Composite glaze layer, ceramic tile with golden velvet texture and preparation method of ceramic tile

Abstract

The invention provides a composite glaze layer, a ceramic tile with a golden velvet texture and a preparation method of the ceramic tile. The composite glaze layer comprises a zirconium ground glaze layer, a golden velvet basic cover glaze layer, an ink-jet decorative layer and a protective glaze layer which are sequentially arranged, the formula of each of the gold velvet basic cover glaze layer and the protective glaze layer comprises high-calcium-magnesium frit powder, high-zinc-aluminum frit powder, high-strontium-aluminum frit powder and kaolin frit powder. According to the invention, the high-calcium-magnesium frit powder, the high-zinc-aluminum frit powder, the high-strontium-aluminum frit powder and the kaolin frit powder are introduced into the formula of the gold velvet basic cover glaze layer and the protective glaze layer at the same time for comprehensive adjustment, so that the comprehensive adjustment capability of the formula on high-temperature viscosity, surface tension, firing range and glaze surface opacity is improved; according to the invention, the content of magnesium oxide can be increased to 5-6%, the content of aluminum oxide can be increased to 15-18%, the content of calcium oxide can be reduced to 4-6%, and meanwhile, the texture effects of high-quality glaze and low surface roughness can still be obtained.

Description

Technical Field

[0001] The present invention relates to the technical field of ceramic production, and particularly relates to a composite glaze layer, a ceramic tile with a velvet texture, and a preparation method thereof. Background Art

[0002] Among various tile products used for indoor and outdoor space decoration, people increasingly prefer products without bright light stimulation. Antique tiles are mainly soft light and matte, without light pollution. Due to their dense surface, they have excellent stain resistance and are easy to clean and maintain. They have now largely replaced materials such as natural stone, wood, wallpaper, and wallcloth, and have gradually become the best choice for wall and floor decoration materials. Therefore, various processes are usually required to simulate numerous textures and develop various ceramic tile products with different surface gloss degrees to meet the different needs of consumers. Among them, ceramic tile products with a suitable surface gloss degree and a smooth and skin-friendly texture are called delicate glaze, velvet, velvet or skin glaze ceramic tiles, which are loved by many consumers.

[0003] The final surface roughness Ra of the glaze surface of the ceramic tile must be controlled to Ra < 2.0 μm so that the texture felt by touching the glaze surface by hand can be relatively delicate and smooth. That is to say, the lower the surface roughness of the product, the more delicate and smooth it is.

[0004] Currently, in most ceramic tiles with a velvet texture in the building ceramics industry with a gloss degree less than 30 degrees, when the alumina content is greater than 15%, the magnesia is less than 4% and the calcium oxide is less than 6%, it is difficult to achieve a surface roughness Ra of less than 1.20 μm for the glaze surface. Therefore, the surface roughness of the existing ceramic tiles with a small gloss degree and a velvet texture is relatively high, resulting in a poor texture of the glaze surface.

[0005] Therefore, the existing technology has defects and needs to be improved and developed. Summary of the Invention

[0006] The technical problem to be solved by the present invention is to provide a composite glaze layer, a ceramic tile with a velvet texture, and a preparation method thereof in view of the above defects of the existing technology, aiming to solve the problem that the surface roughness of the existing ceramic tiles with a small gloss degree and a velvet texture is relatively high, resulting in a poor texture of the glaze surface.

[0007] The technical solution adopted by the present invention to solve the technical problem is as follows:

[0008] The first aspect embodiment of the present application provides a composite glaze layer, wherein the composite glaze layer includes: a zirconium base glaze layer, a velvet base surface glaze layer, an inkjet decoration layer, and a protective glaze layer arranged in sequence; the formulations of the velvet base surface glaze layer and the protective glaze layer both include: high-calcium magnesium frit powder, high-zinc aluminum frit powder, high-strontium aluminum frit powder, and kaolin frit powder.

[0009] In one embodiment of the present application, the protective glaze layer is obtained by electrostatic spraying of glaze.

[0010] In one embodiment of the present application, the raw material formula of the velvet-based glaze layer, by mass, includes:

[0011] 15 - 30 parts of potassium feldspar, 0 - 10 parts of sodium feldspar, 5 - 8 parts of kaolin, 3 - 5 parts of zinc oxide, 0 - 6 parts of dolomite, 0 - 10 parts of calcined talc, 2 - 4 parts of barium carbonate, 2 - 4 parts of strontium carbonate, 6 - 30 parts of high-calcium magnesium frit powder, 10 - 18 parts of high-zinc aluminum frit powder, 5 - 15 parts of high-strontium aluminum frit powder, 7 - 12 parts of kaolin frit powder.

[0012] In one embodiment of the present application, the raw material formula of the protective glaze layer, by mass, includes:

[0013] 15 - 30 parts of potassium feldspar, 0 - 10 parts of sodium feldspar, 5 - 8 parts of kaolin, 3 - 5 parts of zinc oxide, 0 - 6 parts of dolomite, 0 - 10 parts of calcined talc, 2 - 4 parts of barium carbonate, 2 - 4 parts of strontium carbonate, 6 - 30 parts of high-calcium magnesium frit powder, 10 - 18 parts of high-zinc aluminum frit powder, 5 - 15 parts of high-strontium aluminum frit powder, 0 - 8 parts of kaolin frit powder.

[0014] In one embodiment of the present application, the chemical composition of the velvet-based glaze layer, by mass, includes:

[0015] 48 - 51 parts of SiO2, 19 - 25 parts of Al2O3, 4.7 - 6 parts of CaO, 5 - 6 parts of MgO, 3.1 - 5.0 parts of K2O, 0.6 - 1.3 parts of Na2O, 2.8 - 4.0 parts of BaO, 4.0 - 6.0 parts of ZnO, 2.5 - 4.0 parts of ZrO2, 1.5 - 2.5 parts of SrO;

[0016] The chemical composition of the protective glaze layer, by mass, includes:

[0017] 48 - 51 parts of SiO2, 16 - 19 parts of Al2O3, 4.7 - 6 parts of CaO, 5 - 6 parts of MgO, 3.1 - 5.0 parts of K2O, 0.6 - 1.3 parts of Na2O, 2.8 - 4.0 parts of BaO, 4.0 - 6.0 parts of ZnO, 1.5 - 2.5 parts of SrO.

[0018] In one embodiment of the present application, the chemical composition of the high-calcium magnesium frit powder, by mass, includes:

[0019] 48 - 61 parts of SiO2, 10 - 15 parts of Al2O3, 0 - 0.1 part of Fe2O3, 10 - 21 parts of CaO, 10 - 15 parts of MgO, 0.1 - 0.2 part of K2O, 0.1 - 0.2 part of Na2O, 1.3 - 3.5 parts of ZnO;

[0020] The chemical composition of the high - zinc aluminum frit powder, by mass parts, includes:

[0021] 43 - 49 parts of SiO2, 21.0 - 23.5 parts of Al2O3, 0 - 0.1 part of Fe2O3, 15 - 19 parts of CaO, 0.5 - 2.0 parts of MgO, 1.0 - 2.4 parts of K2O, 1.5 - 3.5 parts of Na2O, 6.3 - 7.5 parts of ZnO, 8.5 - 9 parts of BaO;

[0022] The chemical composition of the high - strontium aluminum frit powder, by mass parts, includes:

[0023] 48.9 - 51.6 parts of SiO2, 14.1 - 16.3 parts of Al2O3, 0 - 0.1 part of Fe2O3, 0 - 4 parts of CaO, 0.5 - 2.0 parts of MgO, 0.1 - 0.4 part of K2O, 3.5 - 7.5 parts of Na2O, 15 - 22 parts of SrO, 0.5 - 2.5 parts of BaO;

[0024] The chemical composition of the kaolin frit powder, by mass parts, includes:

[0025] 40 - 45 parts of SiO2, 45 - 55 parts of Al2O3, 0.1 - 0.2 part of Fe2O3, 0 - 0.5 part of TiO2.

[0026] In an embodiment of the present application, the raw material formula of the zirconium bottom glaze layer, by mass parts, includes:

[0027] 7 - 15 parts of quartz, 3 - 11 parts of aluminum zirconium powder, 8 - 11 parts of kaolin, 5 - 25 parts of nepheline syenite, 10 - 20 parts of potassium feldspar, 7 - 18 parts of albite, 2 - 3 parts of calcined talc, 0 - 5 parts of wollastonite, 0 - 4 parts of calcined kaolin, 1 - 10 parts of high - aluminum frit powder, 5 - 15 parts of lithium ore tailings;

[0028] The chemical composition of the zirconium bottom glaze layer, by mass parts, includes:

[0029] 48 - 49 parts of SiO2, 21.5 - 22.1 parts of Al2O3, 0 - 0.1 part of Fe2O3, 8 - 9 parts of CaO, 2.5 - 3 parts of MgO, 1.0 - 1.4 part of K2O, 3.5 - 4 parts of Na2O, 5 - 7 parts of ZrO2, 1.3 - 1.5 parts of ZnO, 8.5 - 9 parts of BaO.

[0030] In the second aspect of the embodiments of the present application, a ceramic tile with a velveteen texture is provided. Among them, the ceramic tile includes a ceramic body and the composite glaze layer as described above applied to the ceramic body; the raw material formula of the ceramic body includes, by mass:

[0031] 8 - 10 parts of sandstone shale powder, 5 - 8 parts of waste porcelain powder, 3 - 5 parts of waste from edge grinding, polishing and pressing mud, 20 - 30 parts of washed potassium - sodium stone particles, 10 - 12 parts of sericite clay material, 18 - 20 parts of washed mud, 3 - 5 parts of ball clay, 1 - 3 parts of bentonite, 8 - 10 parts of kaolin, 2 - 3 parts of magnesia mud, 2 - 15 parts of lithium ore tailings, 0 - 5 parts of biomass ash residue, 0 - 3 parts of secondary denitrified aluminum ash.

[0032] In the third aspect of the embodiments of the present application, a preparation method of the above - mentioned ceramic tile with a velveteen texture is provided. Among them, the method includes:

[0033] Glaze is sprayed on the surface of the pre - prepared ceramic body to form a zirconium bottom glaze layer;

[0034] Glaze is sprayed on the zirconium bottom glaze layer to form a velveteen base glaze layer;

[0035] Ink - jet decoration is carried out on the velveteen base glaze layer to obtain an ink - jet decoration layer;

[0036] A protective glaze layer is sprayed on the ink - jet decoration layer by an electrostatic spraying method, and after firing, a ceramic tile with a velveteen texture is obtained.

[0037] In an embodiment of the present application, a protective glaze layer is sprayed on the ink - jet decoration layer by an electrostatic spraying method, and after firing, a ceramic tile with a velveteen texture is obtained, including:

[0038] The protective glaze layer is sprayed on the ink - jet decoration layer by an electrostatic spraying method with a glaze amount of 150 - 200 g / m 2 , and firing is carried out at a temperature of 1120 - 1180 °C to obtain a ceramic tile with a velveteen texture;

[0039] Among them, the glaze slurry specific gravity of the protective glaze layer is 1.20 - 1.40, the pH is 7 - 8, and the resistivity ≤ 1.2 MΩ·cm.

[0040] The present invention provides a composite glaze layer, a ceramic tile with a velvet texture and a preparation method thereof. The composite glaze layer includes: a zirconium primer glaze layer, a velvet base glaze layer, an inkjet decoration layer, and a protective glaze layer arranged in sequence. In the formulations of both the velvet base glaze layer and the protective glaze layer, there are included: high-calcium magnesium frit powder, high-zinc aluminum frit powder, high-strontium aluminum frit powder, and kaolin frit powder. By comprehensively adjusting by introducing high-calcium magnesium frit powder, high-zinc aluminum frit powder, high-strontium aluminum frit powder, and kaolin frit powder into the formulations of the velvet base glaze layer and the protective glaze layer simultaneously, the present invention improves the comprehensive adjustment ability of the high-temperature viscosity, surface tension, firing range, and glaze turbidity of the formulation, and can increase the magnesium oxide content to 5-6%, the aluminum oxide content to 15-18%, and reduce the calcium oxide content to between 4-6% while still being able to obtain a high-quality glaze surface and a texture effect with low surface roughness. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] Figure 1 is a schematic structural diagram of a ceramic tile with a velvet texture in the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0042] For the purpose, technical solutions and advantages of the present invention to be more clear and definite, the following further describes the present invention in detail with reference to the attached drawings and by way of examples. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0043] For the matte surface glaze formulation, special attention should be paid to the influence relationship of the component matching on the initial melting temperature, high-temperature viscosity, surface tension, and firing range during each firing stage. Especially for the case where the firing temperature is lower than 1150 °C, alumina in the glaze is usually introduced by alumina, calcined kaolin, kaolin, and feldspar materials. When the content is relatively high (if it is greater than 15%), the initial melting point and high-temperature viscosity of the glaze increase particularly rapidly, while the change in surface tension is relatively small, and the surface roughness of the fired product increases significantly. The content of magnesium oxide is usually introduced by dolomite, calcined talc, diopside, etc. However, when its content is relatively high and introduced by natural raw materials (if magnesium oxide is greater than 4%), it will cause the initial melting point, high-temperature viscosity, and surface tension of the glaze to increase particularly rapidly, and the transparency of the glaze will also be greatly reduced. The content of calcium oxide is usually introduced by dolomite, calcite, frit powder, etc. However, when its content is relatively high (if it is greater than 6%), it will cause the initial melting point, high-temperature viscosity, and surface tension of the glaze to decrease particularly rapidly. Therefore, for most ceramic tiles with a velvet texture and a glossiness less than 30 degrees in the current building ceramics industry, when the alumina content in the surface glaze is greater than 15%, the magnesium oxide content is less than 4%, and the calcium oxide content is less than 6%, it is very difficult to achieve a surface roughness Ra of less than 1.20 μm for the glaze surface. To ensure the velvet-like delicate texture and glaze quality of the above-mentioned process ceramic products, the initial melting temperature of the surface glaze needs to be adjusted relatively low. If a relatively thin surface glaze layer is applied by pouring glaze directly on the green body layer, and the thickness of the green body layer is thick, the relatively low-temperature surface glaze will quickly melt and prematurely seal the underlying green body layer, resulting in poor exhaust during firing of the body-glaze bonding layer. The greater the application amount of the low-temperature surface glaze, the more likely it is for the glaze surface to appear with prickly heat, bubbles, and pinholes, which are obvious quality defects. Therefore, it is very difficult to balance the initial melting point, high-temperature viscosity, surface tension, and firing temperature range of the glaze, and the price is often that the quality of the green body materials needs to be significantly improved or the kiln output needs to be sacrificed.

[0044] In addition to the factors in the glaze formulation technology mentioned above, the specific implementation methods of the process may also have a great impact on the realization of the product. In the prior art, the methods for producing ceramic tiles with a velveteen texture generally have two implementation methods: underglaze color and overglaze color. The underglaze color method usually means that a first base glaze layer is applied to the green body, the pattern is inkjet printed, and then the corresponding transparent matte velveteen texture top glaze is applied. Usually, the second top glaze is applied by pouring glaze, and the glaze application amount of the glaze is relatively large, generally with a specific gravity of 1.75 - 1.85 and a glaze amount of 400 - 600 g / square meter. The transparency must be very high, otherwise it will have an unpredictable impact on the overall color and transparent texture of products with darker colors. The process method of the overglaze protective glaze means that a first base glaze layer is applied to the green body, then a layer of corresponding velveteen texture top glaze is applied by pouring glaze, and after the pattern is inkjet printed, the last layer of velveteen texture protective glaze layer is applied. In the above two methods, the main functions of the first base glaze are, firstly, to cover the background color of the green body, and secondly, to effectively buffer and block the adverse effects of harmful gases that may be generated during the firing process on the glaze surface; while the main function of the second top glaze layer is to provide the low surface roughness texture glaze surface effect required by the product; the main function of the third protective layer is to protect the inkjet pattern, and the thickness of the third protective layer will affect the gloss and texture of the second top glaze layer to varying degrees.

[0045] In production practice, in the overglaze color method, there are technical bottleneck problems in the specific implementation method of the protective glaze: since the glaze application amount of the traditional high-pressure glaze spraying cabinet is not less than 250 g / square meter, if the glaze application amount is lower, it means that a lower glaze application specific gravity is required, generally with a glaze application specific gravity less than 1.25. Such a large glaze amount will cause comprehensive defects such as pre-firing explosion of the green body, blistering of the glaze surface, and glaze shrinkage, which have a very great impact on the later quality; some manufacturers also use a rubber roller to apply the protective glaze, but the glaze amount applied by the rubber roller method is too thin, generally less than 5 g / square meter, so there is only a very thin layer for protecting the pattern, and the improvement of the velveteen glaze surface texture completely depends on the second top glaze layer.

[0046] Based on the above deficiencies of the prior art, the first object of the present invention is to develop a new formula of a glaze with a velveteen texture and a low surface roughness, which can flexibly solve the key technical bottleneck problems that are difficult to balance each other in high-temperature properties such as the initial melting point, high-temperature viscosity, surface tension, and firing temperature range of the low surface roughness velveteen texture glaze within the firing range of 1120 - 1180 °C.

[0047] The second object of the present invention is to provide a method for preparing a composite glaze layer by introducing an electrostatic glaze spraying implementation method to replace the traditional high-pressure glaze spraying or rubber roller process used in the implementation of the protective glaze, so as to solve the problems of prickly heat, bubbles, and low production efficiency and poor quality caused by high moisture content in the kiln during the production of underglaze color or overglaze color of traditional velveteen texture ceramic plates.

[0048] The third object of the present invention is to provide a ceramic plate with a velvet texture and low surface roughness and higher production efficiency, which is suitable for the current rigid demands of enterprises for a wider range of raw material selection for wider blanks and rapid firing.

[0049] As Figure 1 shown, an embodiment of the present application provides a composite glaze layer, which includes: a zirconium bottom glaze layer 11, a velvet base glaze layer 12, an inkjet decoration layer 13, and a protective glaze layer 14 arranged in sequence; the formulations of the velvet base glaze layer and the protective glaze layer both include: high-calcium magnesium frit powder, high-zinc aluminum frit powder, high-strontium aluminum frit powder, and kaolin frit powder.

[0050] In the embodiment of the present application, by comprehensively adjusting by introducing high-calcium magnesium frit powder, high-zinc aluminum frit powder, high-strontium aluminum frit powder, and kaolin frit powder into the formulations of the velvet base glaze layer 12 and the protective glaze layer 14 at the same time, the comprehensive adjustment ability of the formulation's high-temperature viscosity, surface tension, firing range, and glaze turbidity is improved, and while the magnesium oxide content is increased to 5-6%, the aluminum oxide content is increased to 15-18%, and the calcium oxide content is reduced to 4-6%, a high-quality glaze surface and a texture effect with low surface roughness can still be obtained.

[0051] Specifically, the raw material formulation of the zirconium bottom glaze layer 11 by mass includes: 7-15 parts of quartz, 3-11 parts of aluminum zirconium powder, 8-11 parts of kaolin, 5-25 parts of nepheline, 10-20 parts of potassium feldspar, 7-18 parts of sodium feldspar, 2-3 parts of calcined talc, 0-5 parts of wollastonite, 0-4 parts of calcined kaolin, 1-10 parts of high-aluminum frit powder, and 5-15 parts of lithium ore tailings.

[0052] The single-firing glossiness of the zirconium bottom glaze layer 11 is controlled to be 3-7 degrees, the glossiness after composite firing of the zirconium bottom glaze layer 11 and the velvet base glaze layer 12 is controlled to be 3-10 degrees, the glossiness after firing of the composite glaze layer is controlled to be 18-25 degrees, and the surface roughness is less than 1.20.

[0053] Among them, the chemical composition of the high-aluminum frit powder by mass includes:

[0054] 48-49 parts of SiO2, 21.5-22.1 parts of Al2O3, 0-0.1 parts of Fe2O3, 8-9 parts of CaO, 2.5-3 parts of MgO, 1.0-1.4 parts of K2O, 3.5-4 parts of Na2O, 5-7 parts of ZrO2, 1.3-1.5 parts of ZnO, 8.5-9 parts of BaO, and 2.5-4 parts of loss on ignition.

[0055] In the embodiment of the present application, the protective glaze layer is obtained by electrostatic spraying.

[0056] The embodiment of the present application uses an electrostatic spraying process to implement high-quality spraying of a protective glaze layer with a higher specific gravity (1.35-1.45) and less glaze amount (100-200 g / m2). Compared with traditional high-pressure glaze spraying (specific gravity below 1.25 and glaze amount of 250 g / m2 or more to achieve the same glaze quality), the moisture entering the kiln can be greatly reduced, thereby reducing the defects of blasting or bubbling of the glaze surface before entering the kiln. Compared with the rubber roller process, the electrostatic spraying protective glaze layer can implement a larger amount of glaze to make up for the texture of the velvet base glaze layer. Since the velvet base glaze layer and the protective glaze layer use the same matte glaze structure, it is technically equivalent to reducing the total amount of effective velvet base glaze, that is, the velvet base glaze layer can further increase the initial melting point (up to 25% of the original initial melting point). A certain amount of zirconium silicate can also be added to replace part of the cosmetic clay to increase the whiteness before inkjet decoration, further cover and suppress defects, and have a very obvious effect on solving the glaze pinhole and bubble defect problems formed in the firing stage of the green body.

[0057] In one embodiment of the present application, the raw material formula of the golden velvet base glaze layer 12 comprises, by weight:

[0058] 15-30 parts of potassium feldspar, 0-10 parts of sodium feldspar, 5-8 parts of kaolin, 3-5 parts of zinc oxide, 0-6 parts of dolomite, 0-10 parts of calcined talc, 2-4 parts of barium carbonate, 2-4 parts of strontium carbonate, 6-30 parts of high calcium magnesium frit powder, 10-18 parts of high zinc aluminum frit powder, 5-15 parts of high strontium aluminum frit powder, and 7-12 parts of kaolin frit powder.

[0059] In one embodiment of the present application, the raw material formula of the protective glaze layer 14 includes, by weight:

[0060] 15-30 parts of potassium feldspar, 0-10 parts of sodium feldspar, 5-8 parts of kaolin, 3-5 parts of zinc oxide, 0-6 parts of dolomite, 0-10 parts of calcined talc, 2-4 parts of barium carbonate, 2-4 parts of strontium carbonate, 6-30 parts of high calcium magnesium frit powder, 10-18 parts of high zinc aluminum frit powder, 5-15 parts of high strontium aluminum frit powder, and 0-8 parts of kaolin frit powder.

[0061] Specifically, the particle size of each frit powder in the formula raw materials of the protective glaze layer is D97≤60μm, and the particle size of the remaining materials is D97≤45μm.

[0062] In the embodiment of the present application, the chemical composition of the gold velvet base glaze layer 12 is calculated by weight and includes:

[0063] 48 - 51 parts of SiO2, 19 - 25 parts of Al2O3, 4.7 - 6 parts of CaO, 5 - 6 parts of MgO, 3.1 - 5.0 parts of K2O, 0.6 - 1.3 parts of Na2O, 2.8 - 4.0 parts of BaO, 4.0 - 6.0 parts of ZnO, 2.5 - 4.0 parts of ZrO2, 1.5 - 2.5 parts of SrO, and 0 - 3.5 parts of loss on ignition and trace impurities.

[0064] The chemical composition of the protective glaze layer 14, by mass parts, includes:

[0065] 48 - 51 parts of SiO2, 16 - 19 parts of Al2O3, 4.7 - 6 parts of CaO, 5 - 6 parts of MgO, 3.1 - 5.0 parts of K2O, 0.6 - 1.3 parts of Na2O, 2.8 - 4.0 parts of BaO, 4.0 - 6.0 parts of ZnO, 1.5 - 2.5 parts of SrO, and 0 - 3.5 parts of loss on ignition and trace impurities.

[0066] In the embodiments of the present application, the chemical composition of the high - calcium - magnesium frit powder, by mass parts, includes:

[0067] 48 - 61 parts of SiO2, 10 - 15 parts of Al2O3, 0 - 0.1 part of Fe2O3, 10 - 21 parts of CaO, 10 - 15 parts of MgO, 0.1 - 0.2 part of K2O, 0.1 - 0.2 part of Na2O, 1.3 - 3.5 parts of ZnO, and 0 - 0.5 part of loss on ignition.

[0068] The chemical composition of the high - zinc - aluminum frit powder, by mass parts, includes:

[0069] 43 - 49 parts of SiO2, 21.0 - 23.5 parts of Al2O3, 0 - 0.1 part of Fe2O3, 15 - 19 parts of CaO, 0.5 - 2.0 parts of MgO, 1.0 - 2.4 parts of K2O, 1.5 - 3.5 parts of Na2O, 6.3 - 7.5 parts of ZnO, 8.5 - 9 parts of BaO, and 0 - 0.5 part of loss on ignition;

[0070] The chemical composition of the high - strontium - aluminum frit powder, by mass parts, includes:

[0071] 48.9 - 51.6 parts of SiO2, 14.1 - 16.3 parts of Al2O3, 0 - 0.1 part of Fe2O3, 0 - 4 parts of CaO, 0.5 - 2.0 parts of MgO, 0.1 - 0.4 part of K2O, 3.5 - 7.5 parts of Na2O, 15 - 22 parts of SrO, 0.5 - 2.5 parts of BaO;

[0072] The chemical composition of the kaolin frit powder, by mass parts, includes:

[0073] 40 - 45 parts of SiO2, 45 - 55 parts of Al2O3, 0.1 - 0.2 parts of Fe2O3, 0 - 0.5 parts of TiO2, and 0 - 0.5 parts of loss on ignition.

[0074] In the embodiment of the present application, the raw material formula of the zirconium base glaze layer, by mass, includes:

[0075] 7 - 15 parts of quartz, 3 - 11 parts of aluminum zirconium powder, 8 - 11 parts of kaolin, 5 - 25 parts of nepheline syenite, 10 - 20 parts of potassium feldspar, 7 - 18 parts of albite, 2 - 3 parts of calcined talc, 0 - 5 parts of wollastonite, 0 - 4 parts of calcined kaolin, 1 - 10 parts of high - alumina frit powder, 5 - 15 parts of lithium ore tailings;

[0076] The chemical composition of the zirconium base glaze layer, by mass, includes:

[0077] 48 - 49 parts of SiO2, 21.5 - 22.1 parts of Al2O3, 0 - 0.1 parts of Fe2O3, 8 - 9 parts of CaO, 2.5 - 3 parts of MgO, 1.0 - 1.4 parts of K2O, 3.5 - 4 parts of Na2O, 5 - 7 parts of ZrO2, 1.3 - 1.5 parts of ZnO, 8.5 - 9 parts of BaO.

[0078] The present application also provides a ceramic tile with a velvet texture. Among them, the ceramic tile includes a ceramic body 10 and the composite glaze layer as described above applied on the ceramic body 10; the raw material formula of the ceramic body 10, by mass, includes:

[0079] 8 - 10 parts of sandstone shale powder, 5 - 8 parts of waste porcelain powder, 3 - 5 parts of waste mud from edge grinding, polishing and pressing, 20 - 30 parts of washed potassium - sodium stone particles, 10 - 12 parts of sericite clay material, 18 - 20 parts of washed mud, 3 - 5 parts of ball clay, 1 - 3 parts of bentonite, 8 - 10 parts of kaolin, 2 - 3 parts of magnesia mud, 2 - 15 parts of lithium ore tailings, 0 - 5 parts of biomass ash residue, 0 - 3 parts of secondary denitrified aluminum ash.

[0080] Specifically, the chemical composition of the sandstone shale powder, by mass, includes:

[0081] 71.3 - 73 parts of SiO2, 16.3 - 17.1 parts of Al2O3, 0 - 1 part of Fe2O3, 3.5 - 5.5 parts of CaO, 0.7 - 1.2 parts of MgO, 5.5 - 7.5 parts of K2O and Na2O, 1.5 - 2 parts of loss on ignition.

[0082] The chemical composition of the sericite clay material, by mass, includes:

[0083] 51.01 - 53 parts of SiO2, 29.52 - 33.65 parts of Al2O3, 7.5 - 8.5 parts of K2O, 3.2 - 4 parts of Na2O, 0 - 1.2 parts of Fe2O3, and 5.5 - 6.5 parts of loss on ignition.

[0084] The chemical composition of the waste porcelain powder by mass fraction includes:

[0085] 63 - 66 parts of SiO2, 20 - 22 parts of Al2O3, 0 - 0.8 parts of Fe2O3, 0.5 - 0.6 parts of CaO, 1.2 - 1.8 parts of MgO, 1 - 2 parts of K2O, and 2.5 - 3.5 parts of Na2O.

[0086] The chemical composition of the edge - grinding, polishing, and pressing mud waste by mass fraction includes:

[0087] 59 - 61 parts of SiO2, 15 - 17 parts of Al2O3, 0 - 1.0 parts of Fe2O3, 6 - 8 parts of CaO, 1.5 - 2.0 parts of MgO, 1.5 - 2.0 parts of K2O, 3 - 4 parts of Na2O, 1.5 - 2.5 parts of ZnO, 6 - 8 parts of BaO, 0 - 3 parts of SrO, and 0.5 - 0.7 parts of C.

[0088] The chemical composition of the lithium ore tailings by mass fraction includes:

[0089] 67 - 70 parts of SiO2, 17 - 20 parts of Al2O3, 0.5 - 1 part of CaO, 0.1 - 0.3 part of MgO, 3 - 5 parts of K2O, 3 - 5 parts of Na2O, 0.2 - 0.6 part of Li2O, 0.8 - 1.5 parts of Fe2O3, 0.1 - 0.3 part of MnO, and 3 - 5 parts of loss on ignition.

[0090] The biomass ash includes, by mass percentage (wt%): 0.5% of loss on ignition, 47.84% of SiO2, 25.96% of ZrO2, 15.42% of Al2O3, 5.45% of CaO, 2.06% of K2O, 1.53% of MgO, 0.84% of Na2O, and 0.40% of Fe2O3.

[0091] The chemical composition of the secondary denitrification aluminum ash by mass fraction includes:

[0092] 60 - 69 parts of SiO2, 11 - 15 parts of Al2O3, 1.5 - 3.0 parts of Fe2O3, 3 - 5 parts of CaO, 9 - 11 parts of MgO, 0.1 - 0.6 part of K2O, 0.1 - 0.6 part of Na2O, 0 - 0.7 part of TiO2, and 5.5 - 6 parts of loss on ignition.

[0093] In one embodiment, the chemical composition of the ceramic green body, by mass, includes:

[0094] 65 - 66.5 parts of SiO2, 21.8 - 23 parts of Al2O3, 0 - 0.7 parts of Fe2O3, 0.35 - 0.55 parts of CaO, 1.0 - 1.4 parts of MgO, 0.8 - 1.8 parts of K2O, 2.5 - 3 parts of Na2O, and 5.5 - 6 parts of loss on ignition.

[0095] This application also provides a method for preparing the above - described ceramic tile with a velvet texture. Among them, the method includes:

[0096] Glaze is applied to the surface of the pre - prepared ceramic green body 10 to form a zirconium bottom glaze layer 11;

[0097] Glaze is applied on the zirconium bottom glaze layer 11 to form a velvet - based surface glaze layer 12;

[0098] Ink - jet decoration is performed on the velvet - based surface glaze layer 12 to obtain an ink - jet decoration layer 13;

[0099] A protective glaze layer 14 is sprayed on the ink - jet decoration layer 13 by electrostatic spraying method, and after firing, a ceramic tile with a velvet texture is obtained.

[0100] Specifically, the raw materials are ball - milled according to the green body formula to prepare a slurry. After aging, it enters the spray granulation process for powder making to obtain powder. The drying air heat source is a biomass fluidized - bed furnace. After the powder is aged, it is pressed by an automatic stamping machine to obtain a ceramic green body.

[0101] A conventional zirconium bottom glaze layer is formed by applying glaze on the surface of the ceramic green body. According to the raw material formula and mass ratio of the velvet - based surface glaze layer, it is mixed with water and additives to form a slurry, obtaining a velvet - based surface glaze. The velvet - based surface glaze is applied on the zirconium bottom glaze layer by the glaze application method to form a velvet - based surface glaze layer. After ink - jet decoration on the above two layers, according to the raw material formula and mass ratio of the protective glaze layer, it is mixed with water and additives to form an electrostatic spraying velvet - based protective glaze layer. After firing, a ceramic plate with a velvet texture is obtained.

[0102] In the embodiment of this application, spraying a protective glaze layer on the ink - jet decoration layer by electrostatic spraying method and obtaining a ceramic tile with a velvet texture after firing includes:

[0103] Spraying a protective glaze layer on the ink - jet decoration layer by electrostatic spraying method with a glaze amount of 150 - 200 g / m 2 and firing at a temperature of 1120 - 1180 °C to obtain a ceramic tile with a velvet texture;

[0104] Among them, the glaze slurry of the protective glaze layer has a specific gravity of 1.20 - 1.40, a pH of 7 - 8, and a resistivity ≤ 1.2 MΩ·cm.

[0105] Specifically, the particle size of the particles in the slurry of the protective glaze layer is D97 ≤ 45 μm, the specific gravity of the slurry of the protective glaze layer is 1.20 - 1.40, the flow rate of the slurry of the protective glaze layer is 11 - 13 s, the pH of the slurry of the protective glaze layer is 7 - 8, and the resistivity of the slurry of the protective glaze layer ≤ 1.2 MΩ·cm. On a disk - type electrostatic spraying device, the slurry of the protective glaze layer is sprayed on the zirconium bottom glaze layer, the velvet - based surface glaze layer, and the ink - jet decoration layer stacked in sequence by electrostatic spraying method at a glaze amount of 150 - 200 g / m 2 to form a composite glaze layer.

[0106] In the present invention, a velvet - based surface glaze layer is poured on the zirconium bottom glaze layer, and then after ink - jet decoration, a thin velvet - based primary glaze protective glaze layer is electrostatically sprayed to form a composite glaze layer. This process uses complementary adjustment by introducing a variety of frit powders in the formulations of the surface glaze layer and the protective glaze layer, effectively improving the comprehensive adjustment ability of the high - temperature performance of the formulation; using electrostatic spraying to apply the protective glaze reduces the total thickness of the effective velvet glaze layer, enhances the covering ability of the makeup soil and the ability to suppress pinholes and bubble defects, and at the same time greatly reduces the moisture content in the kiln, broadening the selection range of raw materials for the blank, and ensuring the improvement of product quality.

[0107] Specific examples are listed below for illustration.

[0108] Design comparative experiments, including: three comparative examples 1, 2, 3 corresponding to the conventional process, and three examples 4, 5, 6 corresponding to the electrostatic process of the present invention.

[0109] Comparative Example 1:

[0110] Both the bottom glaze and the surface glaze are applied by bell - jar glazing on the brick blank, that is, the glaze layer on the blank body includes a conventional zirconium bottom glaze glazing layer, an ink - jet decoration layer, and a basic velvet surface glaze glazing layer.

[0111] Specifically, since the ink - jet decoration layer of the conventional under - glaze color implementation scheme is under the basic velvet surface glaze glazing layer and the velvet glaze layer is the last glaze layer, when using the glazing implementation method, the specific gravity of the glaze material generally needs to be adjusted to more than 1.75, and the glaze amount exceeds 350 grams per square. In order to ensure the transparency, color development, and glaze surface texture, the setting of the alumina content in the formulation components needs to be lowered (generally less than 18.5%). Therefore, during the firing process, the firing temperature is low and the initial melting point is low. This kind of low - temperature glaze material melts quickly and prematurely seals the underlying blank body layer, resulting in poor exhaust of the body - glaze bonding layer during firing and prone to the appearance of prickly heat bubble phenomena, which are obvious quality defects.

[0112] Comparative Example 2:

[0113] The base glaze and the top glaze are applied to the brick blank by bell jar glazing, and the implementation method of the protective glaze layer is high-pressure spraying. The glaze layer on the blank body includes a conventional zircon base glaze layer, a basic velvet top glaze layer, an inkjet decoration layer, and a high-pressure sprayed velvet basic protective glaze.

[0114] Comparative Example 3:

[0115] The base glaze and the top glaze are applied to the brick blank by bell jar glazing, and the implementation method of the protective glaze layer is rubber roller printing and spraying. The glaze layer on the blank body includes a conventional zircon base glaze layer, a basic velvet top glaze layer, an inkjet decoration layer, and a rubber roller printed velvet basic protective glaze.

[0116] In Comparative Examples 1, 2, and 3, the raw material formulas and chemical compositions of the basic velvet top glaze layer, the high-pressure sprayed velvet basic protective glaze, and the rubber roller printed velvet basic protective glaze are the same. The raw material formula is calculated by mass and includes:

[0117] 22 parts of potassium feldspar, 7 parts of sodium feldspar, 8 parts of kaolin, 3.5 parts of zinc oxide, 5.7 parts of dolomite, 5 parts of calcined talc, 2.7 parts of barium carbonate, 2 parts of strontium carbonate, 25 parts of high-calcium magnesium frit powder, 10 parts of high-zinc aluminum frit powder, and 12 parts of high-strontium aluminum frit powder.

[0118] In Comparative Examples 1, 2, and 3, whether it is the conventional underglaze color or overglaze color process, the alumina content in the basic velvet formula composition also needs to be very low (generally less than 18.5%). Coupled with the relatively thick second top glaze layer, the firing temperature is also relatively low during the firing process, and the initial melting point is low, which has a great impact on the later production efficiency and quality, and it is difficult to adapt to the industrial application of green recycled blanks.

[0119] Example 4:

[0120] The implementation method of electrostatic spraying is used to replace the traditional high-pressure spraying or rubber roller process. The raw material formula and chemical composition of the zircon base glaze layer are the same as those of the conventional zircon base glaze layer in Comparative Examples 1, 2, and 3.

[0121] The raw material formula of the velvet basic top glaze layer is calculated by mass and includes:

[0122] 22 parts of potassium feldspar, 7 parts of sodium feldspar, 8 parts of kaolin, 3.5 parts of zinc oxide, 5.7 parts of dolomite, 5 parts of calcined talc, 2.7 parts of barium carbonate, 2 parts of strontium carbonate, 25 parts of high-calcium magnesium frit powder, 7 parts of high-zinc aluminum frit powder, 7 parts of high-strontium aluminum frit powder, 10 parts of kaolin frit powder, and 6 parts of ultra-fine zirconium silicate.

[0123] The raw material formula of the electrostatically sprayed protective glaze layer is calculated by mass and includes:

[0124] 22 parts of potassium feldspar, 7 parts of albite, 8 parts of kaolin, 3.5 parts of zinc oxide, 5.7 parts of dolomite, 5 parts of calcined talc, 2.7 parts of barium carbonate, 2 parts of strontium carbonate, 25 parts of high-calcium magnesium frit powder, 10 parts of high-zinc aluminum frit powder, 12 parts of high-strontium aluminum frit powder.

[0125] In the formula raw materials of the protective glaze layer, the particle size of each frit powder is D97 ≤ 60 μm, and the particle size of the remaining materials is D97 ≤ 45 μm.

[0126] Apply glaze on the surface of the ceramic green body to form a conventional zirconium bottom glaze layer. According to the raw material formula and mass ratio of the velvet base glaze layer, mix it with water and additives to form a slurry, and obtain the velvet base glaze. Use the glaze application method to apply it on the zirconium bottom glaze layer to form a velvet base glaze layer. After inkjet decoration on the surfaces of the above two layers, then according to the raw material formula and mass ratio of the protective glaze layer, mix it with water and additives to form an electrostatic spraying velvet base protective glaze layer, and obtain a ceramic board with a velvet texture after firing.

[0127] The particle size of the particles in the slurry of the protective glaze layer is D97 ≤ 45 μm, the specific gravity of the slurry of the protective glaze layer is 1.20 - 1.40, the flow rate of the slurry of the protective glaze layer is 11 - 13 s, the pH of the slurry of the protective glaze layer is 7 - 8, and the resistivity of the slurry of the protective glaze layer ≤ 1.2 MΩ·cm. On a disk-type electrostatic spraying device, use the electrostatic spraying method to spray the slurry of the protective glaze layer on the zirconium bottom glaze layer, velvet base glaze layer and inkjet decoration layer stacked in sequence at a glaze application amount of 150 g / m 2 to form a composite glaze layer.

[0128] During firing, the temperature is 1120 - 1180 °C.

[0129] Example 5:

[0130] Use the implementation method of electrostatic glaze spraying to replace the traditional high-pressure glaze spraying or rubber roller process. The raw material formula and chemical composition of the zirconium bottom glaze layer are the same as those of the conventional zirconium bottom glaze spraying layer in Comparative Examples 1, 2 and 3.

[0131] The raw material formula of the velvet base glaze layer by mass includes:

[0132] 30 parts of potassium feldspar, 5 parts of albite, 8 parts of kaolin, 5 parts of zinc oxide, 3.7 parts of dolomite, 8 parts of calcined talc, 4 parts of barium carbonate, 4 parts of strontium carbonate, 22 parts of high-calcium magnesium frit powder, 10 parts of high-zinc aluminum frit powder, 5 parts of high-strontium aluminum frit powder, 10 parts of kaolin frit powder, 6 parts of ultrafine zirconium silicate.

[0133] The raw material formula of the electrostatic spraying protective glaze layer by mass includes:

[0134] 30 parts of potassium feldspar, 5 parts of sodium feldspar, 8 parts of kaolin, 5 parts of zinc oxide, 3.7 parts of dolomite, 8 parts of calcined talc, 4 parts of barium carbonate, 4 parts of strontium carbonate, 22 parts of high-calcium magnesium frit powder, 18 parts of high-zinc aluminum frit powder, 15 parts of high-strontium aluminum frit powder.

[0135] In the formula raw materials of the protective glaze layer, the particle size of each frit powder is D97≤60μm, and the particle size of the remaining materials is D97≤45μm.

[0136] A conventional zirconium base glaze layer is formed by glazing on the surface of the ceramic body. According to the raw material formula and mass ratio of the velvet base glaze layer, it is mixed with water and additives to form a slurry, and the velvet base glaze is obtained. The velvet base glaze is applied on the zirconium base glaze layer by the glazing method to form a velvet base glaze layer. After inkjet decoration on the above two layers, according to the raw material formula and mass ratio of the protective glaze layer, it is mixed with water and additives to form an electrostatic spraying velvet base protective glaze layer, and a ceramic plate with a velvet texture is obtained after firing.

[0137] The particle size of the particles in the slurry of the protective glaze layer is D97≤45μm, the specific gravity of the slurry of the protective glaze layer is 1.20 - 1.40, the flow rate of the slurry of the protective glaze layer is 11 - 13s, the pH of the slurry of the protective glaze layer is 7 - 8, and the resistivity of the slurry of the protective glaze layer is ≤1.2MΩ·cm. On a disk-type electrostatic spraying device, the slurry of the protective glaze layer is sprayed on the zirconium base glaze layer, velvet base glaze layer and inkjet decoration layer stacked in sequence by the electrostatic spraying method at a glaze application amount of 180g / m 2 to form a composite glaze layer.

[0138] The firing temperature is 1150℃.

[0139] Example 6:

[0140] The implementation method of electrostatic glaze spraying is used to replace the traditional high-pressure glaze spraying or rubber roller process. The raw material formula and chemical composition of the zirconium base glaze layer are the same as those of the conventional zirconium base glaze glazing layer in Comparative Examples 1, 2 and 3.

[0141] The raw material formula of the velvet base glaze layer by mass includes:

[0142] 30 parts of potassium feldspar, 5 parts of sodium feldspar, 8 parts of kaolin, 3 parts of zinc oxide, 1 part of dolomite, 10 parts of calcined talc, 4 parts of barium carbonate, 4 parts of strontium carbonate, 6 parts of high-calcium magnesium frit powder, 10 parts of high-zinc aluminum frit powder, 5 parts of high-strontium aluminum frit powder, 10 parts of kaolin frit powder, 6 parts of ultrafine zirconium silicate.

[0143] The raw material formula of the electrostatic spraying protective glaze layer by mass includes:

[0144] 30 parts of potassium feldspar, 5 parts of sodium feldspar, 8 parts of kaolin, 3 parts of zinc oxide, 1 part of dolomite, 10 parts of calcined talc, 4 parts of barium carbonate, 4 parts of strontium carbonate, 6 parts of high-calcium magnesium frit powder, 18 parts of high-zinc aluminum frit powder, 10 parts of high-strontium aluminum frit powder.

[0145] The particle size of each frit powder in the formula raw materials of the protective glaze layer is D97 ≤ 60 μm, and the particle size of the remaining materials is D97 ≤ 45 μm.

[0146] Apply glaze by pouring on the surface of the ceramic green body to form a conventional zirconium primer glaze layer. According to the raw material formula and mass proportion of the velvet base glaze layer, mix with water and additives to form a slurry, and obtain the velvet base glaze. Apply it on the zirconium primer glaze layer by the pouring glaze method to form a velvet base glaze layer. After inkjet decoration on the above two layers, then according to the raw material formula and mass proportion of the protective glaze layer, mix with water and additives to form an electrostatic spraying velvet base protective glaze layer, and obtain a ceramic board with a velvet texture after firing.

[0147] The particle size of the particles in the slurry of the protective glaze layer is D97 ≤ 45 μm, the specific gravity of the slurry of the protective glaze layer is 1.20 - 1.40, the flow rate of the slurry of the protective glaze layer is 11 - 13 s, the pH of the slurry of the protective glaze layer is 7 - 8, and the resistivity of the slurry of the protective glaze layer is ≤ 1.2 MΩ·cm. On a disc-type electrostatic spraying device, use the electrostatic spraying method to spray the slurry of the protective glaze layer on the zirconium primer glaze layer, velvet base glaze layer and inkjet decoration layer stacked in sequence at a glaze application amount of 200 g / m 2 to form a composite glaze layer.

[0148] The firing temperature is 1180 °C.

[0149] In all the above comparative examples and examples, the formula of the zirconium primer glaze layer is basically the same, with slight adjustments according to the firing temperature, and the temperature is controlled according to the glossiness of the glaze surface.

[0150] The raw material formula of the zirconium primer glaze layer is by mass parts, including:

[0151] 7 - 15 parts of quartz, 3 - 11 parts of aluminum zirconium powder, 8 - 11 parts of kaolin, 5 - 25 parts of nepheline, 10 - 20 parts of potassium feldspar, 7 - 18 parts of sodium feldspar, 2 - 3 parts of calcined talc, 0 - 5 parts of wollastonite, 0 - 4 parts of calcined kaolin, 1 - 10 parts of high-aluminum frit powder, 5 - 15 parts of lithium ore tailings.

[0152] Among them, the chemical composition of the high-aluminum frit powder is by mass parts, including:

[0153] 49 parts of SiO2, 22.0 parts of Al2O3, 0.1 part of Fe2O3, 8 parts of CaO, 2.5 parts of MgO, 1.0 part of K2O, 3.5 parts of Na2O, 6 parts of ZrO2, 1.3 parts of ZnO, 8.5 parts of BaO, and 1.5 parts of loss on ignition.

[0154] The specific implementation effects of the above Comparative Examples 1, 2, 3 and Examples 4, 5, 6 are compared as shown in Table 1:

[0155] Table 1

[0156]

[0157]

[0158] In Table 1, for the stain resistance performance, according to the national standard: "Test Method for Performance of Photocatalytic Self-Cleaning Materials (GB / T 23764-2009)", the easy-cleaning performance of the ceramic tiles in Examples 4 - 6 and Comparative Examples 1 - 3 was tested, and the test results are shown in Table 2. Among them, A represents the residual amount of oil stain per unit area on the surface of the ceramic tile, and the unit is g / m 2 .

[0159] Table 2

[0160]

[0161] As can be seen from Table 2, in Examples 4, 5, and 6, the electrostatic spraying process is adopted. Since the initial melting temperature of the surface glaze layer is increased by nearly 30 - 40 degrees compared with the conventional process, when 6% ultrafine zirconium silicate is contained in the surface glaze formula, the opacifying effect of adding zirconium silicate externally is improved synchronously, the whiteness before inkjet decoration increases, and the equivalent effect is that the surface glaze realizes part of the effect of the make-up clay, which can effectively cover and suppress the adverse effects such as prickly heat, pinholes, and dot-like dirt absorption caused by using green and environmentally friendly green bodies, improve the kiln speed and apparent quality, increase the output and the first-class rate, and the product quality finally meets the requirements of the national standard and the enterprise standard. Therefore, the present invention solves the problems of prickly heat, bubbles, and low production efficiency and poor quality caused by high moisture content in the kiln during the production of underglaze color or overglaze color of traditional velvet-textured ceramic plates.

[0162] The present invention provides a composite glaze layer, a ceramic tile with a velveteen texture and a preparation method thereof. The composite glaze layer includes: a zirconium primer glaze layer, a velveteen base glaze layer, an inkjet decoration layer, and a protective glaze layer arranged in sequence; the formulations of the velveteen base glaze layer and the protective glaze layer both include: high-calcium magnesium frit powder, high-zinc aluminum frit powder, high-strontium aluminum frit powder, and kaolin frit powder. By comprehensively adjusting by introducing high-calcium magnesium frit powder, high-zinc aluminum frit powder, high-strontium aluminum frit powder, and kaolin frit powder into the formulations of the velveteen base glaze layer and the protective glaze layer simultaneously, the present invention improves the comprehensive adjustment ability of the high-temperature viscosity, surface tension, firing range, and glaze turbidity of the formulation, and can still obtain a high-quality glaze surface and a texture effect with low surface roughness while increasing the magnesium oxide content to 5-6%, increasing the aluminum oxide content to 15-18%, and reducing the calcium oxide content to 4-6%.

[0163] It should be understood that the application of the present invention is not limited to the above examples. For those of ordinary skill in the art, improvements or transformations can be made according to the above description, and all such improvements and transformations should fall within the protection scope of the appended claims of the present invention.

Claims

1. A composite glaze layer, characterized in that, The composite glaze layer includes: a zirconium primer glaze layer, a velvet-based surface glaze layer, an inkjet decoration layer, and a protective glaze layer, which are arranged in sequence; the formulations of both the velvet-based surface glaze layer and the protective glaze layer include: high-calcium magnesium frit powder, high-zinc aluminum frit powder, high-strontium aluminum frit powder, and kaolin frit powder.

2. The composite glaze layer according to claim 1, characterized in that The protective glaze layer is obtained by means of electrostatic spraying glaze.

3. The composite glaze layer according to claim 1, characterized in that, The raw material formulation of the velvet-based surface glaze layer, by mass, includes: 15 - 30 parts of potassium feldspar, 0 - 10 parts of sodium feldspar, 5 - 8 parts of kaolin, 3 - 5 parts of zinc oxide, 0 - 6 parts of dolomite, 0 - 10 parts of calcined talc, 2 - 4 parts of barium carbonate, 2 - 4 parts of strontium carbonate, 6 - 30 parts of high-calcium magnesium frit powder, 10 - 18 parts of high-zinc aluminum frit powder, 5 - 15 parts of high-strontium aluminum frit powder, and 7 - 12 parts of kaolin frit powder.

4. The composite glaze layer according to claim 1, characterized in that, The raw material formulation of the protective glaze layer, by mass, includes: 15 - 30 parts of potassium feldspar, 0 - 10 parts of sodium feldspar, 5 - 8 parts of kaolin, 3 - 5 parts of zinc oxide, 0 - 6 parts of dolomite, 0 - 10 parts of calcined talc, 2 - 4 parts of barium carbonate, 2 - 4 parts of strontium carbonate, 6 - 30 parts of high-calcium magnesium frit powder, 10 - 18 parts of high-zinc aluminum frit powder, 5 - 15 parts of high-strontium aluminum frit powder, and 0 - 8 parts of kaolin frit powder.

5. The composite glaze layer according to claim 1, characterized in that The chemical composition of the velvet-based surface glaze layer, by mass, includes: 48 - 51 parts of SiO2, 19 - 25 parts of Al2O3, 4.7 - 6 parts of CaO, 5 - 6 parts of MgO, 3.1 - 5.0 parts of K2O, 0.6 - 1.3 parts of Na2O, 2.8 - 4.0 parts of BaO, 4.0 - 6.0 parts of ZnO, 2.5 - 4.0 parts of ZrO2, 1.5 - 2.5 parts of SrO; The chemical composition of the protective glaze layer, by mass, includes: 48 - 51 parts of SiO2, 16 - 19 parts of Al2O3, 4.7 - 6 parts of CaO, 5 - 6 parts of MgO, 3.1 - 5.0 parts of K2O, 0.6 - 1.3 parts of Na2O, 2.8 - 4.0 parts of BaO, 4.0 - 6.0 parts of ZnO, 1.5 - 2.5 parts of SrO.

6. The composite glaze layer according to claim 1, characterized in that The chemical composition of the high-calcium magnesium frit powder, by mass, includes: 48 - 61 parts of SiO2, 10 - 15 parts of Al2O3, 0 - 0.1 parts of Fe2O3, 10 - 21 parts of CaO, 10 - 15 parts of MgO, 0.1 - 0.2 parts of K2O, 0.1 - 0.2 parts of Na2O, 1.3 - 3.5 parts of ZnO; The chemical composition of the high-zinc aluminum frit powder, by mass, includes: 43 - 49 parts of SiO2, 21.0 - 23.5 parts of Al2O3, 0 - 0.1 parts of Fe2O3, 15 - 19 parts of CaO, 0.5 - 2.0 parts of MgO, 1.0 - 2.4 parts of K2O, 1.5 - 3.5 parts of Na2O, 6.3 - 7.5 parts of ZnO, 8.5 - 9 parts of BaO; The chemical composition of the high-strontium aluminum frit powder, by mass, includes: 48.9 - 51.6 parts of SiO2, 14.1 - 16.3 parts of Al2O3, 0 - 0.1 part of Fe2O3, 0 - 4 parts of CaO, 0.5 - 2.0 parts of MgO, 0.1 - 0.4 part of K2O, 3.5 - 7.5 parts of Na2O, 15 - 22 parts of SrO, 0.5 - 2.5 parts of BaO; The chemical composition of the kaolin frit powder, by mass parts, includes: 40 - 45 parts of SiO2, 45 - 55 parts of Al2O3, 0.1 - 0.2 part of Fe2O3, 0 - 0.5 part of TiO2.

7. The composite glaze layer according to claim 1, characterized in that The raw material formula of the zirconium bottom glaze layer, by mass parts, includes: 7 - 15 parts of quartz, 3 - 11 parts of aluminum zirconium powder, 8 - 11 parts of kaolin, 5 - 25 parts of nepheline syenite, 10 - 20 parts of potassium feldspar, 7 - 18 parts of albite, 2 - 3 parts of calcined talc, 0 - 5 parts of wollastonite, 0 - 4 parts of calcined kaolin, 1 - 10 parts of high - alumina frit powder, 5 - 15 parts of lithium ore tailings; The chemical composition of the zirconium bottom glaze layer, by mass parts, includes: 48 - 49 parts of SiO2, 21.5 - 22.1 parts of Al2O3, 0 - 0.1 part of Fe2O3, 8 - 9 parts of CaO, 2.5 - 3 parts of MgO, 1.0 - 1.4 parts of K2O, 3.5 - 4 parts of Na2O, 5 - 7 parts of ZrO2, 1.3 - 1.5 parts of ZnO, 8.5 - 9 parts of BaO.

8. A ceramic tile with a velveteen texture, characterized in that, The ceramic tile includes a ceramic body and a composite glaze layer as described in any one of claims 1 - 7 applied on the ceramic body; The raw material formula of the ceramic body, by mass parts, includes: 8 - 10 parts of sandstone shale powder, 5 - 8 parts of waste porcelain powder, 3 - 5 parts of waste mud from edge grinding, polishing and pressing, 20 - 30 parts of washed potassium - sodium stone particles, 10 - 12 parts of sericite clay material, 18 - 20 parts of washed mud, 3 - 5 parts of ball clay, 1 - 3 parts of bentonite, 8 - 10 parts of kaolin, 2 - 3 parts of magnesian mud, 2 - 15 parts of lithium ore tailings, 0 - 5 parts of biomass ash residue, 0 - 3 parts of secondary denitrified aluminum ash.

9. A preparation method of a ceramic tile with a velveteen texture as described in claim 8, characterized in that, The method includes: Glazing the surface of a pre - prepared ceramic body to form a zirconium bottom glaze layer; Glazing on the zirconium bottom glaze layer to form a velvet - like base glaze layer; Performing ink - jet decoration on the velvet - like base glaze layer to obtain an ink - jet decoration layer; Spraying a protective glaze layer on the ink - jet decoration layer by electrostatic spraying method, and firing to obtain a ceramic tile with a velvet - like texture.

10. The preparation method of the ceramic tile with a velveteen texture according to claim 9, characterized in that, Spraying a protective glaze layer on the ink - jet decoration layer by electrostatic spraying method, and firing to obtain a ceramic tile with a velvet - like texture, including: Use the electrostatic spraying method to spray a protective glaze layer on the inkjet decoration layer with a glaze amount of 150 - 200 g / m 2 and fire at a temperature of 1120 - 1180 °C to obtain a ceramic tile with a velvet texture; Among them, the glaze slurry specific gravity of the protective glaze layer is 1.20 - 1.40, the pH is 7 - 8, and the resistivity ≤ 1.2 MΩ·cm.

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