness, and water molecules in air are not easy to hang on the wall, which indicates that the glass powder is not easy to absorb water. Through tests, the glass powder glaze layer on the test sample of the embodiment 1-3 can pass 65kA heavy current tests twice, the surface of the glaze layer is clean, and the side face of the valve plate is well protected. The results in table 1 show that the test samples in examples 1 to 3 have good heavy current resistance, wherein the test sample in example 1 can resist heavy current for three times without damage, after the zinc oxide valve plate with the D30 model uses the insulating glaze layer in example 1, the maximum 4/10 mus heavy current impact resistance can reach 71.24kA, and the examples 2 to 3 can reach more than 68 kA; compared with the comparative examples 1-2, the high-current resistance effect is not the same as that of the comparative examples 1-2, after the D30 type zinc oxide valve plate uses the insulating glaze layer in the comparative examples 1-2, the highest 4/10 mu s high-current impact resistance is only 64.53kA, the sintering temperature of the comparative example 1 is higher, the glass powder vitrification effect is poor in the sintering process, and the side surface of the valve plate cannot be well coated, so that the valve plate structure of the comparative example 1 cannot resist the high-current impact. The above test results show that when the content of the components of the glass frit is out of the range of the present application, the performance effect of the glass frit is not as good as that of the glass frit of the present application.

In conclusion, the glass provided by the applicationA powder comprising a matrix glass powder and a filler; the matrix glass frit comprises, based on the total weight of the matrix glass frit: bi₂O₃ 55-65wt％，B₂O₃ 25-30wt％，ZnO 5-15wt％，SiO₂ 2-6wt％，Al₂O₃3-5 wt% and 0-3 wt% of regulating material; the weight ratio of the matrix glass powder to the filler is (60-90): (10-40). The glass powder has no pollution to the environment, good temperature resistance, high strength, difficult water absorption, thermal expansion coefficient matched with the valve block, stable physical and chemical properties and good protection effect on the valve block, and can avoid the problem of poor stability when the glass powder is subjected to thermal shock.

The above description is only for the preferred embodiment of the present application and is not intended to limit the scope of the present application. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application are included in the protection scope of the present application.