A wear-resistant matte ceramic rock plate and a preparation method thereof

Abstract

The application belongs to the technical field of building ceramics, and particularly discloses a wear-resistant matte ceramic rock plate and a preparation method thereof. The wear-resistant matte ceramic rock plate comprises, from bottom to top, a body, a first surface glaze layer, a second surface glaze layer, a pattern layer and a dry particle glaze layer, and the initial melting temperature of the second surface glaze layer is between the initial melting temperature of the first surface glaze layer and the initial melting temperature of the dry particle glaze layer; the chemical composition of the dry particle glaze layer contains Y2O3, and the proportion of the network structure of silicon oxygen tetrahedron [SiO4] in the dry particle microstructure is increased to improve the hardness and wear resistance of the dry particle glaze. The ceramic rock plate prepared by the application has a stain resistance level of 5, and the stain resistance level after wear resistance can still be maintained at 4, the color development effect of the pattern is good, and the stereoscopic sense is strong; the wear resistance level can reach 5, and the rotation speed is 12000.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of building ceramics, and particularly relates to a wear-resistant matte ceramic rock plate and a preparation method thereof. BACKGROUND

[0002] With the paving and long-term use of building ceramics on the ground, the polished glaze layer of the rock plate will be worn by sand particles and the like, which will affect the effects such as the gloss and pattern display of the glaze layer surface. Therefore, improving the wear resistance of the rock plate glaze layer has been the improvement direction of the ceramic rock plate glaze layer.

[0003] For the wear resistance of the ceramic rock plate glaze layer, on the one hand, the aluminum content of the overall glaze layer is directly increased, and on the other hand, the thickness of the glaze layer is reduced, so as to improve the wear resistance of the glaze layer without affecting the gloss of the tile surface. On the other hand, the main components of the glaze layer are treated by a higher-temperature melting water quenching process to obtain corresponding frit dry particles. The dry particles and glue are mixed to form a dry particle glaze slurry. After glazing by a bell jar or a high-pressure glazing cabinet, a wear-resistant glaze layer is realized on the surface of the rock plate.

[0004] For the first approach, increasing the aluminum content in the glaze will reduce the thickness of the glaze layer to a certain extent, and the deformation requirement of the rock plate body is high. For the second approach, different particle sizes and initial melting temperatures of the dry particles are mixed in a certain proportion. The dry particles with low initial melting temperature are used to bond the dry particles with high initial melting temperature, so as to improve the wear resistance of the rock plate glaze layer. Under this condition, the gaps of the dry particles with high initial melting temperature will be wrapped by the dry particles with low initial melting temperature, and air bubbles or pores will be left in the glaze layer, which will affect the stain resistance of the rock plate surface.

[0005] Therefore, there is an urgent need for a matte ceramic rock plate that has stain resistance and wear resistance and has good glaze quality. SUMMARY

[0006] The present application aims to at least solve one of the technical problems existing in the prior art. To this end, the present application provides a wear-resistant matte ceramic rock plate and a preparation method thereof. The ceramic rock plate is provided with double-layer glaze layers (first and second surface glaze layers), and the initial melting temperature relationship between the double-layer glaze layers and the dry particle glaze layer is controlled. The dry particle glaze layer with specific components solves the problems of wear resistance and stain resistance of the ceramic rock plate.

[0007] To solve the above technical problems, a first aspect of the present application provides a wear-resistant matte ceramic rock plate, which comprises, from bottom to top, a body, a first surface glaze layer, a second surface glaze layer, a pattern layer and a dry particle glaze layer, and the initial melting temperature of the second surface glaze layer is between the initial melting temperature of the first surface glaze layer and the initial melting temperature of the dry particle glaze layer.

[0008] The chemical composition of the dry particle glaze layer includes, by weight percentage, 50.00-53.00% of SiO2, 22.00-24.00% of Al2O3, 0.05-0.15% of Fe2O3, 0.05-0.15% of TiO2, 7.00-7.70% of CaO, 1.50-2.00% of MgO, 4.50-5.20% of K2O, 1.20-1.70% of Na2O, 0.30-0.50% of ZrO2, 3.50-4.50% of ZnO, 4.40-5.60% of BaO, 0.70-0.85% of SrO, 0.50-1.00% of Y2O3, and a loss on ignition of 0.10-0.30%.

[0009] Specifically, in the process of densifying the sintered body of the ceramic rock plate, the voids in the sintered body become smaller and fewer, and the gas in the voids will be discharged upward, causing defects such as pinholes and bubbles on the surface of the ceramic rock plate. The ceramic rock plate of the present application reduces the generation of pinholes and bubbles on the surface of the ceramic rock plate by setting two layers of surface glaze layers (the first surface glaze layer and the second surface glaze layer) with different initial melting temperatures and controlling the initial melting temperature relationship between the double-layer surface glaze layer and the dry particle glaze layer. On the one hand, the initial melting temperature of the first surface glaze layer, which is close to that of the sintered body, is increased to ensure that the voids in the first surface glaze layer with a higher temperature are not closed when the gas in the sintered body is discharged, and the bubbles and pinholes in the second surface glaze layer with a lower temperature, which is far away from the sintered body, are reduced, thereby improving the stain resistance of the ceramic rock plate. On the other hand, the dry particle glaze is fixed on the surface of the second surface glaze layer with a relatively lower initial melting temperature, which realizes the good combination of the dry particle glaze on the surface of the ceramic rock plate and is conducive to the durability of the stain resistance of the ceramic rock plate. In addition, the dry particle glaze is fixed on the surface of the second surface glaze layer with a low initial melting point, which can form islands on the molten surface layer and form undulations with the pattern layer, thereby increasing the three-dimensional effect of the pattern layer.

[0010] At the same time, the present application adjusts the chemical composition of the dry particle glaze layer to increase the proportion of the network structure of silicon-oxygen tetrahedron [SiO4] in the dry particle microstructure, thereby improving the hardness and wear resistance of the dry particle glaze. The Mohs hardness of pure quartz crystal is 7, while the hardness of the glaze layer of general ceramic tiles is only 4-5, and the wear resistance of quartz crystal is 6-7, which can reach 25,000 revolutions. Therefore, increasing the network structure of [SiO4] in the dry particle glaze helps to improve its wear resistance. In addition, Y 3+ which can slow down the destruction of the [SiO4] network structure by alkali metals, thereby adding a certain amount of Y2O3 helps to form micro-nano crystalline phase in the glass phase, further improving the wear resistance of the dry particle glaze.

[0011] As a further improvement of the above-mentioned solution, the initial melting temperature of the first surface glaze layer is 1245-1275℃, and the higher initial melting temperature of the first surface glaze layer can effectively reduce the defects such as bubbles and pinholes in the second surface glaze layer with a lower temperature caused by the discharge of gas from the sintered body during high-temperature firing.

[0012] Preferably, the chemical composition of the first face glaze layer comprises, by weight percentage: 48.50-54.00% of SiO2, 33.00-37.50% of Al2O3, 0.05-0.15% of Fe2O3, 0.30-0.50% of TiO2, 0.80-1.20% of CaO, 0.30-0.50% of MgO, 0.70-1.20% of K2O, 4.00-4.80% of Na2O, 0.30-0.50% of ZrO2, 1.50-2.50% of ZnO, 2.00-3.00% of loss on ignition.

[0013] Preferably, the raw material components of the first face glaze layer comprise, by weight: 20-25 parts of feldspar powder, 25-30 parts of quartz, 30-35 parts of calcined kaolin, 3-8 parts of talc, 3-5 parts of calcium carbonate, and 5-10 parts of alumina.

[0014] As a further improvement of the above scheme, the initial melting temperature of the second face glaze layer is 1080-1110℃, and the lower initial melting temperature of the second face glaze layer can better fix the dry particle glaze and form a good bond on the ceramic rock plate.

[0015] Preferably, the preparation raw material of the second face glaze layer comprises a base face glaze and a calcium feldspar powder, and the amount of the calcium feldspar powder accounts for 1-3wt% of the solid mass of the base face glaze.

[0016] Preferably, the particle size of the calcium feldspar powder is D90=200-500nm, which is submicron.

[0017] Specifically, in the low-temperature second face glaze layer, the relatively high content of glass phase will adversely affect the color of the pattern layer and affect the normal color development effect of the pattern. The present application improves the opalescent effect of the second face glaze layer and optimizes the color development effect of the pattern layer by adding a certain amount of submicron calcium feldspar powder as a crystal seed in the base face glaze. At the same time, in the solid-phase synthesis of calcium carbonate, alumina, and silicon oxide, a reaction temperature of 1280℃ or higher is required to form calcium feldspar crystal phase; therefore, it is difficult to form a large amount of calcium feldspar crystal phase in a high-calcium face glaze. The present application is more conducive to the precipitation of calcium feldspar crystals by adding an appropriate amount of submicron calcium feldspar as a crystal seed in the base face glaze, thereby improving the opalescent effect of the second face glaze layer and improving the color development of the pattern layer.

[0018] Preferably, the chemical composition of the base face glaze includes, by weight percentage: 48.00-55.00% of SiO2, 17.00-19.00% of Al2O3, 0.35.0-0.45% of Fe2O3, 0.15-0.20% of TiO2, 5.50-7.00% of CaO, 3.00-3.50% of MgO, 4.50-5.20% of K2O, 1.00-1.50% of Na2O, 0.30-0.50% of ZrO2, 2.50-3.50% of ZnO, 8.50-11.00% of loss on ignition.

[0019] Preferably, the raw material components of the base body, by weight parts, include: potassium feldspar powder 10-15 parts, quartz 25-30 parts, potassium sodium stone powder 15-20 parts, kaolin 20-25 parts, talc 3-8 parts, calcium carbonate 8-13 parts, alumina 1-5 parts.

[0020] Preferably, the initial melting temperature of the dry particle glaze layer is 1140-1170℃.

[0021] Preferably, the particle size of the dry particle in the dry particle glaze is D90=200-400 mesh.

[0022] Preferably, the raw material components of the base body, by weight parts, include: ball clay 10-15 parts, potassium sodium stone powder 15-20 parts, potassium sand 10-15 parts, potassium feldspar powder 15-20 parts, sodium feldspar powder 10-15 parts, bentonite 1-5 parts, water-washed mud 5-10 parts, ditch mud 5-10 parts, bauxite 1-5 parts.

[0023] Preferably, the chemical composition of the base body, by weight percentage, includes: 66.00-72.00% of SiO2, 18.20-20.10% of Al2O3, 0.20-0.40% of Fe2O3, 0.10-0.30% of TiO2, 0.30-1.00% of CaO, 0.10-0.50% of MgO, 2.40-2.80% of K2O, 3.20-3.70% of Na2O, 4.00-4.80% of loss on ignition.

[0024] The second aspect of the present application provides a preparation method of the above-mentioned wear-resistant matte ceramic rock plate, comprising the following steps:

[0025] After the preparation raw materials of the first and second face glaze layers are taken respectively, the first and second face glaze slurries are prepared, and then applied to the surface of the base body in sequence to form the first and second face glaze layers; then, the pattern layer and the dry particle glaze layer are formed by inkjet printing a pattern on the surface of the second face glaze layer and applying a dry particle glaze; after drying and firing, the wear-resistant matte ceramic rock plate is obtained.

[0026] As a further improvement of the above-mentioned scheme, the preparation process of the second face glaze paste is:

[0027] Take the preparation raw materials of the base face glaze to obtain the base face glaze paste;

[0028] The calcic plagioclase powder is first dispersed in the aqueous solution of sodium carboxymethyl cellulose to obtain a calcic plagioclase suspension;

[0029] The calcic plagioclase suspension, the aqueous solution of sodium tripolyphosphate, the aqueous solution of sodium carboxymethyl cellulose and water are added to the base face glaze paste, mixed to obtain the wear-resistant matte ceramic rock plate.

[0030] Specifically, in the preparation of the second face glaze paste, the sub-micron calcic plagioclase powder is first dispersed in the aqueous solution of sodium carboxymethyl cellulose to form a uniformly dispersed suspension; then mixed with the base face glaze paste, which can effectively prevent the agglomeration of the calcic plagioclase powder and better play the role of the crystal seed.

[0031] Preferably, the concentration of the aqueous solution of sodium carboxymethyl cellulose is 1-2wt%.

[0032] Preferably, the concentration of the aqueous solution of sodium tripolyphosphate is 3-5wt%.

[0033] Preferably, the specific gravity of the second face glaze paste is 1.75-2.05g / cm 3 The flow rate measured by the Coating-4 cup is 25-35 seconds.

[0034] Preferably, the process conditions of the firing are as follows: the highest firing temperature is 1170-1210℃, the firing period is 55-65min, and the holding time at the highest firing temperature is 7-15min.

[0035] The above technical scheme of the present application has at least the following technical effects or advantages compared with the prior art:

[0036] (1) The ceramic rock plate of the present application is provided with two layers of face glaze layers (the first face glaze layer and the second face glaze layer) with different initial melting temperatures, and the initial melting temperature of the second face glaze layer is between the initial melting temperatures of the first face glaze layer and the dry particle glaze layer, so as to reduce the generation of brick face pinholes and bubbles, improve the stain resistance of the ceramic rock plate; at the same time, the second face glaze layer with relatively lower initial melting temperature is used to fix the dry particle glaze, realizing the good combination of the dry particle glaze on the surface of the ceramic rock plate, improving the durability of the stain resistance of the ceramic rock plate, and enhancing the color development and stereoscopic effect of the pattern layer. The stain resistance level of the product can reach level 5, and the stain resistance level after wear and tear can still reach level 4, the color development effect of the pattern is good, and the stereoscopic effect is strong.

[0037] (2) The application adjusts the chemical composition of the dry particle glaze layer, increases the proportion of the network structure of silicon oxygen tetrahedron [SiO4] in the dry particle microstructure, and adds a certain amount of Y2O3, so that the wear resistance of the ceramic rock plate is greatly improved, and the wear resistance of the product reaches level 5, 12000 revolutions. DETAILED DESCRIPTION

[0038] The application will be specifically described below in combination with examples for the understanding of the persons skilled in the art. It is necessary to particularly point out here that the examples are only used for further illustrating the application and cannot be understood as limiting the protection scope of the application. The non-essential improvements and adjustments made to the application by the persons skilled in the art according to the above application content shall still belong to the protection scope of the application. Meanwhile, the raw materials mentioned below which are not specifically described are all commercially available products; the process steps or preparation methods which are not specifically mentioned are all the process steps or preparation methods known by the persons skilled in the art.

[0039] Example 1

[0040] A wear-resistant matte ceramic rock plate comprises, from bottom to top, a body, a first surface glaze layer, a second surface glaze layer, a pattern layer and a dry particle glaze layer.

[0041] The raw material components of the body include, by weight fraction, 14 parts of ball clay, 18 parts of potash and soda stone powder, 13 parts of potash sand, 16 parts of potash feldspar powder, 14 parts of soda feldspar powder, 4.2 parts of bentonite, 8.8 parts of water-washed mud, 7.5 parts of water ditch mud and 4.5 parts of bauxite; the chemical composition of the body includes, by weight percentage, 68.23% of SiO2, 19.35% of Al2O3, 0.31% of Fe2O3, 0.19% of TiO2, 0.86% of CaO, 0.32% of MgO, 2.64% of K2O, 3.56% of Na2O and 4.54% of loss on ignition.

[0042] The raw material components of the first surface glaze layer include, by weight fraction, 23.5 parts of feldspar powder, 28 parts of quartz, 32.5 parts of calcined kaolin, 4.5 parts of talc, 3.5 parts of calcium carbonate and 8 parts of aluminum oxide; the chemical composition of the first surface glaze layer includes, by weight percentage, 51.73% of SiO2, 35.74% of Al2O3, 0.08% of Fe2O3, 0.36% of TiO2, 1.14% of CaO, 0.37% of MgO, 0.95% of K2O, 4.48% of Na2O, 0.43% of ZrO2, 2.24% of ZnO, 2.48% of loss on ignition; the initial melting temperature of the first surface glaze layer is about 1250℃.

[0043] The raw material components of the second glaze layer, by weight fraction, include 100 parts of base glaze and 2 parts of calcium feldspar powder with D90=348 nm; wherein: the raw material components of the base glaze, by weight fraction, include 19 parts of potassium feldspar powder, 27 parts of quartz, 12 parts of potassium-sodium stone powder, 21 parts of kaolin, 7 parts of talc, 11 parts of calcium carbonate, and 3 parts of aluminum oxide; the chemical composition of the base glaze, by weight percentage, includes 52.34% of SiO2, 17.68% of Al2O3, 0.39% of Fe2O3, 0.17% of TiO2, 6.43% of CaO, 3.25% of MgO, 5.04% of K2O, 1.28% of Na2O, 0.37% of ZrO2, 3.14% of ZnO, and 9.91% of loss on ignition; the initial melting temperature of the second glaze layer is about 1100℃.

[0044] The chemical composition of the dry granular glaze, by weight percentage, includes 50.33% of SiO2, 22.29% of Al2O3, 0.11% of Fe2O3, 0.12% of TiO2, 7.43% of CaO, 1.82% of MgO, 4.82% of K2O, 1.48% of Na2O, 0.39% of ZrO2, 4.05% of ZnO, 5.21% of BaO, 0.78% of SrO, 0.95% of Y2O3, and a loss on ignition of 0.22%. The initial melting temperature of the dry granular glaze is 1155℃; and the particle size of the dry granules in the dry granular glaze is D90=325 mesh.

[0045] A preparation method of a wear-resistant matte ceramic rock plate, comprising the following steps:

[0046] (1) The raw materials are weighed according to the raw material components of the body, 0.35% of sodium tripolyphosphate and 0.25% of sodium carboxymethyl cellulose are added to the total amount of raw materials, water is added for ball milling, a body slurry with a solid content of 68.3wt%, a flow rate of 53 seconds measured by cup-4, and a fineness of 325 mesh with a residue of 0.42wt% is obtained, then the body slurry is spray granulated to obtain a body powder, and then the body powder is aged, pressed and formed, and dried to obtain a body;

[0047] (2) The raw materials are weighed according to the raw material components of the first glaze layer, 0.35% of sodium tripolyphosphate and 0.30% of sodium carboxymethyl cellulose are added to the total amount of raw materials, water is added for ball milling, and then a first glaze slurry with a specific gravity of 1.91g / cm 3 , a flow rate of 29 seconds measured by cup-4 is obtained, then the first glaze slurry is sprayed on the surface of the body by bell jar glazing, and the glazing amount is 580g / m 2 ;

[0048] (3) The base glaze raw materials and the anorthite powder are weighed according to the raw material composition of the second glaze layer, then 0.30% of sodium tripolyphosphate and 0.25% of sodium carboxymethyl cellulose are added to the base glaze raw materials, and water is added for ball milling, and then the mixture is passed through a 100-mesh screen to obtain a base glaze slurry with a specific gravity of 1.91 g / cm 3 ; 2%wt of the anorthite powder of the base glaze raw materials is dispersed in a 1% sodium carboxymethyl cellulose aqueous solution to obtain an anorthite suspension; then the anorthite suspension is added to the base glaze slurry, and then 5%wt of a sodium tripolyphosphate aqueous solution and 1%wt of a sodium carboxymethyl cellulose aqueous solution are added, and water is added for mixing and stirring to obtain a second glaze slurry with a specific gravity of 1.90 g / cm 3 ; the second glaze slurry is applied to the surface of the first glaze layer by bell jar spraying, and the application amount is 583 g / m 2 ;

[0049] (4) The surface of the second glaze layer is inkjet printed with a pattern to obtain a pattern layer;

[0050] (5) The dry particle glaze is mixed with glue at a mass ratio of 60:40 under the condition of adding water, and a matt dry particle glaze slurry with a specific gravity of 1.25 g / cm 3 is obtained; the matt dry particle glaze slurry is applied to the pattern layer using a high-pressure spray glaze cabinet, and the application amount is 443 g / m 2 ; after drying, it is fired in a kiln, and the firing temperature system is as follows: the firing period is 66 min, the maximum firing temperature is 1186℃, and the holding time at the maximum firing temperature is 14 min; a wear-resistant matt ceramic rock plate of the present embodiment is obtained.

[0051] Example 2

[0052] A wear-resistant matt ceramic rock plate comprises a body, a first glaze layer, a second glaze layer, a pattern layer, and a dry particle glaze layer from bottom to top.

[0053] The raw material composition of the body includes, by weight, 14 parts of ball clay, 18 parts of potash-soda stone powder, 13 parts of potash sand, 16 parts of potash feldspar powder, 14 parts of soda feldspar powder, 4.2 parts of bentonite, 8.8 parts of water-washed mud, 7.5 parts of water ditch mud, and 4.5 parts of bauxite; the chemical composition of the body includes, by weight percentage, 68.23% of SiO2, 19.35% of Al2O3, 0.31% of Fe2O3, 0.19% of TiO2, 0.86% of CaO, 0.32% of MgO, 2.64% of K2O, 3.56% of Na2O, and 4.54% of loss on ignition.

[0054] The raw material components of the first surface glaze layer include, in parts by weight, feldspar powder 22.5 parts, quartz 29 parts, calcined kaolin clay 33.4 parts, talc 3.5 parts, calcium carbonate 3.6 parts, and aluminum oxide 8 parts; the chemical composition of the first surface glaze layer includes, in percentage by weight, 52.18% of SiO2, 36.57% of Al2O3, 0.07% of Fe2O3, 0.31% of TiO2, 1.11% of CaO, 0.34% of MgO, 0.88% of K2O, 4.13% of Na2O, 0.36% of ZrO2, 1.96% of ZnO, and 2.09% of loss on ignition; the initial melting temperature of the first surface glaze layer is about 1260℃.

[0055] The raw material components of the second surface glaze layer include, in parts by weight, 100 parts of base surface glaze and 2.5 parts of calcium feldspar powder with D90=295nm; wherein the raw material components of the base surface glaze include, in parts by weight, potassium feldspar powder 19 parts, quartz 27.5 parts, potassium-sodium stone powder 11.5 parts, kaolin clay 21 parts, talc 7.5 parts, calcium carbonate 10.5 parts, and aluminum oxide 3 parts; the chemical composition of the base surface glaze includes, in percentage by weight, 53.12% of SiO2, 17.48% of Al2O3, 0.41% of Fe2O3, 0.18% of TiO2, 5.96% of CaO, 3.32% of MgO, 5.10% of K2O, 1.42% of Na2O, 0.38% of ZrO2, 3.21% of ZnO, and 9.42% of loss on ignition; the initial melting temperature of the second surface glaze layer is about 1095℃.

[0056] The chemical composition of the dry particle glaze includes, in percentage by weight, 51.13% of SiO2, 22.94% of Al2O3, 0.09% of Fe2O3, 0.11% of TiO2, 7.14% of CaO, 1.67% of MgO, 4.62% of K2O, 1.41% of Na2O, 0.36% of ZrO2, 3.52% of ZnO, 5.06% of BaO, 0.81% of SrO, 0.88% of Y2O3, and 0.26% of loss on ignition. The initial melting temperature of the dry particle glaze is 1160℃; the particle size of the dry particle in the dry particle glaze is D90=325 mesh.

[0057] A preparation method of a wear-resistant matte ceramic rock plate, comprising the following steps:

[0058] (1) The raw materials are weighed according to the raw material components of the body, and 0.35% of sodium tripolyphosphate and 0.25% of sodium carboxymethyl cellulose are added to the total amount of the raw materials, and then water is added for ball milling to obtain a body slurry with a solid content of 68.3wt%, a flow rate of 53 seconds through a No. 4 cup, and a fineness of 0.42wt% on a 325 mesh sieve; then the body slurry is spray granulated to obtain a body powder; and then the body powder is aged and pressed into a body after drying.

[0059] (2) The raw materials of the first glaze layer were weighed according to the raw material composition, 0.30% of sodium tripolyphosphate and 0.30% of sodium carboxymethyl cellulose were added to the total amount of raw materials, and water was added for ball milling. After being screened through a 100-mesh screen, a first glaze slurry with a specific gravity of 1.89 g / cm 3 was obtained. The first glaze slurry was then applied to the surface of the body by bell jar spraying, and the glaze application amount was 590 g / m 2 ;

[0060] (3) The base glaze raw materials and calcium feldspar powder of the second glaze layer were weighed according to the raw material composition, and then 0.35% of sodium tripolyphosphate and 0.20% of sodium carboxymethyl cellulose were added to the total amount of raw materials. Water was added for ball milling, and then the mixture was screened through a 100-mesh screen to obtain a base glaze slurry with a specific gravity of 1.92 g / cm 3 . The calcium feldspar powder was dispersed in a 1% sodium carboxymethyl cellulose aqueous solution to obtain a calcium feldspar suspension. Then, the calcium feldspar suspension was added to the base glaze slurry, and then an appropriate amount of 5 wt% sodium tripolyphosphate aqueous solution and 1 wt% sodium carboxymethyl cellulose aqueous solution were added. The mixture was stirred with water to obtain a second glaze slurry with a specific gravity of 1.91 g / cm 3 , which was measured by a No. 4 cup to have a flow rate of 29 seconds. Then, the second glaze slurry was applied to the surface of the first glaze layer by bell jar spraying, and the glaze application amount was 580 g / m 2 .

[0061] (4) A pattern layer was obtained by inkjet printing a pattern on the surface of the second glaze layer.

[0062] (5) The dry granular glaze was mixed with glue in a mass ratio of 60:40 under the condition of adding water, and a matte dry granular glaze slurry with a specific gravity of 1.24 g / cm 3 was obtained. The matte dry granular glaze slurry was applied to the pattern layer using a high-pressure spray glaze cabinet, and the glaze application amount was 448 g / m 2 . After drying, the glaze was fired in a kiln, and the firing temperature schedule was as follows: the firing period was 68 min, the maximum firing temperature was 1188°C, and the holding time at the maximum firing temperature was 15 min. A wear-resistant matte ceramic rock plate of the present embodiment was obtained.

[0063] Example 3

[0064] A wear-resistant matte ceramic rock plate comprises, from bottom to top, a body, a first glaze layer, a second glaze layer, a pattern layer, and a dry granular glaze layer.

[0065] The raw material components of the body include, in parts by weight, 14 parts of ball clay, 18 parts of potash-soda stone powder, 13 parts of potash sand, 16 parts of potash feldspar powder, 14 parts of soda feldspar powder, 4.2 parts of bentonite, 8.8 parts of water-washed mud, 7.5 parts of gully mud, and 4.5 parts of bauxite; the chemical composition of the body includes, in percentage by weight, 68.23% of SiO2, 19.35% of Al2O3, 0.31% of Fe2O3, 0.19% of TiO2, 0.86% of CaO, 0.32% of MgO, 2.64% of K2O, 3.56% of Na2O, and 4.54% of loss on ignition.

[0066] The raw material components of the first glaze layer include, in parts by weight, 23 parts of feldspar powder, 25.5 parts of quartz, 34.5 parts of calcined kaolin, 3.5 parts of talc, 3.5 parts of calcium carbonate, and 10 parts of alumina; the chemical composition of the first glaze layer includes, in percentage by weight, 49.41% of SiO2, 37.42% of Al2O3, 0.07% of Fe2O3, 0.34% of TiO2, 1.16% of CaO, 0.45% of MgO, 1.06% of K2O, 4.68% of Na2O, 0.41% of ZrO2, 2.36% of ZnO, and 2.64% of loss on ignition; the initial melting temperature of the first glaze layer is about 1270℃.

[0067] The raw material components of the second glaze layer include, in parts by weight, 100 parts of base glaze and 3 parts of calcium feldspar powder with D90=325nm; the raw material components of the base glaze include, in parts by weight, 19 parts of potash feldspar powder, 24.5 parts of quartz, 11.5 parts of potash-soda stone powder, 22 parts of kaolin, 6 parts of talc, 13 parts of calcium carbonate, and 4 parts of alumina; the chemical composition of the base glaze includes, in percentage by weight, 53.17% of SiO2, 18.34% of Al2O3, 0.36% of Fe2O3, 0.19% of TiO2, 6.32% of CaO, 3.19% of MgO, 4.65% of K2O, 1.12% of Na2O, 0.42% of ZrO2, 3.14% of ZnO, and 9.10% of loss on ignition; the initial melting temperature of the second glaze layer is about 1110℃.

[0068] The chemical composition of the dry granular glaze includes, in percentage by weight, 50.62% of SiO2, 22.54% of Al2O3, 0.09% of Fe2O3, 0.13% of TiO2, 7.28% of CaO, 1.58% of MgO, 5.18% of K2O, 1.63% of Na2O, 0.38% of ZrO2, 3.86% of ZnO, 4.75% of BaO, 0.81% of SrO, 0.90% of Y2O3, and 0.25% of loss on ignition; the initial melting temperature of the dry granular glaze is 1145℃; the particle size of the dry granules in the dry granular glaze is D90=325 mesh.

[0069] A method for preparing a wear-resistant matte ceramic rock plate, comprising the following steps:

[0070] (1) The raw materials are weighed according to the raw material components of the body, 0.35% of sodium tripolyphosphate and 0.25% of sodium carboxymethyl cellulose are added to the total amount of raw materials, and water is added for ball milling to obtain a body slurry with a solid content of 68.3wt%, a flow rate of 53 seconds measured by cup-4, and a fineness of 0.42wt% on a 325 mesh screen; then the body slurry is spray granulated to prepare a body powder; and then the body powder is aged, pressed into shape, and dried to obtain a body.

[0071] (2) The raw materials are weighed according to the raw material components of the first glaze layer, 0.30% of sodium tripolyphosphate and 0.30% of sodium carboxymethyl cellulose are added to the total amount of raw materials, and water is added for ball milling and sieving through a 100 mesh screen to obtain a first glaze slurry with a specific gravity of 1.96g / cm 3 , a flow rate of 26 seconds measured by cup-4; then the first glaze slurry is applied to the surface of the body by bell jar glazing, and the glazing amount is 570g / m 2 .

[0072] (3) The base glaze raw materials and calcium feldspar powder are weighed according to the raw material components of the second glaze layer, and then 0.30% of sodium tripolyphosphate and 0.25% of sodium carboxymethyl cellulose are added to the total amount of raw materials, and water is added for ball milling and sieving through a 100 mesh screen to obtain a base glaze slurry with a specific gravity of 1.94g / cm 3 , a flow rate of 27 seconds measured by cup-4; the calcium feldspar powder is dispersed in a 1% sodium carboxymethyl cellulose aqueous solution to obtain a calcium feldspar suspension; then the calcium feldspar suspension is added to the base glaze slurry, and an appropriate amount of 5wt% sodium tripolyphosphate aqueous solution and 1wt% sodium carboxymethyl cellulose aqueous solution are added, and the mixture is stirred with water to obtain a second glaze slurry with a specific gravity of 1.92g / cm 3 , a flow rate of 28 seconds measured by cup-4; then the second glaze slurry is applied to the surface of the first glaze layer by bell jar glazing, and the glazing amount is 578g / m 2 .

[0073] (4) A pattern layer is obtained by inkjet printing a pattern on the surface of the second glaze layer.

[0074] (5) The dry granular glaze is prepared by mixing the dry granular glaze with glue in a mass ratio of 60:40 under the condition of adding water, and the specific gravity of the matte dry granular glaze slurry is 1.23g / cm 3 , and the matte dry granular glaze slurry is applied to the pattern layer using a high-pressure glaze spraying cabinet, and the glazing amount is 444g / m 2 ; after drying, it is fired in a kiln, and the firing temperature system is: the firing period is 64 minutes, the maximum firing temperature is 1186℃, and the holding time at the maximum firing temperature is 12 minutes; and a wear-resistant matte ceramic rock plate of the present embodiment is obtained.

[0075] Comparative Example 1

[0076] Comparative Example 1 differs from Example 1 only in that the ceramic rock plate of Comparative Example 1 does not contain a second surface glaze layer, and comprises, from bottom to top, a body, a first surface glaze layer, a pattern layer and a dry particle glaze layer.

[0077] Comparative Example 2

[0078] Comparative Example 2 differs from Example 1 only in that the chemical composition of the dry particle glaze of Comparative Example 2 is different, and the chemical composition of the dry particle glaze of Comparative Example 2 comprises, by weight percentage: 50.81% of SiO2, 22.50% of Al2O3, 0.11% of Fe2O3, 0.12% of TiO2, 7.50% of CaO, 1.84% of MgO, 4.87% of K2O, 1.49% of Na2O, 0.39% of ZrO2, 4.09% of ZnO, 5.26% of BaO, 0.79% of SrO, and a loss on ignition of 0.22%. The initial melting temperature of the dry particle glaze is 1150°C; and the particle size of the dry particles in the dry particle glaze is D90 = 325 mesh.

[0079] Comparative Example 3

[0080] Comparative Example 3 differs from Example 1 only in that the raw material components of the second surface glaze layer of Comparative Example 3 are different, and Comparative Example 3 uses an equal amount of wollastonite to replace the anorthite powder in Example 1.

[0081] Comparative Example 4

[0082] Comparative Example 4 differs from Example 1 only in that the raw material components and chemical composition of the base surface glaze in the second surface glaze layer of Comparative Example 4 are different.

[0083] The raw material components of the base surface glaze in Comparative Example 4 comprise, by weight: 19 parts of potassium feldspar powder, 27 parts of quartz, 10 parts of potassium-sodium stone powder, 24 parts of kaolin, 5 parts of talc, 7 parts of calcium carbonate, and 8 parts of alumina; and the chemical composition of the base surface glaze comprises, by weight percentage: 51.37% of SiO2, 27.51% of Al2O3, 0.43% of Fe2O3, 0.22% of TiO2, 3.54% of CaO, 2.45% of MgO, 3.14% of K2O, 1.28% of Na2O, 0.37% of ZrO2, 2.95% of ZnO, and a loss on ignition of 6.74%; and the initial melting temperature of the second surface glaze layer is 1180°C.

[0084] Performance Test

[0085] The ceramic rock plate samples prepared in the above examples 1-3 and comparative examples 1-4 were tested for gloss and wear resistance. The test standards were respectively GB / T 13891-2008 Building Veneer Materials Determination of Gloss in Specular Direction and GB / T 3810.7-2016 Ceramic Tiles-Determination of Wear Resistance of Glazed Tiles. The wear resistance was divided into 0-5 levels, with 0 indicating the worst wear resistance and 5 indicating the best wear resistance. The greater the number of revolutions at the same level, the better the wear resistance. The test method for stain absorption was as follows: ink was applied to the glaze layer of samples of the same size (length x width = 10 cm x 10 cm), and a rubber glove was used to apply the ink for 5 min. After the ink was dried, it was washed with water, dried, and the number of stain absorption points was observed. The stain resistance level was tested according to GB / T 3810.14-2016 Ceramic Tiles-Determination of Stain Resistance. The stain resistance was divided into 1-5 levels, with 1 indicating the worst stain resistance and 5 indicating the best stain resistance. The fewer the number of stain absorption points at the same level, the better the stain resistance. The test results are shown in Table 1.

[0086] Table 1:

[0087]

[0088]

[0089] As can be seen from Table 1, the ceramic rock plate samples of examples 1-3 all have excellent wear resistance, stain resistance and stain resistance durability, and the tile surface color is normal and has a good three-dimensional effect.

[0090] Comparative example 1 relative to example 1, because it does not contain a second glaze layer, i.e. the dry particle glaze layer is directly combined with the first glaze layer (the pattern layer has a weak influence on the glaze layer). The initial melting temperature of the first glaze layer and the dry particle glaze layer is 1250°C and 1155°C, respectively. After firing at 1186°C, the combination of the dry particle glaze layer and the first glaze layer is much weaker than the second glaze layer. Therefore, the stain resistance is significantly reduced, and the glaze surface cannot show a three-dimensional effect.

[0091] Comparative example 2 relative to example 1, because Y2O3 is not contained in the chemical composition of the dry particle glaze, and the proportion of the network structure of silicon-oxygen tetrahedron [SiO4] in the dry particle microstructure is reduced, resulting in a decrease in the wear resistance of the dry particle glaze layer.

[0092] Comparative example 3 relative to example 1, because sub-micron calcium feldspar is not added as a crystal nucleus in the second glaze layer, the opalescence of the second glaze layer is reduced, which is not conducive to the color development effect of the yellow pigment, thereby affecting the pattern color development effect of the tile surface.

[0093] Comparative Example 4, relative to Example 1, has a poor glaze layer bonding effect on the tile surface due to the second face glaze layer having a higher initial melting temperature than the dry granular glaze, resulting in a sharp decline in wear resistance and stain resistance.

[0094] For those skilled in the art of the present application, without departing from the concept of the present application, can make a number of simple deductions or substitutions, without having to go through the creative labor. Therefore, the skilled person according to the disclosure of the present application, the simple improvement of the present application should be within the scope of protection of the present application. The above examples are preferred embodiments of the present application, any equivalent changes made to the process and the equivalent changes should belong to the protection scope of the present application.

Claims

1. A wear-resistant matte ceramic rock plate, characterized in that, From bottom to top, the body, the first surface glaze layer, the second surface glaze layer, the pattern layer and the dry particle glaze layer are sequentially included, the initial melting temperature of the second surface glaze layer is between the initial melting temperature of the first surface glaze layer and the initial melting temperature of the dry particle glaze layer; The chemical composition of the dry particle glaze layer includes, by weight percentage: 50.00-53.00% of SiO2, 22.00-24.00% of Al2O3, 0.05-0.15% of Fe2O3, 0.05-0.15% of TiO2, 7.00-7.70% of CaO, 1.50-2.00% of MgO, 4.50-5.20% of K2O, 1.20-1.70% of Na2O, 0.30-0.50% of ZrO2, 3.50-4.50% of ZnO, 4.40-5.60% of BaO, 0.70-0.85% of SrO, 0.50-1.00% of Y2O3, and a loss on ignition of 0.10-0.30%.

2. The wear-resistant matte ceramic rock plate according to claim 1, characterized in that, The initial melting temperature of the first surface glaze layer is 1245-1275℃.

3. The wear-resistant matte ceramic rock plate according to claim 1 or 2, characterized in that, The chemical composition of the first surface glaze layer includes, by weight percentage: 48.50-54.00% of SiO2, 33.00-37.50% of Al2O3, 0.05-0.15% of Fe2O3, 0.30-0.50% of TiO2, 0.80-1.20% of CaO, 0.30-0.50% of MgO, 0.70-1.20% of K2O, 4.00-4.80% of Na2O, 0.30-0.50% of ZrO2, 1.50-2.50% of ZnO, and a loss on ignition of 2.00-3.00%.

4. The wear-resistant matte ceramic rock plate of claim 1, wherein, The initial melting temperature of the second surface glaze layer is 1080-1110℃.

5. The wear-resistant matte ceramic rock plate according to claim 1 or 4, characterized in that, The preparation raw material of the second surface glaze layer includes base surface glaze and calcium feldspar powder, and the amount of the calcium feldspar powder accounts for 1-3wt% of the solid mass of the base surface glaze.

6. The wear-resistant matte ceramic rock plate of claim 5, wherein, The chemical composition of the base surface glaze includes, by weight percentage: 48.00-55.00% of SiO2, 17.00-19.00% of Al2O3, 0.35-0.45% of Fe2O3, 0.15-0.20% of TiO2, 5.50-7.00% of CaO, 3.00-3.50% of MgO, 4.50-5.20% of K2O, 1.00-1.50% of Na2O, 0.30-0.50% of ZrO2, 2.50-3.50% of ZnO, and a loss on ignition of 8.50-11.00%.

7. The wear-resistant matte ceramic rock plate of claim 5, wherein, The particle size of the calcium feldspar powder is D90=200-500nm.

8. The wear-resistant matte ceramic rock plate according to any one of claims 1, 2, 4, characterized in that, The initial melting temperature of the dry particle glaze layer is 1140-1170℃.

9. A method for preparing the wear-resistant matte ceramic rock plate according to any one of claims 1 to 8, characterized in that, The method comprises the following steps: The preparation raw materials of the first surface glaze layer and the second surface glaze layer are respectively taken to prepare the first surface glaze slurry and the second surface glaze slurry, which are then sequentially applied to the surface of the body to form the first surface glaze layer and the second surface glaze layer; then the pattern is inkjet printed on the surface of the second surface glaze layer, and the dry particle glaze is applied to form the pattern layer and the dry particle glaze layer; and finally the dry particle glaze layer is dried and fired to obtain the wear-resistant matte ceramic rock plate.

10. The method of claim 9, wherein the ceramic rock plate is prepared by the steps of: preparing a ceramic rock plate; and polishing the ceramic rock plate to a thickness of 3 mm or less. The preparation process of the second face glaze paste is: Taking the preparation raw material of the base face glaze, the base face glaze paste is prepared; The calcic feldspar powder is first dispersed in the aqueous solution of sodium carboxymethyl cellulose to obtain a calcic feldspar suspension; The aqueous solution of sodium carboxymethyl cellulose and water are added into the base face glaze paste, mixed to obtain the second face glaze paste; And / or, the process conditions of the firing are as follows: the highest firing temperature is 1170-1210℃, the firing period is 55-65min, and the holding time at the highest firing temperature is 7-15min.

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