Waxy feel anti-fouling matte antique brick and preparation method thereof

Abstract

This invention relates to the field of architectural ceramics technology, and discloses a waxy, stain-resistant matte antique-style tile and its preparation method, comprising: A) preparing a body layer; B) applying a base glaze; C) applying a waxy, stain-resistant matte glaze; and D) firing. The waxy, stain-resistant matte glaze comprises a stain-resistant matte glaze and waxy dry particles, wherein the waxy dry particles are composed of particles with a mesh size ≥150 mesh and <200 mesh and particles with a mesh size of 200-250 mesh. The raw materials for the stain-resistant matte glaze consist 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 calcined talc, 1-3 parts of zinc oxide, 2-5 parts of strontium carbonate, and 20-30 parts of stain-resistant and wear-resistant frit. This solution can simultaneously achieve gloss, stain resistance, hardness, wear resistance, and color performance under existing firing conditions, while also giving antique-style tiles a delicate, oily, and smooth waxy feel, thus improving consumer satisfaction.

Description

Technical Field

[0001] This invention relates to the field of building ceramics technology, and in particular to a waxy, stain-resistant, matte antique-style brick and its preparation method. Background Technology

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

[0003] Considering factors such as gloss, cost, and smoothness, the glaze formulations of existing antique-style tiles typically use all-raw-material formulas, and the fluxing system is generally a potassium-sodium system. However, if the potassium-sodium content in the glaze formulation is high, the glaze is prone to melting and forming a glassy phase at the low-temperature stage of the firing curve. This results in the glaze raw materials being trapped in the glaze layer before they can be degassed during sintering, causing bubbles to appear on the glaze surface and reducing its anti-fouling performance.

[0004] To improve the stain resistance of existing antique-style bricks, technicians typically adjust the formula and firing temperature. However, since the firing curve of antique-style bricks is generally based on the existing vitrification of the body and base glaze, only a small range of temperature adjustments can be made. The room for improvement in stain resistance is very limited, and the improvement is basically achieved by adjusting the glaze formula to adapt to the existing firing conditions.

[0005] Due to the rigidity of the firing process, it is difficult to balance the gloss, stain resistance, hardness, wear resistance and color performance of antique-style brick glaze formulas composed entirely of raw materials. Therefore, it is urgent to break the existing structure of glaze formulas composed entirely of raw materials for antique-style bricks, so that under the existing firing conditions, gloss, stain resistance, hardness, wear resistance and color performance can be taken into account simultaneously, thereby improving consumers' satisfaction with the use of antique-style bricks.

[0006] Furthermore, the application market for architectural ceramics is expanding, while simultaneously placing increasingly stringent demands on ceramic decoration techniques. Enriching ceramic decoration through the cross-integration of other materials, resulting in more diverse and abundant decorative effects, is a significant trend in modern ceramic glaze decoration. For example, using dry wax granules to impart a delicate, oily, and smooth waxy feel to the glaze surface can enhance consumers' satisfaction with the tactile experience of ceramic tiles at a higher level. Summary of the Invention

[0007] The purpose of this invention is to propose a waxy, stain-resistant matte antique-style tile and its preparation method. By optimizing the glaze formula structure of the antique-style tile, it can simultaneously achieve gloss, stain resistance, hardness, wear resistance and color performance under existing firing conditions. It also gives the antique-style tile a delicate, oily and smooth waxy feel, thereby improving consumer satisfaction with the use of antique-style tiles.

[0008] To achieve this objective, the present invention adopts the following technical solution:

[0009] A method for preparing a waxy, stain-resistant, matte antique-style tile includes the following steps:

[0010] A. Prepare ceramic blanks, press the ceramic blanks, and dry them to obtain the blank layer;

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

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

[0013] D. After drying, the bricks are fired in a kiln to obtain waxy, stain-resistant, matte antique-style bricks.

[0014] In step C, the waxy anti-fouling matte glaze includes an anti-fouling matte glaze and waxy dry granules, and the waxy dry granules are composed of particles with a mesh size ≥150 mesh and <200 mesh and particles with a mesh size of 200 to 250 mesh.

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

[0016] The chemical composition of the anti-fouling and wear-resistant fused block, calculated by mass percentage, 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] The chemical composition of the waxy dry granules, calculated by mass percentage, 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 is 1180–1205°C, and the firing time is 45–60 min.

[0019] Preferably, the particle size distribution of the waxy dry granules satisfies the following: based on the total weight of the waxy dry granules, particles with a mesh size ≥150 mesh and <200 mesh account for 70-80%, and the remainder are particles with a mesh size of 200-250 mesh.

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

[0021] Preferably, the chemical composition of the waxy dry granules, calculated by mass percentage, includes 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%.

[0022] Preferably, the firing curve of the anti-fouling and wear-resistant fused block is as follows:

[0023] The time required to heat the temperature from room temperature to 300℃ is 1.5 to 2.5 hours.

[0024] The temperature rises from 300℃ to 1530℃, taking 2-3 hours.

[0025] 1530℃, keep warm for 0.5~1.2h.

[0026] Preferably, step C specifically includes:

[0027] C. Spray a waxy anti-fouling matte glaze onto the surface of the base glaze layer to obtain a waxy anti-fouling matte glaze layer;

[0028] The specific gravity of the waxy anti-fouling matte glaze is 1.5 to 1.55, and the nozzle diameter of the spray gun is 0.62 mm.

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

[0030] Preferably, the raw materials of the antifouling and wear-resistant frit, calculated by mass parts, consist 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, the raw materials for the waxy dry granules, calculated by mass parts, consist of 25-30 parts kaolin, 25-32 parts quartz, 6-10 parts potassium feldspar, 3-8 parts zinc oxide, 3-8 parts dolomite, 8-15 parts calcite, and 12-18 parts barium carbonate.

[0032] A waxy, stain-resistant, matte antique-style tile is prepared using the above-mentioned method for preparing waxy, stain-resistant, matte antique-style tiles. The glaze gloss of the waxy, stain-resistant, matte antique-style tile is 8-12°, the stain resistance level is 5, the Mohs hardness is 7, and the wear resistance is ≥4 (6000 revolutions).

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

[0034] 1. Al in the sintering process of the frit 3+ The presence of aluminum-oxygen tetrahedra within silicon-oxygen tetrahedra creates a dense mullite network structure from the partial silicon oxide and aluminum oxide in the chemical composition. This mullite network structure specifically includes two crystal forms: 3Al₂O₃·2SiO₂ and 2Al₂O₃·SiO₂. When these crystals are uniformly distributed in the glaze layer, they effectively improve the hardness and wear resistance of the glaze. Furthermore, the high silicon-aluminum content in the chemical composition also enhances the acid and alkali resistance of the frit, providing long-term protection against acid and alkali corrosion and contributing to anti-fouling properties. Additionally, the anti-fouling and wear-resistant frit utilizes divalent Sr ions... 2+ and Zn 2+ As a flux system, it can help the frit form a dense internal structure during firing, thus aiding in anti-fouling; at the same time, Sr 2+ and Zn 2+ It also helps the frit to precipitate calcium feldspar crystals during the firing process. On the one hand, calcium feldspar crystals can also help improve the hardness and wear resistance of the glaze. On the other hand, calcium feldspar crystals have high transparency and contain a large amount of ZnO in their chemical composition. Introducing the frit as a raw material into the glaze can effectively improve the color performance of the glaze.

[0035] 2. The anti-fouling matte glaze reduces the proportion of potassium feldspar and sodium feldspar in the raw material formula, while introducing a higher proportion of quartz. This reduces the content of low-temperature fluxes K2O and Na2O, as well as the fusible glass phase, in the glaze. This increases the softening temperature of the glaze during sintering, preventing premature formation of a sealed layer during firing and allowing sufficient time for gas degassing, matching the low-temperature, fast-firing firing regime of existing antique-style tiles. Furthermore, strontium carbonate and strontium oxide are added to the anti-fouling matte glaze raw materials. Strontium carbonate lowers the softening temperature of the glaze, increases its high-temperature fluidity, and expands its firing range, thus promoting the formation of a dense glaze layer structure and improving its anti-fouling performance. Additionally, due to Sr... 2+ The atomic radius of Ca is greater than that of Ca 2+ Mg 2+The large radius and extensive use of strontium oxide create a certain surface roughness between it and the glass phase in the glaze. This roughness, combined with incident light, causes diffuse reflection, reducing the surface gloss and achieving the matte effect of antique-style tiles. Furthermore, the uniform distribution of crystalline phases formed with other divalent metal ions on the glaze surface further controls the surface gloss to 8-12°, meeting the popular aesthetic preference for matte finishes in antique-style tiles. Moreover, calcined kaolin and calcined talc are incorporated into the glaze raw materials. This allows for the additional formation of high-hardness mullite and cordierite crystals during firing. Combined with the existing crystals in the frit and unmelted quartz in the raw materials, the matte glaze layer exhibits a variety of high-hardness crystals, enhancing its hardness and wear resistance. This ensures that the glaze surface properties are not easily damaged during long-term use, achieving lasting stain resistance.

[0036] 3. The waxy dry granules contain a large amount of BaO and CaO in their chemical composition, and very little low-temperature flux (such as K2O and Na2O). This results in a crystal system formed after firing, with barium feldspar as the main crystalline phase and calcium feldspar as the auxiliary crystalline phase. Simultaneously, virtually no glassy material is formed within the dry granules. More specifically, the formulation of the waxy dry granules belongs to a divalent alkaline earth metal system. Compared to the potassium-sodium system, the dry granules have a higher initial melting point and a wider sintering temperature range, reaching 1190–1220℃. When combined with an anti-fouling matte glaze, this is more conducive to creating a textured surface on the glaze layer. Furthermore, because the microcrystalline molecular radius of barium feldspar is larger than that of calcium feldspar, it has a better matte and waxy feel. When the microcrystals formed by the dry granules protrude from the glaze surface, the textured feel created by the microcrystals is even better. In addition, the chemical composition and crystal system of the wax granules prevent them from having an excessively high melting point. When the wax granules are combined with the anti-fouling matte glaze, the wax granules can be slightly melted into the glaze. On the one hand, this ensures that the wax granules basically maintain their initial state and protrude from the glaze surface, improving the feel. On the other hand, it can improve the bonding between the granules and the glaze, preventing a decrease in anti-fouling performance. Attached Figure Description

[0037] Figure 1 This is a microstructure diagram of the surface of the waxy, stain-resistant, matte antique-style brick prepared in Example 2 of the present invention.

[0038] Figure 2 This is the mass spectrum of the waxy dry particles in Example 2 of the present invention. Detailed Implementation

[0039] A method for preparing a waxy, stain-resistant, matte antique-style tile includes the following steps:

[0040] A. Prepare ceramic blanks, press the ceramic blanks, and dry them to obtain the blank layer;

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

[0042] C. Apply a waxy anti-fouling matte glaze to the surface of the base glaze layer to obtain a waxy anti-fouling matte glaze layer;

[0043] D. After drying, the bricks are fired in a kiln to obtain waxy, stain-resistant, matte antique-style bricks.

[0044] In step C, the waxy anti-fouling matte glaze includes an anti-fouling matte glaze and waxy dry granules, and the waxy dry granules are composed of particles with a mesh size ≥150 mesh and <200 mesh and particles with a mesh size of 200 to 250 mesh.

[0045] According to the mass fraction, the raw materials of the anti-fouling matte glaze are composed of 7-10 parts kaolin, 5-10 parts calcined kaolin, 4-8 parts quartz, 20-30 parts potassium feldspar, 8-15 parts sodium feldspar, 5-10 parts calcined talc, 1-3 parts zinc oxide, 2-5 parts strontium carbonate, and 20-30 parts anti-fouling and wear-resistant frit.

[0046] The chemical composition of the anti-fouling and wear-resistant fused block, calculated by mass percentage, 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%.

[0047] The chemical composition of the waxy dry granules, calculated by mass percentage, 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%.

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

[0049] In order to ensure that the glaze of antique-style tiles simultaneously achieves gloss, stain resistance, hardness, wear resistance, and color performance under existing firing conditions (i.e., firing temperature of 1180–1205℃ and firing time of 45–60 min), this solution first designs and optimizes the stain-resistant matte glaze in the wax-based stain-resistant matte glaze. This breaks the existing glaze formula structure of antique-style tiles, which is composed entirely of raw materials, and can effectively improve consumers' satisfaction with the use of antique-style tiles.

[0050] Specifically, the raw material formula of the anti-fouling matte glaze in this solution consists of a raw material component and a calcined material component, with the calcined material being the anti-fouling and wear-resistant frit. It should be noted that in the ceramics industry, calcined material is generally defined as a frit obtained through firing, where the materials are fully matured before application. Calcination of kaolin, talc, and zinc oxide, etc., simply involves calcining a single raw material to allow the organic matter to volatilize and the crystal form to become more stable; these are still considered raw materials. In other words, all materials other than the frit are defined as raw materials.

[0051] Based on the chemical composition of the anti-fouling and wear-resistant fused block in this solution, the Al content of the fused block during the firing process... 3+ The presence of aluminum-oxygen tetrahedra within silicon-oxygen tetrahedra results in a dense mullite network structure formed from some of the silicon oxide and aluminum oxide in the chemical composition. This mullite network structure specifically includes two crystal forms: 3Al₂O₃·2SiO₂ and 2Al₂O₃·SiO₂. When these crystals are uniformly distributed in the glaze layer, they can effectively improve the hardness and wear resistance of the glaze layer. Furthermore, the high silicon-aluminum content in the chemical composition also helps to improve the acid and alkali resistance of the frit, providing long-term protection against the erosion of acidic and alkaline substances and aiding in stain prevention.

[0052] In addition, the chemical composition of the anti-fouling and wear-resistant fused block is dominated by divalent ions Sr. 2+ and Zn 2+ As a flux system, it can help the frit form a dense internal structure during firing, thus aiding in anti-fouling; at the same time, Sr 2+ and Zn 2+ It also helps the frit to precipitate calcium feldspar crystals during the firing process. On the one hand, calcium feldspar crystals can also help improve the hardness and wear resistance of the glaze. On the other hand, calcium feldspar crystals have high transparency and contain a large amount of ZnO in their chemical composition. Introducing the frit as a raw material into the glaze can effectively improve the color performance of the glaze.

[0053] For the raw material portion of the anti-fouling matte glaze, compared to the existing raw material formula structure of antique tiles, this solution reduces the proportion of potassium feldspar and sodium feldspar in the raw material formula, while introducing a higher proportion of quartz. This reduces the content of low-temperature fluxes K2O and Na2O, as well as the fusible glass phase in the glaze, thereby increasing the softening point temperature of the glaze during sintering. This prevents the premature formation of a sealed layer during glaze firing, allowing sufficient time for gas degassing to match the low-temperature, fast-firing firing regime of existing antique tiles. Furthermore, the increased softening point temperature of the glaze also helps to shorten the melting point difference between the anti-fouling matte glaze and the waxy dry granules, preventing the formation of a low-temperature eutectic composition between them. This avoids the crystalline phase formed in the waxy dry granules being eroded by the low-temperature fluxing components and remelted into the glass phase of the glaze, thus preventing the loss of the unique tactile feel brought to the glaze surface by the formation of the crystalline phase.

[0054] Furthermore, to effectively prevent strontium oxide from melting with the glassy phase in the frit and reducing its fluxing activity in the glaze, this solution also introduces strontium carbonate into the anti-fouling matte glaze raw material. Strontium oxide can lower the softening temperature of the glaze, increase its high-temperature fluidity, and expand its firing range, thus facilitating the formation of a dense glaze layer structure and improving its anti-fouling performance. Additionally, due to Sr... 2+ The atomic radius of Ca is greater than that of Ca 2+ Mg 2+ The large radius and extensive use of strontium oxide create a certain surface roughness between the glaze and the glass phase, resulting in diffuse reflection of incident light and reducing the surface gloss of the glaze, thus achieving a matte effect for antique-style tiles. Furthermore, the uniform distribution of the crystalline phase formed with other divalent metal ions on the glaze surface can control the surface gloss of the glaze layer to 8–12°, which meets the general aesthetic preference of consumers for the matte gloss of antique-style tiles.

[0055] Furthermore, since calcined kaolin and calcined talc are also introduced into the raw materials of the glaze, mullite and cordierite crystals with higher hardness can be generated additionally during the firing of the glaze. Combined with the original crystals in the frit and the unmelted quartz in the raw materials, the glaze surface has a variety of crystals with higher hardness, which is more conducive to improving the hardness and wear resistance of the glaze surface. Under the long-term use of antique bricks, the surface performance of the glaze layer is not easily damaged, achieving long-lasting stain resistance.

[0056] Secondly, in order to give antique tiles a delicate, oily and smooth waxy feel while ensuring stain resistance, this solution also developed a waxy dry granule that matches the stain-resistant matte glaze, so that the waxy stain-resistant matte glaze can simultaneously achieve excellent stain resistance and a waxy feel.

[0057] Specifically, the waxy dry granules of this formula contain a large amount of BaO and CaO in their chemical composition, and very little low-temperature flux (such as K2O and Na2O). This results in a crystal system formed after firing, with barium feldspar as the main crystalline phase and calcium feldspar as the auxiliary crystalline phase, while virtually no glassy material is formed in the dry granules. More specifically, the formulation of the waxy dry granules belongs to a divalent alkaline earth metal system. Compared to the potassium-sodium system, the dry granules have a higher initial melting point and a wider sintering temperature range, reaching 1190–1220℃. When combined with the anti-fouling matte glaze, this is more conducive to creating a textured surface on the glaze layer. Furthermore, since the microcrystalline molecular radius of barium feldspar is larger than that of calcium feldspar, it has a better matte and waxy feel. When the microcrystals formed by the dry granules protrude on the glaze surface, the textured feel created by the microcrystals is even better. Furthermore, the chemical composition and crystal system of the wax granules result in a relatively low melting point. When combined with the anti-fouling matte glaze, the wax granules can slightly melt into the glaze. This ensures that the wax granules retain their initial particle state and protrude from the glaze surface, improving the feel. It also enhances the adhesion between the granules and the glaze, preventing a decrease in anti-fouling performance. It's important to note that if the melting point difference between the granules and the glaze is too large (i.e., the melting point of the granules is too high), they will be difficult to bond with the glaze, resulting in an underfired state and creating numerous voids around the granules that trap dirt. However, when the firing temperatures of the wax granules and the anti-fouling matte glaze are matched, the granules can be partially melted but not completely melted, allowing them to bond with the glaze to form a dense glaze layer, thus preventing a decrease in anti-fouling performance.

[0058] Finally, the waxy dry particles in this case consist of particles with a mesh size of ≥150 mesh and <200 mesh and particles with a mesh size of 200 to 250 mesh. Incorporating the waxy dry particles into the glaze with different particle sizes is beneficial to improving the diversity of crystal phase morphology on the glaze surface, thus enriching the tactile feel of the glaze surface. It also effectively enhances the diffuse reflection of the glaze surface and reduces the gloss of the glaze surface.

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

[0060] It should be noted that the ceramic body in step A and the base glaze in step B of this scheme are both ceramic bodies and base glazes commonly used in antique bricks, and are not limited here.

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

[0062] This is more conducive to improving the diversity of crystal phase morphology on the glaze surface, thus enriching the tactile feel of the glaze.

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

[0064] To further explain, the mixing ratio of the anti-fouling matte glaze and the waxy dry granules by mass is 10:(1-2).

[0065] This is to further balance the performance in terms of stain resistance, tactile feel, and operability.

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

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

[0068] To further explain, the firing curve of the anti-fouling and wear-resistant fused block is as follows:

[0069] The time required to heat the temperature from room temperature to 300℃ is 1.5 to 2.5 hours.

[0070] The temperature rises from 300℃ to 1530℃, taking 2-3 hours.

[0071] 1530℃, keep warm for 0.5~1.2h.

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

[0073] Preferably, the firing curve of the anti-fouling and wear-resistant fused block is as follows:

[0074] It takes 2 hours to heat the temperature from room temperature to 300℃.

[0075] The temperature was raised from 300℃ to 1530℃ in 2.5 hours.

[0076] 1530℃, keep warm for 1 hour.

[0077] To elaborate further, step C specifically involves:

[0078] C. Spray a waxy anti-fouling matte glaze onto the surface of the base glaze layer to obtain a waxy anti-fouling matte glaze layer;

[0079] The specific gravity of the waxy anti-fouling matte glaze is 1.5 to 1.55, and the nozzle diameter of the spray gun is 0.62 mm.

[0080] In another specific embodiment of this technical solution, the wax-based anti-fouling matte glaze can be applied by spraying. However, in order to ensure the uniform distribution of the dry wax particles on the glaze surface, this solution also optimizes the specific gravity of the glaze and the nozzle diameter of the spray gun during spraying.

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

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

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

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

[0085] In a preferred embodiment of this technical solution, the waxy dry granules can be made by calcining kaolin, quartz, potassium feldspar, zinc oxide, dolomite, calcite and barium carbonate, followed by water quenching to form a waxy frit, and then crushing the waxy frit.

[0086] A waxy, stain-resistant, matte antique-style tile is prepared using the above-mentioned method for preparing waxy, stain-resistant, matte antique-style tiles. The glaze gloss of the waxy, stain-resistant, matte antique-style tile is 8-12°, the stain resistance level is 5, the Mohs hardness is 7, and the wear resistance is ≥4 (6000 revolutions).

[0087] The proposed waxy, stain-resistant matte antique-style tiles can simultaneously achieve gloss, stain resistance, hardness, wear resistance, and color performance under existing firing conditions. They also give the antique-style tiles a delicate, oily, and smooth waxy feel, improving consumer satisfaction with their use.

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

[0089] Example 1

[0090] A. Prepare ceramic blanks, press the ceramic blanks, and dry them to obtain the blank layer;

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

[0092] C. Apply a waxy anti-fouling matte glaze with a specific gravity of 1.5 to the surface of the base glaze layer using a spray gun with an aperture of 0.62mm to obtain a waxy anti-fouling matte glaze layer.

[0093] D. After drying, the bricks are fired in a kiln to obtain waxy, stain-resistant, matte antique-style bricks.

[0094] In step C, the waxy anti-fouling matte glaze includes anti-fouling matte glaze and waxy dry granules. The mixing ratio of anti-fouling matte glaze and waxy dry granules is 10:1 by mass. The particle size distribution of the waxy dry granules meets the following requirements: based on the total weight of the waxy dry granules, particles with a mesh size ≥150 mesh and <200 mesh account for 70%, and particles with a mesh size of 200-250 mesh account for 30%. The raw material composition of the anti-fouling matte glaze is shown in Table 1 below, the chemical composition of the anti-fouling and wear-resistant frit is shown in Table 2 below, and the chemical composition of the waxy dry granules is shown in Table 3 below.

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

[0096] Example 2

[0097] A. Prepare ceramic blanks, press the ceramic blanks, and dry them to obtain the blank layer;

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

[0099] C. Apply a waxy anti-fouling matte glaze with a specific gravity of 1.5 to the surface of the base glaze layer using a spray gun with an aperture of 0.62mm to obtain a waxy anti-fouling matte glaze layer.

[0100] D. After drying, the bricks are fired in a kiln to obtain waxy, stain-resistant, matte antique-style bricks.

[0101] In step C, the waxy anti-fouling matte glaze includes anti-fouling matte glaze and waxy dry granules. The mixing ratio of anti-fouling matte glaze and waxy dry granules is 10:1.5 by mass. The particle size distribution of the waxy dry granules meets the following requirements: based on the total weight of the waxy dry granules, particles with a mesh size ≥150 mesh and <200 mesh account for 75.8%, and particles with a mesh size of 200 to 250 mesh account for 24.2%. The raw material composition of the anti-fouling matte glaze is shown in Table 1 below, the chemical composition of the anti-fouling and wear-resistant frit is shown in Table 2 below, and the chemical composition of the waxy dry granules 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] like Figure 1 The image shown is a microstructure diagram of the surface of the waxy, stain-resistant, matte antique-style tile prepared in Example 2. Grains can be clearly seen on the glaze of the antique-style tile.

[0104] like Figure 2 The mass spectrum of the waxy dry particles in Example 2 is shown. It can be seen that the chemical composition of the waxy dry particles is mainly barium feldspar crystal structure, accompanied by the formation of anorthosite auxiliary crystals.

[0105] Example 3

[0106] A. Prepare ceramic blanks, press the ceramic blanks, and dry them to obtain the blank layer;

[0107] B. Apply the base glaze to the surface of the body layer to obtain the base glaze layer;

[0108] C. Apply a waxy anti-fouling matte glaze with a specific gravity of 1.5 to the surface of the base glaze layer using a spray gun with an aperture of 0.62mm to obtain a waxy anti-fouling matte glaze layer.

[0109] D. After drying, the bricks are fired in a kiln to obtain waxy, stain-resistant, matte antique-style bricks.

[0110] In step C, the waxy anti-fouling matte glaze includes anti-fouling matte glaze and waxy dry granules. The mixing ratio of anti-fouling matte glaze and waxy dry granules is 10:2 by mass. The particle size distribution of the waxy dry granules meets the following requirements: based on the total weight of the waxy dry granules, particles with a mesh size ≥150 mesh and <200 mesh account for 80%, and particles with a mesh size of 200-250 mesh account for 20%. The raw material composition of the anti-fouling matte glaze is shown in Table 1 below, the chemical composition of the anti-fouling and wear-resistant frit is shown in Table 2 below, and the chemical composition of the waxy dry granules 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] Ingredients (portions) Example 1 Example 2 Example 3 Kaolin 7 8 10 Calcinated kaolin 5 6 10 quartz 4 5 8 Potassium feldspar 20 25 30 Sodium feldspar 8 10 15 calcite 5 7 10 Burning talc 5 8 10 Zinc oxide 1 2 3 Strontium carbonate 2 4 5 Anti-fouling and wear-resistant frit 20 25 30

[0114] Table 2. Chemical composition of each antifouling and wear-resistant fused block 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 composition of each waxy 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, while keeping the rest of the formula and parameters the same.

[0120] According to the mass fraction, the raw materials of the glaze A consist of 8 parts kaolin, 6 parts calcined kaolin, 5 parts quartz, 25 parts potassium feldspar, 10 parts sodium feldspar, 7 parts calcite, 8 parts calcined talc, 2 parts zinc oxide, 4 parts strontium carbonate, and 25 parts of existing matte frit.

[0121] The chemical composition of existing matte ingots, calculated by mass percentage, 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, while keeping the rest of the formula and parameters the same.

[0124] According to the mass fraction, the raw materials of glaze B consist of 15 parts kaolin, 18 parts calcined kaolin, 30 parts potassium feldspar, 20 parts sodium feldspar, 2 parts zinc oxide, 6 parts wollastonite, 5 parts calcined talc, 6 parts wollastonite and 4 parts barium carbonate.

[0125] Comparative Example 3

[0126] Replace the waxy dry granules in Example 2 with existing waxy dry granules, and the existing waxy dry granules have a mesh size of 80-120 mesh, while the rest of the formula and parameters are the same.

[0127] The chemical composition of existing waxy dry granules, calculated by mass percentage, 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-style bricks prepared in Examples 1-3 and Comparative Examples 1-3 were subjected to conventional tests in the field of architectural ceramics, including hardness, wear resistance, glaze gloss, and stain resistance. The results are shown in Table 4 below.

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

[0130]

[0131]

[0132] As can be seen from the performance test results in Table 4, the waxy, stain-resistant, matte antique-style tiles produced by this method can simultaneously achieve gloss, stain resistance, hardness, wear resistance, and color performance under existing firing conditions. It also gives the antique-style tiles a delicate, oily, and smooth waxy feel, thereby improving consumer satisfaction with the use of antique-style tiles.

[0133] The technical principles of the present invention have been described above with reference to specific embodiments. These descriptions are merely for explaining the principles of the invention and should not be construed as limiting the scope of protection of the invention in any way. Based on this explanation, those skilled in the art can readily conceive of other specific embodiments of the invention without inventive effort, and these embodiments will all fall within the scope of protection of the present invention.

Claims

1. A method for preparing a waxy, stain-resistant, matte antique-style tile, characterized in that, Includes the following steps: A. Prepare ceramic blanks, press the ceramic blanks, and dry them to obtain the blank layer; B. Apply the base glaze to the surface of the body layer to obtain the base glaze layer; C. Apply a waxy anti-fouling matte glaze to the surface of the base glaze layer to obtain a waxy anti-fouling matte glaze layer; D. After drying, the bricks are fired in a kiln to obtain waxy, stain-resistant, matte antique-style bricks. In step C, the waxy anti-fouling matte glaze includes an anti-fouling matte glaze and waxy dry granules, and the waxy dry granules are composed of particles with a mesh size ≥150 mesh and <200 mesh and particles with a mesh size of 200 to 250 mesh. According to the mass fraction, the raw materials of the anti-fouling matte glaze are composed of 7-10 parts kaolin, 5-10 parts calcined kaolin, 4-8 parts quartz, 20-30 parts potassium feldspar, 8-15 parts sodium feldspar, 5-10 parts calcined talc, 1-3 parts zinc oxide, 2-5 parts strontium carbonate, and 20-30 parts anti-fouling and wear-resistant frit. The chemical composition of the anti-fouling and wear-resistant frit, calculated by mass percentage, 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%. The chemical composition of the waxy dry granules, calculated by mass percentage, 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, stain-resistant, matte antique-style brick according to claim 1, characterized in that, The particle size distribution of the waxy dry granules satisfies the following: based on the total weight of the waxy dry granules, particles with a mesh size ≥150 mesh and <200 mesh account for 70-80%, and the remainder are particles with a mesh size of 200-250 mesh.

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

4. The method for preparing a waxy, stain-resistant, matte antique-style brick according to claim 1, characterized in that, The chemical composition of the waxy dry granules, calculated by mass percentage, includes 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, stain-resistant, matte antique-style brick according to claim 1, characterized in that, The firing curve of the antifouling and wear-resistant fused block is as follows: The time required to heat the temperature from room temperature to 300℃ is 1.5 to 2.5 hours. The temperature rises from 300℃ to 1530℃, taking 2-3 hours. 1530℃, keep warm for 0.5~1.2h.

6. The method for preparing a waxy, stain-resistant, matte antique-style brick according to claim 1, characterized in that, Step C specifically involves: C. Spray a waxy anti-fouling matte glaze onto the surface of the base glaze layer to obtain a waxy anti-fouling matte glaze layer; The specific gravity of the waxy anti-fouling matte glaze is 1.5 to 1.55, and the nozzle diameter of the spray gun is 0.62 mm.

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

8. The method for preparing a waxy, stain-resistant, matte antique-style brick according to claim 1, characterized in that, According to the mass fractions, the raw materials of the antifouling and wear-resistant fused block 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.

9. The method for preparing a waxy, stain-resistant, matte antique-style brick according to claim 1, characterized in that, According to the mass fractions, the raw materials of the waxy dry granules consist of 25-30 parts kaolin, 25-32 parts quartz, 6-10 parts potassium feldspar, 3-8 parts zinc oxide, 3-8 parts dolomite, 8-15 parts calcite, and 12-18 parts barium carbonate.

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