High-adhesion high-acid-resistance white glaze

Abstract

The application discloses high-adhesion high-acid-resistance white glaze, which comprises solid powder and liquid dispersion medium; the solid powder comprises the following raw materials and the weight parts of the raw materials: inorganic transparent powder 30-56 parts, specially treated etching sericite powder 3-12 parts, lithium mica powder 7-14 parts and titanium white powder 28-52 parts. After the high-adhesion high-acid-resistance white glaze is tempered on base glass, the adhesion is 0 level, and the white glaze does not change color and does not fall off after being soaked in 3.7% hydrochloric acid for 24 hours.

Description

Technical Field

[0001] This invention relates to a white glaze with high adhesion and high acid resistance, belonging to the field of glass glaze technology. Background Technology

[0002] White glass enamel is a widely used type of enamel, with titanium dioxide as its main colorant. Compared to other colors such as cadmium yellow, cadmium selenide red, cobalt blue, cobalt green, and copper chromium black, titanium dioxide has a high melting temperature. When added to the enamel, it easily results in poor adhesion, leading to enamel peeling during use, affecting performance and causing significant economic losses for users. To meet performance requirements, the tempering temperature and tempering time need to be increased, which not only makes the glass prone to deformation but also significantly increases user costs. Furthermore, the reduced enamel adhesion drastically reduces the enamel's acid resistance, further posing risks to users and failing to meet basic usage requirements. Therefore, there is an urgent need for a white enamel with high adhesion and high acid resistance, suitable for crystalline silicon photovoltaic glass backsheets, and also applicable to fields with high acid resistance requirements such as construction and home appliances. Summary of the Invention

[0003] At least to address one of the problems existing in the prior art, the present invention provides a high-adhesion, high-acid-resistant white glaze. After being tempered on the base glass, the adhesion is grade 0, and it does not change color or peel off after being soaked in 3.7% hydrochloric acid for 24 hours. It is suitable for photovoltaic glass backsheets of crystalline silicon modules, and is also suitable for fields with high acid resistance requirements such as construction and home appliances.

[0004] To achieve the above objectives, the present invention adopts the following technical solution: a white glaze with high adhesion and high acid resistance, the white glaze comprising solid powder and liquid dispersion medium; the solid powder comprising the following raw materials and their weight parts: 30-56 parts of inorganic transparent powder, 3-12 parts of specially treated etched sericite powder, 7-14 parts of lithium mica powder, and 28-52 parts of titanium dioxide.

[0005] Preferably, the special treatment method for etching sericite powder is as follows: the sericite powder is placed in hydrochloric acid solution at room temperature, stirred evenly and soaked thoroughly, then filtered, washed 3 to 5 times, dried at low temperature, and sieved to obtain the special treatment etched sericite powder.

[0006] Preferably, the hydrochloric acid solution has a mass fraction of 5-10%.

[0007] Preferably, the soaking time is 2 to 8 hours.

[0008] Preferably, the particle size of the specially treated etched sericite powder is 1250–2500 mesh.

[0009] Preferably, the particle size of the inorganic transparent powder is 2500-3500 mesh.

[0010] Preferably, the particle size of the lepidolite powder is 1250–2500 mesh.

[0011] Preferably, the inorganic transparent powder comprises the following raw materials and their weight parts: 25-44 parts quartz powder, 8-22 parts borax decahydrate, 7-11 parts zinc oxide, 9-15 parts zirconium silicate, 2-4 parts calcium triphosphate, 1-7 parts strontium carbonate, 2-7 parts sodium fluoride, 5-12 parts potassium carbonate, 1-5 parts calcined alumina, and 6-12 parts sodium hexametaphosphate.

[0012] Preferably, the preparation steps of the inorganic transparent powder are as follows: quartz powder, borax decahydrate, zinc oxide, zirconium silicate, calcium triphosphate, strontium carbonate, sodium fluoride, potassium carbonate, calcined alumina, and sodium hexametaphosphate are thoroughly mixed, then placed in a muffle furnace at 1000-1200℃ to melt and hold for 1-3 hours. After the melt is homogenized and clarified, a uniform glass liquid is formed. The glass liquid is then water-quenched, wet-milled for 3 hours, dried, and sieved to obtain the inorganic transparent powder.

[0013] Preferably, the preparation method of the white glaze is as follows: inorganic transparent powder, specially treated etched sericite powder, lithium mica powder and titanium dioxide are mixed to form a solid powder, and then the solid powder is added to a liquid dispersion medium, stirred and mixed evenly, ground once and then finely ground 3 to 5 times to obtain the white glaze.

[0014] Preferably, after the white glaze is tempered on the base glass, its adhesion is grade 0, and it does not change color or peel off after being soaked in 3.7% hydrochloric acid for 24 hours.

[0015] The beneficial effects of this invention are:

[0016] 1. In the white glaze of the present invention, serpentine powder with good acid resistance is specially treated to obtain etched serpentine powder, thereby increasing its bonding ability with inorganic transparent powder, maintaining good adhesion while improving acid resistance.

[0017] 2. The white glaze of the present invention also contains lithium mica powder, which works synergistically with the erosion sericite powder to further improve adhesion, reduce the porosity of the glaze layer, and enhance acid resistance.

[0018] 3. The white glaze of this invention has an adhesion grade of 0 and does not change color or peel off after being soaked in 3.7% hydrochloric acid for 24 hours. It has excellent performance and a wide range of applications. Detailed Implementation

[0019] The technical solutions in the embodiments of the present invention are described clearly and completely below. The described embodiments are only a part of the embodiments of the present invention, and not all of them. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall be followed. Where the manufacturers of reagents, instruments, or components are not specified, they are all conventional products that can be purchased commercially.

[0020] Example

[0021] A white glaze with high adhesion and high acid resistance is prepared by the following steps:

[0022] (1) Preparation of inorganic transparent powder: Weigh 25-44 parts of quartz powder, 8-22 parts of borax decahydrate, 7-11 parts of zinc oxide, 9-15 parts of zirconium silicate, 2-4 parts of calcium triphosphate, 1-7 parts of strontium carbonate, 2-7 parts of sodium fluoride, 5-12 parts of potassium carbonate, 1-5 parts of calcined alumina and 6-12 parts of sodium hexametaphosphate according to the weight ratio and put them into a mixer to mix thoroughly. Then place them in a muffle furnace for melting. The melting temperature is 1000-1200℃ and the holding time is 1-3h. After the melt is homogenized and clarified, a uniform glass liquid is formed. Then pour the glass liquid into deionized water for water quenching to obtain glass fragments. Then wet grind the glass fragments in a planetary ball mill for 3h, dry them, and sieve them to obtain inorganic transparent powder with a particle size of 2500-3500 mesh.

[0023] (2) Preparation of etched sericite powder: Hydrochloric acid and water are mixed to prepare a hydrochloric acid solution. The mass fraction of the hydrochloric acid solution is controlled at 5-10%. The sericite powder is placed in the hydrochloric acid solution at room temperature, stirred evenly, and soaked for 2-8 hours. Then it is filtered, washed with deionized water 3-5 times, dried at low temperature, and sieved to obtain specially treated etched sericite powder with a particle size controlled at 1250-2500 mesh.

[0024] (3) Preparation of white glaze: 30-56 parts of inorganic transparent powder, 3-12 parts of specially treated etched sericite powder, 7-14 parts of 1250-2500 mesh lithium mica powder and 28-52 parts of titanium dioxide are mixed to form a solid powder. The solid powder is then added to a liquid dispersion medium, with the amount of liquid dispersion medium added being 20-35% of the weight of the solid powder. The mixture is stirred and mixed evenly to obtain a mixture. The mixture is then coarsely ground once by a sand mill to obtain a coarsely ground material. The coarsely ground material is then finely ground 3-5 times by a three-roll mill to obtain a white glaze.

[0025] Preliminary Example

[0026] The specially treated etched sericite powder was prepared according to step (2) in the embodiment. The treatment method is shown in Table 1.

[0027] Table 1. Processing methods for etching sericite powder

[0028] Handling method hydrochloric acid concentration Soaking time (h) Should deionized water be used for cleaning? A1 5％ 8 yes A2 8％ 5 yes A3 10％ 2 yes B1 2％ 8 yes B2 15％ 1 yes B3 10％ 2 no B4 15％ 2 yes B5 5％ 9 yes

[0029] Examples 1 to 5 and Comparative Examples 1 to 11

[0030] The inorganic transparent powder prepared according to step (2) in the embodiment, combined with the etched sericite powder prepared in the preliminary embodiment, and the finished white glaze prepared according to step (3) in the embodiment, are shown in Table 2.

[0031] Table 2 Raw material ratio of solid powder

[0032]

[0033]

[0034] Effect Example

[0035] The finished white glazes prepared in Examples 1-5 and Comparative Examples 1-11 were screen-printed onto base glass with dimensions of 100*100mm and a thickness of 4mm. The semi-finished product was dried in a high-temperature drying tunnel at 150-220℃. This semi-finished product was then tempered at 680-720℃ for 100-400s to obtain finished glass with the printed white glaze. The glaze layer was then tested for adhesion and acid resistance. Adhesion was tested using a cross-cut tester according to GB / T 9286-2021 standard. Acid resistance was tested by immersing the finished glass in 3.7% hydrochloric acid at room temperature for 24 hours, followed by observation of discoloration and peeling of the glaze layer. The performance test results are shown in Table 3 below.

[0036] Table 3 Properties of White Glaze

[0037] Adhesion (Grade) Acid resistant (immersion in 3.7% hydrochloric acid at room temperature for 24 hours) Example 1 0 No discoloration or peeling Example 2 0 No discoloration or peeling Example 3 0 No discoloration or peeling Example 4 0 No discoloration or peeling Example 5 0 No discoloration or peeling Comparative Example 1 1 Partial detachment Comparative Example 2 3 Completely detached Comparative Example 3 0 Completely detached Comparative Example 4 3 Completely detached Comparative Example 5 0 Partial detachment Comparative Example 6 4 Completely detached Comparative Example 7 0 Partial detachment Comparative Example 8 2 Partial detachment Comparative Example 9 2 Partial detachment Comparative Example 10 1 Partial detachment Comparative Example 11 0 Completely detached

[0038] As can be seen from Table 3 above, compared with Example 1, although the sericite powder in Comparative Examples 1 to 5 was treated with hydrochloric acid, the etching degree of the sericite powder in Comparative Examples 1 and 2 was not thorough enough, and it could not bond well with the inorganic transparent powder. The adhesion still did not meet the requirements, which increased the porosity of some parts of the glaze layer, making it susceptible to erosion by the acid solution. In Comparative Example 3, the sericite powder was not cleaned after being etched with hydrochloric acid, resulting in some residue. After mixing with the inorganic transparent powder, it was eroded by the residual acid, causing part or even complete peeling off of the glaze layer. Therefore, the etching degree of the sericite powder in Comparative Examples 1 to 5 was not thorough enough, and it could not bond well with the inorganic transparent powder. The adhesion still did not meet the requirements, which increased the porosity of some parts of the glaze layer, making it susceptible to erosion by the acid solution. An inappropriate hydrochloric acid etching method for sericite powder can prevent the etched sericite powder from effectively wetting the inorganic transparent powder, resulting in reduced adhesion and decreased acid resistance. In Comparative Example 4, the etching time for sericite powder was extended, but due to the excessive hydrochloric acid concentration, the reaction was sluggish and effective etching could not be achieved, resulting in a similar effect to Comparative Example 2. In Comparative Example 5, the etching time for sericite powder was extended under a suitable hydrochloric acid concentration, resulting in a greater degree of etching and excellent adhesion. However, this significantly reduced the acid resistance inherent in the sericite powder, leading to a marked decrease in the acid resistance of the glaze layer.

[0039] Compared to Example 1, the untreated sericite powder in Comparative Example 6, although possessing good acid resistance, has a high melting temperature. Direct addition would result in insufficient adhesion, and with poor adhesion, the porosity in the glaze layer increases, making it more susceptible to acid erosion and drastically reducing acid resistance. In contrast, Examples 1 to 5 of the present invention subject the sericite powder to hydrochloric acid etching in the early stages, followed by thorough etching and cleaning, which increases its surface activity. This significantly improves the wettability of the etched sericite powder with the inorganic transparent powder, enhancing adhesion, sintering performance, reducing porosity, and improving acid resistance.

[0040] Compared with Example 1, Comparative Example 8 did not add lepidolite powder, and the adhesion could not reach level 0. At the same time, due to the presence of specially treated etched sericite powder, it has certain acid resistance, so the glaze layer did not completely fall off.

[0041] Compared with Example 2, Comparative Example 7, which did not add etched sericite powder or untreated sericite powder, although had excellent adhesion, lacked the synergistic effect of specially treated etched sericite powder, resulting in a severe reduction in the acid resistance of the glaze layer, making it easy for the glaze layer to peel off.

[0042] Compared to Example 3, the lepidolite powder in Comparative Examples 9 and 10 had a larger particle size, requiring more inorganic transparent powder for encapsulation and bonding during tempering. Under the same conditions, it did not achieve a level 10 adhesion, which correspondingly reduced the acid resistance. In Comparative Example 11, the lepidolite powder had a smaller particle size, which not only significantly increased the cost of use but also, due to its significantly better adhesion and sintering performance, significantly reduced the reflectivity of the glaze, resulting in a poorer performance. Therefore, adding lepidolite powder with a particle size of 1250-2500 mesh to solid powder to prepare white glaze has better adhesion than untreated sericite powder and inorganic transparent powder. At the same time, it has a synergistic effect with the etched sericite powder, further improving the adhesion and acid resistance of the glaze.

[0043] Therefore, in this invention, Examples 1 to 5 use etched sericite powder, which is obtained by treating sericite powder with a 5-10% hydrochloric acid solution for 2-8 hours. The etched sericite is then mixed with lepidolite (1250-2500 mesh particle size), inorganic transparent powder, and titanium dioxide in a certain ratio to form a solid powder. The solid powder is then mixed with a liquid dispersion medium to prepare a white glaze. After printing and tempering, the glaze layer adhesion is grade 0, and it does not change color or peel off after being soaked in 3.7% hydrochloric acid for 24 hours, exhibiting good performance.

[0044] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from its spirit and essential characteristics. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, it is intended that all variations falling within the meaning and scope of equivalents of the claims be included within the present invention.

[0045] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A white glaze with high adhesion and high acid resistance, characterized in that, The white glaze comprises solid powder and liquid dispersion medium; the solid powder comprises the following raw materials and their weight parts: 30-56 parts of inorganic transparent powder, 3-12 parts of specially treated etched sericite powder, 7-14 parts of lithium mica powder, and 28-52 parts of titanium dioxide; The processing method of specially treated etchable sericite powder is as follows: sericite powder is placed in hydrochloric acid solution at room temperature, stirred evenly, and fully soaked. Then it is filtered, washed 3-5 times, dried at low temperature, and sieved to obtain specially treated etchable sericite powder; the mass fraction of the hydrochloric acid solution is 5-10%; the soaking time is 2-8 hours. The inorganic transparent powder comprises the following raw materials and their weight parts: 25-44 parts quartz powder, 8-22 parts borax decahydrate, 7-11 parts zinc oxide, 9-15 parts zirconium silicate, 2-4 parts calcium triphosphate, 1-7 parts strontium carbonate, 2-7 parts sodium fluoride, 5-12 parts potassium carbonate, 1-5 parts calcined alumina, and 6-12 parts sodium hexametaphosphate.

2. The high-adhesion, high-acid-resistant white glaze according to claim 1, characterized in that, The specially treated etched sericite powder has a particle size of 1250~2500 mesh.

3. The high-adhesion, high-acid-resistant white glaze according to claim 1, characterized in that, The inorganic transparent powder has a particle size of 2500-3500 mesh; the lithium mica powder has a particle size of 1250-2500 mesh.

4. The high-adhesion, high-acid-resistant white glaze according to claim 1, characterized in that, The preparation steps of the inorganic transparent powder are as follows: Quartz powder, borax decahydrate, zinc oxide, zirconium silicate, calcium triphosphate, strontium carbonate, sodium fluoride, potassium carbonate, calcined alumina and sodium hexametaphosphate are thoroughly mixed, and then placed in a muffle furnace at 1000~1200℃ to melt and keep warm for 1~3 hours. After the melt is homogenized and clarified, a uniform glass liquid is formed. The glass liquid is then water-quenched, wet-milled for 3 hours, dried and sieved to obtain the inorganic transparent powder.

5. The high-adhesion, high-acid-resistant white glaze according to claim 1, characterized in that, The preparation method of the white glaze is as follows: inorganic transparent powder, specially treated etched sericite powder, lithium mica powder and titanium dioxide are mixed to form a solid powder. The solid powder is then added to a liquid dispersion medium and stirred and mixed evenly. The mixture is first ground once and then finely ground 3 to 5 times to obtain the white glaze.

6. A high-adhesion, high-acid-resistant white glaze according to claim 1 or 5, characterized in that, After being tempered on the base glass, the white glaze has an adhesion rating of 0 and does not change color or peel off after being soaked in 3.7% hydrochloric acid for 24 hours.

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