Archaized brick with antiskid and antifouling functions and preparation method of archaized brick
By using a combination of coarse and fine anti-slip dry particles, optimizing shear rate and dispersant in antique-style bricks, a uniformly dispersed anti-slip and anti-fouling glaze is formed. During the firing process, a continuous glaze glass phase is formed, which solves the problem of uneven anti-slip and anti-fouling performance of antique-style bricks, and achieves uniform anti-slip performance and durable anti-fouling performance.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- FOSHAN DONGPENG CERAMIC
- Filing Date
- 2026-02-12
- Publication Date
- 2026-05-01
AI Technical Summary
Existing antique-style bricks are difficult to achieve effective and uniform anti-slip performance and effective and uniform anti-fouling performance. In the existing technology, the anti-slip dry particles are prone to breakage or agglomeration during ball milling, resulting in decreased anti-slip performance and uneven anti-fouling performance.
By combining coarse and fine anti-slip dry granules, and optimizing the moisture content and shear rate, sodium polyacrylate and sodium carboxymethyl cellulose are used as dispersants to form a uniformly dispersed anti-slip and anti-fouling glaze. During the calcination process, the glaze surface glass phase is formed by encapsulating the frit and fluxing frit, sealing the interface between the anti-slip dry granules and the glass phase, as well as the micropores inside the glaze layer.
It achieves strong mechanical interlocking and drainage channels in both dry and wet conditions for antique-style bricks, ensuring uniformity and durability of anti-slip performance, while completely blocking stain penetration and providing excellent stain resistance.
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Abstract
Description
Technical Field
[0001] This invention relates to the field of building ceramics technology, and in particular to an antique-style brick with anti-slip and anti-fouling functions and its preparation method. Background Technology
[0002] Antique-style tiles, 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 spaces, and cultural tourism scenic spots. With the development of technology and the improvement of people's living standards, people have higher and higher requirements for the quality of life, which means that in addition to stain resistance, antique-style tiles are also expected to have a certain degree of slip resistance.
[0003] To achieve both slip resistance and stain resistance in antique-style tiles, current techniques commonly involve introducing anti-slip dry granules into a matte protective glaze. After sintering, the presence of these dry granules creates an undulating glaze surface. This undulation, combined with the mechanical interlocking action between the glaze and the sole of a shoe under pressure, achieves the slip resistance. The matte protective glaze fully melts to form a continuous, non-porous, dense glassy phase. This glassy phase encapsulates the anti-slip dry granules, filling grain boundary voids and strengthening the bond between crystal particles, thus blocking the penetration channels of stains and giving the antique-style tiles their stain-resistant properties, resulting in slip-resistant and stain-resistant antique-style tiles. The main methods for introducing anti-slip dry granules into the matte protective glaze include the following two: (1) Ball milling and blending method: This process involves adding anti-slip dry particles with a high firing temperature to a matte protective glaze and then ball milling them to obtain an anti-slip and anti-fouling glaze. However, this process can easily cause the anti-slip dry particles (especially those with small particle sizes) to break during the ball milling process, causing them to lose the microscopic rough structure and edges required to provide effective anti-slip properties, resulting in a decrease in anti-slip performance. At the same time, the broken anti-slip dry particles (high melting point components) are mixed into the matte protective glaze (low melting point matrix), and as a high melting point heterogeneous component, the broken anti-slip dry particles can easily increase the overall initial melting temperature and firing temperature of the anti-slip and anti-fouling glaze. This means that at the original firing temperature, the anti-slip and anti-fouling glaze cannot fully melt and vitrify, resulting in incomplete firing (i.e., underfiring). Consequently, the glaze surface fails to form a dense and non-porous glassy structure, resulting in a large number of micropores and defects. Ultimately, stains (such as ink, soy sauce, and tea stains) can easily penetrate into the glaze layer through these pores and cannot be removed by regular cleaning, resulting in permanent stains and a decrease in anti-fouling performance. It should be noted that the matte protective glaze (low-melting-point matrix) constitutes the majority of the volume of the glaze layer obtained from firing the anti-slip and anti-fouling glaze, forming the main body of the continuous glassy phase. The anti-slip dry granules are a functional additive designed to maintain their granular form or not fully melt at the firing temperature of the matte protective glaze to provide the micro-protrusion structure required for anti-slip properties. Therefore, the original firing temperature mainly refers to the firing temperature of the "matte protective glaze (low-melting-point matrix)" in the anti-slip and anti-fouling glaze.
[0004] (2) Simple stirring method: This process mixes anti-slip dry granules into the matte protective glaze through mechanical stirring to obtain an anti-slip and anti-fouling glaze. Although this process can avoid damage to the anti-slip dry granules, the large specific surface area of the fine anti-slip dry granules makes them prone to agglomeration. At the same time, the coarse and fine anti-slip dry granules are prone to segregation due to differences in settling rates, making it difficult to achieve uniform and stable dispersion of anti-slip dry granules of different sizes in the matte protective glaze. Agglomeration and sedimentation segregation of anti-slip dry granules easily occur, resulting in uneven distribution, local aggregation, or scarcity of anti-slip dry granules on the tile surface after glazing. As a result, the anti-slip performance not only exhibits patchy differences and instability, but also affects the uniformity of the anti-slip and anti-fouling glaze's coating and melting due to uneven anti-slip distribution, leading to inconsistent local microstructures on the glaze surface and huge differences in anti-fouling performance in different areas of the tile surface, resulting in uneven anti-fouling performance.
[0005] Therefore, existing antique-style bricks generally suffer from difficulty in achieving effective and uniform anti-slip performance and effective and uniform anti-fouling performance. Summary of the Invention
[0006] The purpose of this invention is to propose an antique-style brick with anti-slip and anti-fouling functions and its preparation method. While making the antique-style brick have effective and uniform anti-slip properties, it also has effective and uniform anti-fouling properties, so as to overcome the shortcomings of the prior art.
[0007] To achieve this objective, the present invention adopts the following technical solution: A method for preparing antique-style bricks with anti-slip and anti-fouling functions includes the following steps: A. According to the mass fractions, mix 25-35 parts of the coating frit, 15-25 parts of the fluxing frit, 8-12 parts of the washed kaolin, 10-15 parts of the quartz powder, 3-6 parts of the zinc oxide, 4-8 parts of the barium carbonate and 5-10 parts of the zirconium silicate evenly to obtain the dry protective glaze. Sodium carboxymethyl cellulose, sodium polyacrylate, and water are added to the dry protective glaze and then ball-milled to obtain the protective glaze; wherein, the water content in the protective glaze is 28-35% by mass percentage. B. Shear the protective glaze at a shearing speed of 1200-1500 rpm, and add coarse anti-slip dry granules during the shearing process. After the coarse anti-slip dry granules are added, continue shearing at a constant speed for 15-30 minutes to obtain the first intermediate slurry. Add fine anti-slip dry granules to the first intermediate slurry under constant speed shearing. After the fine anti-slip dry granules are added, continue constant speed shearing for 10 to 20 minutes to obtain the second intermediate slurry. Wherein, the mesh count of the fine anti-slip dry granules is greater than that of the coarse anti-slip dry granules; The shearing speed of the second intermediate slurry was reduced to 400-500 rpm, and shearing was continued at the reduced shearing speed for 15-30 minutes to obtain the anti-slip and anti-fouling glaze. C. Apply anti-slip and anti-fouling glaze to the surface of the body layer to form an anti-slip and anti-fouling glaze layer. After drying, it is fired in a kiln to obtain an antique-style brick with anti-slip and anti-fouling functions.
[0008] Further, in step A, the chemical composition of the encapsulated molten block, calculated by mass percentage, includes 30-40% SiO2, 8-12% Al2O3, 8-12% B2O3, 3-5% K2O, 3-5% Na2O, 8-12% CaO, 2-3% MgO, and 3-6% ZrO2, with the remainder being loss on ignition.
[0009] Further, in step A, the chemical composition of the fluxing block, calculated by mass percentage, includes 25-30% SiO2, 2-5% Al2O3, 20-30% CaO, 15-25% ZnO, 0-4% BaO, and 0-4% SrO, with the remainder being loss on ignition.
[0010] Furthermore, in step A, the quartz powder has a mesh size of 300 to 325.
[0011] Furthermore, in step A, the water content in the protective glaze is 30-32% by mass percentage.
[0012] Further, in step A, the content of sodium carboxymethyl cellulose in the protective glaze is calculated as 0.2-0.4% by mass percentage.
[0013] Further, in step A, the content of sodium polyacrylate in the protective glaze is calculated as 0.1-0.5% by mass percentage.
[0014] Further, in step B, the coarse anti-slip dry granules have a mesh size of 80-150 mesh, and the fine anti-slip dry granules have a mesh size of 200-325 mesh; Calculated by mass percentage, the amount of coarse anti-slip dry particles added is 10-20% of the amount of protective glaze dry material added, and the amount of fine anti-slip dry particles added is 3-10% of the amount of protective glaze dry material added.
[0015] Further, in step B, the coarse anti-slip dry granules have a mesh size of 125, and the fine anti-slip dry granules have a mesh size of 300. Based on mass percentage, the amount of coarse anti-slip dry granules added is 14% of the amount of protective glaze dry material added, and the amount of fine anti-slip dry granules added is 6% of the amount of protective glaze dry material added.
[0016] An antique-style brick with anti-slip and anti-fouling functions is prepared using the above-mentioned method for preparing antique-style bricks with anti-slip and anti-fouling functions.
[0017] The technical solution provided by this invention may include the following beneficial effects: 1. This technical solution uses a combination of coarse and fine anti-slip granules. The coarse granules serve as the main load-bearing framework, providing macroscopic protrusions to ensure strong mechanical interlocking and drainage channels in both dry and wet conditions, thus establishing anti-slip performance. The fine granules fill the spaces between and around the coarse granules, forming a secondary rough surface that effectively improves the distribution density and uniformity of the anti-slip particles, enhancing microscopic grip under extreme wet and slippery conditions such as oil stains. The combined effect of these two components helps ensure effective anti-slip performance.
[0018] 2. This technical solution creates an operable fluid environment through optimized moisture content; the sequential addition of coarse-to-fine particles constructs a uniformly dispersed spatial arrangement; the step energy transition from high to low shear rates provides kinetic support for achieving this spatial arrangement; and sodium polyacrylate, as a highly efficient dispersant, along with the suspension system composed of washed kaolin and sodium carboxymethyl cellulose, fixes and stabilizes the spatial arrangement. These four elements work together to achieve uniform dispersion and long-term stability of the anti-slip dry particles in the anti-slip and anti-fouling glaze.
[0019] 3. The flux in the protective glaze melts first during the initial firing stage, forming a moderately viscous initial glass phase. This phase initially positions and encapsulates both coarse and fine anti-slip dry particles (i.e., anti-slip dry particles), constructing a stable initial structural framework and preventing displacement or aggregation of the anti-slip dry particles during subsequent high-temperature stages. The flux can drastically reduce the high-temperature viscosity and surface tension of the anti-slip and anti-fouling melt formed by calcining the glaze during the high-temperature stage of firing, giving it high fluidity. This allows it to fully wet, penetrate, and fill the surface micropores, interparticle gaps, and remaining micropores after the initial encapsulation by the flux. Simultaneously, zinc oxide and barium carbonate in the protective glaze formula act as powerful fluxes, synergistically lowering the melting temperature and promoting melt homogenization; quartz powder provides structural support as a network forging body; Al2O3 introduced by water-washed kaolin enhances the chemical stability and mechanical strength of the glass network; and zirconium silicate, as an opacifying and hardening component, is uniformly dispersed in the glass matrix. The combined effect of these raw materials ultimately forms a continuous, dense glaze glass phase without macroscopic pores. The combined action of these raw materials ultimately forms a continuous, dense glaze glass phase without macroscopic pores. This glaze glass phase firmly embeds the anti-slip dry particles into the glaze layer and completely seals the interface between the anti-slip dry particles and the glass phase, as well as the micropores inside the glaze layer. This completely blocks the channels for stains (such as ink, tea stains, etc.) to penetrate into the glaze layer, giving the product excellent anti-fouling properties. Detailed Implementation
[0020] This technical solution provides a method for preparing antique-style bricks with anti-slip and anti-fouling functions, including the following steps: A. According to the mass fractions, mix 25-35 parts of the coating frit, 15-25 parts of the fluxing frit, 8-12 parts of the washed kaolin, 10-15 parts of the quartz powder, 3-6 parts of the zinc oxide, 4-8 parts of the barium carbonate and 5-10 parts of the zirconium silicate evenly to obtain the dry protective glaze. Sodium carboxymethyl cellulose, sodium polyacrylate, and water are added to the dry protective glaze and then ball-milled to obtain the protective glaze; wherein, the water content in the protective glaze is 28-35% by mass percentage. B. Shear the protective glaze at a shearing speed of 1200-1500 rpm, and add coarse anti-slip dry granules during the shearing process. After the coarse anti-slip dry granules are added, continue shearing at a constant speed for 15-30 minutes to obtain the first intermediate slurry. Add fine anti-slip dry granules to the first intermediate slurry under constant speed shearing. After the fine anti-slip dry granules are added, continue constant speed shearing for 10 to 20 minutes to obtain the second intermediate slurry. Wherein, the mesh count of the fine anti-slip dry granules is greater than that of the coarse anti-slip dry granules; The shearing speed of the second intermediate slurry was reduced to 400-500 rpm, and shearing was continued at the reduced shearing speed for 15-30 minutes to obtain the anti-slip and anti-fouling glaze. C. Apply anti-slip and anti-fouling glaze to the surface of the body layer to form an anti-slip and anti-fouling glaze layer. After drying, it is fired in a kiln to obtain an antique-style brick with anti-slip and anti-fouling functions.
[0021] To address the technical problem of existing antique-style bricks failing to achieve effective and uniform anti-slip and anti-fouling properties, this technical solution proposes a method for preparing antique-style bricks with anti-slip and anti-fouling functions. The method comprises three steps: A (preparing a protective glaze), B (preparing an anti-slip and anti-fouling glaze), and C (firing in a kiln). By designing the preparation method and the raw materials for the protective glaze, this method aims to achieve both effective and uniform anti-slip and anti-fouling properties in the antique-style bricks. It should be noted that the body layer in this solution is formed by pressing and drying conventional ceramic blanks; further description of the ceramic blanks is omitted here.
[0022] Specifically, the anti-slip and anti-fouling glaze of this technical solution includes a protective glaze, coarse anti-slip dry granules, and fine anti-slip dry granules. After the anti-slip and anti-fouling glaze is fired, the coarse and fine anti-slip dry granules remain solid and together form a micro-undulating structure on the glaze surface. This micro-undulating structure can work synergistically with the mechanical interlocking effect generated by the sole of a shoe under pressure, giving the antique-style bricks anti-slip properties.
[0023] Meanwhile, this technical solution employs a combination of coarse and fine anti-slip granules. The coarse granules serve as the main load-bearing framework, providing macroscopic protrusions to ensure strong mechanical interlocking and drainage channels in both dry and wet conditions, thus establishing the anti-slip performance. The fine anti-slip granules fill the spaces between and around the coarse granules, forming a secondary rough surface that effectively improves the distribution density and uniformity of the anti-slip particles, enhancing microscopic grip under extreme wet and slippery conditions such as oil stains. The combined effect of these two components helps ensure the anti-slip performance.
[0024] Furthermore, the anti-slip dry granules can be directly added to the protective glaze without ball milling. This process avoids the breakage of the anti-slip dry granules during ball milling, thus maintaining their complete surface morphology and angular structure, ensuring the provision of the microscopic roughness characteristics required for effective anti-slip, and thus improving anti-slip performance.
[0025] Secondly, this technical solution limits the moisture content of the protective glaze to 28-35%. At this moisture content, when anti-slip dry particles (including coarse and fine anti-slip dry particles) are added to the protective glaze and sheared at a shear rate of 1200-1500 rpm, the shear energy can be effectively transferred to the anti-slip dry particles and disrupt the agglomeration between the anti-slip dry particles, especially the fine ones. Simultaneously, the aforementioned moisture content allows for the complete solubilization of water-washed kaolin and sodium carboxymethyl cellulose, forming a highly thixotropic three-dimensional gel network, providing the necessary medium for the subsequent locking of the skeleton-filler structure.
[0026] Simultaneously, in the optimized moisture content medium, coarse anti-slip dry granules are first added and dispersed by high-speed shearing. Under the action of shear force, the coarse anti-slip dry granules repel each other, forming a stable skeleton within the glaze slurry. Subsequently, fine anti-slip dry granules are added. At this time, under the action of shear force, the fine anti-slip dry granules are oriented and guided, embedding themselves in the gaps of the skeleton formed by the coarse anti-slip dry granules, achieving a spatial arrangement similar to the densest packing. The sequential addition of the coarse and fine anti-slip dry granules avoids segregation of particles of different sizes due to different settling velocities in terms of spatial arrangement, and constructs a more thermodynamically stable and less segregated particle distribution state in terms of microstructure, laying the structural foundation for uniform dispersion.
[0027] In addition, to construct the aforementioned uniformly dispersed microstructure, the technical solution simultaneously designed a stepped energy input strategy. Specifically, during the stages of adding coarse and fine anti-slip dry particles, a high-speed shearing of 1200–1500 rpm was used to provide sufficient kinetic energy to break up the agglomeration of the anti-slip dry particles, achieve monomer dispersion, and establish a strong turbulent flow field. After all the anti-slip dry particles were added, the shearing speed was reduced to 400–500 rpm, switching to gentle laminar flow stirring. The relatively low kinetic energy provided by this speed eliminated the air bubbles introduced by the previous turbulence, promoted further uniform dispersion of the anti-slip dry particles, and maintained the already formed skeleton-filling structure, ultimately obtaining a glaze slurry system with strong thixotropy and stable suspension.
[0028] Furthermore, this technical solution uses sodium polyacrylate as a highly efficient dispersant, which can quickly wet the surface of the anti-slip dry granules, break up the agglomerates formed by the anti-slip dry granules, and maintain the electrostatic repulsion between the anti-slip dry granules. Simultaneously, this technical solution also uses washed kaolin and sodium carboxymethyl cellulose as a suspension system. The washed kaolin provides permanent charge and a lamellar structure, assisting in steric stabilization. Sodium carboxymethyl cellulose, as a polymeric thickener and water-retaining agent, forms a three-dimensional thixotropic network under optimized moisture content, achieving statically stable and shear-thinning rheological behavior. This three-dimensional thixotropic network can strongly lock the completed skeleton-filled distribution of the anti-slip dry granules when stationary, preventing them from settling and re-agglomerating; it can also temporarily disintegrate during glazing shearing, ensuring process fluidity.
[0029] In summary, this technical solution creates an operable fluid environment through optimized moisture content; the sequential addition of coarse-to-fine particles constructs a uniformly dispersed spatial arrangement; the step energy transition from high to low shear rates provides kinetic support for achieving this spatial arrangement; and sodium polyacrylate, as a highly efficient dispersant, along with the suspension system composed of washed kaolin and sodium carboxymethyl cellulose, fixes and stabilizes the spatial arrangement. These four elements work together to achieve uniform dispersion and long-term stability of the anti-slip dry granules in the anti-slip and anti-fouling glaze. The uniform dispersion and long-term stability of the anti-slip dry granules in the anti-slip and anti-fouling glaze prevents instability in anti-slip performance, thus ensuring the uniformity of anti-slip performance.
[0030] Furthermore, the anti-slip and anti-fouling glaze in this technical solution includes a protective glaze, coarse anti-slip dry particles, and fine anti-slip dry particles. The raw materials of the protective glaze include encapsulated frit, fluxing frit, washed kaolin, quartz powder, zinc oxide, barium carbonate, and zirconium silicate. Among them, the encapsulated frit in the protective glaze melts first in the early stage of firing, forming a moderately viscous initial glassy phase, which initially positions and encapsulates the coarse and fine anti-slip dry particles (i.e., anti-slip dry particles), constructing a stable initial structural framework and preventing the anti-slip dry particles from shifting or agglomerating in the subsequent high-temperature stage.
[0031] Based on this, the fluxing ingot can drastically reduce the high-temperature viscosity and surface tension of the anti-slip and anti-fouling melt formed by calcining the anti-slip and anti-fouling glaze during the high-temperature stage of the calcination process, giving it high fluidity. This allows it to fully wet, penetrate, and fill the surface micropores, interparticle gaps, and remaining micropores after the initial coating by the fluxing ingot. Simultaneously, zinc oxide and barium carbonate in the protective glaze formulation act as powerful fluxing agents, synergistically lowering the melting temperature and promoting melt homogenization; quartz powder provides structural support as a network forging body; Al2O3 introduced from water-washed kaolin enhances the chemical stability and mechanical strength of the glass network; and zirconium silicate, as an opacifying and hardening component, is uniformly dispersed in the glass matrix. The combined effect of these raw materials ultimately forms a continuous, dense glaze glass phase free of macropores.
[0032] The aforementioned glaze glass phase firmly embeds the anti-slip dry particles into the glaze layer and completely seals the interface between the anti-slip dry particles and the glass phase, as well as the micropores within the glaze layer. This effectively blocks the channels for stains (such as ink and tea stains) to penetrate into the glaze layer, giving the product excellent stain resistance. It should be noted that although the glaze surface has protrusions formed by the anti-slip dry particles, these surfaces are completely covered by a smooth glaze glass phase, achieving a balance between anti-slip and stain resistance.
[0033] In this technical solution, the anti-slip dry granules are directly added to the protective glaze without ball milling, avoiding the problems of under-firing and decreased anti-fouling performance caused by ball milling, which leads to the breakage of the anti-slip dry granules and an increase in the initial melting temperature of the glaze. Furthermore, the anti-slip dry granules can be uniformly dispersed and remain stable in the anti-slip and anti-fouling glaze, ensuring the uniformity of the anti-slip and anti-fouling melt formed during firing and preventing local microstructural differences caused by uneven distribution, thus guaranteeing the uniformity of anti-fouling performance.
[0034] Finally, through the initial positioning and encapsulation of the molten ingot, and the thorough wetting and penetration of the active melt into the anti-slip dry particles during the high-temperature stage, the anti-slip and anti-fouling glaze forms a continuous, dense, and crack-free glass phase structure after firing. This structure not only strengthens the bond between the anti-slip dry particles and the glaze matrix (i.e., the protective glaze), preventing micro-cracks or peeling at the root of the anti-slip dry particles and ensuring the durability of the anti-slip effect, but also fundamentally blocks the physical pathways of stain penetration, thus contributing to long-lasting anti-fouling performance.
[0035] In addition, the quartz network in the glaze system, together with the Al2O3 introduced from the washed kaolin, forms a chemically stable and mechanically strong glass skeleton, giving the glaze excellent hardness and wear resistance. This effectively resists daily wear and tear, which helps improve the overall service reliability of the anti-slip and anti-fouling glaze layer, thereby further enhancing the durability of the stain resistance and anti-slip performance of the antique bricks.
[0036] To further explain, in step A, the chemical composition of the encapsulated molten block, calculated by mass percentage, includes 30-40% SiO2, 8-12% Al2O3, 8-12% B2O3, 3-5% K2O, 3-5% Na2O, 8-12% CaO, 2-3% MgO, and 3-6% ZrO2, with the remainder being loss on ignition.
[0037] The preferred technical solution is to add a frit containing 8-12% B2O3, 3-5% K2O, 3-5% Na2O, 8-12% CaO, and 2-3% MgO by mass percentage to the protective glaze. This facilitates the formation of a moderately viscous initial glass phase at a lower temperature, which is used for initial positioning and coating of the anti-slip dry particles.
[0038] To further explain, in step A, the chemical composition of the fluxing block, calculated by mass percentage, includes 25-30% SiO2, 2-5% Al2O3, 20-30% CaO, 15-25% ZnO, 0-4% BaO, and 0-4% SrO, with the remainder being loss on ignition.
[0039] This technical solution preferably adds a fluxing block with a CaO content of 20-30% and a ZnO content of 15-25% by mass percentage to the protective glaze, so that the sum of CaO and ZnO content is ≥35%, which is significantly higher than the sum of CaO and ZnO content in conventional glaze formulations (the sum of CaO and ZnO content in conventional glaze formulations is usually ≤20%). This allows the fluxing block to drastically reduce the surface tension of the anti-slip and anti-fouling melt during the high-temperature stage of glaze calcination, giving the anti-slip and anti-fouling melt high fluidity. It can not only fully wet, penetrate and fill the surface micropores, particle gaps and remaining micropores after the initial coating by the fluxing block, but also strengthen the bonding between the anti-slip dry particles and the glaze matrix (i.e., the protective glaze), thereby improving the anti-slip and anti-fouling performance.
[0040] To further explain, in step A, the quartz powder has a mesh size of 300 to 325.
[0041] This technical solution limits the mesh size of quartz powder to 300-325 mesh (corresponding to a particle size of approximately 45-48 micrometers). Within this particle size range, not only can quartz, as a network forger, have sufficient dissolution reactivity in the anti-slip and anti-fouling melt to promote the formation of a uniform and dense glass phase, but it can also avoid the problem of excessively high viscosity and strong thixotropy of the anti-slip and anti-fouling glaze due to excessively fine particle size, which would affect the uniformity of glazing. This helps to ensure the ease of glazing and the quality of the product.
[0042] To further explain, in step A, the water content in the protective glaze is 30-32% by mass percentage.
[0043] This technical solution limits the water content in the protective glaze to 30-32%. This water content synergizes with the suspension system formed by the combination of water-washed kaolin and sodium carboxymethyl cellulose, creating a highly thixotropic three-dimensional network structure. This three-dimensional network structure not only strongly resists the settling of anti-slip dry particles under static conditions (with a settling rate of <2%), but also rapidly thins under glaze application shear, thus simultaneously ensuring both uniform dispersion and ease of glazing.
[0044] To further explain, in step A, the content of sodium carboxymethyl cellulose in the protective glaze is 0.2-0.4% by mass percentage.
[0045] If the amount of sodium carboxymethyl cellulose added is too low, it will reduce the viscosity and suspension stability of the system, leading to sedimentation of the anti-slip dry particles, separation, or poor leveling properties. If the amount of sodium carboxymethyl cellulose added is too high, it will cause excessive thickening, deteriorating the fluidity of the glaze, reducing its workability, and may even affect the mixing uniformity and the density of the final product due to excessive viscosity. Therefore, this technical solution limits the amount of sodium carboxymethyl cellulose added to the protective glaze, which is beneficial to improving the workability and performance of sodium carboxymethyl cellulose.
[0046] To further explain, in step A, the content of sodium polyacrylate in the protective glaze is 0.1-0.5% by mass percentage.
[0047] If the amount of sodium polyacrylate added is too high, it will disrupt the thixotropic structure of the glaze, leading to increased sedimentation of the anti-slip dry particles or affecting the suspension stability of the glaze. If the amount of sodium polyacrylate added is too low, it will easily cause the anti-slip dry particles to agglomerate and the glaze to thicken. Therefore, this technical solution limits the amount of sodium polyacrylate added to the protective glaze, which is beneficial to achieving uniform dispersion and stable storage of the anti-slip and anti-fouling glaze.
[0048] To further explain, in step B, the coarse anti-slip dry granules have a mesh size of 80-150 mesh, and the fine anti-slip dry granules have a mesh size of 200-325 mesh. Calculated by mass percentage, the amount of coarse anti-slip dry particles added is 10-20% of the amount of protective glaze dry material added, and the amount of fine anti-slip dry particles added is 3-10% of the amount of protective glaze dry material added.
[0049] This technical solution limits the mesh size of coarse and fine anti-slip dry granules, as well as the amount of coarse and fine anti-slip dry granules added. The coarser granules serve as the main framework, providing the primary macroscopic protrusions and mechanical interlocking to ensure a basic anti-slip level. The finer granules fill the gaps between the coarse granules, increasing micro-roughness to enhance wet-state anti-slip capability and optimizing particle packing density to reduce glaze defects. This helps to avoid problems such as difficulty in bonding the anti-slip and anti-fouling glaze, non-dense glaze, and easy granule detachment caused by excessive total amount of anti-slip dry granules or improper particle size distribution, while ensuring anti-slip performance. Ultimately, it achieves a balance between anti-slip properties, glaze bonding strength, and anti-fouling properties.
[0050] To further explain, in step B, the coarse anti-slip dry granules have a mesh size of 125, and the fine anti-slip dry granules have a mesh size of 300. Based on mass percentage, the amount of coarse anti-slip dry granules added is 14% of the amount of protective glaze dry material added, and the amount of fine anti-slip dry granules added is 6% of the amount of protective glaze dry material added.
[0051] This technical solution further limits the mesh size of coarse anti-slip dry granules, the mesh size of fine anti-slip dry granules, the amount of coarse anti-slip dry granules added, and the amount of fine anti-slip dry granules added, which helps to ensure anti-fouling and anti-slip performance.
[0052] An antique-style brick with anti-slip and anti-fouling functions is prepared using the above-mentioned method for preparing antique-style bricks with anti-slip and anti-fouling functions.
[0053] This technical solution also proposes an antique brick with anti-slip and anti-fouling functions prepared by the above-mentioned method for preparing antique bricks with anti-slip and anti-fouling functions. This method is beneficial to ensure that the antique bricks have effective and uniform anti-slip performance as well as effective and uniform anti-fouling performance.
[0054] The technical solution of the present invention will be further illustrated below through specific embodiments.
[0055] Performance testing: Stain resistance: Take at least 10 antique-style tiles from the same batch, and select a test point in the central area of each tile. According to the test method in GB / T3810.14-2016 "Test Methods for Ceramic Tiles Part 14: Determination of Stain Resistance (Building Materials Standard)," use a green dye in light oil as the staining agent to test the stain resistance of each antique-style tile's test point. If the stain resistance of all test points on the antique-style tiles is level 5, then the stain resistance performance is qualified.
[0056] Anti-slip performance: Take at least 10 antique-style tiles from the same batch, and select a test point in the central area of each tile. Test the coefficient of friction at the test point of each tile according to GB / T 4100-2015 "Ceramic Tiles" (Appendix M). If the wet static friction coefficient of all test points of the antique-style tiles is ≥0.75 and the dry static friction coefficient is ≥0.84, then the anti-slip performance is qualified.
[0057] Stain resistance uniformity: Take at least 3 antique-style tiles from the same batch, and select 5 test points (center and four corners) for each tile. Test the stain resistance of the antique-style tiles at each test point according to the test method in GB / T3810.14-2016 "Test Methods for Ceramic Tiles Part 14: Determination of Stain Resistance (Building Materials Standard)". Use a green dye in light oil as the staining agent. Record the stain resistance level of all test points and calculate the level difference (level difference = highest level - lowest level). If the stain resistance level of all test points is 5 and the grade is 0, then the stain resistance uniformity is qualified.
[0058] Anti-slip uniformity: Take at least 3 antique tiles from the same batch, and select 5 test points at the center and four corners of each antique tile; test the dry and wet static friction coefficients at each test point according to GB / T 4100-2015 "Ceramic Tiles" (Appendix M), record the measured values of all test points, and calculate the overall average value (μ) and standard deviation (σ). If the following conditions are met simultaneously: (1) the wet static friction coefficient of all test points is ≥0.75 and the dry static friction coefficient is ≥0.84; (2) the deviation of the measured value of each test point from the overall average value μ does not exceed ±10%, then the anti-slip uniformity is qualified.
[0059] In the embodiments and comparative examples of the present invention, the chemical composition of the encapsulated molten ingot, calculated by mass percentage, includes 38% SiO2, 12% Al2O3, 10% B2O3, 5% K2O, 4% Na2O, 12% CaO, 3% MgO, and 25% ZrO, with the remainder being loss on ignition. The chemical composition of the fluxing ingot, calculated by mass percentage, includes 28% SiO2, 35% Al2O3, 26% CaO, 22% ZnO, 2% BaO, and 4% SrO, with the remainder being loss on ignition.
[0060] Example 1 A. According to the mass fractions, mix 30 parts of the coating frit, 20 parts of the fluxing frit, 10 parts of the washed kaolin, 12 parts of the quartz powder, 4 parts of the zinc oxide, 6 parts of the barium carbonate and 8 parts of the zirconium silicate evenly to obtain the dry protective glaze. Sodium carboxymethyl cellulose, sodium polyacrylate, and water were added to the dry protective glaze and ball-milled to obtain the protective glaze. Specifically, by mass percentage, the water content in the protective glaze is 30%; the sodium carboxymethyl cellulose content is 0.3%; and the sodium polyacrylate content is 0.1%. B. The protective glaze is sheared at a shearing speed of 1500 rpm, and coarse anti-slip dry granules are added during the shearing process. After the coarse anti-slip dry granules are added, the shearing is continued at a constant speed for 20 minutes to obtain the first intermediate slurry. Fine anti-slip dry granules were added to the first intermediate slurry under constant shearing. After the fine anti-slip dry granules were added, constant shearing was continued for 15 minutes to obtain the second intermediate slurry. The shearing speed of the second intermediate slurry was reduced to 400 rpm, and shearing was continued at the reduced shearing speed for 20 minutes to obtain the anti-slip and anti-fouling glaze. The coarse anti-slip dry granules have a mesh size of 125 mesh, and the fine anti-slip dry granules have a mesh size of 300 mesh. Based on mass percentage, the amount of coarse anti-slip dry granules added is 14% of the amount of protective glaze dry material added, and the amount of fine anti-slip dry granules added is 6% of the amount of protective glaze dry material added. C. Apply anti-slip and anti-fouling glaze to the surface of the body layer to form an anti-slip and anti-fouling glaze layer. After drying, it is fired in a kiln to obtain an antique-style brick with anti-slip and anti-fouling functions.
[0061] Example 2 A. According to the mass fractions, 25 parts of the coating frit, 25 parts of the fluxing frit, 8 parts of the washed kaolin, 15 parts of the quartz powder, 3 parts of the zinc oxide, 8 parts of the barium carbonate and 6 parts of the zirconium silicate are mixed evenly to obtain the dry protective glaze. Sodium carboxymethyl cellulose, sodium polyacrylate, and water were added to the dry protective glaze and ball-milled to obtain the protective glaze. Specifically, by mass percentage, the water content in the protective glaze is 32%; the sodium carboxymethyl cellulose content in the protective glaze is 0.2%; and the sodium polyacrylate content in the protective glaze is 0.2%. B. The protective glaze is sheared at a shearing speed of 1400 rpm, and coarse anti-slip dry granules are added during the shearing process. After the coarse anti-slip dry granules are added, the shearing is continued at a constant speed for 30 minutes to obtain the first intermediate slurry. Fine anti-slip dry granules were added to the first intermediate slurry under constant shearing. After the fine anti-slip dry granules were added, constant shearing was continued for 20 minutes to obtain the second intermediate slurry. The shearing speed of the second intermediate slurry was reduced to 500 rpm, and shearing was continued at the reduced shearing speed for 15 minutes to obtain the anti-slip and anti-fouling glaze. The coarse anti-slip dry granules have a mesh size of 150 mesh, and the fine anti-slip dry granules have a mesh size of 200 mesh. Based on mass percentage, the amount of coarse anti-slip dry granules added is 10% of the amount of protective glaze dry material added, and the amount of fine anti-slip dry granules added is 5% of the amount of protective glaze dry material added. C. Apply anti-slip and anti-fouling glaze to the surface of the body layer to form an anti-slip and anti-fouling glaze layer. After drying, it is fired in a kiln to obtain an antique-style brick with anti-slip and anti-fouling functions.
[0062] Example 3 A. According to the mass fractions, mix 35 parts of the coating frit, 15 parts of the fluxing frit, 12 parts of the washed kaolin, 10 parts of the quartz powder, 6 parts of the zinc oxide, 4 parts of the barium carbonate and 8 parts of the zirconium silicate evenly to obtain the dry protective glaze. Sodium carboxymethyl cellulose, sodium polyacrylate, and water were added to the dry protective glaze and ball-milled to obtain the protective glaze. Specifically, by mass percentage, the water content in the protective glaze is 35%; the sodium carboxymethyl cellulose content is 0.4%; and the sodium polyacrylate content is 0.3%. B. Shear the protective glaze at a shearing speed of 1200 rpm, and add coarse anti-slip dry granules during the shearing process. After the coarse anti-slip dry granules are added, continue shearing at a constant speed for 30 minutes to obtain the first intermediate slurry. Fine anti-slip dry granules were added to the first intermediate slurry under constant shearing. After the fine anti-slip dry granules were added, constant shearing was continued for 20 minutes to obtain the second intermediate slurry. The shearing speed of the second intermediate slurry was reduced to 450 rpm, and shearing was continued at the reduced shearing speed for 30 minutes to obtain the anti-slip and anti-fouling glaze. The coarse anti-slip dry granules have a mesh size of 80 mesh, and the fine anti-slip dry granules have a mesh size of 325 mesh. Based on mass percentage, the amount of coarse anti-slip dry granules added is 12% of the amount of protective glaze dry material added, and the amount of fine anti-slip dry granules added is 8% of the amount of protective glaze dry material added. C. Apply anti-slip and anti-fouling glaze to the surface of the body layer to form an anti-slip and anti-fouling glaze layer. After drying, it is fired in a kiln to obtain an antique-style brick with anti-slip and anti-fouling functions.
[0063] Comparative Example 1 The preparation method and raw materials of this comparative example are the same as those of Example 1. The difference is that a simple mixing method is used to prepare the anti-slip and anti-fouling glaze in this comparative example. That is, the preparation method of the antique-style brick with anti-slip and anti-fouling functions in Comparative Example 1 is as follows: A. Mix 30 parts of the coating frit, 20 parts of the fluxing frit, 10 parts of the washed kaolin, 12 parts of the quartz powder, 4 parts of the zinc oxide, 6 parts of the barium carbonate and 8 parts of the zirconium silicate evenly to obtain the dry protective glaze. Sodium carboxymethyl cellulose, sodium polyacrylate, and water were added to the dry protective glaze and ball-milled to obtain the protective glaze. Specifically, by mass percentage, the water content in the protective glaze is 30%; the sodium carboxymethyl cellulose content is 0.3%; and the sodium polyacrylate content is 0.1%. B. After adding coarse and fine anti-slip dry particles to the protective glaze, shear it at a shearing speed of 1500 rpm for 20 minutes to obtain an anti-slip and anti-fouling glaze. The coarse anti-slip dry granules have a mesh size of 125 mesh, and the fine anti-slip dry granules have a mesh size of 300 mesh. Based on mass percentage, the amount of coarse anti-slip dry granules added is 14% of the amount of protective glaze dry material added, and the amount of fine anti-slip dry granules added is 6% of the amount of protective glaze dry material added. C. Apply anti-slip and anti-fouling glaze to the surface of the body layer to form an anti-slip and anti-fouling glaze layer. After drying, it is fired in a kiln to obtain an antique-style brick with anti-slip and anti-fouling functions.
[0064] The anti-slip and anti-fouling tiles prepared in the examples and comparative examples were subjected to performance tests, and the results are shown in Table 1 below: Table 1. Performance test results of antique-style bricks with anti-slip and anti-fouling functions in the examples and comparative examples.
[0065] As can be seen from the test data in Table 1, the antique-style bricks obtained by this technical solution have a stain resistance level of 5, a wet static friction coefficient ≥0.75, and a dry static friction coefficient ≥0.84. This is beneficial for the antique-style bricks to have both effective and uniform anti-slip performance and effective and uniform stain resistance, so as to meet the actual use requirements.
[0066] 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 antique-style bricks with anti-slip and anti-fouling functions, characterized in that, Includes the following steps: A. According to the mass fractions, mix 25-35 parts of the coating frit, 15-25 parts of the fluxing frit, 8-12 parts of the washed kaolin, 10-15 parts of the quartz powder, 3-6 parts of the zinc oxide, 4-8 parts of the barium carbonate and 5-10 parts of the zirconium silicate evenly to obtain the dry protective glaze. Sodium carboxymethyl cellulose, sodium polyacrylate, and water are added to the dry protective glaze and then ball-milled to obtain the protective glaze; wherein, the water content in the protective glaze is 28-35% by mass percentage. B. Shear the protective glaze at a shearing speed of 1200-1500 rpm, and add coarse anti-slip dry granules during the shearing process. After the coarse anti-slip dry granules are added, continue shearing at a constant speed for 15-30 minutes to obtain the first intermediate slurry. Add fine anti-slip dry granules to the first intermediate slurry under constant speed shearing. After the fine anti-slip dry granules are added, continue constant speed shearing for 10 to 20 minutes to obtain the second intermediate slurry. Wherein, the mesh count of the fine anti-slip dry granules is greater than that of the coarse anti-slip dry granules; The shearing speed of the second intermediate slurry was reduced to 400-500 rpm, and shearing was continued at the reduced shearing speed for 15-30 minutes to obtain the anti-slip and anti-fouling glaze. C. Apply anti-slip and anti-fouling glaze to the surface of the body layer to form an anti-slip and anti-fouling glaze layer. After drying, it is fired in a kiln to obtain an antique-style brick with anti-slip and anti-fouling functions.
2. The method for preparing an antique-style brick with anti-slip and anti-fouling functions according to claim 1, characterized in that, In step A, the chemical composition of the encapsulated molten block, calculated by mass percentage, includes 30-40% SiO2, 8-12% Al2O3, 8-12% B2O3, 3-5% K2O, 3-5% Na2O, 8-12% CaO, 2-3% MgO, and 3-6% ZrO2, with the remainder being loss on ignition.
3. The method for preparing an antique-style brick with anti-slip and anti-fouling functions according to claim 1, characterized in that, In step A, the chemical composition of the fluxing block, calculated by mass percentage, includes 25-30% SiO2, 2-5% Al2O3, 20-30% CaO, 15-25% ZnO, 0-4% BaO, and 0-4% SrO, with the remainder being loss on ignition.
4. The method for preparing an antique-style brick with anti-slip and anti-fouling functions according to claim 1, characterized in that, In step A, the quartz powder has a mesh size of 300 to 325.
5. The method for preparing an antique-style brick with anti-slip and anti-fouling functions according to claim 1, characterized in that, In step A, the water content in the protective glaze is 30-32% by mass percentage.
6. The method for preparing an antique-style brick with anti-slip and anti-fouling functions according to claim 1, characterized in that, In step A, the content of sodium carboxymethyl cellulose in the protective glaze is calculated as 0.2-0.4% by mass percentage.
7. The method for preparing an antique-style brick with anti-slip and anti-fouling functions according to claim 1, characterized in that, In step A, the content of sodium polyacrylate in the protective glaze is calculated as 0.1-0.5% by mass percentage.
8. The method for preparing an antique-style brick with anti-slip and anti-fouling functions according to claim 1, characterized in that, In step B, the coarse anti-slip dry granules have a mesh size of 80-150 mesh, and the fine anti-slip dry granules have a mesh size of 200-325 mesh. Calculated by mass percentage, the amount of coarse anti-slip dry particles added is 10-20% of the amount of protective glaze dry material added, and the amount of fine anti-slip dry particles added is 3-10% of the amount of protective glaze dry material added.
9. A method for preparing an antique-style brick with anti-slip and anti-fouling functions according to claim 8, characterized in that, In step B, the coarse anti-slip dry granules have a mesh size of 125, and the fine anti-slip dry granules have a mesh size of 300. Based on mass percentage, the amount of coarse anti-slip dry granules added is 14% of the amount of protective glaze dry material added, and the amount of fine anti-slip dry granules added is 6% of the amount of protective glaze dry material added.
10. An antique-style brick with anti-slip and anti-fouling functions, characterized in that, It is prepared using the method for preparing antique-style bricks with anti-slip and anti-fouling functions as described in any one of claims 1 to 9.