Wear-resistant protective glaze, wear-resistant ceramic and preparation method thereof

Abstract

The present application relates to a kind of wear-resistant protective glaze, wear-resistant ceramic and its preparation method, belong to ceramic production manufacturing technical field.The mineral composition of the wear-resistant protective glaze includes: by mass percentage, kaolin 3%~8%, quartz 10%~20%, wollastonite 15%~25%, calcined talc 3%~5%, iron-aluminium garnet 8%~12%, calcium-aluminium clinker 30%~40%, alumina 3%~8%, zinc oxide 2%~5%, iron oxide 1%~3%.The reinforcing effect of the present application does not simply rely on a large number of additional particles, but utilizes multi-stage reinforcing mechanism to achieve high performance under lower particle addition amount.The micro-nano scale hematite crystals precipitated in situ are relatively weak in light scattering effect due to small size (micro-nano scale), while maintaining high transparency and gloss, the wear resistance is greatly improved.

Description

Technical Field

[0001] This invention relates to a wear-resistant protective glaze, wear-resistant ceramics, and their preparation methods, belonging to the field of ceramic production and manufacturing technology. Background Technology

[0002] Ceramic slabs (tiles) are traditional decorative products in the field of building ceramics. With the continuous expansion of ceramic applications, from traditional residential flooring to public buildings such as large commercial complexes, airports, train stations, medical institutions, and educational institutions, the market demand for highly wear-resistant ceramics is becoming increasingly urgent. At the same time, as consumers' requirements for product quality increase, maintaining a pristine appearance has become one of the core demands of end-users regarding the surface performance of building ceramics. Therefore, relevant researchers are focusing their research on improving the wear resistance of ceramic surfaces.

[0003] From the perspective of glaze formulation, the mainstream reinforcement technologies currently include the following three aspects: 1. External high-hardness crystal particle reinforcement technology: Increasing the content of high-hardness components in the glaze by introducing hard crystals such as corundum, spinel phase, and zirconium silicate can improve hardness when added in appropriate amounts. The principle is that hard crystal particles can generate hard phase dispersion reinforcement in the glaze layer, which plays a physical role in hindering abrasive wear and surface scratches. 2. In-situ crystallization reinforcement technology: This technology controls the composition of the glaze formulation and the firing regime to allow the target crystal phase to precipitate from the glass matrix during the cooling or holding stage of firing, and uses the in-situ grown crystals to achieve glaze surface reinforcement. 3. Microcrystallization treatment technology: This technology introduces special frits or nucleating agents (such as TiO2, ZrO2, P2O5, etc.) to create a large number of nucleation points in the glaze layer, inducing the overall microcrystallization or nanocrystallization of the glaze layer, forming a microcrystalline glass structure to achieve a comprehensive improvement in hardness and wear resistance.

[0004] Currently, most mainstream technologies rely on a single reinforcement mechanism, such as external high-hardness particle reinforcement, in-situ crystallization reinforcement, or densification relying on nucleating agents. A single mechanism has inherent limitations: hardness without toughness leads to brittle fracture, and bonding without hardness results in insufficient resistance to abrasive indentation. Achieving synergistic effects of multiple mechanisms within the same system is key to overcoming performance bottlenecks. Furthermore, high-end wear-resistant technologies often come with high material costs (superhard materials, nano-nucleating agents), limiting their widespread application in large-scale industrial production. Summary of the Invention

[0005] The technical objective of this invention is achieved through the following technical means: In a first aspect, the present invention provides a wear-resistant protective glaze. The mineral composition of the wear-resistant protective glaze includes, by mass percentage: 3%~8% kaolin, 10%~20% quartz, 15%~25% wollastonite, 3%~5% calcined talc, 8%~12% almandine, 30%~40% calcium aluminum frit, 3%~8% alumina, 2%~5% zinc oxide, and 1%~3% iron oxide.

[0006] In an optional embodiment, the chemical composition of the calcium-aluminum frit includes, by mass percentage: IL: 0~1%, SiO2: 48%~52%, Al2O3: 18%~22%, Fe2O3: 0.01~0.2%, TiO2: 0.01~0.2%, CaO: 13%~18%, MgO: 3%~6%, K2O: 3%~5%, Na2O: 2%~3%, ZnO: 1%~2%, BaO: 2%~5%.

[0007] In an optional embodiment, the mineral composition of the calcium-aluminum frit includes, by mass percentage: 3%~7% quartz, 8%~12% kaolin, 17%~21% potassium feldspar, 15%~17% sodium feldspar, 10%~14% calcined talc, 20%~26% calcite, 1%~3% zinc oxide, 2%~6% barium carbonate, and 6%~8% aluminum oxide.

[0008] In an optional embodiment, the D of the almandine is... 50 The particle size is 2~15μm.

[0009] In an optional embodiment, the chemical composition of the wear-resistant protective glaze includes, by mass percentage: IL: 1%~2%, SiO2: 50%~54%, Al2O3: 15%~18%, Fe2O3: 3%~6%, TiO2: 0.1%~1%, CaO: 13%~17%, MgO: 2%~4%, K2O: 1%~3%, Na2O: 1%~3%, ZnO: 4%~6%, BaO: 1%~2%.

[0010] Secondly, the present invention provides a method for preparing wear-resistant ceramics. The preparation method includes the following steps: applying a surface glaze to the surface of a green body; inkjet printing an ink pattern on the surface of the green body after applying the surface glaze; applying the aforementioned wear-resistant protective glaze to the surface of the green body after inkjet printing the ink pattern; firing and polishing the green body after applying the wear-resistant protective glaze to obtain wear-resistant ceramics.

[0011] In an optional embodiment, the wear-resistant protective glaze is applied by spraying; the specific gravity of the wear-resistant protective glaze is 1.5~1.6 g / cm³. 3 The glazing weight is 580~750 g / m² 2 .

[0012] In an optional embodiment, the chemical composition of the surface glaze includes, by mass percentage: SiO2: 50%~60%, Al2O3: 25%~35%, Fe2O3: 0.1%~1%, TiO2: 0.1%~1%, CaO: 0.1%~3%, MgO: 0.1%~2%, K2O: 3%~6%, Na2O: 2%~5%, P2O5: 0.01%~1%, ZrO2: 2%~6%, IL: 3%~6%.

[0013] In an optional embodiment, the glaze is applied by spraying, and the specific gravity of the glaze is 1.4~1.5 g / cm³. 3 The glazing weight is 600~750 g / m 2 .

[0014] In an optional embodiment, the high-temperature firing temperature is 1140~1160℃, and the firing time is 40~60 minutes.

[0015] In an optional embodiment, the chemical composition of the billet includes, by mass percentage: SiO2: 65%~70%, Al2O3: 17%~19%, Fe2O3: 0.1%~2%, TiO2: 0.1%~0.3%, CaO: 2.5%~5%, MgO: 0.5%~1%, K2O: 2.5%~4%, Na2O: 1.5%~3%, IL: 4%~6%.

[0016] Thirdly, the present invention provides a wear-resistant ceramic. The wear-resistant ceramic is obtained according to the preparation method of the wear-resistant ceramic described in any of the preceding claims.

[0017] Compared with the prior art, the present invention has the following beneficial effects: This invention overcomes the performance bottleneck of a single reinforcement mechanism. The reinforcement effect of this invention does not solely rely on a large amount of added particles, but rather utilizes a multi-level reinforcement mechanism to achieve high performance with a relatively low particle addition amount. This invention proposes an "external skeleton + in-situ growth + toughening" mechanism, which works simultaneously from three dimensions: hardness, interfacial bonding, and toughness. Experimental results show that the wear-resistant protective glaze of this invention can achieve a wear resistance of level 4 or higher (GB / T 3810.7-2016 standard, 6000 revolutions), and a Mohs hardness of 7-8, which is significantly improved compared to the benchmark formula. The in-situ precipitated micro-nano-sized hematite crystals, due to their small size (micro-nano scale), have a relatively weak light scattering effect, achieving a significant improvement in wear resistance while maintaining high transparency and gloss. The nucleation and growth of hematite microcrystals fill the micropores between almandine garnet particles and in the glass matrix, reducing the microporosity and venting of the glaze layer, improving the overall density of the glaze surface, and simultaneously improving its anti-fouling performance. Almandine garnet is a natural mineral abrasive with abundant global reserves, large annual production, and a price far lower than corundum (approximately 1 / 3 to 1 / 5 of the price of corundum) and artificially synthesized superhard materials such as silicon carbide. Attached Figure Description

[0018] Figure 1 This is a glaze effect diagram of Example 1.

[0019] Figure 2 This is the XRD analysis result of the glaze in Example 1. Detailed Implementation

[0020] The present invention is further illustrated by the following embodiments. It should be understood that the following embodiments are for illustrative purposes only and are not intended to limit the present invention.

[0021] This invention proposes a synergistic system of triple reinforcement mechanisms: hard framework introduction, in-situ microcrystalline growth, and crack deflection / bridging toughening. Specifically: the hard framework introduction involves adding almandine garnet powder to construct a high-hardness, uniformly dispersed hard particle framework network within the glaze layer, providing the first line of defense against abrasive indentation and ploughing. In-situ microcrystalline growth utilizes the dissolution-diffusion-precipitation mechanism of iron in almandine garnet at high temperatures to grow micro- and nano-sized hematite (α-Fe₂O₃) crystals in situ around the framework particles and within the glass matrix, forming a secondary reinforcing phase chemically bonded to the matrix. This compensates for weak areas between framework particles, constructing a multi-level gradient reinforcement structure. Crack deflection / bridging toughening improves the fracture toughness of the glaze surface through crack deflection and bridging effects, resolving the contradiction of high hardness and low toughness.

[0022] The mineral composition of the wear-resistant protective glaze of the present invention includes, by mass percentage: 3%~8% kaolin, 10%~20% quartz, 15%~25% wollastonite, 3%~5% calcined talc, 8%~12% almandine, 30%~40% calcium aluminum frit, 3%~8% alumina, 2%~5% zinc oxide, and 1%~3% iron oxide. The use of iron oxide as an iron source supplement in the wear-resistant glaze formulation aims to synergize with the iron content in almandine to ensure that the glaze melt reaches the supersaturated concentration required for hematite crystallization during the cooling stage. A low iron oxide content results in an excessively low concentration of iron in the melt, hindering the effective precipitation of the hematite crystal phase. A high iron oxide content leads to over-firing of the glaze surface, resulting in an uneven glaze surface, and the free iron elements causing the glaze to turn brown.

[0023] The advantage of using almandine is that almandine (chemical formula Fe3Al2[SiO4]3) is the hardest variety among the garnet group minerals, with a Mohs hardness of 7.5~8.0. Its crystal structure contains Al... 3+ Occupying the octahedral position, Fe 2+ Occupying dodecahedral positions and connected by SiO4 tetrahedra to form a stable island-like silicate structure, this structure endows it with excellent hardness, toughness, and natural self-sharpening properties. The chemical composition of almandine garnet contains abundant iron and aluminum elements. During the high-temperature firing of the glaze, the iron on the surface of its particles can dissolve and diffuse into the glaze melt, providing a material source for the subsequent in-situ nucleation and precipitation of iron oxide-based crystals. This unique chemical property provides a natural material basis and chemical driving force for constructing a dual-phase synergistic reinforcement structure of external framework + in-situ growth.

[0024] A low content of almandine garnet will result in a low content of almandine garnet / hematite crystal phases in the glaze layer, failing to achieve the goal of improving the wear resistance of the glaze surface. A high content of almandine garnet will lead to increased bubbles in the glaze layer, an uneven glaze surface, and loss of glaze transparency; at the same time, excessive almandine garnet will lead to poor adhesion between it and the glaze, which is not conducive to improving the fracture toughness of the glaze surface.

[0025] D of iron-aluminum garnet micro powder 50 The particle size is 2~15μm. The purpose is that within this particle size range, the iron-aluminum garnet particles can play an effective role in supporting the hard framework, without increasing the roughness of the glaze surface due to excessively large particle size.

[0026] In an optional embodiment, the chemical composition of the calcium-aluminum frit includes, by mass percentage: IL: 0~1%, SiO2: 48%~52%, Al2O3: 18%~22%, Fe2O3: 0.01~0.2%, TiO2: 0.01~0.2%, CaO: 13%~18%, MgO: 3%~6%, K2O: 3%~5%, Na2O: 2%~3%, ZnO: 1%~2%, BaO: 2%~5%.

[0027] It should be understood that any calcium-aluminum frit formulation that results in a chemical composition falling within the above-mentioned range is applicable to the present invention. In an optional embodiment, the mineral composition of the calcium-aluminum frit includes, by mass percentage: 3%–7% quartz, 8%–12% kaolin, 17%–21% potassium feldspar, 15%–17% sodium feldspar, 10%–14% calcined talc, 20%–26% calcite, 1%–3% zinc oxide, 2%–6% barium carbonate, and 6%–8% alumina. The raw materials are weighed according to the mineral composition of the calcium-aluminum frit, mixed evenly, and melted at 1400–1500°C for 1–2 hours to obtain a glass melt. The glass melt is then water-quenched and crushed to obtain the calcium-aluminum frit.

[0028] In an optional embodiment, the chemical composition of the wear-resistant protective glaze includes, by mass percentage: IL: 1%~2%, SiO2: 50%~54%, Al2O3: 15%~18%, Fe2O3: 3%~6%, TiO2: 0.1%~1%, CaO: 13%~17%, MgO: 2%~4%, K2O: 1%~3%, Na2O: 1%~3%, ZnO: 4%~6%, BaO: 1%~2%.

[0029] The most fundamental difference between this invention and the aforementioned external particle reinforcement technologies lies in the fact that this invention no longer simply embeds high-hardness particles into a glass matrix. Instead, it utilizes the chemical reactivity of the particles themselves to grow a chemically bonded transition layer between the particles and the matrix, transforming the physical-mechanical interlocking into a chemically bonded interface. The most fundamental difference from in-situ crystallization reinforcement technologies is that this invention does not rely solely on a single medium-hardness silicate crystal. Instead, it constructs a multi-level gradient reinforcement architecture consisting of a high-hardness framework (garnet, hardness 8.0) + secondary reinforcing microcrystals (hematite, hardness 5.5~6.5), achieving continuous and effective hardness support at different scales.

[0030] The following example illustrates a method for preparing wear-resistant ceramic plates (bricks).

[0031] Preparation of green body powder. The green body powder used is conventional imitation stone green body. For example, the chemical composition of the green body includes, by mass percentage: SiO2: 65%~70%, Al2O3: 17%~19%, Fe2O3: 0.1%~2%, TiO2: 0.1%~0.3%, CaO: 2.5%~5%, MgO: 0.5%~1%, K2O: 2.5%~4%, Na2O: 1.5%~3%, IL: 4%~6%. It should be understood that any mineral composition formula that meets the above chemical composition of the green body powder is applicable to this invention. The raw materials are weighed according to the formula and subjected to ball milling, spray granulation, aging, etc., to prepare the green body powder.

[0032] Pressing and molding. The powdered material is pressed and molded according to conventional production processes, and then dried in a drying kiln. The drying temperature can be 180~220℃, and the drying time can be 40~60 minutes.

[0033] A surface glaze is applied to the dried blank surface. The surface glaze is a conventional zirconium white surface glaze. For example, the chemical composition of the surface glaze includes, by mass percentage: SiO2: 50%~60%, Al2O3: 25%~35%, Fe2O3: 0.1%~1%, TiO2: 0.1%~1%, CaO: 0.1%~3%, MgO: 0.1%~2%, K2O: 3%~6%, Na2O: 2%~5%, P2O5: 0.01%~1%, ZrO2: 2%~6%, IL: 3%~6%. The surface glaze is applied by spraying. Optionally, the specific gravity of the surface glaze is 1.4~1.5 g / cm³. 3 The glaze application rate is 600~750 g / m². 2 .

[0034] Ink patterns are printed onto the surface of the glazed body using inkjet printing. Digital inkjet printers can be used for inkjet printing decoration.

[0035] A wear-resistant protective glaze is applied to the surface of the substrate after inkjet printing the ink pattern. The glaze is applied by spraying. Optionally, the specific gravity of the glaze is 1.5~1.6 g / cm³. 3 The glaze application rate is 580~750 g / m². 2 .

[0036] High-temperature firing. The high-temperature firing temperature is 1140~1160℃, and the firing time is 40~60 minutes. The high-temperature firing temperature here refers to the temperature of the temperature measuring ring. The actual temperature inside the kiln is about 20℃ higher than the temperature of the temperature measuring ring.

[0037] Polishing and grading. The fired ceramics are then polished.

[0038] The wear-resistant ceramic slabs (bricks) prepared using the wear-resistant protective glaze of the present invention can achieve a wear resistance of level 4 or above (GB / T3810.7-2016 standard above 6000 revolutions), and a Mohs hardness of 7 to 8. Compared with ordinary polished glazed products, the wear and tear is reduced by 40% to 50%.

[0039] The following examples further illustrate the present invention in detail. It should also be understood that the following examples are only for further explanation of the present invention and should not be construed as limiting the scope of protection of the present invention. Any non-essential improvements and adjustments made by those skilled in the art based on the above description of the present invention are within the scope of protection of the present invention. The specific process parameters, etc., in the following examples are merely examples within a suitable range; that is, those skilled in the art can make appropriate selections within the appropriate range based on the description herein, and are not intended to be limited to the specific values ​​in the examples below.

[0040] Example 1

[0041] The preparation method of wear-resistant ceramics includes the following steps: Step 1. Prepare the green body and dry it. The chemical composition of the green body includes, by mass percentage: SiO2: 66.5%, Al2O3: 18.4%, Fe2O3: 0.5%, TiO2: 0.1%, CaO: 3.5%, MgO: 0.8%, K2O: 3.2%, Na2O: 2.2%, and loss on ignition: 4.8%.

[0042] Step 2. Apply a top coat of glaze to the dried body. The chemical composition of the glaze is as follows (by mass percentage): SiO2: 54.54%, Al2O3: 27.6%, Fe2O3: 0.4%, TiO2: 0.12%, CaO: 0.21%, MgO: 0.25%, K2O: 4.62%, Na2O: 2.42%, P2O5: 0.2%, ZrO2: 5.74%, Loss on ignition: 3.9%. The glaze is applied by spraying, and its specific gravity is approximately 1.5 g / cm³. 3 Glazing amount is 650 g / m 2 .

[0043] Step 3. Inkjet print an ink pattern onto the surface of the glazed body.

[0044] Step 4. Apply a wear-resistant protective glaze to the surface of the blank after inkjet printing the ink pattern. The mineral composition of the wear-resistant protective glaze includes, by mass percentage: 5% kaolin, 15% quartz, 19% wollastonite, 4% calcined talc, 10% almandine, 36% calcium aluminum frit, 5% alumina, 4% zinc oxide, and 2% iron oxide. The chemical composition of the calcium aluminum frit includes, by mass percentage: 0.5% IL, 50.18% SiO2, 19.7% Al2O3, 0.06% Fe2O3, 0.02% TiO2, 14.8% CaO, 3.5% MgO, 4.11% K2O, 2.33% Na2O, 1.3% ZnO, and 3.5% BaO. The D of the almandine... 50 The particle size is 3~8μm. A wear-resistant protective glaze is applied using a spray glazing method, with a specific gravity of 1.55 g / cm³. 3 Glazing amount is 680 g / m 2 .

[0045] Step 5. Firing and polishing the green body after applying the wear-resistant protective glaze to obtain wear-resistant ceramic. The firing temperature is 1145℃, and the firing time is 45 minutes.

[0046] The in-situ precipitated micro-nano-sized hematite crystals, due to their small size (micro-nano scale), exhibit relatively weak light scattering effects, achieving a significant improvement in wear resistance while maintaining high transparency and gloss. Figure 1 The nucleation and growth of hematite microcrystals filled the micropores between almandine garnet particles and in the glass matrix, reducing the microporosity and venting of the glaze layer, improving the overall density of the glaze surface, and simultaneously improving its anti-fouling performance. Figure 2 ).

[0047] Example 2

[0048] The preparation method of wear-resistant ceramics includes the following steps: Step 1. Prepare the green body and dry it. The chemical composition of the green body includes, by mass percentage: SiO2: 66.5%, Al2O3: 18.4%, Fe2O3: 0.5%, TiO2: 0.1%, CaO: 3.5%, MgO: 0.8%, K2O: 3.2%, Na2O: 2.2%, and loss on ignition: 4.8%.

[0049] Step 2. Apply a top coat of glaze to the dried body. The chemical composition of the glaze is as follows (by mass percentage): SiO2: 54.2%, Al2O3: 27.6%, Fe2O3: 0.4%, TiO2: 0.46%, CaO: 0.21%, MgO: 0.25%, K2O: 4.62%, Na2O: 2.42%, P2O5: 0.2%, ZrO2: 5.74%, Loss on ignition: 3.9%. The glaze is applied by spraying, with a specific gravity of 1.5 g / cm³. 3 Glazing amount is 650 g / m 2 .

[0050] Step 3. Inkjet print an ink pattern onto the surface of the glazed body.

[0051] Step 4. Apply a wear-resistant protective glaze to the surface of the blank after inkjet printing the ink pattern. The mineral composition of the wear-resistant protective glaze includes, by mass percentage: 5% kaolin, 16% quartz, 20% wollastonite, 5% calcined talc, 8% almandine, 33% calcium aluminum frit, 6% alumina, 4% zinc oxide, and 3% iron oxide. The chemical composition of the calcium aluminum frit includes, by mass percentage: 0.5% IL, 50.18% SiO2, 19.7% Al2O3, 0.06% Fe2O3, 0.02% TiO2, 14.8% CaO, 3.5% MgO, 4.11% K2O, 2.33% Na2O, 1.3% ZnO, and 3.5% BaO. The D of the almandine... 50 The particle size is 3~8μm. A wear-resistant protective glaze is applied using a spray glazing method, with a specific gravity of 1.55 g / cm³. 3 Glazing amount is 680 g / m 2 .

[0052] Step 5. Firing and polishing the green body after applying the wear-resistant protective glaze to obtain wear-resistant ceramic. The firing temperature is 1145℃, and the firing time is 45 minutes.

[0053] Comparative Example 1 (Basic Formula) The preparation method of wear-resistant ceramics includes the following steps: Step 1. Prepare the green body and dry it. The chemical composition of the green body includes, by mass percentage: SiO2: 66.5%, Al2O3: 18.4%, Fe2O3: 0.5%, TiO2: 0.1%, CaO: 3.5%, MgO: 0.8%, K2O: 3.2%, Na2O: 2.2%, and loss on ignition: 4.8%.

[0054] Step 2. Apply a top coat of glaze to the dried body. The chemical composition of the glaze is as follows (by mass percentage): SiO2: 54.54%, Al2O3: 27.6%, Fe2O3: 0.4%, TiO2: 0.12%, CaO: 0.21%, MgO: 0.25%, K2O: 4.62%, Na2O: 2.42%, P2O5: 0.2%, ZrO2: 5.74%, Loss on ignition: 3.9%. The glaze is applied by spraying, and its specific gravity is approximately 1.5 g / cm³. 3 Glazing amount is 650 g / m 2 .

[0055] Step 3. Inkjet print an ink pattern onto the surface of the glazed body.

[0056] Step 4. Apply a wear-resistant protective glaze to the surface of the blank after inkjet printing the ink pattern. The mineral composition of the wear-resistant protective glaze includes, by mass percentage: 5% kaolin, 20% quartz, 20% wollastonite, 6% calcined talc, 40% calcium aluminum frit, 5% alumina, and 4% zinc oxide. The chemical composition of the calcium aluminum frit includes, by mass percentage: 0.5% IL, 50.18% SiO2, 19.7% Al2O3, 0.06% Fe2O3, 0.02% TiO2, 14.8% CaO, 3.5% MgO, 4.11% K2O, 2.33% Na2O, 1.3% ZnO, and 3.5% BaO. The wear-resistant protective glaze is applied by spraying, with a specific gravity of 1.55 g / cm³. 3 Glazing amount is 680 g / m 2 .

[0057] Step 5. Firing and polishing the green body after applying the wear-resistant protective glaze to obtain wear-resistant ceramic. The firing temperature is 1145℃, and the firing time is 45 minutes.

[0058] Comparative Example 2 The preparation method of wear-resistant ceramics includes the following steps: Step 1. Prepare the green body and dry it. The chemical composition of the green body includes, by mass percentage: SiO2: 66.5%, Al2O3: 18.4%, Fe2O3: 0.5%, TiO2: 0.1%, CaO: 3.5%, MgO: 0.8%, K2O: 3.2%, Na2O: 2.2%, and loss on ignition: 4.8%.

[0059] Step 2. Apply a top coat of glaze to the dried body. The chemical composition of the glaze is as follows (by mass percentage): SiO2: 54.54%, Al2O3: 27.6%, Fe2O3: 0.4%, TiO2: 0.12%, CaO: 0.21%, MgO: 0.25%, K2O: 4.62%, Na2O: 2.42%, P2O5: 0.2%, ZrO2: 5.74%, Loss on ignition: 3.9%. The glaze is applied by spraying, and its specific gravity is approximately 1.5 g / cm³. 3 Glazing amount is 650 g / m 2 .

[0060] Step 3. Inkjet print an ink pattern onto the surface of the glazed body.

[0061] Step 4. Apply a wear-resistant protective glaze to the surface of the blank after inkjet printing the ink pattern. The mineral composition of the wear-resistant protective glaze includes, by mass percentage: 5% kaolin, 15% quartz, 19% wollastonite, 4% calcined talc, 12% almandine garnet, 36% calcium aluminum frit, 5% alumina, and 4% zinc oxide. The chemical composition of the calcium aluminum frit includes, by mass percentage: 0.5% IL, 50.18% SiO2, 19.7% Al2O3, 0.06% Fe2O3, 0.02% TiO2, 14.8% CaO, 3.5% MgO, 4.11% K2O, 2.33% Na2O, 1.3% ZnO, and 3.5% BaO. The D of the almandine garnet... 50 The particle size is 3~8μm. A wear-resistant protective glaze is applied using a spray glazing method, with a specific gravity of 1.55 g / cm³. 3 Glazing amount is 680 g / m 2 .

[0062] Step 5. Firing and polishing the green body after applying the wear-resistant protective glaze to obtain wear-resistant ceramic. The firing temperature is 1145℃, and the firing time is 45 minutes.

[0063] Comparative Example 3 The preparation method of wear-resistant ceramics includes the following steps: Step 1. Prepare the green body and dry it. The chemical composition of the green body includes, by mass percentage: SiO2: 66.5%, Al2O3: 18.4%, Fe2O3: 0.5%, TiO2: 0.1%, CaO: 3.5%, MgO: 0.8%, K2O: 3.2%, Na2O: 2.2%, and loss on ignition: 4.8%.

[0064] Step 2. Apply a top coat of glaze to the dried body. The chemical composition of the glaze is as follows (by mass percentage): SiO2: 54.54%, Al2O3: 27.6%, Fe2O3: 0.4%, TiO2: 0.12%, CaO: 0.21%, MgO: 0.25%, K2O: 4.62%, Na2O: 2.42%, P2O5: 0.2%, ZrO2: 5.74%, Loss on ignition: 3.9%. The glaze is applied by spraying, and its specific gravity is approximately 1.5 g / cm³. 3 Glazing amount is 650 g / m 2 .

[0065] Step 3. Inkjet print an ink pattern onto the surface of the glazed body.

[0066] Step 4. Apply a wear-resistant protective glaze to the surface of the blank after inkjet printing the ink pattern. The mineral composition of the wear-resistant protective glaze includes, by mass percentage: 5% kaolin, 15% quartz, 19% wollastonite, 4% calcined talc, 36% calcium aluminum frit, 5% alumina, 4% zinc oxide, and 12% iron oxide. The chemical composition of the calcium aluminum frit includes, by mass percentage: 0.5% IL, 50.18% SiO2, 19.7% Al2O3, 0.06% Fe2O3, 0.02% TiO2, 14.8% CaO, 3.5% MgO, 4.11% K2O, 2.33% Na2O, 1.3% ZnO, and 3.5% BaO. The wear-resistant protective glaze is applied by spraying, with a specific gravity of 1.55 g / cm³. 3 Glazing amount is 680 g / m 2 .

[0067] Step 5. Firing and polishing the green body after applying the wear-resistant protective glaze to obtain wear-resistant ceramic. The firing temperature is 1145℃, and the firing time is 45 minutes.

[0068] Comparative Example 4 The preparation method of wear-resistant ceramics includes the following steps: Step 1. Prepare the green body and dry it. The chemical composition of the green body includes, by mass percentage: SiO2: 66.5%, Al2O3: 18.4%, Fe2O3: 0.5%, TiO2: 0.1%, CaO: 3.5%, MgO: 0.8%, K2O: 3.2%, Na2O: 2.2%, and loss on ignition: 4.8%.

[0069] Step 2. Apply a top coat of glaze to the dried body. The chemical composition of the glaze is as follows (by mass percentage): SiO2: 54.54%, Al2O3: 27.6%, Fe2O3: 0.4%, TiO2: 0.12%, CaO: 0.21%, MgO: 0.25%, K2O: 4.62%, Na2O: 2.42%, P2O5: 0.2%, ZrO2: 5.74%, Loss on ignition: 3.9%. The glaze is applied by spraying, and its specific gravity is approximately 1.5 g / cm³. 3 Glazing amount is 650 g / m 2 .

[0070] Step 3. Inkjet print an ink pattern onto the surface of the glazed body.

[0071] Step 4. Apply a wear-resistant protective glaze to the surface of the blank after inkjet printing the ink pattern. The mineral composition of the wear-resistant protective glaze includes, by mass percentage: 5% kaolin, 15% quartz, 15% wollastonite, 4% calcined talc, 20% almandine garnet, 30% calcium aluminum frit, 5% alumina, 4% zinc oxide, and 2% iron oxide. The chemical composition of the calcium aluminum frit includes, by mass percentage: 0.5% IL, 50.18% SiO2, 19.7% Al2O3, 0.06% Fe2O3, 0.02% TiO2, 14.8% CaO, 3.5% MgO, 4.11% K2O, 2.33% Na2O, 1.3% ZnO, and 3.5% BaO. The D of the almandine garnet... 50 The particle size is 3~8μm. A wear-resistant protective glaze is applied using a spray glazing method, with a specific gravity of 1.55 g / cm³. 3 Glazing amount is 680 g / m 2 .

[0072] Step 5. Firing and polishing the green body after applying the wear-resistant protective glaze to obtain wear-resistant ceramic. The firing temperature is 1145℃, and the firing time is 45 minutes.

[0073] Comparative Example 5 The preparation method of wear-resistant ceramics includes the following steps: Step 1. Prepare the green body and dry it. The chemical composition of the green body includes, by mass percentage: SiO2: 66.5%, Al2O3: 18.4%, Fe2O3: 0.5%, TiO2: 0.1%, CaO: 3.5%, MgO: 0.8%, K2O: 3.2%, Na2O: 2.2%, and loss on ignition: 4.8%.

[0074] Step 2. Apply a top coat of glaze to the dried body. The chemical composition of the glaze is as follows (by mass percentage): SiO2: 54.54%, Al2O3: 27.6%, Fe2O3: 0.4%, TiO2: 0.12%, CaO: 0.21%, MgO: 0.25%, K2O: 4.62%, Na2O: 2.42%, P2O5: 0.2%, ZrO2: 5.74%, Loss on ignition: 3.9%. The glaze is applied by spraying, and its specific gravity is approximately 1.5 g / cm³. 3 Glazing amount is 650 g / m 2 .

[0075] Step 3. Inkjet print an ink pattern onto the surface of the glazed body.

[0076] Step 4. Apply a wear-resistant protective glaze to the surface of the blank after inkjet printing the ink pattern. The mineral composition of the wear-resistant protective glaze includes, by mass percentage: 5% kaolin, 15% quartz, 19% wollastonite, 4% calcined talc, 10% almandine, 36% calcium aluminum frit, 5% alumina, 4% zinc oxide, and 2% iron oxide. The chemical composition of the calcium aluminum frit includes, by mass percentage: 0.5% IL, 50.18% SiO2, 19.7% Al2O3, 0.06% Fe2O3, 0.02% TiO2, 14.8% CaO, 3.5% MgO, 4.11% K2O, 2.33% Na2O, 1.3% ZnO, and 3.5% BaO. The D of the almandine... 50 The particle size is 3~8μm. A wear-resistant protective glaze is applied using a spray glazing method, with a specific gravity of 1.55 g / cm³. 3 Glazing amount is 950 g / m 2 .

[0077] Step 5. Firing and polishing the green body after applying the wear-resistant protective glaze to obtain wear-resistant ceramic. The firing temperature is 1145℃, and the firing time is 45 minutes.

[0078] Comparative Example 6 The preparation method of wear-resistant ceramics includes the following steps: Step 1. Prepare the green body and dry it. The chemical composition of the green body includes, by mass percentage: SiO2: 66.5%, Al2O3: 18.4%, Fe2O3: 0.5%, TiO2: 0.1%, CaO: 3.5%, MgO: 0.8%, K2O: 3.2%, Na2O: 2.2%, and loss on ignition: 4.8%.

[0079] Step 2. Apply a top coat of glaze to the dried body. The chemical composition of the glaze is as follows (by mass percentage): SiO2: 54.54%, Al2O3: 27.6%, Fe2O3: 0.4%, TiO2: 0.12%, CaO: 0.21%, MgO: 0.25%, K2O: 4.62%, Na2O: 2.42%, P2O5: 0.2%, ZrO2: 5.74%, Loss on ignition: 3.9%. The glaze is applied by spraying, and its specific gravity is approximately 1.5 g / cm³. 3 Glazing amount is 650 g / m 2 .

[0080] Step 3. Inkjet print an ink pattern onto the surface of the glazed body.

[0081] Step 4. Apply a wear-resistant protective glaze to the surface of the blank after inkjet printing the ink pattern. The wear-resistant protective glaze is a reinforced formula with added high-hardness particles. The mineral composition of the wear-resistant protective glaze includes, by mass percentage: 5% kaolin, 15% quartz, 19% wollastonite, 4% calcined talc, 36% calcium aluminum frit, 5% alumina, 4% zinc oxide, and 12% magnesium aluminum spinel. The chemical composition of the magnesium aluminum spinel includes, by mass percentage: 0.18% L, 0.5% SiO2, 71% Al2O3, 0.2% Fe2O3, 0.02% TiO2, 0.5% CaO, 27.2% MgO, and 0.4% Na2O. The chemical composition of the calcium-aluminum frit includes, by mass percentage: IL: 0.5%, SiO2: 50.18%, Al2O3: 19.7%, Fe2O3: 0.06%, TiO2: 0.02%, CaO: 14.8%, MgO: 3.5%, K2O: 4.11%, Na2O: 2.33%, ZnO: 1.3%, BaO: 3.5%. A wear-resistant protective glaze is applied using a spray glazing method, with a specific gravity of 1.55 g / cm³. 3 Glazing amount is 680 g / m 2 .

[0082] Step 5. Firing and polishing the green body after applying the wear-resistant protective glaze to obtain wear-resistant ceramic. The firing temperature is 1145℃, and the firing time is 45 minutes.

[0083] Testing of abrasion-resistant ceramic samples: Abrasion resistance grade and rotation count were tested according to GB / T 3810.7-2016 "Test Methods for Ceramic Tiles Part 7: Determination of Abrasion Resistance of Glazed Tiles". The Mohs hardness pen was used to test the glaze hardness (grades 1-10). Stain resistance was tested according to GB / T3810.14 "Test Methods for Ceramic Tiles Part 14: Determination of Stain Resistance". The gloss of the glaze was tested using a gloss meter.

[0084] Table 1 .

[0085] Comparative Example 1, due to the lack of high-hardness additives and the absence of self-crystallization of the glaze, resulted in poor wear resistance of the glaze surface, with a wear resistance level of 3 at 1500 revolutions.

[0086] Comparative Example 2, due to the introduction of only garnet, showed improved wear resistance compared to Comparative Example 1. However, the lack of hematite microcrystals to fill the micropores prevented the reduction of microporosity and venting in the glaze layer, resulting in a lack of toughness and insufficient density, which in turn reduced its stain resistance.

[0087] Comparative Example 3 shows that the use of only iron oxide caused hematite crystals to precipitate in the glaze layer. Since hematite crystals have a Mohs hardness of 5-6, it was impossible to effectively improve the wear resistance of the glaze surface.

[0088] In Comparative Example 4, the excessive introduction of aluminum garnet resulted in too much free iron in the glaze layer, causing the glaze surface to turn brown. At the same time, the excessive garnet dispersed in the glaze layer also led to a decrease in light transmittance and glaze layer opacity.

[0089] Comparative Example 5 showed that due to the increased application of the wear-resistant protective glaze, the glaze layer became thicker, resulting in greater resistance to bubble expulsion and loss of glaze transparency.

[0090] Comparative Example 6 uses the introduction of magnesium aluminum spinel phase reinforcement to improve the wear resistance of the glaze. In terms of wear resistance, Mohs hardness and stain resistance, the effects of Examples 1 and 2 are similar to those of Comparative Example 6. However, magnesium aluminum spinel is expensive and can easily cause the glaze to appear dull white or cloudy.

Claims

1. A wear-resistant protective glaze, characterized in that, The mineral composition of the wear-resistant protective glaze includes, by mass percentage: 3%~8% kaolin, 10%~20% quartz, 15%~25% wollastonite, 3%~5% calcined talc, 8%~12% almandine, 30%~40% calcium aluminum frit, 3%~8% alumina, 2%~5% zinc oxide, and 1%~3% iron oxide.

2. The wear-resistant protective glaze according to claim 1, characterized in that, The chemical composition of the calcium-aluminum ingot includes, by mass percentage: IL: 0~1%, SiO2: 48%~52%, Al2O3: 18%~22%, Fe2O3: 0.01~0.2%, TiO2: 0.01~0.2%, CaO: 13%~18%, MgO: 3%~6%, K2O: 3%~5%, Na2O: 2%~3%, ZnO: 1%~2%, BaO: 2%~5%.

3. The wear-resistant protective glaze according to claim 1 or 2, characterized in that, The mineral composition of the calcium-aluminum frit includes, by mass percentage: quartz 3%~7%, kaolin 8%~12%, potassium feldspar 17%~21%, sodium feldspar 15%~17%, calcined talc 10%~14%, calcite 20%~26%, zinc oxide 1%~3%, barium carbonate 2%~6%, and aluminum oxide 6%~8%.

4. The wear-resistant protective glaze according to claim 1, characterized in that, D of Almandine 50 The particle size is 2~15μm.

5. The wear-resistant protective glaze according to claim 1, characterized in that, The chemical composition of the wear-resistant protective glaze includes, by mass percentage: IL: 1%~2%, SiO2: 50%~54%, Al2O3: 15%~18%, Fe2O3: 3%~6%, TiO2: 0.1%~1%, CaO: 13%~17%, MgO: 2%~4%, K2O: 1%~3%, Na2O: 1%~3%, ZnO: 4%~6%, BaO: 1%~2%.

6. A method for preparing wear-resistant ceramics, characterized in that, The preparation method includes the following steps: Apply a surface glaze to the body; Ink patterns are printed on the surface of the blank after glazing. Apply a wear-resistant protective glaze according to any one of claims 1 to 5 to the surface of the blank after inkjet printing the ink pattern; The green body after applying a wear-resistant protective glaze is fired and polished to obtain wear-resistant ceramics.

7. The preparation method according to claim 6, characterized in that, The wear-resistant protective glaze is applied by spraying; the specific gravity of the wear-resistant protective glaze is 1.5~1.6 g / cm³. 3 The glazing weight is 580~750 g / m² 2 .

8. The preparation method according to claim 6, characterized in that, The chemical composition of the glaze includes, by mass percentage: SiO2: 50%~60%, Al2O3: 25%~35%, Fe2O3: 0.1%~1%, TiO2: 0.1%~1%, CaO: 0.1%~3%, MgO: 0.1%~2%, K2O: 3%~6%, Na2O: 2%~5%, P2O5: 0.01%~1%, ZrO2: 2%~6%, IL: 3%~6%.

9. The preparation method according to claim 6, characterized in that, The glaze is applied by spraying, and its specific gravity is between 1.4 and 1.5 g / cm³. 3 The glaze application rate is 600~750 g / m². 2 .

10. The preparation method according to claim 6, characterized in that, The high-temperature firing temperature is 1140~1160℃, and the firing time is 40~60 minutes.

11. The preparation method according to claim 6, characterized in that, The chemical composition of the billet includes, by mass percentage: SiO2: 65%~70%, Al2O3: 17%~19%, Fe2O3: 0.1%~2%, TiO2: 0.1%~0.3%, CaO: 2.5%~5%, MgO: 0.5%~1%, K2O: 2.5%~4%, Na2O: 1.5%~3%, IL: 4%~6%.

12. A wear-resistant ceramic, characterized in that, The wear-resistant ceramic is obtained by the method for preparing wear-resistant ceramic according to any one of claims 6 to 11.

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