阅读说明：本技术 低膨胀系数的中低温环保型玻璃粉及其制备方法和应用 (Low-expansion-coefficient medium-low temperature environment-friendly glass powder and preparation method and application thereof ) 是由 余仁安 吴斐 施小罗 范文筹 刘志潜 何龙 刘宗玉 于 2019-11-01 设计创作，主要内容包括：本发明公开了一种低膨胀系数的中低温环保型玻璃粉,其主要成分包括由重量百分比为50～70wt%的SiO<Sub>2</Sub>、5～15wt%的Al<Sub>2</Sub>O<Sub>3</Sub>、5～10wt%的Li<Sub>2</Sub>O、3～8wt%的B<Sub>2</Sub>O<Sub>3</Sub>、0～5wt%的ZrO<Sub>2</Sub>、0～5wt%的MgO、0～5wt%的ZnO、0～5wt%的BaO和0～10wt%的β-锂霞石的原料制备而成。通过备料、混磨、烧制熔块,制玻璃粉等步骤制得玻璃粉成品。本发明制得的玻璃粉是一种热膨胀系数低、温度低的环保型玻璃粉,可作为保护层可应用于微晶玻璃表面,应用效果好。(The invention discloses low-expansion-coefficient medium-low temperature environment-friendly glass powder, which mainly comprises 50-70 wt% of SiO 2 5 to 15wt% of Al 2 O 3 5 to 10wt% of Li 2 O, 3-8 wt% of B 2 O 3 0 to 5wt% of ZrO 2 The glass powder is an environment-friendly glass powder with low thermal expansion coefficient and low temperature, can be used as a protective layer to be applied to the surface of microcrystalline glass, and has a good application effect.)

1. The low-expansion-coefficient medium-low temperature environment-friendly glass powder is characterized by mainly comprising 50-70 wt% of SiO2, 5-15 wt% of Al2O3, 5-10 wt% of Li2O, 3-8 wt% of B2O3, 0-5 wt% of ZrO2, 0-5 wt% of MgO, 0-5 wt% of ZnO, 0-5 wt% of BaO or 0-10 wt% of β -eucryptite.

2. The low-expansion-coefficient medium-low temperature environment-friendly glass frit as claimed in claim 1, wherein the particle size of the raw material particle size is less than 10 μm.

3. The method for preparing the low-expansion-coefficient medium-low temperature environment-friendly glass powder according to any one of claims 1 to 2, which is characterized by comprising the following steps of:

s1: mixing and grinding, namely weighing the raw materials of the components according to the weight percentage of claim 1 or 2, uniformly mixing, and performing dry ball milling for 6H for later use;

s2: sintering the frits, namely sintering, water quenching and drying the raw materials subjected to ball milling in the step S1;

s3: and (4) preparing glass powder, performing wet ball milling on the frit dried in the step S2 for 6H, drying, and screening to obtain a finished glass powder product.

4. The method for preparing low-expansion-coefficient medium-low temperature environment-friendly glass powder according to claim 3, wherein the firing condition in the step S2 is that the melting temperature is 1500-1600 ℃, and the heat preservation time is 30 min.

5. The low-temperature environment-friendly glass powder with low expansion coefficient and medium-low temperature as claimed in claim 3, wherein the particle size of the powder material in the step S3 is less than 3 μm, and the powder material is sieved by a 400-mesh sieve.

6. The low-expansion-coefficient medium-low temperature environment-friendly glass powder and the preparation method thereof according to claim 3, wherein the step S3 further comprises the following steps:

s31, fine grinding, adding β -eucryptite into the glass powder prepared in the step S3, performing wet ball milling on the 2H, drying and screening;

s32: and (4) sintering the clinker, namely sintering, water quenching and drying the raw material dried in the step S31.

7. The low-expansion coefficient medium-low temperature environment-friendly glass powder and the preparation method thereof as claimed in claim 6, wherein in the step S31, the β -eucryptite is added in a proportion of 0-10 wt%.

8. The low-temperature environment-friendly glass powder with low expansion coefficient and medium-low temperature as claimed in claim 6, wherein the particle size of the powder material in the step S31 is less than 10 μm, and the powder material is sieved by a 200-mesh sieve.

9. The low-expansion-coefficient medium-low temperature environment-friendly glass powder and the preparation method thereof according to claim 7, wherein the firing condition in the step S32 is that the melting temperature is 1300-1350 ℃, and the heat preservation time is 30 min.

10. The application of the low-expansion-coefficient medium-low temperature environment-friendly glass powder is characterized in that the glass powder prepared by the method in the claims 3-9 is made into glass slurry, screen-printed on the surface of a microcrystalline glass product, and then glaze firing is carried out, wherein the glaze firing temperature is 835 ℃, the heat preservation time is 10min, and the thickness of a glass glaze layer coated on the surface of the microcrystalline glass is 20-30 mu m.

Technical Field

The invention relates to the field of glass powder, in particular to low-expansion-coefficient medium-low temperature environment-friendly glass powder and a preparation method and application thereof.

Background

The glaze is a thin layer of glass body applied on the surface of a product, and aims to improve the physical and chemical properties and mechanical properties of the surface of the product, decorate the surface of the product and be increasingly widely applied in the field of product surface packaging protection.

The glass glaze is tightly combined with the matrix, the problems of cracking, peeling and the like are frequently found, the glass glaze is more prominent particularly under the high-temperature condition (above 300 ℃), and the main factor is the matching of the expansion coefficients of the glaze and the matrix. When the expansion coefficient of the glass powder is lower than that of the matrix, the glaze shrinks less than the matrix in the cooling process, and the glaze is automatically deformed under the self-contraction action and also subjected to the compression action given to the matrix when the matrix contracts, so that the glaze generates compression elastic deformation, and permanent compression stress is reserved in a solidified glaze layer. On the contrary, when the expansion coefficient of the glass glaze is higher than that of the matrix, the glaze shrinks more than the matrix in the cooling process, the glaze is stretched by the matrix to generate stretching elastic deformation, and permanent tensile stress is reserved in the glaze. The glaze with compressive stress is generally called positive glaze, the glaze with tensile stress is called negative glaze, the compressive strength of the glaze is far greater than the tensile strength, and therefore the negative glaze is easy to crack. The positive glaze can reduce the damage of surface crack source and can offset part of the tension load on the product. In contrast, the positive glaze is not cracked, but can improve the mechanical strength of the product and play a good role in improving the mechanical property and the thermal property of the surface.

In recent years, with the great reduction of the manufacturing cost of the glass ceramics, the glass ceramics products are widely applied to daily necessities, and the glass ceramics is also actively developed and popularized in combination with a magnetic conduction film, a thick film resistance electric heating and the like. At this time, it is required to develop an environment-friendly glass glaze with a thermal expansion coefficient equivalent to that of microcrystalline glass, and the glass glaze is used as a protective layer applied to the surface of a microcrystalline glass product. The glass glaze with extremely low thermal expansion coefficient and low temperature has no relevant literature data.

Disclosure of Invention

The invention aims to solve the technical problem of providing low-expansion-coefficient medium-low temperature environment-friendly glass powder for the surface of microcrystalline glass. Aiming at the defects in the prior art, the invention provides a low-expansion-coefficient medium-low temperature environment-friendly glass powder, and the technical scheme adopted for solving the technical problems is as follows:

the medium-low temperature environment-friendly glass powder comprises 50-70 wt% of SiO ₂5 to 15wt% of Al ₂O ₃5 to 10wt% of Li ₂O, 3-8 wt% of B ₂O ₃0 to 5wt% of ZrO ₂0-5 wt% of MgO, 0-5 wt% of ZnO, 0-5 wt% of BaO or 0-10 wt% of β -eucryptite.

Preferably, the particle size of the feedstock is less than 10 μm.

According to another aspect of the invention, the preparation method of the low-expansion coefficient medium-low temperature environment-friendly glass powder comprises the following steps:

s1: mixing and grinding, namely weighing the raw materials of the components according to the weight percentage of claim 1, uniformly mixing, and performing dry ball milling for 6H for later use;

s2: sintering the frits, namely sintering, water quenching and drying the raw materials subjected to ball milling in the step S1;

s3: and (4) preparing glass powder, performing wet ball milling on the frit dried in the step S2 for 6H, drying, and screening to obtain a finished glass powder product.

Preferably, the firing conditions in the step S2 are a melting temperature of 1500-1600 ℃, and a heat preservation time of 30 min.

Preferably, the particle size of the powder lot in the step S3 is less than 3 μm, and the powder lot is sieved by a 400-mesh sieve.

Preferably, the step S3 further includes the steps of:

s31, fine grinding, adding β -eucryptite into the glass powder prepared in the step S3, performing wet ball milling on the 2H, drying and screening;

s32: and (4) sintering the clinker, namely sintering, water quenching and drying the raw material dried in the step S31.

Preferably, in the step S31, the β -eucryptite is added in a proportion of 0-10 wt% by weight.

Preferably, the particle size of the powder lot in the step S31 is less than 10 μm, and the powder lot is sieved by a 200-mesh sieve.

Preferably, the firing conditions in the step S32 are a melting temperature of 1300-1350 ℃, and a heat preservation time of 30 min.

According to another aspect of the invention, the application of the low-expansion-coefficient medium-low temperature environment-friendly glass powder comprises the steps of preparing the glass powder prepared by the method into glass slurry, then performing screen printing on the surface of a microcrystalline glass product, and then performing glaze firing, wherein the glaze firing temperature is 835 ℃, the heat preservation time is 10min, and the thickness of a glass glaze layer coated on the surface of the microcrystalline glass is 20-30 mu m.

Compared with the prior art, the invention has the beneficial technical effects that the invention provides the low-expansion-coefficient medium-low temperature environment-friendly glass powder and the preparation method and the application thereof, the glass powder prepared according to the raw material proportion of the invention is tested according to the thermal expansion coefficient α and the softening temperature Ts of the national standard sample preparation test, and the thermal expansion coefficient α (20-600 ℃) of the glass powder is tested to be 0.4-0.62 multiplied by 10 ^-6The softening temperature Ts is between 720 and 805 ℃ between/° C, the glass ceramic is used as an enamel protective layer on the surface of the microcrystalline glass, the thermal expansion coefficient of the glass ceramic is equivalent to that of the microcrystalline glass, the softening temperature is low, the mechanical strength of the microcrystalline glass product can be improved, and the surface mechanical property and the thermal property of the microcrystalline glass product can be improved.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments adopted to implement the present invention are described.