Preparation method of smooth wear-resistant glaze for building sanitary ceramics

Abstract

The application discloses a preparation method of a smooth wear-resistant glaze for building sanitary ceramics, and the glaze is mainly made of natural minerals, a multicomponent low-temperature eutectic system is constructed by introducing bismuth oxide, antimony oxide, borocalcite and steel slag, and microcrystalline of anorthite and diopside is induced to be cooperatively precipitated in the glaze layer, so that the smooth appearance and wear resistance are simultaneously realized, and the building sanitary ceramic glaze with the smooth surface and high wear resistance is obtained.

Description

Technical Field

[0001] This invention relates to the field of building and sanitary ceramic glaze technology, and in particular to a method for preparing a smooth and wear-resistant glaze for building and sanitary ceramics. Background Technology

[0002] Building and sanitary ceramics (such as ceramic tiles and sanitary ware) have extremely stringent requirements for the performance of their surface glaze. They not only need excellent decorative properties (high whiteness, high gloss, smoothness) but also strong performance characteristics, such as high hardness, high wear resistance, chemical corrosion resistance, and ease of cleaning. Traditional glazes are mostly glassy phases, which have limitations in hardness and wear resistance, making it difficult to meet the durability requirements of floor tiles or frequently used sanitary ware in high-traffic areas (such as airports and shopping malls).

[0003] In-situ precipitation of high-hardness crystals in high-gloss glazes is an effective way to improve wear resistance. Both anorthite and diopside are crystalline phases with high hardness and stable chemical properties. However, simultaneously and controllably precipitating these two crystalline phases while maintaining the ultra-smoothness of the glaze within the commonly used firing temperature range (1180–1250℃) for building and sanitary ceramics is a significant challenge. Summary of the Invention

[0004] The purpose of this invention is to overcome the shortcomings of the prior art and provide a method for preparing a smooth and wear-resistant glaze for building and sanitary ceramics. The method uses natural minerals as the main body and introduces bismuth oxide, antimony oxide, borate, and steel slag to construct a multi-element low-temperature eutectic system. In the glaze layer, the synergistic precipitation of anorthite and diopside microcrystals is induced, thereby simultaneously achieving a smooth appearance and wear resistance, and obtaining a building and sanitary ceramic glaze with a smooth surface and high wear resistance.

[0005] The objective of this invention is achieved through the following technical solution:

[0006] This invention provides a method for preparing a smooth, wear-resistant glaze for building and sanitary ceramics. The raw material composition of the smooth, wear-resistant glaze is as follows: potassium feldspar 27-32 wt%, quartz 15-22 wt%, kaolin 8-13 wt%, talc 5-9 wt%, calcite 10-17 wt%, borocalcite 3-7 wt%, wollastonite 2-5 wt%, steel slag 4-7 wt%, bismuth oxide 2-4 wt%, and antimony oxide 2-5 wt%; the chemical composition of the steel slag is SiO2 12.1. The composition of the following ingredients is as follows: ~16.9wt%, Al2O3 0.64~2.33wt%, K2O 0.01~0.05wt%, Na2O 0.005~0.017wt%, MgO 5.44~8.75wt%, CaO 37.94~46.88wt%, Fe2O3 22.12~28.91wt%, TiO2 0.005~0.15wt%, IL 6.45~11.72wt%; The preparation method includes the following steps:

[0007] (1) Mix the raw materials according to the above composition, place them in a ball mill for ball milling, and then age the resulting slurry to obtain a glaze slurry;

[0008] (2) The glaze slurry is applied to the surface of the unglazed body to obtain a glaze layer with a thickness of 0.12 to 0.18 mm. After drying, it is sintered at a temperature of 1160 to 1190 °C for 15 to 25 min to obtain a smooth and wear-resistant glaze with a Vickers hardness greater than 580 HV and a roughness of <0.0068 μm.

[0009] Furthermore, in step (1) of the present invention, ball milling is performed at a mass ratio of material:ball:water = 1:2-3:0.5-1.5, and the ball milling time is 2-4 hours; the aging time is 24-45 hours.

[0010] The present invention has the following beneficial effects:

[0011] (1) The technical innovation of this invention lies in the fact that the high-valence antimony ions released from the antimony oxide at high temperature can partially integrate into the silicon-oxygen tetrahedral structure of the glaze glass network, serving as network intermediates and connecting with the silicon-oxygen tetrahedra, thereby enhancing the stability of the glass network structure. This process effectively strengthens the glass phase matrix, resulting in a significant improvement in the hardness of the glaze surface.

[0012] (2) By optimizing the raw material formulation, this invention successfully constructed a K-Ca-Mg-Fe-B-Sb-Bi multi-component low-temperature eutectic system. This system can significantly reduce the melting temperature of the glaze and promote the formation of anorthite and diopside crystal phases. Calcite, borate, and wollastonite provide Ca, talc provides MgO, and kaolin and quartz provide Al2O3 and SiO2. Furthermore, under the action of this multi-component low-temperature eutectic system, the firing temperature and holding time are reduced, allowing anorthite and diopside crystals to precipitate in situ in a uniform and fine form within the glaze glass phase, ensuring the high wear resistance of the glaze surface.

[0013] (3) In this invention, bismuth oxide and antimony oxide are used as powerful low-temperature fluxes to reduce the high-temperature viscosity of the glaze and improve the internal fluidity of the melt. The B2O3 component introduced by borate not only reduces the firing temperature of the glaze but also ensures that the glaze melts and flows smoothly and continuously during firing. Steel slag is used as a flux. These functional raw materials, together with the basic minerals such as potassium feldspar and calcite, form a eutectic system that synergistically endows the glaze with excellent high-temperature characteristics of low viscosity, high fluidity, and strong spreading. This characteristic allows the glaze melt to fully fill surface micro-defects and achieves leveling under the action of surface tension, ultimately solidifying to form an ultra-smooth and high-gloss surface. Attached Figure Description

[0014] The present invention will now be described in further detail with reference to the embodiments and accompanying drawings:

[0015] Figure 1 This is a two-dimensional morphological analysis image of the glaze surface of the sample obtained in Embodiment 3 of the present invention using atomic force microscopy;

[0016] Figure 2 This is an atomic force microscope three-dimensional morphology analysis image of the glaze surface of the sample obtained in Embodiment 3 of the present invention;

[0017] Figure 3 This is the crystal phase diagram of the sample obtained in Example 3 of the present invention. Detailed Implementation

[0018] This invention discloses a method for preparing a smooth and wear-resistant glaze for building and sanitary ceramics. The raw material composition of the smooth and wear-resistant glaze is as follows: potassium feldspar 27-32 wt%, quartz 15-22 wt%, kaolin 8-13 wt%, talc 5-9 wt%, calcite 10-17 wt%, borocalcite 3-7 wt%, wollastonite 2-5 wt%, steel slag 4-7 wt%, bismuth oxide 2-4 wt%, and antimony oxide 2-5 wt%. The preparation method comprises the following steps:

[0019] (1) Mix the raw materials according to the above composition, place them in a ball mill and ball mill them at a mass ratio of material:ball:water = 1:2~3:0.5~1.5 for 2~4 hours. Then, age the slurry for 24~45 hours to obtain the glaze slurry.

[0020] (2) The above glaze slurry is applied to the surface of the unglazed body to obtain a glaze layer with a thickness of 0.12 to 0.18 mm. After drying, it is sintered at a temperature of 1160 to 1190 °C for 15 to 25 min to obtain a smooth and wear-resistant glaze.

[0021] The raw material composition of the smooth and wear-resistant glaze in each embodiment of the present invention is shown in Table 1; the chemical composition of each raw material is shown in Table 2.

[0022] Table 1. Raw material composition (wt%) of the smooth and wear-resistant glaze in various embodiments of the present invention.

[0023]

[0024] Table 2 Chemical composition (wt%) of each raw material in the embodiments of the present invention

[0025]

[0026] The process parameters for each embodiment of the present invention are shown in Table 3.

[0027] Table 3 Process parameters of various embodiments of the present invention

[0028]

[0029] Comparative Example 1:

[0030] Four sets of experiments were conducted with borate without the addition of calcium borate as the first control, and the other conditions were the same as in Examples 1, 2, 3, and 4.

[0031] Comparative Example 2:

[0032] Using antimony oxide without its addition as Comparative Example 2, four sets of experiments were conducted under the same conditions as in Examples 1, 2, 3, and 4.

[0033] Comparative Example 3:

[0034] Comparative Example 3 was conducted without the addition of bismuth oxide, and the remaining conditions were the same as in Examples 1, 2, 3, and 4. Four sets of experiments were carried out.

[0035] The atomic force microscopy morphology analysis of the sample prepared in Example 3 of this invention is as follows: Figure 1 , Figure 2 As shown, the results indicate that the sample glaze surface is smooth. Figure 3 As shown, anorthite and diopside crystals can precipitate in situ in a uniform and fine form within the glaze glass phase, which helps improve the wear resistance of the glaze surface. The glaze surface hardness was tested according to the test method of GB 3297-1982; the glaze surface roughness was tested according to the test method of GB / T 3810.14-2016. The performance indicators of the glaze surfaces obtained in the various embodiments and comparative examples of this invention are shown in Table 4.

[0036] Table 4 Performance indicators of various embodiments and comparative examples of the present invention

[0037]

[0038] Note: The performance indicators for each comparative example are the average values ​​of the four experimental groups.

Claims

1. A process for the preparation of a smooth wear-resistant glaze for sanitary ceramics, characterized in that: The raw material composition of the smooth wear-resistant glaze is as follows: 27-32 wt% of potassium feldspar, 15-22 wt% of quartz, 8-13 wt% of kaolin, 5-9 wt% of talc, 10-17 wt% of calcite, 3-7 wt% of borycalcite, 2-5 wt% of wollastonite, 4-7 wt% of steel slag, 2-4 wt% of bismuth oxide, and 2-5 wt% of antimony oxide; the chemical composition of the steel slag is as follows: 12.1-16.9 wt% of SiO2, 0.64-2.33 wt% of Al2O3, 0.01-0.05 wt% of K2O, 0.005-0.017 wt% of Na2O, 5.44-8.75 wt% of MgO, 37.94-46.88 wt% of CaO, 22.12-28.91 wt% of Fe2O3, 0.005-0.15 wt% of TiO2, and 6.45-11.72 wt% of IL; and the preparation method comprises the following steps: (1) the raw materials are mixed according to the above composition, and are subjected to ball milling treatment in a ball mill, and the obtained slurry is subjected to aging treatment to obtain glaze slurry; (2) the glaze slurry is applied to the surface of a blank to obtain a glaze layer with a thickness of 0.12-0.18 mm, and after drying, sintering treatment is carried out at a temperature of 1160-1190 ℃, and the holding time is 15-25 min, to obtain a smooth wear-resistant glaze with a Vickers hardness greater than 580 HV and a roughness less than 0.0068 μm. 2) A process for the preparation of a smooth wear-resistant glaze for architectural sanitary ceramics according to claim 1, characterized in that: In step (1), the ball milling treatment is carried out according to the mass ratio of material: ball: water = 1: 2-3: 0.5-1.5, and the ball milling time is 2-4 h; and the aging time is 24-45 h.

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