An enamel wet-process two-spray one-firing ground coat glaze material and preparation method thereof

Abstract

The present invention discloses an enamel wet-process two-spray one-firing ground coat glaze material and a preparation method therefor. The glaze material comprises the following raw materials in percentage by mass: SiO2 30%-50%, B2O3 10%-20%, Al2O3 3%-8%, CaO 1%-5%, TiO2 2%-8%, BaO 1%-5%, Na2O 10%-20%, K2O 3%-8%, MgO 0.5%-1.0%, CaF2 3%-8%, ZnO 1%-4%, CoO 0.2%-0.8%, CuO 0.3%-1.0%, NiO 0.3%-1.0%, and MnO2 0.2%-0.8%. The preparation method comprises: weighing each raw material, then mixing uniformly to obtain the glaze material. The ground coat glaze of the present invention has a simple priming process, high production efficiency, low production cost, and low firing temperature. Good adhesion can be obtained at low temperature, the fired glaze surface is smooth and fine, after applying the cover coat glaze, there is no show-through of the ground coat, no black exposure, the enamel layer surface has no pinholes, and the enamel surface quality is good.

Description

A wet-process two-spray one-fire base glaze for enamel and its preparation method Technical Field

[0001] This invention relates to the field of enamel glaze technology, and more specifically to an enamel wet-process two-spray one-fire base glaze and its preparation method. Background Technology

[0002] Enameled products are products made by coating a metal blank with enamel glaze, and are commonly referred to simply as enamel. They possess the mechanical strength of metal and the physicochemical properties of enamel, and are decorative. Enameled products are typically categorized by use into daily-use enamel, sanitary enamel, industrial enamel, architectural enamel, medical enamel, artistic enamel, and special enamel.

[0003] Currently, there are basically two methods for applying a base coat to enamel products on the market: electrostatic dry two-spray-one-fire base coat and wet glaze base coat. Electrostatic dry two-spray-one-fire base coat has high production efficiency, low labor intensity, and a relatively high degree of automation; however, it has high material costs, some colors are prone to showing through to reveal the base coat, and it produces a lot of dust, seriously affecting the health of operators. Furthermore, with the diversification of colors and shapes of decorative enamel plates, some colors obtained using the electrostatic dry two-spray-one-fire base coat can no longer meet customer needs, necessitating the use of wet glaze base coat to produce the corresponding color effects.

[0004] Currently, most wet-process base glaze coatings on the market are applied using a two-spray, two-fire method. Specifically, the base glaze is first sprayed onto a steel plate, fired, and cooled, then the top glaze is sprayed on and fired again. However, this method requires two sprayings and two firings at high temperatures, severely impacting production efficiency and increasing costs.

[0005] Therefore, how to improve the production efficiency of wet-process base glaze application while saving costs is a problem that urgently needs to be solved by those skilled in the art. Summary of the Invention

[0006] In view of this, the purpose of this invention is to provide a wet-process two-spray one-fire base glaze for enamel and its preparation method, so as to solve the problems of high firing temperature of enamel glaze, complex base-applying process, low production efficiency, and easy exposure of black through the base in the prior art.

[0007] To achieve the above objectives, the present invention adopts the following technical solution:

[0008] A wet-process two-spray one-fire base glaze for enamel comprises the following raw materials in weight percentages: SiO2 30%-50%, B2O3 10%-20%, Al2O3 3%-8%, CaO 1%-5%, TiO2 2%-8%, BaO 1%-5%, Na2O 10%-20%, K2O 3%-8%, MgO 0.5%-1.0%, CaF2 3%-8%, ZnO 1%-4%, CoO 0.2%-0.8%, CuO 0.3%-1.0%, NiO 0.3%-1.0%, and MnO2 0.2%-0.8%.

[0009] The preferred composition is: SiO2 43.27%, B2O3 14.30%, Al2O3 3.61%, CaO 1.93%, TiO2 3.44%, BaO 1.78%, Na2O 18.49%, K2O 4.28%, MgO 0.73%, CaF2 4.59%, ZnO 1.15%, CoO 0.57%, CuO 0.57%, NiO 0.72%, and MnO 0.57%.

[0010] Alternatively, preferably: SiO2 48%, B2O3 14.3%, Al2O3 2%, CaO 1.93%, TiO2 2%, BaO 1.78%, Na2O 16.81%, K2O 4.28%, MgO 0.73%, CaF2 4.59%, ZnO 1.15%, CoO 0.57%, CuO 0.57%, NiO 0.72%, and MnO2 0.57%.

[0011] Alternatively, preferably: SiO2 40%, B2O3 14.3%, Al2O3 5%, CaO 1.93%, TiO2 5.32%, BaO 1.78%, Na2O 18.49%, K2O 4.28%, MgO 0.73%, CaF2 4.59%, ZnO 1.15%, CoO 0.57%, CuO 0.57%, NiO 0.72%, and MnO 0.57%.

[0012] Alternatively, preferably: SiO2 43.27%, B2O3 18%, Al2O3 3.61%, CaO 1.93%, TiO2 3.44%, BaO 1.78%, Na2O 14.79%, K2O 4.28%, MgO 0.73%, CaF2 4.59%, ZnO 1.15%, CoO 0.57%, CuO 0.57%, NiO 0.72%, and MnO2 0.57%.

[0013] Alternatively, preferably: SiO2 43.27%, B2O3 14.3%, Al2O3 3.61%, CaO 1.93%, TiO2 6%, BaO 1.78%, Na2O 15.93%, K2O 4.28%, MgO 0.73%, CaF2 4.59%, ZnO 1.15%, CoO 0.57%, CuO 0.57%, NiO 0.72%, and MnO 0.57%.

[0014] Alternatively, preferably: SiO2 43.27%, B2O3 12.89%, Al2O3 3.61%, CaO 1.93%, TiO2 3.44%, BaO 1.78%, Na2O 18.49%, K2O 4.28%, MgO 0.73%, CaF2 6%, ZnO 1.15%, CoO 0.57%, CuO 0.57%, NiO 0.72%, and MnO 0.57%.

[0015] Alternatively, preferably: SiO2 43.27%, B2O3 16.39%, Al2O3 3.61%, CaO 1.93%, TiO2 3.44%, BaO 1.78%, Na2O 18.49%, K2O 4.28%, MgO 0.73%, CaF2 2.50%, ZnO 1.15%, CoO 0.57%, CuO 0.57%, NiO 0.72%, and MnO2 0.57%.

[0016] Alternatively, preferably: SiO2 43.27%, B2O3 14.3%, Al2O3 3.61%, CaO 1.93%, TiO2 3.44%, BaO 1.78%, Na2O 18.64%, K2O 4.28%, MgO 0.73%, CaF2 4.59%, ZnO 1.15%, CoO 0.57%, CuO 0.57%, NiO 0.57%, and MnO2 0.57%.

[0017] In this invention, SiO2 is the main component of the glaze and the primary glass network former. The higher the SiO2 content in the glaze, the higher the firing temperature. Within a certain range, increasing the SiO2 content can improve the mechanical strength and hardness of the glaze, as well as its chemical and thermal stability.

[0018] B2O3 is not only a solvent for porcelain glaze but also a network former, promoting the formation of the glassy phase at low temperatures. Increasing the B2O3 content enhances the mechanical strength and abrasion resistance of the porcelain glaze.

[0019] Al2O3 is an intermediate oxide that can combine not only with SiO2 but also with basic oxides. It can not only improve the vitrification ability of porcelain glaze but also inhibit crystallization, significantly improve the elasticity, hardness, and chemical stability of the glaze, and enhance its resistance to chemical corrosion.

[0020] CaO is the main solvent in glazes. It can reduce the viscosity of the glaze melt, improve the fluidity and gloss of the glaze, reduce the coefficient of expansion of the glaze, and improve the mechanical strength of the porcelain glaze.

[0021] TiO2 can enhance the opacity, acid resistance, and gloss of porcelain glaze. Due to its good opacity, only a thin layer of glaze needs to be applied, resulting in a porcelain layer with high thermal stability, impact resistance, and flexural strength.

[0022] BaO is a flux. Ba has the largest ionic radius and the strongest basicity among alkali metals. It is also the best flux among alkali metal oxides and can improve the resistance of glazes to organic acid corrosion.

[0023] Na2O and K2O are strong fluxing agents for glazes, which can significantly reduce the melting temperature and high-temperature viscosity of the glaze, increase the refractive index of the glaze, and thus improve the gloss of the glaze surface.

[0024] MgO is also a flux in glazes. It can not only reduce the viscosity of the melt, but also reduce the coefficient of expansion of the glaze and reduce glaze cracking.

[0025] CaF2 is a strong co-solvent that can reduce the high-temperature viscosity of glazes during melting, and also has a significant promoting effect on adhesion.

[0026] ZnO can act as a good flux over a wide range of applications, reducing the coefficient of expansion of the glaze and improving its gloss. However, excessive use can cause the glaze to crystallize, resulting in a loss of transparency.

[0027] CoO, CuO, NiO, and MnO2 are adhesives. These four adhesives interact with each other, reacting with iron to allow the enamel to penetrate the steel plate surface. This promotes the enamel's wetting of the steel plate surface at high temperatures, facilitates the dissolution of iron and iron oxide, controls the oxidation conditions at the interface, and helps the enamel layer form a more uniform bubble structure, resulting in good adhesion between the base enamel and the steel plate.

[0028] A method for preparing a wet-process two-spray one-fire base glaze for enamel includes the following steps: weighing each raw material according to the mass percentage of the above-mentioned wet-process two-spray one-fire base glaze for enamel, mixing them evenly, and thus obtaining the wet-process two-spray one-fire base glaze for enamel.

[0029] As can be seen from the above technical solution, compared with the prior art, the beneficial effects of the present invention are as follows:

[0030] This invention utilizes the overall proportions of the above components, taking advantage of the strong fluxing effect of Na2O and K2O, combined with the fluxing effect of CaF2, and the promoting effect of CoO, CuO, NiO and MnO2 to achieve close adhesion and mutual combination. Furthermore, through interaction with other components, the resulting wet-process base glaze can be sprayed onto a steel plate and then immediately coated with a wet-process top glaze. After drying, it is fired once to form the base. The process is simple, with high production efficiency and low production cost. Moreover, the firing temperature is low, which can achieve good adhesion at low temperatures. The fired glaze surface is smooth and delicate, and after the top glaze is applied, it does not show the base or black spots. The porcelain surface is free of pinholes, resulting in high-quality porcelain. Detailed Implementation

[0031] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. 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.

[0032] Example 1

[0033] The enamel wet-process two-spray one-fire base glaze material includes the following raw materials by weight: SiO2 43.27g, B2O3 14.30g, Al2O3 3.61g, CaO 1.93g, TiO2 3.44g, BaO 1.78g, Na2O 18.49g, K2O 4.28g, MgO 0.73g, CaF2 4.59g, ZnO 1.15g, CoO 0.57g, CuO 0.57g, NiO 0.72g, and MnO2 0.57g;

[0034] The preparation method of the above-mentioned wet-process two-spray one-fire base glaze for enamel specifically includes the following steps: weigh each raw material according to the mass of the above-mentioned wet-process two-spray one-fire base glaze for enamel, mix them evenly, and the wet-process two-spray one-fire base glaze for enamel is obtained.

[0035] Example 2

[0036] The enamel wet-process two-spray one-fire base glaze material includes the following raw materials by weight: SiO2 48g, B2O3 14.3g, Al2O3 2g, CaO 1.93g, TiO2 2g, BaO 1.78g, Na2O 16.81g, K2O 4.28g, MgO 0.73g, CaF2 4.59g, ZnO 1.15g, CoO 0.57g, CuO 0.57g, NiO 0.72g, and MnO2 0.57g;

[0037] The preparation method of the above-mentioned wet-process two-spray one-fire base glaze for enamel specifically includes the following steps: weigh each raw material according to the mass of the above-mentioned wet-process two-spray one-fire base glaze for enamel, mix them evenly, and the wet-process two-spray one-fire base glaze for enamel is obtained.

[0038] Example 3

[0039] The enamel wet-process two-spray one-fire base glaze material includes the following raw materials by weight: SiO2 40g, B2O3 14.3g, Al2O3 5g, CaO 1.93g, TiO2 5.32g, BaO 1.78g, Na2O 18.49g, K2O 4.28g, MgO 0.73g, CaF2 4.59g, ZnO 1.15g, CoO 0.57g, CuO 0.57g, NiO 0.72g, and MnO2 0.57g;

[0040] The preparation method of the above-mentioned wet-process two-spray one-fire base glaze for enamel specifically includes the following steps: weigh each raw material according to the mass of the above-mentioned wet-process two-spray one-fire base glaze for enamel, mix them evenly, and the wet-process two-spray one-fire base glaze for enamel is obtained.

[0041] Example 4

[0042] The enamel wet-process two-spray one-fire base glaze material includes the following raw materials by weight: SiO2 43.27g, B2O3 18g, Al2O3 3.61g, CaO 1.93g, TiO2 3.44g, BaO 1.78g, Na2O 14.79g, K2O 4.28g, MgO 0.73g, CaF2 4.59g, ZnO 1.15g, CoO 0.57g, CuO 0.57g, NiO 0.72g, and MnO2 0.57g;

[0043] The preparation method of the above-mentioned wet-process two-spray one-fire base glaze for enamel specifically includes the following steps: weigh each raw material according to the mass of the above-mentioned wet-process two-spray one-fire base glaze for enamel, mix them evenly, and the wet-process two-spray one-fire base glaze for enamel is obtained.

[0044] Example 5

[0045] The enamel wet-process two-spray one-fire base glaze material includes the following raw materials by weight: SiO2 43.27g, B2O3 14.3g, Al2O3 3.61g, CaO 1.93g, TiO2 6g, BaO 1.78g, Na2O 15.93g, K2O 4.28g, MgO 0.73g, CaF2 4.59g, ZnO 1.15g, CoO 0.57g, CuO 0.57g, NiO 0.72g, and MnO2 0.57g;

[0046] The preparation method of the above-mentioned wet-process two-spray one-fire base glaze for enamel specifically includes the following steps: weigh each raw material according to the mass of the above-mentioned wet-process two-spray one-fire base glaze for enamel, mix them evenly, and the wet-process two-spray one-fire base glaze for enamel is obtained.

[0047] Example 6

[0048] The enamel wet-process two-spray one-fire base glaze material includes the following raw materials by weight: SiO2 43.27g, B2O3 12.89g, Al2O3 3.61g, CaO 1.93g, TiO2 3.44g, BaO 1.78g, Na2O 18.49g, K2O 4.28g, MgO 0.73g, CaF2 6g, ZnO 1.15g, CoO 0.57g, CuO 0.57g, NiO 0.72g, and MnO2 0.57g;

[0049] The preparation method of the above-mentioned wet-process two-spray one-fire base glaze for enamel specifically includes the following steps: weigh each raw material according to the mass of the above-mentioned wet-process two-spray one-fire base glaze for enamel, mix them evenly, and the wet-process two-spray one-fire base glaze for enamel is obtained.

[0050] Example 7

[0051] The enamel wet-process two-spray one-fire base glaze material includes the following raw materials by weight: SiO2 43.27g, B2O3 16.39g, Al2O3 3.61g, CaO 1.93g, TiO2 3.44g, BaO 1.78g, Na2O 18.49g, K2O 4.28g, MgO 0.73g, CaF2 2.50g, ZnO 1.15g, CoO 0.57g, CuO 0.57g, NiO 0.72g, and MnO2 0.57g;

[0052] The preparation method of the above-mentioned wet-process two-spray one-fire base glaze for enamel specifically includes the following steps: weigh each raw material according to the mass of the above-mentioned wet-process two-spray one-fire base glaze for enamel, mix them evenly, and the wet-process two-spray one-fire base glaze for enamel is obtained.

[0053] Example 8

[0054] The enamel wet-process two-spray one-fire base glaze material includes the following raw materials by weight: SiO2 43.27g, B2O3 14.3g, Al2O3 3.61g, CaO 1.93g, TiO2 3.44g, BaO 1.78g, Na2O 18.64g, K2O 4.28g, MgO 0.73g, CaF2 4.59g, ZnO 1.15g, CoO 0.57g, CuO 0.57g, NiO 0.57g, and MnO2 0.57g;

[0055] The preparation method of the above-mentioned wet-process two-spray one-fire base glaze for enamel specifically includes the following steps: weigh each raw material according to the mass of the above-mentioned wet-process two-spray one-fire base glaze for enamel, mix them evenly, and the wet-process two-spray one-fire base glaze for enamel is obtained.

[0056] Performance testing

[0057] The enamel wet-process two-spray one-fire base glaze materials prepared in Examples 1-8 (specific formulas are shown in Table 1) were used as a control group, and were fired under the following three process conditions:

[0058] 820℃, fired for 4 minutes;

[0059] 840℃, fired for 4 minutes;

[0060] 860℃, fire for 4 minutes.

[0061] The enamel plates obtained by firing at different temperatures under the above process conditions were tested for the thickness of the enamel layer, the adhesion grade (GB / T 31567-2015), and the visual quality of the enamel surface. The main observation indicators were: presence or absence of pinholes, severity of orange peel wrinkles, and presence or absence of glaze nodules.

[0062] The test results are shown in Table 2.

[0063] Table 1. Specific formulations of enamel wet-process two-spray one-fire base glaze materials for Examples 1-8.

[0064] Table 2 Test Results of Enamel Wet Two-Spray One-Fire Base Glaze in Examples 1-8

[0065] As shown in Tables 1 and 2, in Examples 1-8, the enamel plates exhibited good adhesion and surface quality, and were superior to the control group, even with varying component masses and firing processes. Example 1 demonstrated the best performance across all aspects, achieving Grade 1 adhesion at 820℃ for 4 minutes, with a smooth and delicate surface free of pinholes, preventing blackening of the base, and exhibiting only slight orange-peel texture.

[0066] The above experiments demonstrate that the base glaze of this invention has a simple base application process, high production efficiency, low production cost, and low firing temperature. It can achieve good adhesion at low temperatures, and the fired glaze surface is smooth and delicate. After the top glaze is applied, it does not show the bottom or black spots. The porcelain surface is free of pinholes and has good porcelain quality.

[0067] The above description of the disclosed embodiments enables those skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A wet process two spray one fire underglaze enamel, characterized in that, Starting materials comprising the following mass percentages: SiO2 30-50%, B2O3 10-20%, Al2O3 3-8%, CaO 1-5%, TiO2 2-8%, BaO 1-5%, Na2O 10-20%, K2O 3-8%, MgO 0.5-1.0%, CaF2 3-8%, ZnO 1-4%, CoO 0.2-0.8%, CuO 0.3-1.0%, NiO 0.3-1.0% and MnO2 0.2-0.8%.

2. A wet process two spray one fire underglaze enamel according to claim 1, characterized in that, Starting materials comprising the following mass percentages: SiO2 43.27%, B2O3 14.30%, Al2O3 3.61%, CaO 1.93%, TiO2 3.44%, BaO 1.78%, Na2O 18.49%, K2O 4.28%, MgO 0.73%, CaF2 4.59%, ZnO 1.15%, CoO 0.57%, CuO 0.57%, NiO 0.72% and MnO2 0.57%.

3. A wet process two spray one fire underglaze enamel according to claim 1, wherein, Starting materials comprising the following mass percentages: SiO2 48%, B2O3 14.3%, Al2O3 2%, CaO 1.93%, TiO2 2%, BaO 1.78%, Na2O 16.81%, K2O 4.28%, MgO 0.73%, CaF2 4.59%, ZnO 1.15%, CoO 0.57%, CuO 0.57%, NiO 0.72% and MnO2 0.57%.

4. A wet process two spray one fire body enamel according to claim 1, wherein, Starting materials comprising the following mass percentages: SiO2 40%, B2O3 14.3%, Al2O3 5%, CaO 1.93%, TiO2 5.32%, BaO 1.78%, Na2O 18.49%, K2O 4.28%, MgO 0.73%, CaF2 4.59%, ZnO 1.15%, CoO 0.57%, CuO 0.57%, NiO 0.72% and MnO2 0.57%.

5. A wet process two spray one fire body enamel according to claim 1, wherein, Starting materials comprising the following mass percentages: SiO2 43.27%, B2O3 18%, Al2O3 3.61%, CaO 1.93%, TiO2 3.44%, BaO 1.78%, Na2O 14.79%, K2O 4.28%, MgO 0.73%, CaF2 4.59%, ZnO 1.15%, CoO 0.57%, CuO 0.57%, NiO 0.72% and MnO2 0.57%.

6. A wet process two spray one fire body enamel according to claim 1, wherein, Raw materials comprising the following mass percentages: SiO243.27%, B2O314.3%, Al2O33.61%, CaO 1.93%, TiO23.44%, BaO 1.78%, Na2O 18.64%, K2O 4.28%, MgO 0.73%, CaF24.59%, ZnO 1.15%, CoO 0.57%, CuO 0.57%, NiO 0.57%, and MnO20.57%.

7. A wet process two spray one fire body enamel according to claim 1, wherein, Raw materials comprising the following mass percentages: SiO243.27%, B2O312.89%, Al2O33.61%, CaO 1.93%, TiO23.44%, BaO 1.78%, Na2O 18.49%, K2O 4.28%, MgO 0.73%, CaF26%, ZnO 1.15%, CoO 0.57%, CuO 0.57%, NiO 0.72%, and MnO20.57%.

8. A wet process two spray one fire body enamel according to claim 1, wherein, Raw materials comprising the following mass percentages: SiO243.27%, B2O316.39%, Al2O33.61%, CaO 1.93%, TiO23.44%, BaO 1.78%, Na2O 18.49%, K2O 4.28%, MgO 0.73%, CaF22.50%, ZnO 1.15%, CoO 0.57%, CuO 0.57%, NiO 0.72%, and MnO20.57%.

9. A wet process two spray one fire body enamel according to claim 1, wherein, Raw materials comprising the following mass percentages: SiO243.27%, B2O314.3%, Al2O33.61%, CaO 1.93%, TiO23.44%, BaO 1.78%, Na2O 18.64%, K2O 4.28%, MgO 0.73%, CaF24.59%, ZnO 1.15%, CoO 0.57%, CuO 0.57%, NiO 0.57%, and MnO20.57%.

10. A method of preparing a wet process two spray one fire underglaze enamel, characterized in that, Specifically comprising the following steps: The raw materials of the wet-process two-spraying one-firing base glaze of the enamel according to any one of claims 1-9 are weighed according to the mass percentages, and mixed uniformly to obtain the wet-process two-spraying one-firing base glaze of the enamel.

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