Hydrophobic matte archaized brick and preparation method thereof

Abstract

The invention relates to the technical field of architectural ceramics, in particular to a hydrophobic matte archaized brick and a preparation method thereof.The preparation method comprises the following steps that A, a ceramic blank is prepared, pressed and dried to obtain a blank layer; b, applying wax antifouling matte glaze to the surface of the green body layer to obtain a wax antifouling matte glaze layer; c, drying and calcining in a kiln to obtain a semi-finished product of the matte archaized brick; and D, the semi-finished matt archaized brick is soaked in etching hydrophobic liquid, taken out and dried, and then the hydrophobic matt archaized brick is obtained. According to the hydrophobic matte archaized brick and the preparation method thereof provided by the invention, the obtained hydrophobic matte archaized brick not only has excellent and lasting hydrophobic self-cleaning property, but also has relatively high antifouling property, hardness and wear resistance on the premise that the hydrophobic matte archaized brick has matte texture and waxy silky hand feeling.

Description

Technical Field

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

[0002] Antique-style bricks, as an artistic building material that blends classical aesthetics with modern craftsmanship, are highly favored by consumers for their unique antique glaze effect, rich color layers, and strong historical charm. They are widely used in home decoration, commercial venues, and cultural tourism scenic spots.

[0003] To ensure the antique effect of antique-style bricks, their surfaces are usually designed to be uneven. While this uneven surface increases their anti-slip properties, it also easily accumulates dust, oil stains, and other dirt. Ordinary wiping is insufficient for thorough cleaning, and long-term accumulation not only affects the appearance but may also breed bacteria. Traditional cleaning methods typically rely on chemical cleaners or high-pressure water guns, which are not only inefficient but may also cause wear or corrosion to the brick surface.

[0004] To overcome the above defects, existing technologies usually coat the surface of antique bricks with a hydrophobic self-cleaning coating, so that a hydrophobic self-cleaning coating is formed on the surface of the antique bricks, so that water can roll when it comes into contact with the coating surface (that is, the static contact angle between water and coating is large), and water can carry away and remove water-soluble dirt and dust and other stains on the surface of antique bricks, thus achieving the effect of hydrophobic self-cleaning. However, the above methods have the following defects: (1) The hydrophobic self-cleaning coating has poor aging resistance. It is easy to age when exposed to ultraviolet rays, rain and temperature changes for a long time, which leads to the gradual failure of the hydrophobic self-cleaning function and poor hydrophobic self-cleaning durability; (2) The bonding force between the hydrophobic self-cleaning coating and the antique brick substrate is limited. It is easy to peel off under frequent friction or temperature stress, which will also reduce the durability of hydrophobic self-cleaning; (3) The surface of existing antique bricks generally does not have hydrophobic self-cleaning properties, and an additional layer of hydrophobic self-cleaning coating is needed to make it have hydrophobic self-cleaning properties. However, the additional hydrophobic self-cleaning coating generally does not have a matte texture and a waxy silky feel.

[0005] Therefore, how to achieve long-lasting hydrophobic self-cleaning properties while maintaining a matte finish and a waxy, silky feel has become a pressing technical challenge. Summary of the Invention

[0006] The purpose of this invention is to propose a hydrophobic matte antique tile and its preparation method. The resulting hydrophobic matte antique tile, while having a matte texture and a waxy silky feel, not only has excellent and long-lasting hydrophobic self-cleaning properties, but also has high stain resistance, hardness and wear resistance.

[0007] To achieve this objective, the present invention adopts the following technical solution: A method for preparing hydrophobic matte antique-style tiles includes the following steps: A. Prepare ceramic blanks, press the ceramic blanks, and dry them to obtain the blank layer; B. Apply a waxy anti-fouling matte glaze to the surface of the body layer to obtain a waxy anti-fouling matte glaze layer; According to the mass fraction, the waxy anti-fouling matte glaze comprises the following raw materials: 7-10 parts kaolin, 6-15 parts calcined kaolin, 4-8 parts quartz, 20-30 parts potassium feldspar, 5-15 parts sodium feldspar, 5-10 parts wollastonite, 1-5 parts zinc oxide, 5-10 parts strontium carbonate, 5-12 parts barium carbonate, and 10-20 parts crystalline frit; According to the mass fractions, the crystalline frit comprises the following raw materials: 25-35 parts kaolin, 3-8 parts calcined alumina, 20-35 parts calcite, 0.5-3 parts dolomite, 5-10 parts zinc oxide, 25-35 parts potassium feldspar, 0.5-3 parts barium carbonate, and 1-5 parts calcium feldspar powder; C. After drying, the bricks are fired in a kiln to obtain matte antique-style brick semi-finished products. D. Immerse the semi-finished matte antique brick in an etching hydrophobic solution, take it out and dry it to obtain hydrophobic matte antique brick. The raw materials of the etching hydrophobic solution include perfluorosulfonic acid resin, solvent and ammonium fluoride, and the pH value of the etching hydrophobic solution is 6 to 6.9.

[0008] Further, in step D, the solvent includes dimethyl sulfoxide, dimethylhexamethylene amide, and N-methylpyrrolidone; The raw materials for the etching hydrophobic solution, calculated by mass, include 80-120 parts of perfluorosulfonic acid resin, 150-250 parts of dimethyl sulfoxide, 200-400 parts of dimethylhexamethylene amide, 400-600 parts of N-methylpyrrolidone, and 0.5-2 parts of ammonium fluoride.

[0009] Further, in step D, the method for preparing the etching hydrophobic solution is as follows: Under an inert atmosphere, perfluorosulfonic acid resin is added to a solvent, stirred at 150–250°C for 4–8 hours, and then cooled to room temperature to obtain a mixed solution. Ammonium fluoride was added to the mixed solution, stirred at room temperature for 0.5–1 h, and the pH was adjusted to 6–6.9 to obtain the etching hydrophobic solution.

[0010] Furthermore, in step D, the soaking time is 1 to 5 hours.

[0011] Furthermore, in step B, the particle size of the anorthite powder is 10–50 μm.

[0012] Further, in step B, the waxy anti-fouling matte glaze, calculated by mass parts, comprises the following raw materials: 8 parts kaolin, 8 parts calcined kaolin, 6 parts quartz, 28 parts potassium feldspar, 10 parts sodium feldspar, 8 parts wollastonite, 3 parts zinc oxide, 8 parts strontium carbonate, 8 parts barium carbonate, and 13 parts crystalline frit. According to the mass fractions, the crystalline frit comprises the following raw materials: 27 parts kaolin, 4 parts calcined alumina, 27 parts calcite, 1 part dolomite, 7 parts zinc oxide, 29 parts potassium feldspar, 1 part barium carbonate, and 4 parts calcium feldspar powder.

[0013] Further, in step B, the preparation method of the waxy anti-fouling matte glaze includes the following steps: B1. The raw materials for the crystalline frit are mixed evenly and then subjected to calcination, water quenching and crushing in sequence to obtain the crystalline frit; B2. After mixing the raw materials of the waxy anti-fouling matte glaze evenly, add sodium carboxymethyl cellulose, sodium hexametaphosphate and water, ball mill, and sieve to obtain the waxy anti-fouling matte glaze; Specifically, by mass percentage, the amount of water added is 33-50% of the dry material of the waxy antifouling matte glaze, the amount of sodium carboxymethyl cellulose added is 0.4-0.6% of the dry material of the waxy antifouling matte glaze, and the amount of sodium hexametaphosphate added is 0.4-0.8% of the dry material of the waxy antifouling matte glaze.

[0014] Further, in step B1, the calcination temperature curve of the crystalline frit is as follows: It takes 1.5 to 3 hours to heat the temperature from room temperature to 300°C. The temperature rises from 300℃ to 1530℃, taking 1.5 to 2.5 hours. 1530℃, keep warm for 0.5 to 1 hour.

[0015] Furthermore, in step C, the calcination temperature is 1100–1250°C, and the calcination time is 45–60 min.

[0016] A hydrophobic matte antique-style tile is prepared using the above-mentioned method for preparing hydrophobic matte antique-style tiles. The static contact angle of the hydrophobic matte antique-style tile without soaking in boiling water is 135-150°, and the static contact angle after soaking in boiling water for 30 days is 120-130°. The gloss is 12-18°, the stain resistance is level 5, the Mohs hardness is level 7, and the abrasion resistance is ≥4 (2100 revolutions).

[0017] The technical solution provided by this invention may include the following beneficial effects: 1. This application achieves deep activation of the glaze surface of matte antique-style brick semi-finished products by combining the ion exchange effect of the etching hydrophobic solution with the acid-catalyzed etching effect, creating a large number of highly reactive silanol (≡Si-OH) sites. Simultaneously, this technical solution immerses the matte antique-style brick semi-finished products in the etching hydrophobic solution, utilizing the hydrofluoric acid (HF) generated by the decomposition of ammonium fluoride (NH4F) in the liquid phase environment to react with the silanol (≡Si-OH) sites on the surface of the matte antique-style brick semi-finished products, generating stable silicon-fluorine bonds (≡Si-F). This process introduces fluorine atoms with extremely low surface energy into the surface of the matte antique-style brick semi-finished products. The fluorine atoms significantly reduce the surface energy, thereby greatly increasing the contact angle between water droplets and the surface of the hydrophobic matte antique-style brick, thus improving the hydrophobic self-cleaning properties of the hydrophobic matte antique-style brick.

[0018] 2. The glaze surface of the wax-based anti-fouling matte glaze, after firing, contains both nano-sized calcium feldspar microcrystals and micron-sized barium feldspar crystals. These micron-sized barium feldspar crystals and nano-sized calcium feldspar microcrystals are densely distributed within the wax-based anti-fouling matte glaze layer, forming a continuous, dense microstructure with slight undulations on its surface. These numerous micro-undulations act as physical anti-adhesion, significantly reducing the contact area between the skin and the wax-based anti-fouling matte glaze layer. Simultaneously, the extremely small size of the crystals is far below the threshold of human tactile perception, resulting in a waxy, silky-smooth surface on the wax-based anti-fouling matte glaze layer, giving the final matte antique-style tile semi-finished product a waxy, silky-smooth feel. The semi-finished matte antique tiles were then immersed in an etching hydrophobic solution with carefully controlled pH levels. This ensured that the solution only slightly etched the tiles without compromising their overall smoothness, resulting in a final hydrophobic matte antique tile that retained a waxy, silky feel. Simultaneously, the waxy, silky surface of the hydrophobic matte antique tile reduced the contact area between water droplets and its surface, making it difficult for water to penetrate. Water droplets instead formed droplets, increasing the contact angle between the droplets and the tile, thus creating strong hydrophobicity. As the droplets rolled on the tile, they easily absorbed and carried away dirt particles, further enhancing the self-cleaning function of the hydrophobic matte antique tile and giving it excellent self-cleaning properties.

[0019] 3. This technical solution establishes a hydrophobic and self-cleaning effect through a wax-based anti-fouling matte glaze, while a slight etching hydrophobic treatment further enhances this effect. The synergistic effect of these two materials gives the resulting antique-style tiles hydrophobic and self-cleaning properties, making it easier to remove dirt even if it adheres to the surface. Furthermore, compared to conventional hydrophobic self-cleaning coatings, the wax-based anti-fouling matte glaze layer constructed in this solution exhibits significantly improved aging resistance. Simultaneously, fluorine atoms form silicon-fluorine bonds with silicon atoms on the surface of the matte antique-style tile semi-finished product (i.e., the wax-based anti-fouling matte glaze layer). These chemical bonds possess extremely high strength and stability, greatly enhancing the aging resistance of the entire hydrophobic system and effectively overcoming the problem of rapid performance degradation caused by insufficient aging resistance in existing hydrophobic self-cleaning coatings. In addition, the hydrophobic and self-cleaning function of this antique-style tile is achieved jointly by the wax-based anti-fouling matte glaze layer and fluorine atoms. The waxy, anti-fouling matte glaze layer, formed by calcining the corresponding glaze, has become an integral part of the antique-style brick body. Meanwhile, the fluorine atoms, fixed through chemical bonding, form strong silicon-fluorine bonds with the silicon atoms in the glaze layer, exhibiting both high stability and inertness. These structural characteristics ensure that the bonding strength between the hydrophobic functional layer, composed of the waxy, anti-fouling matte glaze layer and fluorine atoms, and the brick body is significantly superior to that of the hydrophobic self-cleaning coating in traditional technologies. This further extends the durability of the hydrophobic self-cleaning performance and overcomes the shortcomings of insufficient timeliness caused by the limited bonding strength between the hydrophobic self-cleaning coating and the antique-style brick surface in existing technologies. Detailed Implementation

[0020] This technical solution provides a method for preparing hydrophobic matte antique-style bricks, including the following steps: A. Prepare ceramic blanks, press the ceramic blanks, and dry them to obtain the blank layer; B. Apply a waxy anti-fouling matte glaze to the surface of the body layer to obtain a waxy anti-fouling matte glaze layer; According to the mass fraction, the waxy anti-fouling matte glaze comprises the following raw materials: 7-10 parts kaolin, 6-15 parts calcined kaolin, 4-8 parts quartz, 20-30 parts potassium feldspar, 5-15 parts sodium feldspar, 5-10 parts wollastonite, 1-5 parts zinc oxide, 5-10 parts strontium carbonate, 5-12 parts barium carbonate, and 10-20 parts crystalline frit; According to the mass fractions, the crystalline frit comprises the following raw materials: 25-35 parts kaolin, 3-8 parts calcined alumina, 20-35 parts calcite, 0.5-3 parts dolomite, 5-10 parts zinc oxide, 25-35 parts potassium feldspar, 0.5-3 parts barium carbonate, and 1-5 parts calcium feldspar powder; C. After drying, the bricks are fired in a kiln to obtain matte antique-style brick semi-finished products. D. Immerse the semi-finished matte antique brick in an etching hydrophobic solution, take it out and dry it to obtain hydrophobic matte antique brick. The raw materials of the etching hydrophobic solution include perfluorosulfonic acid resin, solvent and ammonium fluoride, and the pH value of the etching hydrophobic solution is 6 to 6.9.

[0021] To address the technical challenge of achieving durable hydrophobic self-cleaning properties in existing antique-style bricks while reducing production costs, this technical solution proposes a method for preparing hydrophobic matte antique-style bricks. This method comprises four steps: A (preparing the body layer), B (applying a waxy anti-fouling matte glaze), C (firing in a kiln), and D (immersing in an etching hydrophobic solution). By designing the preparation method and the waxy anti-fouling matte glaze, the resulting hydrophobic matte antique-style bricks not only possess a matte texture and a waxy, silky feel, but also exhibit excellent and durable hydrophobic self-cleaning properties, as well as high anti-fouling performance, hardness, and wear resistance.

[0022] Specifically, the waxy anti-fouling matte glaze of this technical solution, after calcination, forms a glassy phase dominated by a silicon-oxygen network (≡Si-O-Si≡) structure (i.e., the glassy phase of the glaze surface of the semi-finished matte antique tile). The numerous non-bridging oxygen sites present in this silicon-oxygen network structure, along with the sodium feldspar (providing Na) from the waxy anti-fouling matte glaze... + Potassium feldspar (providing K) + ) and zinc oxide (providing Zn 2+ Network-modified ions (such as Na) and other raw materials + K + and Zn 2+ They are bonded by ionic bonds to form ≡Si-O - M + Or (≡Si-O-)2M 2+ The structure, together, maintains the electrochemical neutrality of the waxy, anti-fouling matte glaze surface (i.e., the glaze surface of the matte antique tile semi-finished product). Simultaneously, this technical solution immerses the matte antique tile semi-finished product in an etching hydrophobic solution, the raw materials of which include perfluorosulfonic acid resin, solvent, and ammonium fluoride. The combined effect of the sulfonic acid groups (-SO3H) in the perfluorosulfonic acid resin and the strong acid-weak base salt ammonium fluoride makes the etching solution weakly acidic and provides active hydrogen ions (H+). + ), the above H + Replaceable ≡Si-O - M + Or (≡Si-O-)2M 2+ Metal ions (M) in the structure + Or M 2+ ), generating unstable ≡Si-O - H + The intermediate rapidly reconstitutes into thermodynamically more stable and electrically neutral silanol groups (≡Si-OH). This process not only removes easily soluble and hydrated metal ions from the glaze surface but also transforms ≡Si-O... - M +Or (≡Si-O-)2M 2+ The original low-reactivity ionic bonds in the structure are transformed into highly reactive silanol groups. Simultaneously, the weakly acidic environment provided by the etching hydrophobic solution catalyzes the hydrolysis of the silicon-oxygen bonds (Si-O-Si) on the surface of the matte antique tile semi-finished product, generating silanol groups (≡Si-OH). Additionally, H... + Attacking the lone pair electrons on the bridging oxygen protons significantly weakens the original Si-O-Si bonds, making them more susceptible to breakage by water molecules. This process controllably etches and opens up a dense glass network at the nanoscale, exposing deeper layers of fresh silanol groups and significantly increasing the density of surface active sites.

[0023] That is, this application achieves deep activation of the surface layer of the glaze of the semi-finished matte antique brick by combining the ion exchange effect of etching hydrophobic liquid with the acid-catalyzed etching effect, creating a large number of highly reactive silanol (≡Si-OH) sites.

[0024] Meanwhile, this technical solution involves immersing the matte antique brick semi-finished product in an etching hydrophobic solution, where ammonium fluoride (NH4F) decomposes into NH4 at room temperature. + and F - And F - With part of H in the etching hydrophobic solution + The hydrofluoric acid (HF) combines with the silanol groups (≡Si-OH) on the surface of the matte antique-style tile semi-finished product to form stable silicon-fluorine bonds (≡Si-F). This process introduces fluorine atoms with extremely low surface energy into the surface of the matte antique-style tile semi-finished product. The fluorine atoms significantly reduce the surface energy, thereby greatly increasing the contact angle between water droplets and the surface of the hydrophobic matte antique-style tile, which helps to improve the hydrophobic self-cleaning properties of the hydrophobic matte antique-style tile.

[0025] Furthermore, while this technical solution utilizes etching hydrophobic liquid to soak the semi-finished matte antique-style tiles, which can improve their hydrophobic self-cleaning properties, relying solely on this method will result in limited hydrophobic self-cleaning performance in the final product, failing to meet practical application requirements. Therefore, this technical solution improves the formulation of the wax-based anti-fouling matte glaze. Specifically, the raw materials for the wax-based anti-fouling matte glaze include kaolin, calcined kaolin, quartz, potassium feldspar, sodium feldspar, wollastonite, zinc oxide, strontium carbonate, barium carbonate, and crystalline frit; the raw materials for the crystalline frit include kaolin, calcined alumina, calcite, dolomite, zinc oxide, potassium feldspar, barium carbonate, and calcium feldspar powder. During the calcination of the crystalline frit, calcite (mainly calcium carbonate) and dolomite (mainly calcium magnesium carbonate) both decompose upon heating to generate calcium oxide; kaolin decomposes upon heating into aluminum oxide and silicon dioxide, and calcining aluminum oxide also provides aluminum oxide. The calcium oxide, aluminum oxide, and silicon dioxide in the formulation react to form anorthite crystals (CaAl2Si2O8). Simultaneously, anorthite powder is introduced into the crystalline frit formulation as a nucleating agent. During the high-temperature calcination of the crystalline frit, this readily available anorthite powder acts as a seed crystal, greatly promoting and guiding the precipitation of anorthite crystals. It also provides a massive and uniformly distributed number of crystallization starting points. In subsequent firing, the crystallizing material in the melt grows simultaneously around these numerous starting points, rapidly depleting the limited surrounding "raw materials," thus ensuring that each crystal grows only slightly, ultimately resulting in a large number of tiny nanoscale anorthite microcrystals within the crystalline frit. Furthermore, by limiting the amount of calcite and dolomite added to the crystalline frit, this technical solution ensures that calcium ions in the crystalline frit formulation are in a supersaturated state, which is also conducive to the existence of anorthite crystals in the form of nano-sized anorthite microcrystals.

[0026] Simultaneously, during the high-temperature calcination of the wax-based anti-fouling matte glaze, the following reactions occur: barium carbonate (BaCO3) decomposes upon heating to generate active barium oxide, while potassium feldspar (K2O·Al2O3·6SiO2), sodium feldspar (Na2O·Al2O3·6SiO2), and kaolin (Al2O3·2SiO2·2H2O) decompose upon heating to generate aluminum oxide and silicon dioxide. The barium oxide, aluminum oxide, and silicon dioxide in the formulation react to form barium feldspar crystals. Furthermore, since barium feldspar powder is not added as a seed crystal or crystallizing agent to the wax-based anti-fouling matte glaze, the generated barium feldspar crystals exist in the form of micron-sized barium feldspar crystals. Furthermore, when crystalline frit is introduced into the wax-based anti-fouling matte glaze system, within the calcination temperature range, the nano-sized anorthite microcrystals contained in the crystalline frit remain essentially stable and infusible. This results in the glaze surface of the wax-based anti-fouling matte glaze containing both nano-sized anorthite microcrystals and micron-sized barium feldspar crystals. These micron-sized barium feldspar crystals and nano-sized anorthite microcrystals are densely distributed within the wax-based anti-fouling matte glaze layer, collectively forming a continuous, dense microstructure with micro-undulations on its surface. These numerous micro-undulations act as physical anti-adhesion agents, significantly reducing the contact area between the skin and the wax-based anti-fouling matte glaze layer. Simultaneously, the extremely small size of the crystals is far below the threshold of human tactile perception, giving the surface of the wax-based anti-fouling matte glaze layer a waxy, silky feel, ultimately resulting in the waxy, silky feel of the final matte antique-style tile semi-finished product.

[0027] Furthermore, the semi-finished matte antique tiles are subsequently immersed in an etching hydrophobic solution with carefully controlled pH levels. This ensures the solution only slightly etches the tiles without compromising their overall smoothness, resulting in a final hydrophobic matte antique tile that retains a waxy, silky feel. Simultaneously, the waxy, silky surface of the hydrophobic matte antique tile minimizes the contact area between water droplets and its surface, making it difficult for water to penetrate. Water droplets instead shrink into droplets, increasing the contact angle between the droplets and the tile, thus creating strong hydrophobicity. As the droplets roll within the tile, they easily absorb and carry away dirt particles, further enhancing the self-cleaning function of the hydrophobic matte antique tile and giving it excellent self-cleaning properties.

[0028] In summary, this technical solution establishes a hydrophobic and self-cleaning effect through a wax-based anti-fouling matte glaze, while a slight etching hydrophobic treatment further enhances this effect. The synergistic effect of these two materials gives the resulting antique-style tiles hydrophobic and self-cleaning properties, making it easier to remove dirt even if it adheres to the surface. Furthermore, compared to conventional hydrophobic self-cleaning coatings, the wax-based anti-fouling matte glaze layer constructed in this solution exhibits significantly improved aging resistance. Simultaneously, fluorine atoms form silicon-fluorine bonds with silicon atoms on the surface of the matte antique-style tile semi-finished product (i.e., the wax-based anti-fouling matte glaze layer). These chemical bonds possess extremely high strength and stability, greatly enhancing the aging resistance of the entire hydrophobic system and effectively overcoming the problem of rapid performance degradation caused by insufficient aging resistance in existing hydrophobic self-cleaning coatings. Moreover, the hydrophobic and self-cleaning function of this antique-style tile is achieved jointly by the wax-based anti-fouling matte glaze layer and fluorine atoms. The waxy, anti-fouling matte glaze layer, formed by calcining the corresponding glaze, has become an integral part of the antique-style brick body. Meanwhile, the fluorine atoms, fixed through chemical bonding, form strong silicon-fluorine bonds with the silicon atoms in the glaze layer, exhibiting both high stability and inertness. These structural characteristics ensure that the bonding strength between the hydrophobic functional layer, composed of the waxy, anti-fouling matte glaze layer and fluorine atoms, and the brick body is significantly superior to that of the hydrophobic self-cleaning coating in traditional technologies. This further extends the durability of the hydrophobic self-cleaning performance and overcomes the shortcomings of insufficient timeliness caused by the limited bonding strength between the hydrophobic self-cleaning coating and the antique-style brick surface in existing technologies.

[0029] Secondly, as described above, the wax-based anti-fouling matte glaze obtained by firing can form countless micro-undulations, thus giving the surface of the hydrophobic matte antique tile countless micro-undulations. These numerous micro-undulations can diffusely reflect light, reducing the gloss of the glaze. Furthermore, an increase in the glass phase in the wax-based anti-fouling matte glaze makes the surface of the wax-based anti-fouling matte glaze smoother, thereby making the surface of the hydrophobic matte antique tile smoother and increasing its gloss. Conversely, if an increase in the crystalline phase in the wax-based anti-fouling matte glaze makes the surface of the wax-based anti-fouling matte glaze rougher, thereby making the surface of the hydrophobic matte antique tile rougher and reducing its gloss. Therefore, this technical solution limits the amount of strontium carbonate added to the waxy anti-fouling matte glaze formulation system, thereby using the strontium oxide introduced by strontium carbonate to adjust the ratio of crystalline phase to glassy phase in the microstructure of the waxy anti-fouling matte glaze layer (where the greater the amount of strontium oxide added, the more glassy phase is generated), thereby adjusting the proportion of micro-undulations on the antique tile glaze surface, so that the gloss of the glaze surface is controlled at 12~18°, giving the glaze surface a matte texture.

[0030] Furthermore, the mechanism by which the waxy anti-fouling matte glaze forms a glassy phase dominated by a silicon-oxygen network structure after calcination is as follows: During the calcination of the crystalline frit, calcite and dolomite in the crystalline frit can introduce calcium oxide, barium carbonate decomposes to generate barium oxide, and potassium feldspar introduces potassium oxide. The calcium oxide, strontium oxide, potassium oxide, and barium oxide generated above, together with zinc oxide in the crystalline frit raw materials, synergistically constitute a calcium-strontium-potassium-zinc-barium composite flux. This composite flux can accelerate the dissolution-precipitation mass transfer process, promote the rearrangement and densification of solid particles, thereby enabling the composite flux to react with calcined alumina and kaolin to form a dense silicate glass network, thus forming the glassy phase of the crystalline frit. When the crystalline frit is introduced into the wax-based anti-fouling matte glaze system, under high-temperature calcination, the glass phase within the crystalline frit completely enters a liquid molten state. As a precursor to the pre-formed glass phase, it first melts with kaolin, calcined kaolin, and quartz in the wax-based anti-fouling matte glaze formulation, forming a low-viscosity silicate glass matrix. Simultaneously, raw materials such as potassium feldspar, sodium feldspar, wollastonite, and zinc oxide in the wax-based anti-fouling matte glaze formulation dissolve into an alkali metal aluminum silicate liquid phase, which fuses and diffuses with the low-viscosity silicate glass matrix, ultimately forming a continuous and dense glass phase in the wax-based anti-fouling matte glaze layer.

[0031] Furthermore, the glass phase of the aforementioned waxy anti-fouling matte glaze significantly reduces the surface porosity of the waxy anti-fouling matte glaze by filling grain boundary voids and strengthening crystal particle adhesion, thus blocking stain penetration channels and resulting in excellent anti-fouling performance of the waxy anti-fouling matte glaze surface. Simultaneously, the waxy anti-fouling matte glaze of this technical solution contains 5-10 parts of strontium carbonate and 0.5-3 parts of barium carbonate. The high strontium oxide content introduced by strontium carbonate and the barium oxide introduced by barium carbonate not only provide fluxing effects but also improve the high-temperature fluidity of the glaze during calcination, ensuring the glaze surface density after degassing, reducing surface porosity, and thereby improving anti-fouling performance. Furthermore, compared to existing glazes, the raw material formula of this technical solution for a waxy anti-fouling matte glaze reduces the proportion of potassium feldspar and sodium feldspar, 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 point temperature of the glaze during sintering, preventing premature formation of a sealed layer during firing and allowing sufficient time for gas degassing. This not only matches the existing low-temperature, fast-firing firing regime for antique tiles but also avoids the defect of excessive porosity on the surface of the waxy anti-fouling matte glaze layer caused by insufficient degassing time. This ensures the density of the waxy anti-fouling matte glaze layer surface, thus improving its anti-fouling performance. In short, through the above-mentioned multiple effects, this technical solution provides the waxy anti-fouling matte glaze layer with excellent anti-fouling properties, thereby endowing the semi-finished matte antique tile with superior anti-fouling performance. Although the semi-finished matte antique tiles were subsequently immersed in an etching hydrophobic solution to cause slight corrosion of the glass phase on the surface of the matte antique tiles, the degree of corrosion of the surface glass phase of the matte antique tiles was limited, so the final hydrophobic matte antique tiles still had good anti-fouling properties.

[0032] Furthermore, this technical solution controls the gloss of the glaze within the range of 12~18°, avoiding the defect that excessively low gloss leads to excessive micro-roughness of the glaze surface, which in turn "pins" stains and affects the anti-fouling performance, thus helping to ensure the anti-fouling performance.

[0033] Finally, as described above, the calcination process in the formula system generates calcium feldspar microcrystals and barium feldspar crystals with high hardness. Combined with the unmelted quartz in the formula system, the surface of the waxy anti-fouling matte glaze layer is distributed with a variety of crystals with high hardness. As a result, the final hydrophobic matte antique tile has high hardness and wear resistance. Under long-term use, the surface properties of the hydrophobic matte antique tile are not easily damaged, achieving long-lasting anti-fouling properties.

[0034] It should be noted that the anti-fouling performance refers to the glaze's ability, thanks to its high density and smoothness, to effectively resist the penetration and adhesion of contaminants such as oil. The hydrophobic self-cleaning property, on the other hand, stems from the glaze's hydrophobic effect, allowing it to automatically remove surface dust and soluble impurities through the rolling of water. It is worth noting that even if the glaze itself has poor physical anti-fouling properties, as long as it possesses hydrophobic properties, it can still achieve self-cleaning performance against water droplets and water-soluble stains.

[0035] Furthermore, the anorthite crystals generated by this technical solution belong to the triclinic crystal system, with a dense crystal structure and a refractive index similar to that of the glaze glass phase. The absence of significant light scattering centers gives the anorthite crystals extremely high transparency, providing a clear, light-loss-free carrier substrate for the colorant and preventing the color from becoming cloudy and dull due to scattering. Simultaneously, the waxy, anti-fouling matte glaze and the crystalline frit contain a large amount of zinc oxide, which contributes to color development. By stabilizing the valence state of the color-producing ions and optimizing the chemical environment of the glaze melt, it directly enhances the color intensity and saturation of the colorant, ultimately resulting in an excellent color development effect for the glaze.

[0036] To further explain, in step D, the solvent includes dimethyl sulfoxide, dimethylhexamethylene amide, and N-methylpyrrolidone; The raw materials for the etching hydrophobic solution, calculated by mass, include 80-120 parts of perfluorosulfonic acid resin, 150-250 parts of dimethyl sulfoxide, 200-400 parts of dimethylhexamethylene amide, 400-600 parts of N-methylpyrrolidone, and 0.5-2 parts of ammonium fluoride.

[0037] This technical solution utilizes solvents including dimethyl sulfoxide (boiling point 189℃), dimethylhexamethylene (boiling point 165℃), and N-methylpyrrolidone (boiling point 202℃) to dissolve perfluorosulfonic acid resin, thereby extending its molecular chains, exposing the sulfonic acid groups, and dissociating H+. + This makes the etching hydrophobic solution weakly acidic, which is conducive to the formation of silanol groups (≡Si-OH), thereby promoting the replacement of hydroxyl groups in the surface silanol groups by fluorine atoms and improving the hydrophobic self-cleaning properties of the glaze.

[0038] Furthermore, this technical solution optimizes the formulation of the etching hydrophobic liquid, which helps to ensure the performance of the final hydrophobic matte antique-style brick.

[0039] It should be noted that the manufacturer of the perfluorosulfonic acid resin is Guangdong Wengjiang Chemical Reagent Co., Ltd., and the model number is PA06988.

[0040] To further explain, in step D, the method for preparing the etching hydrophobic solution is as follows: Under an inert atmosphere, perfluorosulfonic acid resin is added to a solvent, stirred at 150–250°C for 4–8 hours, and then cooled to room temperature to obtain a mixed solution. Ammonium fluoride was added to the mixed solution, stirred at room temperature for 0.5–1 h, and the pH was adjusted to 6–6.9 to obtain the etching hydrophobic solution.

[0041] This technical solution, through the preparation method of the etching hydrophobic liquid, helps to ensure the full decomposition of perfluorosulfonic acid resin and ammonium fluoride, improves the dissolution uniformity of perfluorosulfonic acid resin and ammonium fluoride, and thus ensures the performance of hydrophobic matte antique bricks.

[0042] It should be noted that the inert atmosphere can be nitrogen atmosphere or argon atmosphere, etc., and the specific type is not limited here.

[0043] To further explain, in step D, the soaking time is 1 to 5 hours.

[0044] This technical solution limits the immersion time of the matte antique tile semi-finished product in the etching hydrophobic solution, thereby achieving a balance between the hydrophobic and anti-fouling properties of the glaze while meeting the ion exchange efficiency requirements.

[0045] To further clarify, in step B, the particle size of the anorthite powder is 10–50 μm.

[0046] If the particle size of the calcium feldspar powder is too large, the resulting calcium feldspar microcrystals will also be too large. This will make the micro-undulation structure formed by the barium feldspar crystals and calcium feldspar microcrystals too rough, affecting the waxy, silky feel and matte finish of the glaze. Simultaneously, the micro-roughness will trap stains, reducing the glaze's stain resistance. If the particle size of the calcium feldspar powder is too small, the particles will easily agglomerate, and the resulting calcium feldspar microcrystals will also tend to agglomerate. This will similarly make the micro-undulation structure formed by the barium feldspar crystals and calcium feldspar microcrystals too rough, affecting the waxy, silky feel, matte finish, and stain resistance of the glaze.

[0047] To further explain, in step B, the waxy anti-fouling matte glaze, calculated by mass, includes the following raw materials: 8 parts kaolin, 8 parts calcined kaolin, 6 parts quartz, 28 parts potassium feldspar, 10 parts sodium feldspar, 8 parts wollastonite, 3 parts zinc oxide, 8 parts strontium carbonate, 8 parts barium carbonate, and 13 parts crystalline frit. According to the mass fractions, the crystalline frit comprises the following raw materials: 27 parts kaolin, 4 parts calcined alumina, 27 parts calcite, 1 part dolomite, 7 parts zinc oxide, 29 parts potassium feldspar, 1 part barium carbonate, and 4 parts calcium feldspar powder.

[0048] This technical solution further optimizes the formulations of crystalline frit and waxy anti-fouling matte glaze, which helps ensure the formation of nano-sized calcium feldspar microcrystals in the crystalline frit and micron-sized barium feldspar crystals in the waxy anti-fouling matte glaze. This helps ensure the matte texture, hydrophobicity, and waxy silky smooth feel of the waxy anti-fouling matte glaze.

[0049] To further explain, in step B, the preparation method of the waxy anti-fouling matte glaze includes the following steps: B1. The raw materials for the crystalline frit are mixed evenly and then subjected to calcination, water quenching and crushing in sequence to obtain the crystalline frit; B2. After mixing the raw materials of the waxy anti-fouling matte glaze evenly, add sodium carboxymethyl cellulose, sodium hexametaphosphate and water, ball mill, and sieve to obtain the waxy anti-fouling matte glaze; Specifically, by mass percentage, the amount of water added is 33-50% of the dry material of the waxy antifouling matte glaze, the amount of sodium carboxymethyl cellulose added is 0.4-0.6% of the dry material of the waxy antifouling matte glaze, and the amount of sodium hexametaphosphate added is 0.4-0.8% of the dry material of the waxy antifouling matte glaze.

[0050] This technical solution also proposes a method for preparing waxy anti-fouling matte glaze, which is simple in steps, easy to operate, and helps to ensure the relevant performance of waxy anti-fouling matte glaze during the preparation process.

[0051] To further explain, in step B1, the calcination temperature curve of the crystalline frit is as follows: It takes 1.5 to 3 hours to heat the temperature from room temperature to 300°C. The temperature rises from 300℃ to 1530℃, taking 1.5 to 2.5 hours. 1530℃, keep warm for 0.5 to 1 hour.

[0052] This technical solution limits the calcination temperature curve of the crystalline frit, aiming to ensure the full decomposition and melting of components such as kaolin and potassium feldspar in the raw materials by strictly controlling the heating rate and high-temperature holding time. This promotes the complete decomposition and gas release of carbonates such as calcite and dolomite, avoiding residual bubbles. At the same time, it allows highly active components such as zinc oxide and calcium feldspar powder to fully diffuse and homogenize in the melt, forming a highly uniform and defect-free glass phase and nano-sized calcium feldspar microcrystals, thereby ensuring the performance of the waxy anti-fouling matte glaze.

[0053] To further explain, in step C, the calcination temperature is 1100–1250°C, and the calcination time is 45–60 min.

[0054] This technical solution optimizes the calcination curve, which helps ensure the performance of the resulting matte antique-style brick semi-finished product, thereby ensuring the performance of the hydrophobic matte antique-style brick. Furthermore, the firing conditions used in this solution—a firing temperature of 1100–1250℃ and a firing time of 45–60 minutes—match the existing firing conditions for antique-style bricks, eliminating the need to change existing firing conditions and thus saving costs.

[0055] A hydrophobic matte antique-style tile is prepared using the above-mentioned method for preparing hydrophobic matte antique-style tiles. The static contact angle of the hydrophobic matte antique-style tile without soaking in boiling water is 135-150°, and the static contact angle after soaking in boiling water for 30 days is 120-130°. The gloss is 12-18°, the stain resistance is level 5, the Mohs hardness is level 7, and the abrasion resistance is ≥4 (2100 revolutions).

[0056] This technical solution also proposes a hydrophobic matte antique tile with a static contact angle of 135-150° before being soaked in boiling water, and a static contact angle of 120-130° after being soaked in boiling water for 30 days. The gloss is 12-18°, the stain resistance is level 5, the Mohs hardness is level 7, and the abrasion resistance is ≥4 (2100 revolutions). This allows the resulting hydrophobic matte antique tile to have a matte texture and a waxy, silky feel, while also possessing excellent and long-lasting hydrophobic self-cleaning properties, as well as high stain resistance, hardness, and abrasion resistance.

[0057] The technical solution of the present invention will be further illustrated below through specific embodiments.

[0058] Performance testing Waxy smooth feel: Experience the touch of the hydrophobic matte antique tile glaze with your hands.

[0059] Gloss: The gloss of the soft-polished bricks was tested using an LS191 ceramic gloss meter, and the test was performed in parallel 5 times. The average value of the 5 tests was taken.

[0060] Static contact angle before immersion: The static contact angle of the antique bricks before immersion in boiling water was tested according to the test method of "GB / T 30447-2013 Method for measuring contact angle of nanofilm".

[0061] Static contact angle after soaking: The static contact angle of the antique bricks after soaking in boiling water for 30 days was tested according to the test method of "GB / T 30447-2013 Method for measuring contact angle of nanofilm".

[0062] Stain resistance: The stain resistance of the glaze of the product was tested using the test method of GB / T3810.14-2016 "Test Methods for Ceramic Tiles Part 14: Determination of Stain Resistance - Building Materials Standard", with green dye in light oil as the staining agent.

[0063] Abrasion resistance: The abrasion resistance of the glaze surface of the product was tested using the test method of GB / T3810.7-2016 Test Methods for Ceramic Tiles Part 7: Determination of Abrasion Resistance of Glazed Tiles Surface.

[0064] Mohs hardness: The Mohs hardness of the brick surface was tested according to the European standard EN15771:2010.

[0065] Example 1 A. Prepare ceramic blanks, press the ceramic blanks, and dry them to obtain the blank layer; B. Apply a waxy anti-fouling matte glaze to the surface of the body layer to obtain a waxy anti-fouling matte glaze layer. The waxy anti-fouling matte glaze comprises the following raw materials by mass: 8 parts kaolin, 8 parts calcined kaolin, 6 parts quartz, 28 parts potassium feldspar, 10 parts sodium feldspar, 8 parts wollastonite, 3 parts zinc oxide, 8 parts strontium carbonate, 8 parts barium carbonate, and 13 parts crystalline frit. The crystalline frit comprises the following raw materials by mass: 27 parts kaolin, 4 parts calcined alumina, 27 parts calcite, 1 part dolomite, 7 parts zinc oxide, 29 parts potassium feldspar, 1 part barium carbonate, and 4 parts calcium feldspar powder with a particle size of 30 μm. The preparation method of waxy anti-fouling matte glaze includes the following steps: B1. The raw materials for the crystalline frit are mixed evenly and then subjected to calcination, water quenching and crushing in sequence to obtain the crystalline frit; B2. After uniformly mixing the raw materials of the waxy anti-fouling matte glaze, add sodium carboxymethyl cellulose, sodium hexametaphosphate and water, ball mill, and sieve to obtain the waxy anti-fouling matte glaze; wherein, according to the mass percentage, the amount of water added is 40% of the dry material of the waxy anti-fouling matte glaze, the amount of sodium carboxymethyl cellulose added is 0.5% of the dry material of the waxy anti-fouling matte glaze, and the amount of sodium hexametaphosphate added is 0.6% of the dry material of the waxy anti-fouling matte glaze; The calcination temperature curve of the crystalline frit is as follows: from room temperature to 300℃, it takes 2 hours; from 300℃ to 1530℃, it takes 2.5 hours; and at 1530℃, it is held for 1 hour. C. After drying, the bricks are fired in a kiln to obtain a semi-finished matte antique brick; the firing temperature is 1200℃ and the firing time is 50min. D. The semi-finished matte antique brick is soaked in the etching hydrophobic solution for 3 hours, then removed and dried to obtain the hydrophobic matte antique brick. The etching hydrophobic solution, calculated by mass, comprises 100 parts of perfluorosulfonic acid resin (manufactured by Guangdong Wengjiang Chemical Reagent Co., Ltd., model PA06988), 200 parts of dimethyl sulfoxide, 300 parts of dimethylhexamethylene amide, 500 parts of N-methylpyrrolidone, and 0.5 parts of ammonium fluoride. The preparation method of the etching hydrophobic solution is as follows: Under a nitrogen atmosphere, the perfluorosulfonic acid resin is added to the solvent, stirred at 200℃ for 6 hours, and then cooled to room temperature to obtain a mixed solution. Ammonium fluoride is added to the mixed solution, stirred at room temperature for 0.5 hours, and the pH value is adjusted to 6.5 to obtain the etching hydrophobic solution.

[0066] Example 2 A. Prepare ceramic blanks, press the ceramic blanks, and dry them to obtain the blank layer; B. Apply a waxy anti-fouling matte glaze to the surface of the body layer to obtain a waxy anti-fouling matte glaze layer. The waxy anti-fouling matte glaze comprises the following raw materials by weight: 10 parts kaolin, 10 parts calcined kaolin, 4 parts quartz, 25 parts potassium feldspar, 5 parts sodium feldspar, 10 parts wollastonite, 1 part zinc oxide, 5 parts strontium carbonate, 12 parts barium carbonate, and 20 parts crystalline frit. The crystalline frit comprises the following raw materials by weight: 30 parts kaolin, 8 parts calcined alumina, 20 parts calcite, 2 parts dolomite, 5 parts zinc oxide, 25 parts potassium feldspar, 2 parts barium carbonate, and 2 parts calcium feldspar powder with a particle size of 10 μm. The preparation method of waxy anti-fouling matte glaze includes the following steps: B1. The raw materials for the crystalline frit are mixed evenly and then subjected to calcination, water quenching and crushing in sequence to obtain the crystalline frit; B2. After uniformly mixing the raw materials of the waxy anti-fouling matte glaze, add sodium carboxymethyl cellulose, sodium hexametaphosphate and water, ball mill, and sieve to obtain the waxy anti-fouling matte glaze; wherein, according to the mass percentage, the amount of water added is 33% of the dry material of the waxy anti-fouling matte glaze, the amount of sodium carboxymethyl cellulose added is 0.6% of the dry material of the waxy anti-fouling matte glaze, and the amount of sodium hexametaphosphate added is 0.4% of the dry material of the waxy anti-fouling matte glaze; The calcination temperature curve of the crystalline frit is as follows: from room temperature to 300℃, it takes 3 hours; from 300℃ to 1530℃, it takes 1.5 hours; and at 1530℃, it is held for 1 hour. C. After drying, the bricks are fired in a kiln to obtain a semi-finished matte antique brick; the firing temperature is 1250℃ and the firing time is 45min. D. The semi-finished matte antique brick is soaked in an etching hydrophobic solution for 5 hours, then removed and dried to obtain a hydrophobic matte antique brick. The etching hydrophobic solution, calculated by mass, comprises 80 parts of perfluorosulfonic acid resin (manufactured by Guangdong Wengjiang Chemical Reagent Co., Ltd., model PA06988), 250 parts of dimethyl sulfoxide, 200 parts of dimethylhexamethylene amide, 600 parts of N-methylpyrrolidone, and 1 part of ammonium fluoride. The preparation method of the etching hydrophobic solution is as follows: under an argon atmosphere, the perfluorosulfonic acid resin is added to a solvent, stirred at 150°C for 8 hours, and then cooled to room temperature to obtain a mixed solution. Ammonium fluoride is added to the mixed solution, stirred at room temperature for 0.8 hours, and the pH value is adjusted to 6 to obtain the etching hydrophobic solution.

[0067] Example 3 A. Prepare ceramic blanks, press the ceramic blanks, and dry them to obtain the blank layer; B. Apply a waxy anti-fouling matte glaze to the surface of the body layer to obtain a waxy anti-fouling matte glaze layer. The waxy anti-fouling matte glaze comprises the following raw materials by weight: 7 parts kaolin, 15 parts calcined kaolin, 8 parts quartz, 20 parts potassium feldspar, 15 parts sodium feldspar, 5 parts wollastonite, 5 parts zinc oxide, 10 parts strontium carbonate, 5 parts barium carbonate, and 10 parts crystalline frit. The crystalline frit comprises the following raw materials by weight: 25 parts kaolin, 6 parts calcined alumina, 33 parts calcite, 3 parts dolomite, 10 parts zinc oxide, 35 parts potassium feldspar, 0.5 parts barium carbonate, and 5 parts calcium feldspar powder with a particle size of 50 μm. The preparation method of waxy anti-fouling matte glaze includes the following steps: B1. The raw materials for the crystalline frit are mixed evenly and then subjected to calcination, water quenching and crushing in sequence to obtain the crystalline frit; B2. After uniformly mixing the raw materials of the waxy anti-fouling matte glaze, add sodium carboxymethyl cellulose, sodium hexametaphosphate and water, ball mill, and sieve to obtain the waxy anti-fouling matte glaze; wherein, according to the mass percentage, the amount of water added is 50% of the dry material of the waxy anti-fouling matte glaze, the amount of sodium carboxymethyl cellulose added is 0.4% of the dry material of the waxy anti-fouling matte glaze, and the amount of sodium hexametaphosphate added is 0.6% of the dry material of the waxy anti-fouling matte glaze; The calcination temperature curve of the crystalline frit is as follows: from room temperature to 300℃, it takes 1.5 hours; from 300℃ to 1530℃, it takes 2 hours; and at 1530℃, it is held for 0.8 hours. C. After drying, the bricks are fired in a kiln to obtain a semi-finished matte antique brick product; the firing temperature is 1100℃ and the firing time is 60min. D. The semi-finished matte antique brick is soaked in an etching hydrophobic solution for 2 hours, then removed and dried to obtain a hydrophobic matte antique brick. The etching hydrophobic solution, calculated by mass, comprises 120 parts of perfluorosulfonic acid resin (manufactured by Guangdong Wengjiang Chemical Reagent Co., Ltd., model PA06988), 150 parts of dimethyl sulfoxide, 400 parts of dimethylhexamethylene amide, 400 parts of N-methylpyrrolidone, and 2 parts of ammonium fluoride. The preparation method of the etching hydrophobic solution is as follows: under a nitrogen atmosphere, the perfluorosulfonic acid resin is added to a solvent, stirred at 250°C for 4 hours, and then cooled to room temperature to obtain a mixed solution. Ammonium fluoride is added to the mixed solution, stirred at room temperature for 1 hour, and the pH value is adjusted to 6.9 to obtain the etching hydrophobic solution.

[0068] Comparative Example 1 Comparative Example 1: The hydrophobic matte antique-style brick includes an antique-style brick substrate and a hydrophobic self-cleaning coating distributed from bottom to top; the hydrophobic self-cleaning coating is obtained by curing a hydrophobic self-cleaning nano-composite ceramic coating of model YC-8703 from Youcai (Guangzhou) New Materials Co., Ltd.

[0069] Comparative Example 2 Comparative Example 2 was prepared using the same method and raw materials as Example 1, except that no calcium feldspar powder was added to the crystalline frit of Comparative Example 2.

[0070] Comparative Example 3 Comparative Example 3 uses the same preparation method and raw materials as Example 1, except that step D is not included in Comparative Example 3.

[0071] Comparative Example 4 Comparative Example 4 uses the same preparation method and raw materials as Example 1, except that step B is not included in Comparative Example 4.

[0072] The hydrophobic matte antique-style tiles prepared in the examples and comparative examples were subjected to performance tests, and the results are shown in Table 1 below.

[0073] Table 1. Performance test results of hydrophobic matte antique-style tiles in the examples and comparative examples.

[0074] As shown in Table 1, the hydrophobic matte antique bricks prepared using this technical solution have a static contact angle of 135-150° without being soaked in boiling water, and a static contact angle of 120-130° after being soaked in boiling water for 30 days. The gloss is 12-18°, the stain resistance is level 5, the Mohs hardness is level 7, and the abrasion resistance is ≥4 (2100 revolutions). This allows the obtained hydrophobic matte antique bricks to not only have a matte texture and a waxy silky feel, but also excellent and long-lasting hydrophobic self-cleaning properties, as well as high stain resistance, hardness, and abrasion resistance.

[0075] In Comparative Example 1, a hydrophobic self-cleaning coating was applied to the surface of the antique-style brick substrate to obtain a hydrophobic matte antique-style brick. While the resulting antique-style brick had a large static contact angle with water before immersion, exhibiting good hydrophobic self-cleaning properties, the poor aging resistance of the hydrophobic self-cleaning coating and its limited adhesion to the brick surface caused the coating to peel off after immersion. This resulted in poor durability of the hydrophobic self-cleaning properties, and the static contact angle after immersion could not be measured. Furthermore, the hydrophobic self-cleaning coating in Comparative Example 1 lacked a matte finish and a waxy, silky feel, resulting in an antique-style brick that also lacked these qualities. Additionally, due to the inherent characteristics of the hydrophobic self-cleaning coating, the resulting antique-style brick exhibited insufficient stain resistance, hardness, and abrasion resistance.

[0076] Comparative Example 2: Because no calcium feldspar powder was added to the crystalline frit, the calcium feldspar crystals generated during the calcination of the crystalline frit were too large, resulting in excessive roughness of the glaze surface, which affected the matte texture, the waxy silky feel, the hydrophobic self-cleaning properties, and the anti-fouling performance.

[0077] Comparative Example 3, due to the omission of step D, resulted in a decrease in the hydrophobic self-cleaning properties of the resulting antique-style tiles. It should be noted that stain resistance refers to the glaze's ability, thanks to its high density and smoothness, to effectively resist the penetration and adhesion of contaminants such as oil. Hydrophobic self-cleaning, on the other hand, stems from the hydrophobic effect of the glaze, allowing it to automatically remove surface dust and soluble impurities through the rolling of water. It is worth noting that even if the glaze itself has poor physical stain resistance, as long as it possesses hydrophobic properties, it can still achieve self-cleaning properties against water droplets and water-soluble stains.

[0078] In Comparative Example 4, the performance of the waxy anti-fouling matte glaze was not fully utilized due to the absence of step B. As a result, the antique-style tiles did not have a matte texture or a waxy silky feel, and their hydrophobic self-cleaning properties, stain resistance, hardness, and wear resistance were all reduced.

[0079] 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 hydrophobic matte antique-style bricks, 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 a waxy anti-fouling matte glaze to the surface of the body layer to obtain a waxy anti-fouling matte glaze layer; According to the mass fraction, the waxy anti-fouling matte glaze comprises the following raw materials: 7-10 parts kaolin, 6-15 parts calcined kaolin, 4-8 parts quartz, 20-30 parts potassium feldspar, 5-15 parts sodium feldspar, 5-10 parts wollastonite, 1-5 parts zinc oxide, 5-10 parts strontium carbonate, 5-12 parts barium carbonate, and 10-20 parts crystalline frit; According to the mass fractions, the crystalline frit comprises the following raw materials: 25-35 parts kaolin, 3-8 parts calcined alumina, 20-35 parts calcite, 0.5-3 parts dolomite, 5-10 parts zinc oxide, 25-35 parts potassium feldspar, 0.5-3 parts barium carbonate, and 1-5 parts calcium feldspar powder; C. After drying, the bricks are fired in a kiln to obtain matte antique-style brick semi-finished products. D. Immerse the semi-finished matte antique brick in an etching hydrophobic solution, take it out and dry it to obtain hydrophobic matte antique brick. The raw materials of the etching hydrophobic solution include perfluorosulfonic acid resin, solvent and ammonium fluoride, and the pH value of the etching hydrophobic solution is 6 to 6.

9.

2. The method for preparing a hydrophobic matte antique-style brick according to claim 1, characterized in that, In step D, the solvent includes dimethyl sulfoxide, dimethylhexamethyleneamide, and N-methylpyrrolidone; The raw materials for the etching hydrophobic solution, calculated by mass, include 80-120 parts of perfluorosulfonic acid resin, 150-250 parts of dimethyl sulfoxide, 200-400 parts of dimethylhexamethylene amide, 400-600 parts of N-methylpyrrolidone, and 0.5-2 parts of ammonium fluoride.

3. The method for preparing a hydrophobic matte antique-style brick according to claim 1, characterized in that, In step D, the method for preparing the etching hydrophobic solution is as follows: Under an inert atmosphere, perfluorosulfonic acid resin is added to a solvent, stirred at 150–250°C for 4–8 hours, and then cooled to room temperature to obtain a mixed solution. Ammonium fluoride was added to the mixed solution, stirred at room temperature for 0.5–1 h, and the pH was adjusted to 6–6.9 to obtain the etching hydrophobic solution.

4. The method for preparing a hydrophobic matte antique-style brick according to claim 1, characterized in that, In step D, the soaking time is 1 to 5 hours.

5. The method for preparing a hydrophobic matte antique-style brick according to claim 1, characterized in that, In step B, the particle size of the anorthite powder is 10–50 μm.

6. The method for preparing a hydrophobic matte antique-style brick according to claim 1, characterized in that, In step B, the waxy anti-fouling matte glaze, calculated by mass, comprises the following raw materials: 8 parts kaolin, 8 parts calcined kaolin, 6 parts quartz, 28 parts potassium feldspar, 10 parts sodium feldspar, 8 parts wollastonite, 3 parts zinc oxide, 8 parts strontium carbonate, 8 parts barium carbonate, and 13 parts crystalline frit. According to the mass fractions, the crystalline frit comprises the following raw materials: 27 parts kaolin, 4 parts calcined alumina, 27 parts calcite, 1 part dolomite, 7 parts zinc oxide, 29 parts potassium feldspar, 1 part barium carbonate, and 4 parts calcium feldspar powder.

7. The method for preparing a hydrophobic matte antique-style brick according to claim 1, characterized in that, In step B, the preparation method of the waxy anti-fouling matte glaze includes the following steps: B1. The raw materials for the crystalline frit are mixed evenly and then subjected to calcination, water quenching and crushing in sequence to obtain the crystalline frit; B2. After mixing the raw materials of the waxy anti-fouling matte glaze evenly, add sodium carboxymethyl cellulose, sodium hexametaphosphate and water, ball mill, and sieve to obtain the waxy anti-fouling matte glaze; Specifically, by mass percentage, the amount of water added is 33-50% of the dry material of the waxy antifouling matte glaze, the amount of sodium carboxymethyl cellulose added is 0.4-0.6% of the dry material of the waxy antifouling matte glaze, and the amount of sodium hexametaphosphate added is 0.4-0.8% of the dry material of the waxy antifouling matte glaze.

8. The method for preparing a hydrophobic matte antique-style brick according to claim 7, characterized in that, In step B1, the calcination temperature curve of the crystalline ingot is as follows: It takes 1.5 to 3 hours to heat the temperature from room temperature to 300°C. The temperature rises from 300℃ to 1530℃, taking 1.5 to 2.5 hours. 1530℃, keep warm for 0.5 to 1 hour.

9. The method for preparing a hydrophobic matte antique-style brick according to claim 1, characterized in that, In step C, the calcination temperature is 1100–1250°C, and the calcination time is 45–60 min.

10. A hydrophobic matte antique-style tile, characterized in that: The hydrophobic matte antique-style tile is prepared using the preparation method of any one of claims 1 to 9. The static contact angle of the hydrophobic matte antique-style tile without soaking in boiling water is 135 to 150°, and the static contact angle after soaking in boiling water for 30 days is 120 to 130°. The gloss is 12 to 18°, the stain resistance is level 5, the Mohs hardness is level 7, and the wear resistance is ≥ level 4 (2100 revolutions).

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