Waxy antifouling matte archaized brick and preparation method thereof

Abstract

The invention relates to the technical field of architectural ceramics, and discloses a waxy antifouling matte archaized brick and a preparation method thereof.The preparation method comprises the steps that A, a green body layer is prepared; b, applying ground coat; c, applying wax antifouling matte glaze; d, firing; the waxy antifouling matte glaze comprises an antifouling matte glaze and waxy dry particles, wherein the waxy dry particles are composed of particles with the mesh number being larger than or equal to 150 and smaller than 200 and particles with the mesh number being 200-250; the antifouling matte glaze is prepared from the following raw materials in parts by weight: 7-10 parts of kaolin, 5-10 parts of calcined kaolin, 4-8 parts of quartz, 20-30 parts of potassium feldspar, 8-15 parts of albite, 5-10 parts of calcite, 5-10 parts of calcined talc, 1-3 parts of zinc oxide, 2-5 parts of strontium carbonate and 20-30 parts of antifouling wear-resistant frit. According to the scheme, glossiness, antifouling performance, hardness, abrasion resistance and color development performance can be considered at the same time under the existing firing condition, the archaized brick is endowed with fine, oily and smooth waxy hand feeling, and the use satisfaction degree of consumers is improved.

Description

Technical Field

[0001] The invention relates to the technical field of building ceramics, and in particular to a waxy anti-fouling matte antique brick and a preparation method thereof. Background Art

[0002] In the field of architectural ceramics, the glaze surface of antique tiles is generally not polished, so that the glaze surface retains the sintered state and presents an original matte texture similar to natural stone.

[0003] Based on considerations of glossiness, cost and flatness, the existing glaze formula structure of antique tiles usually uses a full raw material formula, and the flux system is generally a potassium-sodium system. However, if the potassium-sodium content in the glaze formula structure is high, the glaze is easy to melt and produce a glass phase at the low temperature stage of the firing curve, resulting in the glaze raw materials being sealed in the glaze layer before they can be exhausted during the sintering process, causing bubbles to appear on the glaze surface and causing a decrease in anti-fouling performance.

[0004] In order to improve the anti-fouling performance of existing antique tiles, technicians generally adjust the formula and firing temperature. However, since the firing curve of antique tiles is generally based on the existing body and base glaze being vitrified, only a small range of temperature adjustment can be made, and the room for improvement in anti-fouling performance is very limited. Basically, the formula structure of the glaze is adjusted to adapt to the existing firing conditions.

[0005] Due to the rigidification of the firing system, it is difficult to strike a balance between glossiness, anti-fouling performance, hardness, wear resistance and color development performance for the glaze formula of antique tiles composed entirely of raw materials. Therefore, it is urgent to break the existing glaze formula structure of antique tiles composed entirely of raw materials so that under the existing firing conditions, glossiness, anti-fouling performance, hardness, wear resistance and color development performance can be taken into account at the same time, thereby improving consumers' satisfaction with the use of antique tiles.

[0006] In addition, the current application market of architectural ceramics is becoming more and more extensive, and at the same time, there are more and more stringent requirements for ceramic decoration technology. The cross-integration of other materials to enrich ceramic decoration and make ceramic decoration effects more diverse is one of the important trends in modern ceramic glaze decoration. For example, by using wax dry particles to give the glaze layer a delicate, oily and smooth waxy feel, consumers can be more satisfied with the feel of tiles at a higher level. Summary of the invention

[0007] The purpose of the present invention is to provide a waxy anti-fouling matte antique tile and a preparation method thereof. By optimizing the glaze formula structure of the antique tile, the gloss, anti-fouling performance, hardness, wear resistance and color development performance are taken into account under the existing firing conditions, and the antique tile is given a delicate, oily and smooth waxy feel, thereby improving consumers' satisfaction with the use of the antique tile.

[0008] To achieve this purpose, the present invention adopts the following technical solutions:

[0009] A preparation method of a wax-textured anti-fouling matte antique brick, comprising the following steps:

[0010] A. Prepare a ceramic blank, press the ceramic blank, and obtain a blank layer after drying;

[0011] B. Apply a base glaze to the surface of the blank layer to obtain a base glaze layer;

[0012] C. Apply a wax-textured anti-fouling matte glaze to the surface of the base glaze layer to obtain a wax-textured anti-fouling matte glaze layer;

[0013] D. After drying, fire in a kiln to obtain a wax-textured anti-fouling matte antique brick;

[0014] Among them, in step C, the wax-textured anti-fouling matte glaze includes an anti-fouling matte glaze and wax dry particles, and the wax dry particles are composed of particles with a mesh number ≥ 150 meshes and < 200 meshes and particles with 200 - 250 meshes;

[0015] Calculated by mass parts, the raw materials of the anti-fouling matte glaze are composed of 7 - 10 parts of kaolin, 5 - 10 parts of calcined kaolin, 4 - 8 parts of quartz, 20 - 30 parts of potassium feldspar, 8 - 15 parts of sodium feldspar, 5 - 10 parts of calcite, 5 - 10 parts of burnt talc, 1 - 3 parts of zinc oxide, 2 - 5 parts of strontium carbonate, and 20 - 30 parts of anti-fouling and wear-resistant frit;

[0016] Calculated by mass percentage, the chemical composition of the anti-fouling and wear-resistant frit includes SiO2 32 - 40%, Al2O3 18 - 20%, CaO 18 - 20%, K2O 0.5 - 1.5%, ZnO 10 - 12%, BaO 1 - 2.5%, and SrO 12 - 15%;

[0017] Calculated by mass percentage, the chemical composition of the wax dry particles includes SiO2 51 - 53.8%, Al2O3 13 - 15%, Fe2O3 0.2 - 0.7%, TiO2 0.02 - 0.12%, CaO 10 - 12%, MgO 1 - 3%, K2O 1 - 3%, ZnO 7 - 9%, and BaO 10 - 12%;

[0018] In step D, the firing temperature for the firing is 1180 - 1205 °C, and the firing time is 45 - 60 min.

[0019] Preferably, the particle size distribution of the wax dry particles satisfies: calculated based on the total weight of the wax dry particles, the particles with a mesh number ≥ 150 meshes and < 200 meshes account for 70 - 80%, and the remaining are particles with 200 - 250 meshes.

[0020] Preferably, by mass ratio, the mixing ratio of the antifouling matte glaze and the waxy dry granules is 10:(1-2).

[0021] Preferably, calculated by mass percentage, the chemical composition of the waxy dry granules includes 52.656% of SiO2, 13.966% of Al2O3, 0.544% of Fe2O3, 0.096% of TiO2, 10.935% of CaO, 1.382% of MgO, 1.882% of K2O, 7.296% of ZnO, and 10.868% of BaO.

[0022] Preferably, the firing curve of the antifouling and wear-resistant frit is as follows:

[0023] Heating from room temperature to 300°C takes 1.5-2.5 h;

[0024] Heating from 300°C to 1530°C takes 2-3 h;

[0025] At 1530°C, hold for 0.5-1.2 h.

[0026] Preferably, step C is specifically:

[0027] C. Spraying the waxy antifouling matte glaze on the surface of the underglaze layer to obtain a waxy antifouling matte glaze layer;

[0028] Among them, the specific gravity of the waxy antifouling matte glaze is 1.5-1.55, and the aperture of the spraying gun is 0.62 mm.

[0029] Preferably, calculated by mass percentage, the chemical composition of the antifouling and wear-resistant frit includes 34.81% of SiO2, 18.66% of Al2O3, 19.16% of CaO, 0.81% of K2O, 11.23% of ZnO, 1.76% of BaO, and 13.46% of SrO.

[0030] Preferably, calculated by mass parts, the raw materials of the antifouling and wear-resistant frit are composed of 12-18 parts of quartz, 15-20 parts of calcined alumina, 30-38 parts of wollastonite, 8-12 parts of zinc oxide, 18-22 parts of strontium carbonate, and 1-5 parts of barium carbonate.

[0031] Preferably, calculated by mass parts, the raw materials of the waxy dry granules are composed of 25-30 parts of kaolin, 25-32 parts of quartz, 6-10 parts of potassium feldspar, 3-8 parts of zinc oxide, 3-8 parts of dolomite, 8-15 parts of calcite, and 12-18 parts of barium carbonate.

[0032] A wax-textured anti-fouling matte antique brick, prepared by using the above-mentioned preparation method of the wax-textured anti-fouling matte antique brick, and the glossiness of the glaze surface of the wax-textured anti-fouling matte antique brick is 8-12°, the anti-fouling grade is 5, the Mohs hardness is 7, and the abrasion resistance is ≥4 (6000 revolutions).

[0033] The technical solution provided by the present invention may include the following beneficial effects:

[0034] 1. In the firing process of the frit, Al 3+ exists in the form of alumina tetrahedrons in the silica tetrahedrons, so that part of the silica and alumina in the chemical composition form a dense mullite network structure. And the above-mentioned mullite network structure specifically includes two crystal forms, namely 3Al2O3·2SiO2 and 2Al2O3.SiO2. When the above crystals are evenly distributed in the glaze layer, it can effectively improve the hardness and abrasion resistance of the glaze layer; and the high silicon-aluminum content in the chemical composition is also beneficial to improving the acid and alkali resistance of the frit, resisting the erosion of acid and alkaline substances for a long time, and contributing to anti-fouling. In addition, the anti-fouling and wear-resistant frit uses divalent ions Sr 2+ and Zn 2+ as the flux system, which can make the frit form a dense internal structure during the firing process, thus contributing to anti-fouling; at the same time, Sr 2+ and Zn 2+ also help the frit to precipitate anorthite crystals during the firing process. On the one hand, the anorthite crystals can also be beneficial to improving the hardness and abrasion resistance of the glaze layer. On the other hand, the anorthite crystals have high transparency, and at the same time, the chemical composition contains a large amount of ZnO. Introducing the frit as a raw material into the glaze can effectively improve the color development performance of the glaze.

[0035] 2. The anti-fouling matte glaze reduces the addition ratio of potassium feldspar and sodium feldspar in the raw material formula, and at the same time introduces a relatively high proportion of quartz, thereby reducing the content of low-temperature fluxes K2O, Na2O and easily fusible glass phase in the glaze, so that the softening point temperature of the glaze during sintering is increased, and it is not easy to form a closed layer prematurely during the firing of the glaze, so that the gas generated during firing has sufficient exhaust time to match the existing low-temperature and fast-firing firing system of antique bricks. Further, strontium carbonate is additionally introduced into the raw materials of the anti-fouling matte glaze. Strontium oxide can reduce the softening temperature of the glaze, increase the high-temperature fluidity of the glaze, and increase the firing range of the glaze, so as to be more conducive to forming a dense glaze layer structure and improving the anti-fouling performance of the glaze layer. In addition, because the atomic radius of Sr 2+ is larger than that of Ca 2+ and Mg 2+A large radius and the application of a large amount of strontium oxide result in a certain surface roughness between it and the glass phase in the glaze. When interacting with incident light, it forms diffuse reflection, reducing the surface gloss of the glaze and achieving the matte effect of antique tiles. After the crystal phases formed with other divalent metal ions are evenly distributed on the glaze surface, the surface gloss of the glaze layer can also be controlled within 8 - 12°, meeting the general aesthetic of consumers for the matte gloss of antique tiles. Further, calcined kaolin and burnt talc are introduced into the raw materials of the glaze. Therefore, when the glaze is fired, mullite and cordierite crystals with higher hardness can be additionally generated. Coupled with the original crystals in the frit and the unmolten quartz in the raw materials, the glaze surface of the anti-fouling matte glaze layer is distributed with various crystals with higher hardness, which is more conducive to improving the hardness and wear resistance of the glaze surface. During the long-term use of antique tiles, it is not easy to damage the surface properties of the glaze layer, achieving long-lasting anti-fouling performance.

[0036] 3. The chemical composition of the waxy dry particles contains a large amount of BaO and CaO, and the content of low-temperature flux components (such as K2O, Na2O) is extremely low. After the dry particles are fired, a crystal system with main crystal phase of celsian and auxiliary crystal phase of anorthite is formed, and basically no vitreous substance is generated in the dry particles. More specifically, the formula body of the waxy dry particles belongs to the divalent alkaline earth metal system. Compared with the potassium-sodium system, the dry particles have a higher initial melting point and a wider sintering temperature range, reaching 1190 - 1220 °C. After combining with the anti-fouling matte glaze, it is more conducive to forming a concave-convex feel on the glaze surface. Further, since the microcrystalline molecular radius of celsian is larger than that of anorthite, it has a better matte and waxy feel. When the microcrystals formed by the dry particles protrude from the glaze surface, the concave-convex feel brought by the microcrystals is better. In addition, the chemical composition and crystal system of the waxy dry particles make their melting point not too high. When the waxy dry particles are combined with the anti-fouling matte glaze, the waxy dry particles can slightly melt in the glaze. On the one hand, it can ensure that the waxy dry particles basically maintain their initial particle state and protrude from the glaze surface, improving the feel. On the other hand, it can improve the bonding between the dry particles and the glaze layer, avoiding the decline of anti-fouling performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 is the surface microstructure diagram of the waxy texture anti-fouling matte antique tile prepared in Example 2 of the present invention.

[0038] Figure 2 is the mass spectrum of the waxy dry particles in Example 2 of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0039] A preparation method of a waxy texture anti-fouling matte antique tile includes the following steps:

[0040] A. Prepare a ceramic blank, press the ceramic blank, and obtain a green body layer after drying;

[0041] B. Apply a base glaze to the surface of the green body layer to obtain a base glaze layer;

[0042] C. Apply a wax-based stain-resistant matte glaze to the surface of the base glaze layer to obtain a wax-based stain-resistant matte glaze layer;

[0043] D. After drying, fire in a kiln to obtain a wax-textured stain-resistant matte antique brick;

[0044] Among them, in step C, the wax-based stain-resistant matte glaze includes a stain-resistant matte glaze and wax dry particles, and the wax dry particles are composed of particles with a mesh number of ≥150 mesh and <200 mesh and particles with a mesh number of 200 - 250 mesh;

[0045] Calculated by mass parts, the raw materials of the stain-resistant matte glaze are composed of 7 - 10 parts of kaolin, 5 - 10 parts of calcined kaolin, 4 - 8 parts of quartz, 20 - 30 parts of potassium feldspar, 8 - 15 parts of sodium feldspar, 5 - 10 parts of calcite, 5 - 10 parts of burnt talc, 1 - 3 parts of zinc oxide, 2 - 5 parts of strontium carbonate, and 20 - 30 parts of stain-resistant and wear-resistant frit;

[0046] Calculated by mass percentage, the chemical composition of the stain-resistant and wear-resistant frit includes 32 - 40% of SiO2, 18 - 20% of Al2O3, 18 - 20% of CaO, 0.5 - 1.5% of K2O, 10 - 12% of ZnO, 1 - 2.5% of BaO, and 12 - 15% of SrO;

[0047] Calculated by mass percentage, the chemical composition of the wax dry particles includes 51 - 53.8% of SiO2, 13 - 15% of Al2O3, 0.2 - 0.7% of Fe2O3, 0.02 - 0.12% of TiO2, 10 - 12% of CaO, 1 - 3% of MgO, 1 - 3% of K2O, 7 - 9% of ZnO, and 10 - 12% of BaO;

[0048] In step D, the firing temperature for the firing is 1180 - 1205 °C, and the firing time is 45 - 60 min.

[0049] In order to make the glaze layer of the antique brick simultaneously take into account glossiness, stain resistance, hardness, wear resistance, and color development performance under the existing firing conditions (i.e., the firing temperature is 1180 - 1205 °C, and the firing time is 45 - 60 min), this solution first designs and optimizes the stain-resistant matte glaze in the wax-based stain-resistant matte glaze, breaks the glaze formula structure composed of all raw materials in the existing antique bricks, and can effectively improve the satisfaction of consumers with the use of antique bricks.

[0050] Specifically, the raw material formula structure of the anti-fouling matte glaze in this solution consists of a raw material part and a clinker part, and the clinker part is the anti-fouling and wear-resistant frit. It should be noted that the clinker in the ceramic industry is generally defined as the frit obtained after firing, and the materials in the frit are fully matured before application. Calcined kaolin, calcined talc, calcined zinc oxide, etc. are only the single raw materials calcined to volatilize the organic matter of the raw materials and make the crystal form more stable, and they still belong to the raw materials. That is to say, the materials outside the frit are all defined as raw materials.

[0051] Based on the chemical composition of the anti-fouling and wear-resistant frit in this solution, during the firing process of the frit, Al 3+ exists as aluminum-oxygen tetrahedrons in silicon-oxygen tetrahedrons, so that part of the silica and alumina in the chemical composition form a dense mullite network structure. And the above-mentioned mullite network structure specifically includes two crystal forms, namely 3Al2O3·2SiO2 and 2Al2O3.SiO2. When the above crystals are evenly distributed in the glaze layer, it can effectively improve the hardness and wear resistance of the glaze layer; and the high silicon-aluminum content in the chemical composition is also beneficial to improving the acid and alkali resistance of the frit, resisting the erosion of acid and alkaline substances for a long time, and contributing to anti-fouling.

[0052] In addition, in the chemical composition of the anti-fouling and wear-resistant frit, divalent ions Sr 2+ and Zn 2+ are used as the flux system, which can make the frit form a dense internal structure during the firing process, thus contributing to anti-fouling; at the same time, Sr 2+ and Zn 2+ also help the frit to precipitate anorthite crystals during the firing process. On the one hand, the anorthite crystals can also contribute to improving the hardness and wear resistance of the glaze layer. On the other hand, the anorthite crystals have high transparency, and at the same time, the chemical composition contains a large amount of ZnO. Introducing the frit as a raw material into the glaze can effectively improve the color development performance of the glaze.

[0053] For the raw material part of the anti-fouling matte glaze, compared with the raw material formula structure of the existing antique tiles, this solution reduces the addition ratio of potassium feldspar and sodium feldspar in the raw material formula, and at the same time introduces a relatively high proportion of quartz, thereby reducing the content of low-temperature fluxes K2O, Na2O and easily fusible glass phase in the glaze, increasing the softening point temperature of the glaze during the sintering process, making it not easy to form a closed layer prematurely during the firing of the glaze, and allowing sufficient exhaust time for the gases generated during firing to match the low-temperature and fast-firing firing system of the existing antique tiles. In addition, the increase in the softening point temperature of the glaze is also beneficial to shortening the melting point gap between the anti-fouling matte glaze and the wax dry particles, preventing the anti-fouling matte glaze and the wax dry particles from forming a low-temperature eutectic composition, and avoiding the crystal phase generated in the wax dry particles from being eroded by low-temperature flux components and remelting into the glass phase of the glaze, thus losing the unique feel brought to the glaze surface due to the formation of the crystal phase.

[0054] Furthermore, to effectively prevent strontium oxide from reducing its fluxing activity in the glaze after melting with the glass phase in the frit, strontium carbonate is additionally introduced into the antifouling matte glaze raw materials of this solution. Strontium oxide can reduce the softening temperature of the glaze, increase the high-temperature fluidity of the glaze, and increase the firing range of the glaze, thus being more conducive to the formation of a dense glaze layer structure and improving the antifouling performance of the glaze layer. Additionally, since the atomic radius of Sr 2+ is larger than that of Ca 2+ and Mg 2+ a large amount of strontium oxide forms a certain surface roughness between it and the glass phase in the glaze, which forms diffuse reflection with incident light, reduces the surface gloss of the glaze surface, and achieves the matte effect of antique tiles; after the crystal phases formed with other divalent metal ions are evenly distributed on the glaze surface, the surface gloss of the glaze layer can also be controlled within 8 - 12°, meeting the public aesthetic of consumers for the matte gloss of antique tiles.

[0055] Furthermore, since calcined kaolin and calcined talc are also introduced into the raw materials of the glaze, during the firing of the glaze, harder mullite and cordierite crystals can be additionally generated. Coupled with the original crystals in the frit and the unmolten quartz in the raw materials, the glaze surface of the glaze layer is distributed with various hard crystalline substances, which is more conducive to improving the hardness and wear resistance of the glaze surface. During the long-term use of antique tiles, it is not easy to damage the surface performance of the glaze layer, achieving long-lasting antifouling.

[0056] Secondly, to endow antique tiles with a delicate, greasy, and smooth waxy feel on the premise of ensuring antifouling performance, this solution also develops a waxy dry granule that matches the antifouling matte glaze, enabling the waxy texture antifouling matte glaze to simultaneously take into account excellent antifouling performance and waxy feel.

[0057] Specifically, the chemical composition of the waxy dry granules in this solution contains a large amount of BaO and CaO, and the content of low-temperature flux components (such as K2O, Na2O) is extremely small, resulting in a crystal system with main crystal phase of celsian and auxiliary crystal phase of anorthite after firing the dry granules. At the same time, there is basically no generation of vitreous substance in the dry granules. More specifically, the formula body of the waxy dry granules belongs to the divalent alkaline earth metal system. Compared with the potassium-sodium system, the dry granules have a higher initial melting point and a wider sintering temperature range, reaching 1190-1220 °C. After being combined with the antifouling matte glaze, it is more conducive to forming a concave-convex feel on the surface of the glaze layer. Further, since the microcrystalline molecular radius of celsian is larger than that of anorthite, it has a better matte and waxy feel. When the microcrystals formed by the dry granules protrude from the surface of the glaze layer, the concave-convex feel brought by the microcrystals is better. In addition, the chemical composition and crystal system of the waxy dry granules make their melting point not too high. When the waxy dry granules are combined with the antifouling matte glaze, the waxy dry granules can be slightly melted in the glaze. On the one hand, it can ensure that the waxy dry granules basically maintain their initial particle state and protrude from the surface of the glaze layer, improving the feel. On the other hand, it can improve the bonding between the dry granules and the glaze layer, avoiding the decline of antifouling performance. It should be noted that if the melting point difference between the dry granules and the glaze is too large, that is, when the melting point of the dry granules is too high, it is difficult to combine with the glaze, resulting in the dry granules showing an underfired state and forming more dirt-trapping voids around the dry granules; when the firing temperatures of the waxy dry granules and the antifouling matte glaze match each other, it can ensure that the dry granules are in a state of being slightly melted but not flattened, combined with the glaze into a whole and forming a dense glaze layer, thus avoiding the decline of antifouling performance.

[0058] Finally, the waxy dry granules in this case are composed of particles with a mesh number ≥ 150 mesh and < 200 mesh and particles with a mesh number of 200-250 mesh. Incorporating the waxy dry granules into the glaze with different particle gradations is beneficial to improving the diversity of the crystal phase morphology on the surface of the glaze layer, enriching the touch of the glaze surface, and effectively enhancing the diffuse reflection on the surface of the glaze layer and reducing the glossiness of the glaze surface.

[0059] Preferably, calculated by mass fraction, the raw materials of the antifouling matte glaze are composed of 8 parts of kaolin, 6 parts of calcined kaolin, 5 parts of quartz, 25 parts of potassium feldspar, 10 parts of sodium feldspar, 7 parts of calcite, 8 parts of calcined talc, 2 parts of zinc oxide, 4 parts of strontium carbonate, and 25 parts of antifouling and wear-resistant frit.

[0060] It should be noted that the ceramic blank in step A and the base glaze in step B in this solution are both common ceramic blanks and base glazes for antique bricks, and are not limited here.

[0061] Furthermore, the particle size distribution of the waxy dry granules satisfies that, calculated based on the total weight of the waxy dry granules, the particles with a mesh number ≥ 150 mesh and < 200 mesh account for 70-80%, and the remaining are particles with a mesh number of 200-250 mesh.

[0062] In this way, it is more conducive to improving the diversity of the crystal phase morphology on the surface of the glaze layer to enrich the touch of the glaze surface.

[0063] Preferably, the particle size distribution of the waxy dry granules satisfies that, calculated based on the total weight of the waxy dry granules, the particles with a mesh number ≥ 150 and < 200 account for 75.8%, and the particles with a mesh number of 200 - 250 account for 24.2%.

[0064] Furthermore, by mass ratio, the mixing ratio of the antifouling matte glaze and the waxy dry granules is 10:(1 - 2).

[0065] In this way, the performance in terms of antifouling, touch, and operability can be further balanced.

[0066] Preferably, by mass ratio, the mixing ratio of the antifouling matte glaze and the waxy dry granules is 10:1.5.

[0067] Furthermore, calculated by mass percentage, the chemical composition of the waxy dry granules includes 52.656% of SiO2, 13.966% of Al2O3, 0.544% of Fe2O3, 0.096% of TiO2, 10.935% of CaO, 1.382% of MgO, 1.882% of K2O, 7.296% of ZnO, and 10.868% of BaO.

[0068] Furthermore, the firing curve of the antifouling and wear-resistant frit is as follows:

[0069] Heating from room temperature to 300 °C takes 1.5 - 2.5 h;

[0070] Heating from 300 °C to 1530 °C takes 2 - 3 h;

[0071] At 1530 °C, keep warm for 0.5 - 1.2 h.

[0072] In this way, the softening point temperature of the frit can also be matched with the firing system of existing antique bricks, so that tiny rough surfaces can be generated between the tiny particles of the frit after ball milling and pulping and the glass phase plane formed after glaze firing, further ensuring the formation of a matte glaze surface.

[0073] Preferably, the firing curve of the antifouling and wear-resistant frit is as follows:

[0074] Heating from room temperature to 300 °C takes 2 h;

[0075] Heating from 300 °C to 1530 °C takes 2.5 h;

[0076] At 1530 °C, keep warm for 1 h.

[0077] Furthermore, step C is specifically:

[0078] C. Spray the waxy antifouling matte glaze on the surface of the base glaze layer to obtain a waxy antifouling matte glaze layer;

[0079] Among them, the specific gravity of the waxy antifouling matte glaze is 1.5 - 1.55, and the aperture of the spray gun for spraying is 0.62 mm.

[0080] In another specific embodiment of this technical solution, the waxy antifouling matte glaze can be applied by spraying. However, in order to make the waxy dry particles evenly distributed on the surface of the glaze layer, the specific gravity of the glaze material and the aperture of the spray gun are optimized during spraying in this solution.

[0081] Furthermore, calculated by mass percentage, the chemical composition of the antifouling and wear-resistant frit includes 34.81% of SiO2, 18.66% of Al2O3, 19.16% of CaO, 0.81% of K2O, 11.23% of ZnO, 1.76% of BaO, and 13.46% of SrO.

[0082] Furthermore, calculated by mass parts, the raw materials of the antifouling and wear-resistant frit are composed of 12 - 18 parts of quartz, 15 - 20 parts of calcined alumina, 30 - 38 parts of wollastonite, 8 - 12 parts of zinc oxide, 18 - 22 parts of strontium carbonate, and 1 - 5 parts of barium carbonate.

[0083] In a preferred embodiment of this technical solution, the antifouling and wear-resistant frit can be obtained by firing quartz, calcined alumina, wollastonite, zinc oxide, strontium carbonate, and barium carbonate and then water quenching.

[0084] Furthermore, calculated by mass parts, the raw materials of the waxy dry particles are composed of 25 - 30 parts of kaolin, 25 - 32 parts of quartz, 6 - 10 parts of potassium feldspar, 3 - 8 parts of zinc oxide, 3 - 8 parts of dolomite, 8 - 15 parts of calcite, and 12 - 18 parts of barium carbonate.

[0085] In a preferred embodiment of this technical solution, the waxy dry particles can be obtained by firing kaolin, quartz, potassium feldspar, zinc oxide, dolomite, calcite, and barium carbonate to form a waxy frit, and then crushing the waxy frit.

[0086] A waxy texture antifouling matte antique brick is prepared by using the preparation method of the above-mentioned waxy texture antifouling matte antique brick, and the glaze surface glossiness of the waxy texture antifouling matte antique brick is 8 - 12°, the antifouling grade is 5, the Mohs hardness is 7, and the wear resistance is ≥ 4 (6000 revolutions).

[0087] The waxy texture antifouling matte antique brick proposed in this solution can balance the glossiness, antifouling performance, hardness, wear resistance, and color development performance under the existing firing conditions, and also endow the antique brick with a delicate, oily, and smooth waxy hand feeling, improving the satisfaction of consumers with the use of the antique brick.

[0088] The technical solution of the present invention will be further described below through specific embodiments.

[0089] Example 1

[0090] A. Prepare a ceramic blank, press the ceramic blank, and obtain a green body layer after drying;

[0091] B. Apply the base glaze on the surface of the green body layer to obtain a base glaze layer;

[0092] C. Spray the waxy antifouling matte glaze with a specific gravity of 1.5 on the surface of the base glaze layer using a spray gun with a pore size of 0.62 mm to obtain a waxy antifouling matte glaze layer;

[0093] D. After drying, fire in a kiln to obtain a waxy texture antifouling matte antique brick;

[0094] Among them, in step C, the waxy antifouling matte glaze includes an antifouling matte glaze and waxy dry particles. And by mass ratio, the mixing ratio of the antifouling matte glaze and the waxy dry particles is 10:1. The particle size distribution of the waxy dry particles satisfies: calculated based on the total weight of the waxy dry particles, the particles with a mesh number ≥ 150 mesh and < 200 mesh account for 70%, and the particles with a mesh number of 200 - 250 mesh account for 30%; the raw material composition of the antifouling matte glaze is shown in Table 1 below, the chemical composition of the antifouling and wear-resistant frit is shown in Table 2 below, and the chemical composition of the waxy dry particles is shown in Table 3 below.

[0095] In step D, the firing temperature for the firing is 1180 - 1205 °C, and the firing time is 45 - 60 min.

[0096] Example 2

[0097] A. Prepare a ceramic blank, press the ceramic blank, and obtain a green body layer after drying;

[0098] B. Apply the base glaze on the surface of the green body layer to obtain a base glaze layer;

[0099] C. Spray the waxy antifouling matte glaze with a specific gravity of 1.5 on the surface of the base glaze layer using a spray gun with a pore size of 0.62 mm to obtain a waxy antifouling matte glaze layer;

[0100] D. After drying, fire in a kiln to obtain a waxy texture antifouling matte antique brick;

[0101] Among them, in step C, the waxy antifouling matte glaze includes an antifouling matte glaze and waxy dry particles. And by mass ratio, the mixing ratio of the antifouling matte glaze to the waxy dry particles is 10:1.5. The particle size distribution of the waxy dry particles satisfies that, calculated based on the total weight of the waxy dry particles, the particles with a mesh number ≥ 150 and < 200 account for 75.8%, and the particles with a mesh number of 200 - 250 account for 24.2%. The raw material composition of the antifouling matte glaze is shown in Table 1 below, the chemical composition of the antifouling and wear-resistant frit is shown in Table 2 below, and the chemical composition of the waxy dry particles is shown in Table 3 below.

[0102] In step D, the firing temperature is 1180 - 1205 °C, and the firing time is 45 - 60 min.

[0103] As Figure 1 shown is the surface microstructure diagram of the waxy texture antifouling matte antique brick prepared in Example 2. It can be clearly seen that there are crystal grains on the glaze surface of the antique brick.

[0104] As Figure 2 shown is the mass spectrometry diagram of the waxy dry particles in Example 2. It can be seen that the chemical composition of the waxy dry particles is a structure with anorthoclase as the main crystal form, and accompanied by the formation of anorthite auxiliary crystals.

[0105] Example 3

[0106] A. Prepare a ceramic blank, press the ceramic blank, and obtain a green body layer after drying.

[0107] B. Apply the base glaze on the surface of the green body layer to obtain a base glaze layer.

[0108] C. Spray the waxy antifouling matte glaze with a specific gravity of 1.5 on the surface of the base glaze layer using a spray gun with a pore diameter of 0.62 mm to obtain a waxy antifouling matte glaze layer.

[0109] D. After drying, put it into the kiln for firing to obtain a waxy texture antifouling matte antique brick.

[0110] Among them, in step C, the waxy antifouling matte glaze includes an antifouling matte glaze and waxy dry particles. And by mass ratio, the mixing ratio of the antifouling matte glaze to the waxy dry particles is 10:2. The particle size distribution of the waxy dry particles satisfies that, calculated based on the total weight of the waxy dry particles, the particles with a mesh number ≥ 150 and < 200 account for 80%, and the particles with a mesh number of 200 - 250 account for 20%. The raw material composition of the antifouling matte glaze is shown in Table 1 below, the chemical composition of the antifouling and wear-resistant frit is shown in Table 2 below, and the chemical composition of the waxy dry particles is shown in Table 3 below.

[0111] In step D, the firing temperature is 1180 - 1205 °C, and the firing time is 45 - 60 min.

[0112] Table 1 Raw material composition of each antifouling matte glaze in Examples 1 - 3

[0113] Raw materials (parts) Example 1 Example 2 Example 3 Kaolin 7 8 10 Calcined kaolin 5 6 10 Quartz 4 5 8 Potassium feldspar 20 25 30 Albite 8 10 15 Calcite 5 7 10 Calcined talc 5 8 10 Zinc oxide 1 2 3 Strontium carbonate 2 4 5 Antifouling and wear-resistant frit 20 25 30

[0114] Table 2 Chemical Compositions of Each Anti-Fouling and Wear-Resistant Frit in Examples 1-3

[0115] Chemical composition (%) Example 1 Example 2 Example 3 <![CDATA[SiO2]]> 33.63 34.81 36.85 <![CDATA[Al2O3]]> 18.02 18.66 18.76 CaO 18.22 19.16 19.03 <![CDATA[K2O]]> 0.53 0.81 1.42 ZnO 11.89 11.23 10.16 BaO 2.48 1.76 1.18 SrO 14.96 13.46 12.31

[0116] Table 3 Chemical Compositions of Each Wax Dry Granule in Examples 1-3

[0117] Chemical composition (%) Example 1 Example 2 Example 3 <![CDATA[SiO2]]> 51.023 52.656 53.785 <![CDATA[Al2O3]]> 14.865 13.966 13.195 <![CDATA[Fe2O3]]> 0.203 0.544 0.685 <![CDATA[TiO2]]> 0.022 0.096 0.117 CaO 10.539 10.935 11.376 MgO 2.635 1.382 1.021 <![CDATA[K2O]]> 1.859 1.882 1.689 ZnO 7.632 7.296 8.036 BaO 11.163 10.868 10.014

[0118] Comparative Example 1

[0119] Replace the anti-fouling matte glaze in Example 2 with glaze A, and the remaining formulations and parameters are the same.

[0120] Among them, calculated by mass parts, the raw materials of the glaze A are composed of 8 parts of kaolin, 6 parts of calcined kaolin, 5 parts of quartz, 25 parts of potassium feldspar, 10 parts of sodium feldspar, 7 parts of calcite, 8 parts of burnt talc, 2 parts of zinc oxide, 4 parts of strontium carbonate, and 25 parts of existing matte frit;

[0121] Calculated by mass percentage, the chemical composition of the existing matte frit includes SiO2 55%, Al2O3 17%, BaO 10%, ZnO 4%, SrO 4.5%, K2O 2.65%, Na2O 3.7%, CaO 2.5%, MgO 0.05%, P2O5 0.3%, and CaF2 0.3%.

[0122] Comparative Example 2

[0123] Replace the anti-fouling matte glaze in Example 2 with glaze B, and the remaining formulations and parameters are the same.

[0124] Among them, calculated by mass parts, the raw materials of the glaze B are composed of 15 parts of kaolin, 18 parts of calcined kaolin, 30 parts of potassium feldspar, 20 parts of sodium feldspar, 2 parts of zinc oxide, 6 parts of wollastonite, 5 parts of burnt talc, 6 parts of wollastonite, and 4 parts of barium carbonate.

[0125] Comparative Example 3

[0126] Replace the existing wax dry granule in Example 2 with a wax dry granule, and the mesh number of the existing wax dry granule is 80-120 mesh, and the remaining formulations and parameters are the same.

[0127] Among them, calculated by mass percentage, the chemical composition of the existing waxy dry particles includes IL: 0.3-0.5%, SiO2: 54-58%, Al2O3: 16-20%, CaO: 15-18%, MgO: 0.3-0.5%, K2O: 2.0-3.0%, Na2O: 3.0-4.0%, ZnO: 4-5%, BaO: 0.2-0.3% and SrO: 0.5-0.8%.

[0128] The antique bricks prepared in Examples 1-3 and Comparative Examples 1-3 were respectively tested for hardness, wear resistance, glaze glossiness and antifouling grade conventional in the field of architectural ceramics. The results are shown in Table 4 below:

[0129] Table 4 Performance test results of antique tiles in Examples 1-3 and Comparative Examples 1-3

[0130]

[0131]

[0132] From the performance test results in Table 4, it can be seen that the waxy anti-fouling matte antique tiles prepared by this scheme can take into account gloss, anti-fouling performance, hardness, wear resistance and color development performance under the existing firing conditions, and also give the antique tiles a delicate, oily and smooth waxy feel, thereby improving consumers' satisfaction with the use of antique tiles.

[0133] The technical principle of the present invention is described above in conjunction with specific embodiments. These descriptions are only for explaining the principle of the present invention and cannot be interpreted as limiting the scope of protection of the present invention in any way. Based on the explanations herein, those skilled in the art can associate other specific implementations of the present invention without paying creative labor, and these methods will fall within the scope of protection of the present invention.

Claims

1. A method for preparing waxy anti-fouling matte antique tiles, characterized in that: The following steps are involved: A. preparing a ceramic blank, pressing the ceramic blank, and obtaining a blank layer after drying; B. applying a base glaze to the surface of the green body layer to obtain a base glaze layer; C. applying a waxy antifouling matte glaze to the surface of the base glaze layer to obtain a waxy antifouling matte glaze layer; D. After drying, put it into the kiln for firing to obtain waxy anti-fouling matte antique tiles; Wherein, in step C, the wax antifouling matte glaze comprises antifouling matte glaze and wax dry particles, and the wax dry particles consist of particles with a mesh size of ≥150 mesh and <200 mesh and particles with a mesh size of 200-250 mesh; Calculated by weight, the raw materials of the antifouling matte glaze are composed of 7 to 10 parts of kaolin, 5 to 10 parts of calcined kaolin, 4 to 8 parts of quartz, 20 to 30 parts of potassium feldspar, 8 to 15 parts of sodium feldspar, 5 to 10 parts of calcite, 5 to 10 parts of burned talc, 1 to 3 parts of zinc oxide, 2 to 5 parts of strontium carbonate and 20 to 30 parts of antifouling and wear-resistant frit; Calculated by mass percentage, the chemical composition of the antifouling and wear-resistant frit includes SiO2 32-40%, Al2O3 18-20%, CaO 18-20%, K2O 0.5-1.5%, ZnO 10-12%, BaO 1-2.5% and SrO 12-15%; Calculated by mass percentage, the chemical composition of the waxy dry particles includes SiO2 51-53.8%, Al2O3 13-15%, Fe2O3 0.2-0.7%, TiO2 0.02-0.12%, CaO 10-12%, MgO 1-3%, K2O 1-3%, ZnO 7-9% and BaO 10-12%; In step D, the firing temperature is 1180-1205° C., and the firing time is 45-60 min.

2. The method for preparing a waxy anti-fouling matte antique tile according to claim 1, characterized in that: The particle size distribution of the waxy dry particles satisfies that, based on the total weight of the waxy dry particles, particles with a mesh size of ≥150 mesh and <200 mesh account for 70-80%, and the rest are particles with a mesh size of 200-250 mesh.

3. The method for preparing a waxy anti-fouling matte antique tile according to claim 1, characterized in that: According to the mass ratio, the mixing ratio of the antifouling matte glaze and the waxy dry particles is 10:(1-2).

4. The method for preparing a waxy anti-fouling matte antique tile according to claim 1, characterized in that: Calculated by mass percentage, the chemical components of the waxy dry particles include SiO2 52.656%, Al2O3 13.966%, Fe2O3 0.544%, TiO2 0.096%, CaO 10.935%, MgO 1.382%, K2O 1.882%, ZnO 7.296% and BaO 10.868%.

5. The method for preparing a waxy anti-fouling matte antique tile according to claim 1, characterized in that: The firing curve of the anti-fouling and wear-resistant frit is: It takes 1.5 to 2.5 hours to heat from room temperature to 300°C; It takes 2 to 3 hours to heat from 300°C to 1530°C; 1530℃, keep warm for 0.5~1.2h.

6. The method for preparing a waxy anti-fouling matte antique tile according to claim 1, characterized in that: Step C is specifically as follows: C. spraying a waxy antifouling matte glaze on the surface of the base glaze layer to obtain a waxy antifouling matte glaze layer; Wherein, the specific gravity of the waxy antifouling matte glaze is 1.5-1.55, and the aperture of the spray gun is 0.62 mm.

7. The method for preparing a waxy anti-fouling matte antique tile according to claim 1, characterized in that: Calculated by mass percentage, the chemical composition of the antifouling and wear-resistant frit includes SiO2 34.81%, Al2O3 18.66%, CaO 19.16%, K2O 0.81%, ZnO 11.23%, BaO 1.76% and SrO 13.46%.

8. The method for preparing a waxy anti-fouling matte antique tile according to claim 1, characterized in that: Calculated by weight, the raw materials of the antifouling and wear-resistant frit are composed of 12 to 18 parts of quartz, 15 to 20 parts of calcined alumina, 30 to 38 parts of wollastonite, 8 to 12 parts of zinc oxide, 18 to 22 parts of strontium carbonate and 1 to 5 parts of barium carbonate.

9. The method for preparing a waxy anti-fouling matte antique tile according to claim 1, characterized in that: Calculated by weight, the raw materials of the waxy dry particles are composed of 25 to 30 parts of kaolin, 25 to 32 parts of quartz, 6 to 10 parts of potassium feldspar, 3 to 8 parts of zinc oxide, 3 to 8 parts of dolomite, 8 to 15 parts of calcite and 12 to 18 parts of barium carbonate.

10. A waxy anti-fouling matte antique tile, characterized in that: The waxy anti-fouling matte antique brick is prepared by the preparation method of any one of claims 1 to 9, and the waxy anti-fouling matte antique brick has a glaze gloss of 8 to 12°, an anti-fouling grade of 5, a Mohs hardness of 7, and a wear resistance of ≥ 4 (6000 revolutions).

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