Anti-cutting and anti-cracking ceramic tile and preparation method thereof

Abstract

The invention belongs to the technical field of architectural ceramics, and discloses an anti-cutting and anti-cracking ceramic tile and a preparation method thereof. The anti-cutting ceramic tile sequentially comprises a green body layer, a ground glaze layer and a cover glaze layer from bottom to top, wherein the green body layer comprises the following raw material components: a basic blank, silicon carbide whiskers and white carbon black modified alumina fibers; the ground glaze layer comprises the following raw material components: basic ground glaze and composite inorganic particles, and the composite inorganic particles comprise nano silicon dioxide and niobium pentoxide; the cover glaze layer comprises the following raw material components: basic cover glaze, zirconium oxide whiskers, rare earth metal oxides and a reinforcing agent, and the reinforcing agent comprises at least one of titanium carbide, silicon carbide and carbon nanotubes. By arranging the multi-layer composite structure and adding the specific reinforcing and toughening material in each layer, the cutting stress is reduced, the reinforced particles are uniformly dispersed, the agglomeration is reduced, the local stress concentration is prevented, and the generation of cracks is reduced, so that the cutting and cracking resistance of the ceramic tile is improved.

Description

Technical Field

[0001] The invention belongs to the technical field of building ceramics, and particularly relates to a cutting-resistant ceramic tile and a preparation method thereof. Background Art

[0002] Ceramic tiles have been widely used in the construction industry due to their high chemical stability, wear resistance, and decorative properties. However, traditional ceramic tiles are primarily made from silicate minerals (such as kaolin, quartz, and feldspar). After high-temperature sintering, they form a glassy-crystalline composite structure that is highly brittle and has low toughness. Consequently, the chemical bonds and microstructure of ceramic tiles determine their brittleness, a crucial weakness. During the laying process, ceramic tiles inevitably need to be cut. Due to the high brittleness of ceramic tiles, the external forces of cutting can easily induce localized stress concentrations, leading to edge chipping or through-cracks. Furthermore, due to the lack of plastic strain within the tile, once cut cracks develop, they rapidly propagate, causing a sharp drop in product strength or even rupture.

[0003] Existing technologies typically use fiber reinforcement, composite ceramic materials, self-toughening ceramic materials, laminated composite materials, grain boundary stress in ceramic materials, functionally gradient ceramics, and nanoceramics to improve the brittleness of ceramic tiles. However, these approaches still suffer from technical issues such as the inability to control homogenized materials through multi-scale structures; irrational structural design, which prevents the gradual attenuation of cutting stress; uneven dispersion of reinforcement particles, which are prone to agglomeration and form local stress concentration points that become crack initiations; and poor compatibility between the reinforcement and the ceramic matrix, which can easily lead to cracking at the interface.

[0004] Therefore, there is an urgent need to develop a ceramic tile with high toughness and strength to effectively reduce the chipping rate of the cut edge of the ceramic tile; at the same time, it has high wear resistance to be suitable for the production of high-quality ceramic tiles. Summary of the Invention

[0005] The present invention aims to address at least one of the technical problems existing in the above-mentioned prior art. To this end, the present invention provides a cut-resistant ceramic tile and a method for preparing the same. The ceramic tile has a rational composite layer structure and includes specific reinforcing and toughening materials in each layer to improve the dispersion of raw material particles and reduce the generation of internal stress in the tile body, thereby increasing the toughness and strength of the ceramic tile and thereby enhancing the cut-resistant performance of the ceramic tile.

[0006] To solve the above technical problems, the first aspect of the present invention provides a cut-resistant ceramic tile, which comprises, from bottom to top, a body layer, a bottom glaze layer, and a top glaze layer, wherein the raw material components of the body layer include a base blank, silicon carbide whiskers, and white carbon black modified alumina fibers; The raw material components of the base glaze layer include basic base glaze and composite inorganic particles, and the composite inorganic particles include nano-silicon dioxide and niobium pentoxide; The raw material components of the glaze layer include basic glaze, zirconium oxide whiskers, rare earth metal oxides and reinforcing agents, and the reinforcing agent includes at least one of titanium carbide, silicon carbide and carbon nanotubes.

[0007] The present invention sets up a multi-layer composite structure and adds specific reinforcing and toughening materials in each layer to reduce cutting stress, make the reinforcing particles evenly dispersed, reduce agglomeration, prevent local stress concentration, and reduce the generation of cracks, thereby improving the cutting crack resistance of ceramic tiles.

[0008] Specifically, the ceramic tile of the present invention includes a body layer, a surface glaze layer and an intermediate bottom glaze layer. Among them: silicon carbide whiskers and white carbon black modified alumina fibers are added to the body layer, and both silicon carbide whiskers and alumina fibers have the characteristics of high strength, high modulus and high temperature resistance. When cracks occur in the ceramic matrix, the whiskers and fibers will work together to span the two sides of the crack to form a "bridging" structure, resisting the opening of the crack through interfacial bonding force, thereby absorbing energy and inhibiting crack propagation. When the crack extends to the whiskers or fibers, the whiskers and fibers can be pulled out of the matrix. During the pulling out process, the friction between the whiskers and the matrix will consume a lot of energy, thereby inhibiting the expansion of the crack. At the same time, the whiskers and fibers are randomly distributed in the body. When the crack propagates and encounters whiskers and fibers, the crack path will be deflected. This deflection makes the crack propagation path more tortuous and slows down the crack propagation speed. Therefore, introducing silicon carbide whiskers and alumina fibers into the green body can jointly improve the fracture toughness and flexural strength of the ceramic through multiple mechanisms such as bridging, deflection, and pull-out; in addition, alumina and silicon carbide are both silicate ceramic materials with good compatibility and interfacial bonding with the green body, and have a good reinforcing and toughening effect on the green body; and the hardness of alumina and silicon carbide are both high, which is beneficial to improving the mechanical strength of ceramic tiles.

[0009] However, the dispersibility of alumina fibers in the blank is a key factor affecting its reinforcing effect. Since the surface of alumina fibers has a high surface energy, the fibers are easily adsorbed to each other through van der Waals forces or electrostatic attraction to form agglomerates. The agglomerates are unevenly distributed in the matrix, becoming stress concentration points, which is not conducive to the reinforcing effect. At the same time, alumina fibers have a large aspect ratio, and the fibers are easily entangled or interwoven with each other to form clusters. The entanglement makes it difficult for the fibers to be evenly dispersed, which is not conducive to the reinforcing effect. Based on this, the present invention uses white carbon black to modify the alumina fibers. White carbon black has a three-dimensional nanoparticle skeleton structure. After being compounded with the alumina fibers, it will fill the gaps between the alumina fibers, reduce the mutual entanglement or interweaving between the fibers, and weaken the mutual adsorption between the fibers, thereby enhancing the dispersibility of the alumina fibers, and thus better exerting their reinforcing and toughening effects on the blank.

[0010] The base glaze layer of the present invention contains nano-silicon dioxide and niobium pentoxide, wherein: the nano-silicon dioxide acts as a filler and is incorporated into the grain boundaries or pores, reducing pores and microcracks, increasing the density of the base glaze layer, inhibiting crack initiation, and delaying crack propagation; the niobium pentoxide acts as a flux, and together with the nano-silicon dioxide, increases the density of the glaze layer. Simultaneously, during the sintering process, the nano-silicon dioxide particles inhibit abnormal grain growth and refine the grain size in the glaze layer, thereby increasing the strength and toughness of the brick. Furthermore, the nano-silicon dioxide particles and niobium pentoxide form a strong interface bond with the body and the top glaze layer, enhancing grain boundary strength and reducing intergranular fracture; and they synergize with the whiskers and fibers in the body layer and the top glaze layer to form a scale-enhanced network, thereby enhancing the overall mechanical properties of the brick.

[0011] The surface glaze layer of the present invention contains zirconium oxide whiskers, rare earth metal oxides and reinforcing agents (such as at least one of titanium carbide, silicon carbide and carbon nanotubes), wherein: zirconium oxide exists in three crystal phases at room temperature: monoclinic phase (m-ZrO2), tetragonal phase (t-ZrO2) and cubic phase (c-ZrO2); rare earth metal oxides act as stabilizers, which can enable the zirconium oxide whiskers to retain the high-temperature tetragonal phase (t-ZrO2) during the sintering process; when the ceramic is subjected to cutting external force, the stress at the crack tip will trigger the phase change from t-ZrO2 to m-ZrO2, and the phase change is accompanied by volume expansion, which generates compressive stress on the crack tip and passivates the crack propagation; and the phase change process will absorb a large amount of energy, thereby significantly improving the fracture toughness of the brick body; titanium carbide, silicon carbide and carbon nanotubes act as reinforcing agents, inhibiting the generation of brittle phases, reducing the tendency of the glaze layer to crack, and jointly improving the glaze layer's anti-cutting cracking performance with the rare earth metal oxides.

[0012] In some embodiments of the present invention, the silicon carbide whisker has a diameter of 0.1-1 μm and a length of 10-100 μm.

[0013] In some embodiments of the present invention, the diameter of the alumina fiber in the silica-modified alumina fiber is 10-20 μm and the length is 100-500 μm.

[0014] In some embodiments of the present invention, the average particle size of the nano-silica is 10-100 nm.

[0015] In some embodiments of the present invention, the zirconia whiskers have a diameter of 5-10 μm and a length of 100-200 μm.

[0016] In some embodiments of the present invention, the reinforcing agent is titanium carbide.

[0017] In some embodiments of the present invention, the raw material components of the basic blank include, by weight, 30-40 parts of kaolin, 10-20 parts of potassium sand, 10-20 parts of sodium sand, 2-5 parts of wollastonite, and 2-5 parts of talc.

[0018] In some embodiments of the present invention, the raw material components of the green body layer include 100 parts by weight of a basic green body, 2-5 parts by weight of silicon carbide whiskers, and 1-4 parts by weight of white carbon black modified alumina fibers.

[0019] In some embodiments of the present invention, the modification process of the silica-modified alumina fiber is as follows: adding a first dispersant and a silane coupling agent to a first solvent to obtain a mixed solution; then dividing the mixed solution into two parts, adding silica and alumina fiber thereto respectively, and dispersing them to obtain suspension A and suspension B; then mixing the suspension A and suspension B, centrifuging, washing, and drying to obtain the silica-modified alumina fiber.

[0020] In some embodiments of the present invention, the first dispersant is selected from polyvinyl alcohol and / or ammonium polyacrylate, which are beneficial to improving the dispersibility of the fiber in the slurry.

[0021] In some embodiments of the present invention, the silane coupling agent is selected from vinyltriethoxysilane.

[0022] In some embodiments of the present invention, the first solvent is selected from at least one of ethylene glycol, dipropylene glycol methyl ether acetate, toluene, and xylene. These solvents are all low-polarity solvents. The solvent containing the silane coupling agent facilitates filling of the voids of the alumina fibers with silica, further preventing agglomeration of the alumina fibers.

[0023] In some embodiments of the present invention, in the mixed solution, the concentration of the silane coupling agent is 1-3 wt %, and the concentration of the dispersant is 0.5-1 wt %.

[0024] In some embodiments of the present invention, the concentration of the alumina fibers in the mixed solution is 5-10 mg / mL.

[0025] In some embodiments of the present invention, the concentration of the white carbon black in the mixed solution is 2-6 mg / mL.

[0026] In some embodiments of the present invention, the mixing is performed by stirring at a speed of 400-1500 rpm for 3-6 hours.

[0027] In some embodiments of the present invention, the centrifugation is performed at a speed of 400-6000 rpm for 10-15 minutes.

[0028] In some embodiments of the present invention, the washing is performed 2-5 times with the first solvent.

[0029] In some embodiments of the present invention, the mass ratio of the basic undercoat to the composite inorganic particles is 1:(0.05-0.1).

[0030] In some embodiments of the present invention, the mass ratio of the nano-silicon dioxide to niobium pentoxide is 1:(0.2-0.5).

[0031] In some embodiments of the present invention, the rare earth metal oxide includes yttrium oxide and / or cerium oxide.

[0032] In some embodiments of the present invention, the raw material components of the basic glaze include, by weight: 25-35 parts of potassium feldspar, 12-16 parts of sodium feldspar, 5-10 parts of nepheline, 5-10 parts of air knife clay, 10-15 parts of calcined kaolin, 12-18 parts of aluminum oxide, 8-12 parts of quartz, and 2-5 parts of talc.

[0033] In some embodiments of the present invention, the raw material components of the glaze layer include, by weight, 100 parts of base glaze, 4-8 parts of zirconium oxide whiskers, 0.5-2 parts of rare earth metal oxide, and 0.1-0.5 parts of reinforcing agent.

[0034] In some embodiments of the present invention, the raw material components of the basic glaze include, by weight: 35-40 parts of potassium feldspar, 6-12 parts of sodium feldspar, 5-10 parts of air knife clay, 6-12 parts of calcined kaolin, 2-6 parts of aluminum oxide, 1-3 parts of wollastonite, 10-20 parts of dolomite, 3-8 parts of talc, 2-6 parts of zinc oxide, and 6-10 parts of strontium carbonate.

[0035] In some embodiments of the present invention, the expansion coefficient of the green body layer at 600°C is 6.6×10 -6 -6.9×10 -6 / ℃, the expansion coefficient of the bottom glaze layer at 600℃ is 6.2×10 -6 -6.5×10 -6 / ℃.

[0036] Specifically, by controlling the expansion coefficient of the body layer to be slightly larger than the expansion coefficient of the base glaze layer, the glaze compressive stress caused by the mismatch between the expansion coefficients of the glaze layer and the body layer during the cooling stage of firing can be reduced, thereby improving the bonding performance of the body and glaze, and preventing the increased risk of cutting cracks due to stress release during use of the ceramic tiles.

[0037] A second aspect of the present invention provides a method for preparing the above-mentioned anti-cutting and cracking ceramic tile, comprising the following steps: (1) After dispersing silicon carbide whiskers, add them to the base blank; after ball milling and spray granulation, obtain a reinforcing powder; then mix the reinforcing powder with white carbon black modified alumina fiber, form and dry them to obtain a blank layer; (2) Raw materials for the base glaze layer and the top glaze layer are respectively taken to prepare base glaze slurry and top glaze slurry, which are then applied to the surface of the green body layer in sequence to form the base glaze layer and the top glaze layer. After drying and firing, the anti-cutting and cracking ceramic tile is obtained.

[0038] In some embodiments of the present invention, the process of dispersing the silicon carbide whiskers is as follows: adding the second dispersant and the silicon carbide whiskers into the second solvent, mixing; and then adjusting the pH value to 4-10.

[0039] In some embodiments of the present invention, the second dispersant is a non-ionic dispersant.

[0040] In some embodiments of the present invention, the nonionic dispersant comprises polyethyleneimine and / or polyacrylamide.

[0041] In some embodiments of the present invention, the amount of the second dispersant added is 0.1-2 wt % of the second solvent.

[0042] In some embodiments of the present invention, the second solvent is an alcohol solvent.

[0043] In some embodiments of the present invention, the alcohol solvent is ethylene glycol.

[0044] In some embodiments of the present invention, the sintering temperature regime is: first, the temperature is increased to 800-850°C at a heating rate of 15-20°C / min, and kept warm for 10-15 minutes; then, the temperature is increased to 1180-1250°C at a heating rate of 10-14°C / min, and kept warm for 8-10 minutes; then, the temperature is cooled to 550-650°C at a cooling rate of 5-9°C / min in an inert atmosphere, and kept warm for 5-10 minutes, and finally, naturally cooled to room temperature.

[0045] Specifically, during the sintering and cooling process of ceramic tiles, thermal stress is mainly caused by uneven temperature distribution and differences in thermal expansion coefficients inside the brick body. Improper firing system may lead to uneven stress, thereby causing cracks. The present invention first heats up to 800-850℃ at a faster rate to expel organic matter; then reduces the heating rate to the highest temperature and keeps it warm to densify the brick body; then cools down to 550-650℃ under an inert atmosphere at a slower rate to reduce thermal stress inside the brick body, thereby reducing the risk of cutting cracks. First, inert gas has good thermal conductivity and fluidity. During the cooling process, it can evenly surround the ceramic tiles, provide a uniform heat exchange environment, and reduce the temperature gradient between the surface and the interior of the ceramic tiles; at the same time, reducing the cooling rate can avoid excessive temperature difference between the surface and the interior caused by rapid cooling, and reduce the thermal stress concentration caused by the temperature difference. Second, slow cooling under an inert atmosphere can make the phase transition process of zirconium oxide in the glaze layer smoother, reduce stress concentration caused by phase transition, and avoid the spread of microcracks. Third, rapid cooling will cause large residual stress inside the material. By slowing down the cooling, the stress inside the brick can be fully released and the accumulation of residual stress can be reduced.

[0046] Compared with the prior art, the above technical solution of the present invention has at least the following technical effects or advantages: (1) Silicon carbide whiskers and white carbon black modified alumina fibers are added to the green body layer of the present invention. Silicon carbide whiskers and alumina fibers improve the fracture toughness, flexural strength and wear resistance of the ceramic through multiple mechanisms such as bridging, deflection and pull-out. The alumina fibers are modified by white carbon black to reduce the mutual entanglement or interweaving between the fibers and weaken the mutual adsorption between the fibers, thereby enhancing the dispersion of the alumina fibers and better exerting their reinforcing and toughening effects on the green body.

[0047] (2) Nano-silicon dioxide and niobium pentoxide are introduced into the base glaze layer of the present invention. Nano-silicon dioxide acts as a filler and fills the grain boundaries or pores, reducing pores and microcracks, improving the density of the base glaze layer, inhibiting crack initiation, and delaying crack propagation. During the sintering process, it inhibits abnormal grain growth and refines the grain size in the glaze layer, thereby improving the strength and toughness of the brick body. Niobium pentoxide acts as a flux and works together with nano-silicon dioxide to improve the density of the glaze layer. At the same time, the nano-silicon dioxide particles and niobium pentoxide form a strong interface bond with the body and the surface glaze layer, enhancing the grain boundary strength and reducing intergranular fracture. They also work synergistically with the whiskers and fibers in the body layer and the surface glaze layer to form a scale-enhanced network, thereby enhancing the overall mechanical properties of the brick body.

[0048] (3) The surface glaze layer of the present invention introduces zirconium oxide whiskers, rare earth metal oxides and reinforcing agents. The rare earth metal oxides act as stabilizers, allowing the zirconium oxide whiskers to retain a high-temperature tetragonal phase during the sintering process. When the ceramic is subjected to cutting external force, the stress at the crack tip will trigger a phase transition from t-ZrO2 to m-ZrO2. The phase transition is accompanied by volume expansion, which generates compressive stress on the crack tip and passivates crack propagation. Titanium carbide, silicon carbide and carbon nanotubes act as reinforcing agents, inhibiting the generation of brittle phases, reducing the tendency of the glaze layer to crack, and together with the rare earth metal oxides, improving the cutting resistance of the glaze layer.

[0049] (4) The present invention reduces cutting stress by creating a multi-layer composite structure and adding specific reinforcing and toughening materials to each layer, thereby evenly dispersing the reinforcing particles, reducing agglomeration, preventing local stress concentration, and reducing the occurrence of cracks, thereby improving the cutting performance of ceramic tiles. The prepared ceramic tiles have a cutting cracking rate as low as 0.5-1.5%, a bending strength of over 60 MPa, and a glaze wear resistance of up to level 5. DETAILED DESCRIPTION

[0050] The present invention is described in detail below with reference to the examples to facilitate understanding of the present invention by those skilled in the art. It is necessary to point out that the examples are only used to further illustrate the present invention and are not to be construed as limiting the scope of protection of the present invention. Non-essential improvements and adjustments made to the present invention by those skilled in the art based on the above-mentioned invention should still fall within the scope of protection of the present invention. At the same time, the raw materials mentioned below that are not described in detail are all commercially available products; the process steps or preparation methods that are not mentioned in detail are all process steps or preparation methods known to those skilled in the art.

[0051] Example 1 The utility model relates to a cutting-resistant ceramic tile, which comprises, from bottom to top, a body layer, a bottom glaze layer and a surface glaze layer.

[0052] The raw material components of the green body layer include, by weight, 100 parts of base green body, 2 parts of silicon carbide whiskers, and 4 parts of white carbon black modified alumina fiber. The diameter of the silicon carbide whiskers is 0.1-1 μm and the length is 10-100 μm; the diameter of the alumina fiber is 10-20 μm and the length is 100-500 μm. The expansion coefficient of the green body layer at 600°C is 6.6×10 -6 / ℃.

[0053] The raw material components of the basic blank include, by weight, 30 parts of kaolin, 10 parts of potassium sand, 10 parts of sodium sand, 2 parts of wollastonite, and 2 parts of talc.

[0054] The modification process of silica-modified alumina fiber is as follows: polyvinyl alcohol and vinyl triethoxysilane are added to ethylene glycol to obtain a mixed solution (in the mixed solution, the concentration of vinyl triethoxysilane is 2wt%, and the concentration of polyvinyl alcohol is 0.5wt%); then the mixed solution is divided into two parts, and silica (the concentration in the mixed solution is 5 mg / mL) and alumina fiber (the concentration in the mixed solution is 2 mg / mL) are added thereto respectively, and dispersed to obtain suspension A and suspension B; then suspension A and suspension B are mixed in a volume ratio of 1:1, centrifuged at a speed of 4000 rpm for 8 minutes, washed 3 times with ethylene glycol, and dried to obtain silica-modified alumina fiber.

[0055] The raw material components of the base glaze layer include, by weight, 100 parts of base glaze and 8 parts of composite inorganic particles. The composite inorganic particles include nano-silicon dioxide (average particle size of 10-100nm) and niobium pentoxide in a mass ratio of 1:0.3. The expansion coefficient of the base glaze layer at 600°C is 6.3×10 -6 / ℃.

[0056] The raw material components of the basic glaze include, by weight, 25 parts of potassium feldspar, 12 parts of sodium feldspar, 5 parts of nepheline, 5 parts of air knife clay, 10 parts of calcined kaolin, 12 parts of aluminum oxide, 8 parts of quartz, and 2 parts of talc.

[0057] The raw material components of the glaze layer include, by weight, 100 parts of base glaze, 6 parts of zirconium oxide whiskers, 1 part of yttrium oxide, 1 part of cerium oxide, and 0.3 parts of titanium carbide. The diameter of the zirconium oxide whiskers is 5-10 μm, and the length is 100-200 μm.

[0058] The raw material components of the basic glaze include, by weight: 37 parts of potassium feldspar, 9 parts of sodium feldspar, 8 parts of air knife clay, 9 parts of calcined kaolin, 3 parts of aluminum oxide, 2 parts of wollastonite, 15 parts of dolomite, 5 parts of talc, 4 parts of zinc oxide, and 8 parts of strontium carbonate.

[0059] A method for preparing a cutting-resistant ceramic tile comprises the following steps: (1) Polyethylene imine and silicon carbide whiskers are added to ethylene glycol, the pH value is adjusted to 6, and mixed to obtain a mixed solution (in the mixed solution, the concentration of silicon carbide whiskers is 2wt% and the concentration of polyethylene imine is 1wt%); then the base blank is added, and the reinforced powder is obtained by ball milling and spray granulation; the reinforced powder is then mixed with white carbon black modified alumina fiber, and the mixture is formed and dried to obtain a green body layer; (2) The base glaze layer and the top glaze layer are prepared by taking the raw materials of the base glaze layer and the top glaze layer, respectively, and applying them to the surface of the green body layer prepared in step (1) in sequence. After drying and firing, the anti-cutting ceramic tile of this embodiment is obtained.

[0060] The sintering temperature regime is as follows: first, heating to 800°C at a heating rate of 15°C / min and keeping warm for 10 minutes; then heating to 1180°C at a heating rate of 10°C / min and keeping warm for 10 minutes; then cooling to 600°C at a cooling rate of 5°C / min in an inert atmosphere and keeping warm for 5 minutes, and finally naturally cooling to room temperature.

[0061] Example 2 The utility model relates to a cutting-resistant ceramic tile, which comprises, from bottom to top, a body layer, a bottom glaze layer and a surface glaze layer.

[0062] The raw material components of the green body layer include, by weight, 100 parts of base green body, 3 parts of silicon carbide whiskers, and 3 parts of white carbon black modified alumina fiber. The diameter of the silicon carbide whiskers is 0.1-1 μm and the length is 10-100 μm; the diameter of the alumina fiber is 10-20 μm and the length is 100-500 μm. The expansion coefficient of the green body layer at 600°C is 6.7×10 -6 / ℃.

[0063] The raw material components of the basic blank include, by weight, 35 parts of kaolin, 15 parts of potassium sand, 15 parts of sodium sand, 4 parts of wollastonite, and 4 parts of talc.

[0064] The modification process of silica-modified alumina fiber is as follows: ammonium polyacrylate and vinyl triethoxysilane are added to ethylene glycol to obtain a mixed solution (in the mixed solution, the concentration of vinyl triethoxysilane is 2wt%, and the concentration of ammonium polyacrylate is 0.5wt%); then the mixed solution is divided into two parts, and silica (the concentration in the mixed solution is 5 mg / mL) and alumina fiber (the concentration in the mixed solution is 2 mg / mL) are added thereto respectively to disperse to obtain suspension A and suspension B; then suspension A and suspension B are mixed in a volume ratio of 1:1, centrifuged at a speed of 4000 rpm for 8 minutes, washed 3 times with ethylene glycol, and dried to obtain silica-modified alumina fiber.

[0065] The raw material components of the base glaze layer include, by weight, 100 parts of base base glaze and 6 parts of composite inorganic particles. The composite inorganic particles include nano-silicon dioxide (average particle size of 10-100nm) and niobium pentoxide in a mass ratio of 1:0.5. The expansion coefficient of the base glaze layer at 600°C is 6.5×10 -6 / ℃.

[0066] The raw material components of the basic glaze include, by weight, 30 parts of potassium feldspar, 14 parts of sodium feldspar, 8 parts of nepheline, 8 parts of air knife clay, 12 parts of calcined kaolin, 15 parts of aluminum oxide, 10 parts of quartz, and 3 parts of talc.

[0067] The raw material components of the glaze layer include, by weight, 100 parts of base glaze, 5 parts of zirconium oxide whiskers, 0.5 parts of yttrium oxide, and 0.2 parts of titanium carbide. The diameter of the zirconium oxide whiskers is 5-10 μm, and the length is 100-200 μm.

[0068] The raw material components of the basic glaze include, by weight: 37 parts of potassium feldspar, 9 parts of sodium feldspar, 8 parts of air knife clay, 9 parts of calcined kaolin, 3 parts of aluminum oxide, 2 parts of wollastonite, 15 parts of dolomite, 5 parts of talc, 4 parts of zinc oxide, and 8 parts of strontium carbonate.

[0069] A method for preparing a cutting-resistant ceramic tile comprises the following steps: (2) Add polyacrylamide and silicon carbide whiskers to ethylene glycol, adjust the pH value to 9, and mix to obtain a mixed solution (in the mixed solution, the concentration of silicon carbide whiskers is 2wt% and the concentration of polyacrylamide is 1wt%); then add the base blank, ball mill and spray granulate to obtain a reinforced powder; then mix the reinforced powder with white carbon black modified alumina fiber, form and dry to obtain a blank layer; (2) The base glaze layer and the top glaze layer are prepared by taking the raw materials of the base glaze layer and the top glaze layer, respectively, and applying them to the surface of the green body layer prepared in step (1) in sequence. After drying and firing, the anti-cutting ceramic tile of this embodiment is obtained.

[0070] The sintering temperature regime is as follows: first, the temperature is raised to 820°C at a heating rate of 18°C / min and kept at that temperature for 12 minutes; then, the temperature is raised to 1200°C at a heating rate of 12°C / min and kept at that temperature for 8 minutes; then, the temperature is cooled to 580°C at a cooling rate of 8°C / min in an inert atmosphere and kept at that temperature for 8 minutes, and finally, the temperature is naturally cooled to room temperature.

[0071] Example 3 The utility model relates to a cutting-resistant ceramic tile, which comprises, from bottom to top, a body layer, a bottom glaze layer and a surface glaze layer.

[0072] The raw material components of the green body layer include, by weight, 100 parts of base green body, 5 parts of silicon carbide whiskers, and 2 parts of white carbon black modified alumina fiber. The diameter of the silicon carbide whiskers is 0.1-1 μm and the length is 10-100 μm; the diameter of the alumina fiber is 10-20 μm and the length is 100-500 μm. The expansion coefficient of the green body layer at 600°C is 6.9×10 -6 / ℃.

[0073] The raw material components of the basic blank include, by weight, 40 parts of kaolin, 20 parts of potassium sand, 20 parts of sodium sand, 5 parts of wollastonite, and 5 parts of talc.

[0074] The modification process of silica-modified alumina fiber is as follows: polyvinyl alcohol and vinyl triethoxysilane are added to ethylene glycol to obtain a mixed solution (in the mixed solution, the concentration of vinyl triethoxysilane is 2wt%, and the concentration of polyvinyl alcohol is 0.5wt%); then the mixed solution is divided into two parts, and silica (the concentration in the mixed solution is 5 mg / mL) and alumina fiber (the concentration in the mixed solution is 2 mg / mL) are added thereto respectively, and dispersed to obtain suspension A and suspension B; then suspension A and suspension B are mixed in a volume ratio of 1:1, centrifuged at a speed of 4000 rpm for 8 minutes, washed 3 times with ethylene glycol, and dried to obtain silica-modified alumina fiber.

[0075] The raw material components of the base glaze layer include, by weight: 100 parts of base base glaze and 10 parts of composite inorganic particles. The composite inorganic particles include nano-silicon dioxide (average particle size of 10-100nm) and niobium pentoxide in a mass ratio of 1:0.5. The expansion coefficient of the base glaze layer at 600°C is 6.2×10 -6 / ℃.

[0076] The raw material components of the basic glaze include, by weight, 35 parts of potassium feldspar, 16 parts of sodium feldspar, 10 parts of nepheline, 10 parts of air knife clay, 15 parts of calcined kaolin, 18 parts of aluminum oxide, 12 parts of quartz, and 5 parts of talc.

[0077] The raw material components of the glaze layer include, by weight, 100 parts of base glaze, 8 parts of zirconium oxide whiskers, 2 parts of yttrium oxide, and 0.5 parts of titanium carbide. The diameter of the zirconium oxide whiskers is 5-10 μm, and the length is 100-200 μm.

[0078] The raw material components of the basic glaze include, by weight: 37 parts of potassium feldspar, 9 parts of sodium feldspar, 8 parts of air knife clay, 9 parts of calcined kaolin, 3 parts of aluminum oxide, 2 parts of wollastonite, 15 parts of dolomite, 5 parts of talc, 4 parts of zinc oxide, and 8 parts of strontium carbonate.

[0079] A method for preparing a cutting-resistant ceramic tile comprises the following steps: (3) Adding polyethyleneimine and silicon carbide whiskers to ethylene glycol, adjusting the pH value to 6, and mixing to obtain a mixed solution (in the mixed solution, the concentration of silicon carbide whiskers is 2wt%, and the concentration of polyethyleneimine is 1wt%); then adding the base blank, ball milling, spray granulation, to obtain a reinforced powder; then mixing the reinforced powder with white carbon black modified alumina fiber, forming, and drying to obtain a green body layer; (2) The base glaze layer and the top glaze layer are prepared by taking the raw materials of the base glaze layer and the top glaze layer, respectively, and applying them to the surface of the green body layer prepared in step (1) in sequence. After drying and firing, the anti-cutting ceramic tile of this embodiment is obtained.

[0080] The sintering temperature regime is as follows: first, the temperature is raised to 850°C at a heating rate of 20°C / min and kept at that temperature for 15 minutes; then, the temperature is raised to 1250°C at a heating rate of 14°C / min and kept at that temperature for 8 minutes; then, the temperature is cooled to 600°C at a cooling rate of 5°C / min in an inert atmosphere and kept at that temperature for 10 minutes, and finally, the temperature is naturally cooled to room temperature.

[0081] Comparative Example 1 The difference between Comparative Example 1 and Example 1 is that the ceramic tiles of Comparative Example 1 include a body layer, a base glaze layer and a surface glaze layer from bottom to top, and the raw material components of each layer do not contain reinforcing and toughening materials, namely the basic body, basic base glaze and basic surface glaze, and the raw material components of the basic body, basic base glaze and basic surface glaze are the same as those in Example 1.

[0082] Comparative Example 2 The only difference between Comparative Example 2 and Example 1 is that the raw material components of the green body layer are different. The raw material components of the green body layer of Comparative Example 2 use an equal amount of white carbon black modified aluminum borate whisker fiber instead of white carbon black modified alumina fiber, and the modification methods and amounts of each raw material used in the two are the same.

[0083] Comparative Example 3 The only difference between Comparative Example 3 and Example 1 is the raw material components of the green body layer. The raw material components of the green body layer of Comparative Example 3 use an equal amount of alumina fiber instead of white carbon black modified alumina fiber, and the raw material components include, by weight: 100 parts of basic green body, 2 parts of silicon carbide whiskers, and 4 parts of alumina fiber.

[0084] Comparative Example 4 The only difference between Comparative Example 4 and Example 1 is that the raw material components of the bottom glaze layer are different. The raw material components of the bottom glaze layer of Comparative Example 4 do not contain niobium pentoxide.

[0085] Comparative Example 5 The only difference between Comparative Example 5 and Example 1 is that the raw material components of the surface glaze layer are different. The raw material components of the surface glaze layer of Comparative Example 5 do not contain titanium carbide.

[0086] Comparative Example 6 The only difference between Comparative Example 6 and Example 1 is that the expansion coefficient of the glaze layer of the green body is larger, which is 7.2×10 -6 / ℃, the raw material components of the basic blank of Comparative Example 6 include, by weight: 25 parts of kaolin, 18 parts of potassium sand, 20 parts of sodium sand, 3 parts of wollastonite, and 3 parts of talc.

[0087] Comparative Example 7 The difference between Comparative Example 7 and Example 1 is only the different firing system. The firing temperature system of Comparative Example 7 is: first increase the temperature to 800°C at a heating rate of 15°C / min and keep warm for 10 minutes; then increase the temperature to 1180°C at a heating rate of 10°C / min and keep warm for 10 minutes; finally, naturally cool to room temperature in an air atmosphere.

[0088] Performance Testing The ceramic tile samples prepared in Examples 1-3 and Comparative Examples 1-7 were subjected to performance tests, wherein: the bending strength was tested according to the test method in GB / T3810.4-2016 Ceramic Tile Test Method; the wear resistance was tested according to GB / T3810.7-2016 "Determination of Surface Wear Resistance of Ceramic Glazed Tiles"; the cutting crack resistance test process was as follows: 200 samples produced on the same production line were randomly selected and cut using a water jet. The number of ceramic tiles with chipped or cracked edges during cutting was counted, and the cutting crack rate was calculated using the following formula: Cutting chipping rate (%) = (number of bricks with chipped or cracked edges / 200) × 100%.

[0089] Table 1: Performance test comparison table of Examples 1-3 and Comparative Examples 1-7

[0090] As can be seen from Table 1, the ceramic tile samples prepared in Examples 1-3 of the present invention have a bending strength of up to 60-65 MPa, far exceeding the national standard of 45 MPa; the cutting cracking rate is as low as 0.5-1%, which is a significant improvement compared to 30% of the ordinary ceramic tiles in Comparative Example 1; and the wear resistance also reaches the highest level 5 of building ceramic products.

[0091] Comparative Example 1 uses traditional basic blank, basic base glaze and basic top glaze, but its bending strength and wear resistance are poor, and the cutting cracking rate is as high as 30%.

[0092] Compared with Example 1, in Comparative Examples 2 and 3, equal amounts of silica-modified aluminum borate whisker fibers were used to replace silica-modified alumina fibers, and equal amounts of alumina fibers were used to replace silica-modified alumina fibers in the green body layer, respectively. The strength of the green bodies decreased, resulting in a decrease in the overall bending strength of the ceramic tiles and a decrease in the cutting cracking rate. This shows that the alumina fibers and silicon carbide whiskers in the green body layer have a synergistic effect, and the unmodified alumina fibers are easy to agglomerate, resulting in stress concentration, which causes a decrease in the green body strength.

[0093] Compared with Example 1, in Comparative Example 4, since niobium pentoxide is not added to the bottom glaze layer, the reinforcing effect of nano-silicon dioxide is weakened, resulting in a decrease in the overall mechanical properties of the brick body and an increase in the cutting cracking rate.

[0094] In Comparative Example 5, compared with Example 1, since the reinforcing agent titanium carbide is not added to the surface glaze layer, the brittleness of the glaze layer increases, and the bending strength, wear resistance and cutting and cracking resistance all decrease accordingly.

[0095] In Comparative Example 6 compared to Example 1, since the expansion coefficient of the green body layer is too large relative to the bottom glaze layer, the compressive stress on the surface glaze layer exceeds the compressive strength of the glaze glass, causing the cutting cracking rate to drop sharply, the thermal stress inside the brick body is concentrated, and the residual stress cannot be released, so the cutting cracking rate also increases significantly.

[0096] Compared with Example 1, in Comparative Example 7, natural cooling in air atmosphere was adopted during the firing process, which resulted in concentrated thermal stress in the brick body and inability to fully release residual stress, resulting in a sharp increase in the cutting cracking rate.

[0097] For those skilled in the art to which the present invention belongs, a number of simple deductions or substitutions can be made without departing from the concept of the present invention, without having to resort to creative work. Therefore, based on the disclosure of the present invention, simple improvements made by those skilled in the art to the present invention should be within the scope of protection of the present invention. The above embodiments are preferred embodiments of the present invention, and all processes similar to the present invention and equivalent changes made should fall within the scope of protection of the present invention.

Claims

1. A cutting-resistant ceramic tile, characterized in that: From bottom to top, it includes a body layer, a bottom glaze layer and a top glaze layer, wherein the raw material components of the body layer include a basic body, silicon carbide whiskers and white carbon black modified alumina fiber; The raw material components of the base glaze layer include basic base glaze and composite inorganic particles, and the composite inorganic particles include nano-silicon dioxide and niobium pentoxide; The raw material components of the glaze layer include basic glaze, zirconium oxide whiskers, rare earth metal oxides and reinforcing agents, and the reinforcing agent includes at least one of titanium carbide, silicon carbide and carbon nanotubes.

2. The anti-cutting ceramic tile according to claim 1, characterized in that: The raw material components of the green body layer include 100 parts of basic green body, 2-5 parts of silicon carbide whiskers, and 1-4 parts of white carbon black modified alumina fibers by weight.

3. The anti-cutting ceramic tile according to claim 1 or 2, characterized in that: The modification process of the silica-modified alumina fiber is as follows: a first dispersant and a silane coupling agent are added to a first solvent to obtain a mixed solution; the mixed solution is then divided into two parts, and silica and alumina fiber are added thereto respectively for dispersion to obtain suspension A and suspension B; the suspension A and suspension B are then mixed, centrifuged, washed, and dried to obtain the silica-modified alumina fiber.

4. The anti-cutting ceramic tile according to claim 1, characterized in that: The mass ratio of the basic enamel to the composite inorganic particles is 1:(0.05-0.1); And / or, the mass ratio of the nano-silicon dioxide to niobium pentoxide is 1:(0.2-0.5).

5. The anti-cutting ceramic tile according to claim 1, characterized in that: The rare earth metal oxide includes yttrium oxide and / or cerium oxide.

6. The anti-cutting ceramic tile according to claim 1 or 5, characterized in that: The raw material components of the surface glaze layer include 100 parts of basic surface glaze, 4-8 parts of zirconium oxide whiskers, 0.5-2 parts of rare earth metal oxide and 0.1-0.5 parts of reinforcing agent in parts by weight.

7. The anti-cutting ceramic tile according to claim 1, characterized in that: The expansion coefficient of the green body layer at 600°C is 6.6×10 -6 -6.9×10 -6 / ℃, the expansion coefficient of the bottom glaze layer at 600℃ is 6.2×10 -6 -6.5×10 -6 / ℃.

8. A method for preparing the anti-cutting crack ceramic tile according to any one of claims 1 to 7, characterized in that: The following steps are involved: (1) After dispersing silicon carbide whiskers, add them to the base blank; after ball milling and spray granulation, obtain a reinforcing powder; then mix the reinforcing powder with white carbon black modified alumina fiber, form and dry them to obtain a blank layer; (2) Raw materials for the base glaze layer and the top glaze layer are respectively taken to prepare base glaze slurry and top glaze slurry, which are then applied to the surface of the green body layer in sequence to form the base glaze layer and the top glaze layer. After drying and firing, the anti-cutting and cracking ceramic tile is obtained.

9. The method for preparing the anti-cutting crack ceramic tile according to claim 8, characterized in that: The process of dispersing the silicon carbide whiskers is as follows: adding the second dispersant and the silicon carbide whiskers into the second solvent, mixing them; and then adjusting the pH value to 4-10.

10. The method for preparing the anti-cutting crack ceramic tile according to claim 8, characterized in that: The sintering temperature regime is as follows: first, heating the temperature to 800-850°C at a heating rate of 15-20°C / min, and keeping the temperature for 10-15 minutes; then heating the temperature to 1180-1250°C at a heating rate of 10-14°C / min, and keeping the temperature for 8-10 minutes; then cooling the temperature to 550-650°C at a cooling rate of 5-9°C / min in an inert atmosphere, keeping the temperature for 5-10 minutes, and finally naturally cooling the temperature to room temperature.

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