A matte wear-resistant glaze, a matte wear-resistant ceramic tile and a preparation method thereof

Abstract

The present application belongs to the field of building ceramics, and discloses a matte wear-resistant glaze, a matte wear-resistant ceramic tile and a preparation method.The solid components of the matte wear-resistant glaze include, in terms of weight fractions, 47-53 parts of fused quartz powder, 11-14 parts of frit powder and 35-40 parts of low-temperature glaze.The chemical components of the matte wear-resistant glaze include SiO2 and Al2O3 in a molar ratio of (17.4-22.0):1.The matte wear-resistant glaze of the present application has high wear resistance, low gloss, high stain resistance and slip resistance by introducing high-temperature super wear-resistant material fused quartz powder and combining with frit powder, low-temperature glaze and other raw materials.The matte wear-resistant ceramic tile using the matte wear-resistant glaze as a surface glaze layer has high hardness, wear resistance, stain resistance, slip resistance and acid and alkali resistance, and low gloss, thereby meeting the requirements of matte ceramic tiles on color development, wear resistance, slip resistance, stain resistance and the like.

Description

Technical Field

[0001] This invention belongs to the field of building ceramics technology, and specifically relates to a matte wear-resistant glaze, matte wear-resistant ceramic bricks, and their preparation method. Background Technology

[0002] Existing matte ceramic tiles typically achieve low surface gloss and good stain resistance by applying a matte glaze to the surface. However, matte wear-resistant ceramic tiles need to further meet the requirements of high hardness and high wear resistance while maintaining the aforementioned low gloss and stain resistance. Currently, the wear-resistant glaze layer on the surface of wear-resistant ceramic tiles mainly improves wear resistance by introducing high-temperature stable, high-hardness raw materials such as corundum, zircon sand, and zirconium silicate. However, the introduction of these raw materials has inherent technical contradictions: although they can significantly improve the wear resistance of the product, they are prone to causing high-temperature opacity and loss of transparency in the glaze, reducing the transparency of the glaze layer and thus affecting the presentation of the patterns and colors on the surface of the ceramic tile; at the same time, during the high-temperature sintering process, defects such as bubbles and pinholes are easily formed on the surface of the glaze layer, ultimately causing the product's stain resistance to fail to meet the usage requirements. Summary of the Invention

[0003] The present invention aims to improve at least one technical problem in the prior art.

[0004] The first aspect of the present invention provides a matte wear-resistant glaze, the solid components of which, by weight, include: 47-53 parts of fused silica powder, 11-14 parts of frit powder, and 35-40 parts of low-temperature glaze;

[0005] Fused silica powder is obtained by calcining and melting silica sand with a SiO2 content >99.5%;

[0006] The frit powder is obtained by calcining and melting the first raw material, which includes, by weight, 24-28 parts of potassium feldspar, 18-22 parts of sodium feldspar, 16.5-19.5 parts of quartz, 12.5-14.5 parts of calcite, 7-8 parts of kaolin, 5-6 parts of calcined talc, 6-7 parts of zinc oxide, and 2.5-3.5 parts of alumina.

[0007] The raw materials for preparing low-temperature glaze include, by weight, 60-66 parts of albite, 12-14 parts of kaolin, 18.5-21.5 parts of dolomite, 1-2 parts of sillimanite, and 2-3 parts of barium carbonate.

[0008] The chemical composition of the matte wear-resistant glaze includes SiO2 and Al2O3 in a molar ratio of (17.4~22.0):1;

[0009] The particle size of fused silica powder is 10µm~15µm, and the particle size of frit powder is 70µm~75µm.

[0010] The matte wear-resistant glaze provided in this application achieves synergistic optimization of comprehensive performance, including matte finish, wear resistance, and stain resistance, through precise proportioning of each solid component and selection of raw materials. Specifically, the fused silica powder in this application uses high-purity quartz sand with a SiO2 content exceeding 99.5% as raw material, obtained through calcination and melting. It possesses a three-dimensional network of pure SiO2 amorphous molecular structure. In this structure, each Si atom forms a stable tetrahedron with four O atoms, and the O atoms bridge adjacent Si atoms to form a dense and robust covalent bond network. The Si-O bond energy is as high as approximately 460 kJ / mol, effectively resisting damage to the molecular structure from external forces. Furthermore, the amorphous structure avoids defects such as grain boundaries and dislocations found in natural quartz, preventing fracture along grain boundaries under stress and significantly enhancing wear resistance and durability. In addition, the high-temperature melting characteristics of fused silica (its melting point exceeds 1700℃) and its suitable particle size prevent it from participating in excessive melting reactions during firing, helping to reduce porosity formation and ensuring the purity and transparency of the glaze layer. The frit powder in this application is obtained by calcining and melting the first raw material. Because a pre-melting and firing process is completed, the reaction is milder when the frit powder is mixed with other solid components and then fired. This effectively reduces the generation of bubbles and allows for faster bonding with other raw materials, promoting eutectic melting. In the low-temperature glaze of this application, albite can begin to melt at 500-600℃. During the firing process, the molten liquid phase rapidly diffuses and encapsulates other solid components, achieving low-temperature eutectic melting of each component. The synergistic effect of the low-temperature glaze and the frit powder not only reduces the overall sintering temperature of the solid components but also ensures that each component is fully integrated, avoiding excessive volatilization of solid components at high temperatures that would generate bubbles.

[0011] By adjusting the proportions of each raw material, the molar ratio of SiO2 to Al2O3 in the chemical composition of the matte wear-resistant glaze of this application is controlled at (17.4~22.0):1. This specific ratio improves the overall performance by optimizing the chemical structure of the glaze layer. An appropriate amount of Al2O3 can form dense Al-O-Si bonds, which greatly increases the density of the glaze layer and thus enhances its acid and alkali resistance. If the Al2O3 content is too low, it cannot fill the gaps in the glaze glass network, resulting in a loose and non-dense structure that is easily etched by acids and dissolved by alkalis. If the content is too high, it will increase the firing temperature of the glaze layer, increase the exhaust volume, and lead to an increase in pinholes on the glaze surface, which will reduce the density and acid and alkali resistance.

[0012] In some preferred embodiments, the matte wear-resistant glaze comprises, by weight percentage: 80.0%~84.0% SiO2, 6.5%~7.8% Al2O3, 2.8%~3.5% CaO, 1.3%~1.8% MgO, 0.8%~1.2% K2O, 1.6%~2.2% Na2O, 1.7%~2.3% BaO, 0.9%~1.3% ZnO, with the remainder being loss on ignition and impurities.

[0013] The matte wear-resistant glaze of this application controls the content of potassium oxide and sodium oxide to avoid weakening the Si-O network and forming weak bonds that are easily attacked by acids and alkalis, thereby reducing the corrosion and dissolution phenomenon on the glaze surface caused by acid and alkali ion replacement. The alkaline earth metal oxides in the formula play a synergistic role, with zinc oxide helping to improve acid resistance, and barium oxide and magnesium oxide helping to improve alkali resistance.

[0014] In some preferred embodiments, the contents of different phases in the matte wear-resistant glaze are as follows: 5%~7% quartz crystal phase, 1%~2.5% cristobalite crystal phase, 1%~3% sillimanite crystal phase, and 87.5%~93% amorphous phase.

[0015] Quartz crystal phase plays a role in improving mechanical strength; cristobalite crystal phase, in addition to ensuring effective hardness, also effectively improves the color effect of the board surface due to its transparency; while sillimanite crystal phase, with its unique needle-like particle characteristics, stands on the surface and greatly improves the anti-slip properties.

[0016] In some preferred embodiments, the frit powder comprises, by mass percentage: 62.5%~67.7% SiO2, 11.0%~13.0% Al2O3, 7.5%~8.5% CaO, 1.4%~1.8% MgO, 4.0%~4.8% K2O, 2.0%~2.5% Na2O, 6.0%~7.0% ZnO, with the remainder being loss on ignition and impurities.

[0017] In this application, ZnO in the frit powder can form a ZnO-Al2O3-SiO2 eutectic system with Al2O3 and SiO2, and CaO can form a CaO-SiO2 eutectic phase with SiO2. These components work synergistically with the albite in the low-temperature glaze to further optimize the melting effect.

[0018] In some preferred embodiments, the low-temperature glaze comprises, by mass percentage: 53.0%~57.0% SiO2, 19.0%~22.0% Al2O3, 6.2%~7.2% CaO, 4.4%~5.2% MgO, 1.2%~1.7% K2O, 7.4%~8.5% Na2O, 1.8%~2.5% BaO, with the remainder being loss on ignition and impurities.

[0019] The above-mentioned method for preparing fused silica powder includes the following steps:

[0020] Quartz sand is calcined and melted at 1700℃-1800℃, cooled, and crushed to obtain fused quartz powder.

[0021] The above-mentioned method for preparing frit powder includes the following steps:

[0022] The first raw material is mixed and then calcined at 1350℃-1450℃ to melt, cooled, and crushed to obtain frit powder.

[0023] The above-mentioned method for preparing matte wear-resistant glaze includes the following steps:

[0024] Fused quartz powder, frit powder, low-temperature glaze slurry, water, and suspending agent are mixed to obtain a matte wear-resistant glaze.

[0025] The low-temperature glaze slurry is prepared from a low-temperature glaze.

[0026] A second aspect of the present invention provides a matte wear-resistant ceramic tile, comprising a body layer and a matte wear-resistant glaze layer; the matte wear-resistant glaze layer is formed by the aforementioned matte wear-resistant glaze. The gloss of this matte wear-resistant ceramic tile is 3°~5°.

[0027] The fused silica powder introduced as a glassy substance in this application has a coefficient of thermal expansion of 5.5 × 10⁻⁶. -7 / ℃) is much smaller than the bulk layer (approximately 7.3×10). -7 (℃), in addition, the three-dimensional network SiO2 covalent crystal structure has strong bond energy and dense arrangement, with no weak points such as intermolecular gaps and grain boundaries. Its high stability and low expansion characteristics can effectively reduce glaze cracking. During the later stage of firing, the relatively high expansion coefficient of the body will cause a large shrinkage, which will compress the surface glaze layer and form a certain compressive stress on the surface of the matte wear-resistant glaze layer, further improving the density of the matte wear-resistant glaze layer.

[0028] The matte wear-resistant glaze of this application provides reliable acid and alkali resistance, high hardness and high wear resistance for matte wear-resistant ceramic tiles while ensuring an antique matte visual effect (gloss level is stably controlled at 3°~5°).

[0029] In some preferred embodiments, the matte wear-resistant ceramic tile comprises, in sequence, a body layer, a glaze layer, a pattern layer, and a matte wear-resistant glaze layer.

[0030] A third aspect of this invention provides a method for preparing the above-mentioned matte wear-resistant ceramic tile, comprising the following steps:

[0031] A matte, wear-resistant glaze is applied to the surface of the body layer, fired, and then brushed and polished to obtain matte, wear-resistant ceramic tiles.

[0032] The specific gravity of the matte wear-resistant glaze is 1.14 g / cm³. 3 ~1.18g / cm 3 The application rate is 260g / m 2 ~280g / m 2 .

[0033] In some preferred embodiments, the matte wear-resistant ceramic tile sequentially comprises a body layer, a surface glaze layer, a pattern layer, and a matte wear-resistant glaze layer; wherein the surface glaze layer is formed by surface glaze, and the pattern layer is formed by colored ink; its preparation method includes the following steps:

[0034] A surface glaze is applied to the surface of the body layer, then colored ink is printed, followed by the application of a matte wear-resistant glaze, firing, and brushing and polishing to obtain a matte wear-resistant ceramic tile.

[0035] The beneficial effects of this invention are as follows: The matte wear-resistant glaze provided by this invention introduces high-temperature ultra-wear-resistant fused silica powder and combines it with raw materials such as frit powder and low-temperature glaze, giving the matte wear-resistant glaze high wear resistance while also maintaining low gloss, high stain resistance, and anti-slip properties. Matte wear-resistant ceramic tiles using this matte wear-resistant glaze as the surface glaze layer exhibit high hardness, wear resistance, stain resistance, anti-slip properties, and acid and alkali resistance, while having a low gloss level, thus meeting a series of requirements for matte ceramic tiles in terms of color development, wear resistance, anti-slip properties, and stain resistance. Attached Figure Description

[0036] To more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0037] Figure 1 The image shows the XRD phase diagram of the matte wear-resistant glaze layer of the matte wear-resistant ceramic tile prepared in Example 1. Detailed Implementation

[0038] The present invention will be further described below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Furthermore, it should be understood that after reading the description of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the appended claims.

[0039] Example 1

[0040] A matte wear-resistant glaze, the solid components of which, by weight, include: 50 parts fused silica powder, 12.5 parts frit powder, and 37.5 parts low-temperature glaze.

[0041] The fused silica powder is obtained by calcining and melting silica sand with a SiO2 content >99.5%. The preparation method of the fused silica powder includes the following steps: calcining and melting silica sand at 1750℃, cooling, and crushing to obtain fused silica powder. The particle size of the fused silica powder is 12.5µm.

[0042] The frit powder is obtained by calcining and melting the first raw material, which, by weight, includes: 26 parts potassium feldspar, 20 parts sodium feldspar, 18 parts quartz, 13.5 parts calcite, 7.5 parts kaolin, 5.5 parts calcined talc, 6.5 parts zinc oxide, and 3 parts alumina. The frit powder, by mass percentage, includes: 65.13% SiO2, 12.05% Al2O3, 8.06% CaO, 1.58% MgO, 4.31% K2O, 2.23% Na2O, and 6.47% ZnO, with the remainder being loss on ignition and impurities. The preparation method of the frit powder includes the following steps: mixing the first raw material and calcining and melting it at 1400℃, cooling (rapidly cooling via water-cooled metal rollers), and crushing to obtain the frit powder. The particle size of the frit powder is 72.5µm.

[0043] The raw materials for preparing the low-temperature glaze, by weight, include: 63 parts of albite, 13 parts of kaolin, 20 parts of dolomite, 1.5 parts of sillimanite, and 2.5 parts of barium carbonate; the low-temperature glaze, by mass percentage, includes: 55.38% SiO2, 20.5% Al2O3, 6.68% CaO, 4.84% MgO, 1.47% K2O, 8.01% Na2O, and 2.12% BaO, with the remainder being loss on ignition and impurities.

[0044] The matte wear-resistant glaze comprises, by mass percentage: 82.05% SiO2, 7.17% Al2O3, 3.16% CaO, 1.54% MgO, 0.99% K2O, 1.93% Na2O, 2.02% BaO, and 1.12% ZnO, with the remainder being loss on ignition and impurities; the molar ratio of SiO2 to Al2O3 is 19.45:1.

[0045] The preparation method of this matte wear-resistant glaze includes the following steps:

[0046] First, the raw materials for preparing low-temperature glaze are mixed with water, thickener (methylcellulose), and dispersant (sodium tripolyphosphate) (the mass ratio of raw materials for preparing low-temperature glaze, water, thickener, and dispersant is 100:30:0.15:0.35). Then, the mixture is ground, sieved, and aged to obtain a low-temperature glaze slurry.

[0047] The fused silica powder, frit powder, low-temperature glaze slurry, water (70 parts), and suspending agent (18 parts) are mixed to obtain a matte wear-resistant glaze.

[0048] This embodiment also provides a matte wear-resistant ceramic tile, including a body layer and a matte wear-resistant glaze layer; the matte wear-resistant glaze layer is formed by the matte wear-resistant glaze of this embodiment.

[0049] The preparation method of this matte wear-resistant ceramic tile includes the following steps:

[0050] The pre-dried body layer (with a moisture content controlled below 0.3%; the body layer has a through-body effect, which may be a body layer with a granular effect, a body layer with a linear or blocky pattern effect, or a body layer with a combination of both) is fed into the glaze spraying equipment, and a matte wear-resistant glaze (specific gravity 1.16 g / cm³) is applied to the surface of the body layer. 3 The application rate is 270g / m 2 );

[0051] It is then placed in a kiln for firing (the maximum firing temperature is 1150℃, and the firing time is 50 minutes).

[0052] Remove and polish to obtain matte, wear-resistant ceramic tiles.

[0053] Example 2

[0054] A matte wear-resistant glaze, the solid components of which, by weight, include: 47.5 parts fused silica powder, 14 parts frit powder, and 38.5 parts low-temperature glaze.

[0055] The fused silica powder is obtained by calcining and melting quartz sand with a SiO2 content >99.5%. The preparation method of the fused silica powder includes the following steps: calcining and melting quartz sand at 1800℃, cooling, and crushing to obtain fused silica powder. The particle size of the fused silica powder is 10µm.

[0056] The frit powder is obtained by calcining and melting the first raw material, which, by weight, includes: 24 parts potassium feldspar, 22 parts sodium feldspar, 19 parts quartz, 12.5 parts calcite, 8 parts kaolin, 6 parts calcined talc, 6 parts zinc oxide, and 2.5 parts alumina. The frit powder, by mass percentage, includes: 67.01% SiO2, 11.14% Al2O3, 7.63% CaO, 1.66% MgO, 4.01% K2O, 2.34% Na2O, and 6.06% ZnO, with the remainder being loss on ignition and impurities. The preparation method of the frit powder includes the following steps: mixing the first raw material and calcining and melting it at 1400℃, cooling (rapidly cooling via water-cooled metal rollers), and crushing to obtain the frit powder. The particle size of the frit powder is 70µm.

[0057] The raw materials for preparing the low-temperature glaze, by weight, include: 65.5 parts of albite, 12 parts of kaolin, 18.5 parts of dolomite, 2 parts of sillimanite, and 2 parts of barium carbonate; the low-temperature glaze, by mass percentage, includes: 56.5% SiO2, 19.4% Al2O3, 6.36% CaO, 4.47% MgO, 1.63% K2O, 8.39% Na2O, and 1.9% BaO, with the remainder being loss on ignition and impurities.

[0058] The matte wear-resistant glaze comprises, by mass percentage: 83.41% SiO2, 6.63% Al2O3, 2.89% CaO, 1.34% MgO, 0.85% K2O, 2.1% Na2O, 1.77% BaO, and 0.99% ZnO, with the remainder being loss on ignition and impurities; the molar ratio of SiO2 to Al2O3 is 21.39:1.

[0059] The preparation method of this matte wear-resistant glaze includes the following steps:

[0060] First, the raw materials for preparing low-temperature glaze are mixed with water, thickener (methylcellulose), and dispersant (sodium tripolyphosphate) (the mass ratio of raw materials for preparing low-temperature glaze, water, thickener, and dispersant is 100:30:0.15:0.35). Then, the mixture is ground, sieved, and aged to obtain a low-temperature glaze slurry.

[0061] The fused silica powder, frit powder, low-temperature glaze slurry, water (70 parts), and suspending agent (18 parts) are mixed to obtain a matte wear-resistant glaze.

[0062] This embodiment also provides a matte wear-resistant ceramic tile, including a body layer and a matte wear-resistant glaze layer; the matte wear-resistant glaze layer is formed by the matte wear-resistant glaze of this embodiment.

[0063] The preparation method of this matte wear-resistant ceramic tile includes the following steps:

[0064] The pre-dried body layer (with a moisture content controlled below 0.3%; the body layer has a through-body effect, which may be a body layer with a granular effect, a body layer with a linear or block pattern effect, or a body layer with a combination of both) is fed into the glaze spraying equipment, and a matte wear-resistant glaze (specific gravity 1.14 g / cm³) is applied to the surface of the body layer. 3 The application rate is 280g / m 2 );

[0065] It is then placed in a kiln for firing (the maximum firing temperature is 1140℃, and the firing time is 45 minutes).

[0066] Remove and polish to obtain matte, wear-resistant ceramic tiles.

[0067] Example 3

[0068] A matte wear-resistant glaze, the solid components of which, by weight, include: 52.5 parts fused silica powder, 11 parts frit powder, and 36.5 parts low-temperature glaze.

[0069] The fused silica powder is obtained by calcining and melting quartz sand with a SiO2 content >99.5%. The preparation method of the fused silica powder includes the following steps: calcining and melting quartz sand at 1750℃, cooling, and crushing to obtain fused silica powder. The particle size of the fused silica powder is 15µm.

[0070] The frit powder is obtained by calcining and melting the first raw material, which, by weight, includes: 28 parts potassium feldspar, 18 parts sodium feldspar, 17 parts quartz, 14.5 parts calcite, 7 parts kaolin, 5 parts calcined talc, 7 parts zinc oxide, and 3.5 parts alumina. The frit powder, by mass percentage, includes: 62.98% SiO2, 12.86% Al2O3, 8.43% CaO, 1.45% MgO, 4.51% K2O, 2.05% Na2O, and 6.85% ZnO, with the remainder being loss on ignition and impurities. The preparation method of the frit powder includes the following steps: mixing the first raw material and calcining and melting it at 1400℃, cooling (rapidly cooling via water-cooled metal rollers), and crushing to obtain the frit powder. The particle size of the frit powder is 75µm.

[0071] The raw materials for preparing the low-temperature glaze, by weight, include: 60.5 parts of albite, 14 parts of kaolin, 21.5 parts of dolomite, 1 part of sillimanite, and 3 parts of barium carbonate; the low-temperature glaze, by mass percentage, includes: 53.37% SiO2, 21.6% Al2O3, 7.08% CaO, 5.07% MgO, 1.34% K2O, 7.57% Na2O, and 2.39% BaO, with the remainder being loss on ignition and impurities.

[0072] The matte wear-resistant glaze comprises, by mass percentage: 80.68% SiO2, 7.65% Al2O3, 3.43% CaO, 1.68% MgO, 1.16% K2O, 1.65% Na2O, 2.21% BaO, and 1.23% ZnO, with the remainder being loss on ignition and impurities; the molar ratio of SiO2 to Al2O3 is 17.93:1.

[0073] The preparation method of this matte wear-resistant glaze includes the following steps:

[0074] First, the raw materials for preparing low-temperature glaze are mixed with water, thickener (methylcellulose), and dispersant (sodium tripolyphosphate) (the mass ratio of raw materials for preparing low-temperature glaze, water, thickener, and dispersant is 100:30:0.15:0.35). Then, the mixture is ground, sieved, and aged to obtain a low-temperature glaze slurry.

[0075] The fused silica powder, frit powder, low-temperature glaze slurry, water (70 parts), and suspending agent (18 parts) are mixed to obtain a matte wear-resistant glaze.

[0076] This embodiment also provides a matte wear-resistant ceramic tile, including a body layer and a matte wear-resistant glaze layer; the matte wear-resistant glaze layer is formed by the matte wear-resistant glaze of this embodiment.

[0077] The preparation method of this matte wear-resistant ceramic tile includes the following steps:

[0078] The pre-dried body layer (with a moisture content controlled below 0.3%; the body layer has a through-body effect, which may be a body layer with a granular effect, a body layer with a linear or blocky pattern effect, or a body layer with a combination of both) is fed into the glaze spraying equipment, and a matte wear-resistant glaze (specific gravity 1.18 g / cm³) is applied to the surface of the body layer. 3 The application rate is 260g / m 2 );

[0079] It is then placed in a kiln for firing (the maximum firing temperature is 1160℃, and the firing time is 45 minutes).

[0080] Remove and polish to obtain matte, wear-resistant ceramic tiles.

[0081] Example 4

[0082] This embodiment provides a matte wear-resistant glaze and the resulting matte wear-resistant ceramic tile, which differs from Embodiment 1 in that:

[0083] Matte wear-resistant ceramic tiles consist of a body layer, a glaze layer, a pattern layer, and a matte wear-resistant glaze layer; the glaze layer is formed by glaze, and the pattern layer is formed by colored ink.

[0084] The preparation method of this matte wear-resistant ceramic includes the following steps:

[0085] The pre-dried body layer (with moisture content controlled below 0.3%; the body layer may or may not have a through-body effect, where the through-body effect is a body layer containing granular texture or linear / block pattern effects) is fed into the first glaze spraying equipment. A surface glaze is applied to the surface of the body layer. The surface glaze is prepared by the following raw materials by weight: 14 parts potassium feldspar powder, 10 parts sodium feldspar powder, 10 parts calcined alumina, 5 parts calcined kaolin, 23 parts quartz powder, 10 parts kaolin, 18 parts nepheline powder, 2 parts calcined talc powder, and 8 parts zirconium silicate; the surface glaze by mass percentage includes: 56.0% SiO2, 27.26% Al2O3, 0.6% MgO, 2.0% K2O, 4.45% Na2O, and 8.0% ZrO2, with the remainder being loss on ignition and impurities; the specific gravity of the surface glaze is 1.86 g / cm³. 3 The application rate is 450g / m 2 );

[0086] The second glaze is applied using a matte, wear-resistant glaze (specific gravity 1.16 g / cm³). 3 The application rate is 270g / m 2 );

[0087] It is then placed in a kiln for firing (the maximum firing temperature is 1150℃, and the firing time is 50 minutes).

[0088] Remove and polish to obtain matte, wear-resistant ceramic tiles.

[0089] Everything else is the same as in Example 1.

[0090] Comparative Example 1

[0091] This comparative example provides a protective glaze and the ceramic tile formed therefrom, which differs from Example 1 in that:

[0092] The solid components of the protective glaze, by weight, include: 40 parts fused silica powder, 22.5 parts frit powder, and 37.5 parts low-temperature glaze;

[0093] The protective glaze comprises, by mass percentage: 77.61% SiO2, 8.58% Al2O3, 3.7% CaO, 2.35% MgO, 1.33% K2O, 2.56% Na2O, 2.4% BaO, and 1.41% ZnO, with the remainder being loss on ignition and impurities; the molar ratio of SiO2 to Al2O3 is 15.38:1.

[0094] Everything else is the same as in Example 1.

[0095] Comparative Example 2

[0096] This comparative example provides a protective glaze and the ceramic tile formed therefrom, which differs from Example 1 in that:

[0097] The solid components of the protective glaze, by weight, include: 60 parts fused silica powder, 2.5 parts frit powder, and 37.5 parts low-temperature glaze;

[0098] The protective glaze comprises, by mass percentage: 87.58% SiO2, 5.66% Al2O3, 1.93% CaO, 1.01% MgO, 0.57% K2O, 1.22% Na2O, 1.43% BaO, and 0.51% ZnO, with the remainder being loss on ignition and impurities; the molar ratio of SiO2 to Al2O3 is 26.3:1.

[0099] Everything else is the same as in Example 1.

[0100] Comparative Example 3

[0101] This comparative example provides a protective glaze and the ceramic tile formed therefrom, which differs from Example 1 in that:

[0102] The solid components of the protective glaze, by weight, include: 40 parts fused silica powder, 12.5 parts frit powder, and 47.5 parts low-temperature glaze;

[0103] The protective glaze, by mass percentage, comprises: 74.19% SiO2, 9.18% Al2O3, 3.95% CaO, 2.4% MgO, 1.34% K2O, 2.36% Na2O, 2.43% BaO, and 1.51% ZnO, with the remainder being loss on ignition and impurities; the molar ratio of SiO2 to Al2O3 is 13.74:1.

[0104] Everything else is the same as in Example 1.

[0105] Comparative Example 4

[0106] This comparative example provides a protective glaze and the ceramic tile formed therefrom, which differs from Example 1 in that:

[0107] The solid components of the protective glaze, by weight, include: 60 parts fused silica powder, 12.5 parts frit powder, and 27.5 parts low-temperature glaze;

[0108] The protective glaze comprises, by mass percentage: 87.27% SiO2, 5.65% Al2O3, 2.09% CaO, 0.93% MgO, 0.61% K2O, 1.23% Na2O, 1.4% BaO, and 0.76% ZnO, with the remainder being loss on ignition and impurities; the molar ratio of SiO2 to Al2O3 is 26.26:1.

[0109] Everything else is the same as in Example 1.

[0110] Comparative Example 5

[0111] This comparative example provides a protective glaze and the ceramic tile formed therefrom, which differs from Example 1 in that:

[0112] The solid components of the protective glaze, by weight, include: 50 parts fused silica powder, 5 parts frit powder, and 45 parts low-temperature glaze;

[0113] The protective glaze comprises, by mass percentage: 78.52% SiO2, 8.21% Al2O3, 3.6% CaO, 1.87% MgO, 0.75% K2O, 2.39% Na2O, 2.42% BaO, and 0.77% ZnO, with the remainder being loss on ignition and impurities; the molar ratio of SiO2 to Al2O3 is 16.26:1.

[0114] Everything else is the same as in Example 1.

[0115] Comparative Example 6

[0116] This comparative example provides a protective glaze and the ceramic tile formed therefrom, which differs from Example 1 in that:

[0117] The solid components of the protective glaze, by weight, include: 50 parts fused silica powder, 20 parts frit powder, and 30 parts low-temperature glaze;

[0118] The protective glaze comprises, by mass percentage: 85.15% SiO2, 6.03% Al2O3, 2.57% CaO, 1.0% MgO, 1.23% K2O, 1.27% Na2O, 1.4% BaO, and 1.32% ZnO, with the remainder being loss on ignition and impurities; the molar ratio of SiO2 to Al2O3 is 24.0:1.

[0119] Everything else is the same as in Example 1.

[0120] Comparative Example 7

[0121] This comparative example provides a protective glaze and the ceramic tile formed therefrom, which differs from Example 1 in that the particle size of the fused silica powder is greater than 15µm. Everything else is the same as in Example 1.

[0122] Comparative Example 8

[0123] This comparative example provides a protective glaze and the ceramic tile formed therefrom, which differs from Example 1 in that the particle size of the fused silica powder is less than 10µm. Everything else is the same as in Example 1.

[0124] Comparative Example 9

[0125] This comparative example provides a protective glaze and the ceramic tile formed therefrom, which differs from Example 1 in that the particle size of the frit powder is greater than 75µm. Everything else is the same as in Example 1.

[0126] Comparative Example 10

[0127] This comparative example provides a protective glaze and the ceramic tile formed therefrom, which differs from Example 1 in that the particle size of the frit powder is less than 70µm. Everything else is the same as in Example 1.

[0128] Performance testing

[0129] (1) Semi-quantitative phase analysis

[0130] The matte wear-resistant glaze layer of the matte wear-resistant ceramic tiles prepared in Examples 1-4, and the protective glaze layer (formed by protective glaze) of the ceramic tiles prepared in Comparative Examples 1-6, were semi-quantitatively analyzed by X-ray diffraction (XRD). The test results are shown in Table 1. The XRD phase diagram of the matte wear-resistant glaze layer of the matte wear-resistant ceramic tile prepared in Example 1 is shown in Table 1. Figure 1 As shown.

[0131] Table 1

[0132]

[0133] (2) Tests for abrasion resistance, stain resistance, Mohs hardness, slip resistance, acid and alkali resistance and surface quality.

[0134] The matte wear-resistant ceramic tiles prepared in Examples 1-4 and the ceramic tiles prepared in Comparative Examples 1-10 were tested for wear resistance, stain resistance, Mohs hardness, and surface quality. Wear resistance was tested using the method in GB / T 3810.7; stain resistance and surface quality were tested using the method in GB / T 3810.14-2016; surface hardness was tested using a Mohs hardness scratch tester; wear resistance was tested using the method in GB / T 37798-2019 (pendulum method); acid and alkali resistance was tested using the method in GB / T 3810.13-2016; and gloss was tested using a gloss meter. The test results are shown in Tables 2-3.

[0135] Table 2

[0136]

[0137] Table 3

[0138]

[0139] As shown in the test data in Table 2 above, the wear-resistant ceramic tiles prepared using the technical solution of this invention have a gloss of 3~5°, an antique matte visual effect, wear resistance up to level 4 at 6000 revolutions, stain resistance up to level 5, Mohs hardness up to level 7, slip resistance up to level P5, corrosion resistance level A, and are of excellent quality.

[0140] Referring to Table 2, a comparison of Example 1 and Comparative Examples 1-2 shows that when there is less fused silica powder and more frit powder, the high-temperature melting is faster, which leads to a lower reaction melt viscosity during firing, making crystallization more likely, resulting in poor venting and reduced overall transparency of the glaze. Simultaneously, a lower silicon-to-aluminum molar ratio and lower silicon content with higher aluminum content result in more pores on the glaze surface, insufficient density, and consequently, reduced stain resistance, acid and alkali resistance, and hardness. Furthermore, a lower proportion of fused silica powder also leads to a smaller distribution of quartz particles across the entire surface, resulting in poor wear resistance. Conversely, when there is more fused silica powder and less frit powder, high-temperature melting is slower, leading to a higher reaction temperature during firing, resulting in more thorough sintering and better wear resistance. However, the higher silicon content and lower aluminum content result in insufficient Al-O-Si bonds in the glaze layer, preventing it from filling the glass network and resulting in a less dense structure, leading to poor stain resistance, hardness, and acid and alkali resistance.

[0141] Referring to Table 2, a comparison of Example 1 and Comparative Examples 3-4 shows that when there is less fused quartz powder and more low-temperature glaze, the low-temperature melting is obvious, the glaze surface is prone to glaze flow, the glaze surface is not smooth, and the excessively low temperature eventually leads to overfiring, resulting in poor crystallization, poor transparency, and increased surface capillary pores, resulting in poor stain resistance and wear resistance. When there is more fused quartz powder and less low-temperature glaze, the low-temperature fluxing is insufficient, the overall sintering and melting are poor, the glaze surface is dry and rough, the pores are obvious, and the poor mechanical strength and chemical stability result in poor stain resistance, hardness, and acid and alkali resistance.

[0142] Referring to Tables 2 and 3, a comparison of Example 1 and Comparative Examples 5-6 shows that when there is less frit powder and more low-temperature glaze, the low-temperature melting is obvious, and the glaze layer is prone to glaze flow, resulting in surface defects. At the same time, due to the excessive raw material glaze component and the lack of frit, the melting reaction is also more intense, leading to easy crystallization, poor transparency, and increased surface capillary pores, resulting in poor resistance to contamination, wear, and acids and alkalis. When there is more frit powder and less low-temperature glaze, the filling of frit and fused quartz during low-temperature melting is insufficient, which leads to uneven melting and uneven crystallization, resulting in poor local resistance to contamination, acids and alkalis, and wear on the plate surface.

[0143] Referring to Tables 2 and 3, a comparison of Example 1 and Comparative Examples 7-8 shows that when the particle size of the fused silica powder is large, its particle content decreases accordingly, resulting in uneven particle distribution, a rougher glaze surface, and poor stain resistance and wear resistance. When the particle size of the fused silica powder is small, its particle content increases accordingly, which makes the high-temperature fused silica powder easier to melt and reduces its wear resistance.

[0144] Referring to Tables 2 and 3, a comparison of Example 1 and Comparative Examples 9-10 shows that when the particle size of the frit powder is large, its particle content is reduced accordingly, resulting in a rougher surface, poorer surface smoothness, and poor stain resistance and wear resistance. When the particle size of the frit powder is small, the frit powder melts more quickly, making it easier for surface defects to occur, resulting in poor stain resistance, acid and alkali resistance, and wear resistance.

[0145] In the description of this specification, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of indicated technical features. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one of that feature.

[0146] The above description is only a preferred embodiment of the present invention. It should be noted that those skilled in the art can make several improvements and additions without departing from the method of the present invention, and these improvements and additions should also be considered within the scope of protection of the present invention.

Claims

1. A matte wear-resistant glaze, characterized by, The solid components of the matte wear-resistant glaze include, in parts by weight, 47-53 parts of fused quartz powder, 11-14 parts of frit powder, and 35-40 parts of low-temperature glaze; The fused quartz powder is obtained by calcining and fusing quartz sand with a SiO2 content of >99.5%; The frit powder is obtained by calcining and fusing the first raw material, which includes, in parts by weight, 24-28 parts of potassium feldspar, 18-22 parts of sodium feldspar, 16.5-19.5 parts of quartz, 12.5-14.5 parts of calcite, 7-8 parts of kaolin, 5-6 parts of calcined talc, 6-7 parts of zinc oxide, and 2.5-3.5 parts of aluminum oxide; The preparation raw material of the low-temperature glaze includes, in parts by weight, 60-66 parts of sodium feldspar, 12-14 parts of kaolin, 18.5-21.5 parts of dolomite, 1-2 parts of sillimanite, and 2-3 parts of barium carbonate; The chemical components of the matte wear-resistant glaze include SiO2 and Al2O3 in a molar ratio of (17.4-22.0):1; The particle size of the fused quartz powder is 10-15 µm, and the particle size of the frit powder is 70-75 µm.

2. The matte wear-resistant glaze according to claim 1, wherein The matte wear-resistant glaze includes, in mass percentage, 80.0-84.0% of SiO2, 6.5-7.8% of Al2O3, 2.8-3.5% of CaO, 1.3-1.8% of MgO, 0.8-1.2% of K2O, 1.6-2.2% of Na2O, 1.7-2.3% of BaO, and 0.9-1.3% of ZnO, with the remainder being ignition loss and impurities.

3. The matte wear-resistant glaze of claim 1, wherein The contents of different phases in the matte wear-resistant glaze are as follows: 5-7% of quartz crystal phase, 1-2.5% of cristobalite crystal phase, 1-3% of sillimanite crystal phase, and 87.5-93% of amorphous phase.

4. The matte wear-resistant glaze of claim 1, wherein The preparation method of the fused quartz powder includes the following steps: The quartz sand is calcined and fused at 1700-1800 °C, cooled, and crushed to obtain the fused quartz powder.

5. The matte wear-resistant glaze of claim 1, wherein The preparation method of the frit powder includes the following steps: The first raw material is mixed and then calcined and fused, cooled, and crushed to obtain the frit powder.

6. The matte wear-resistant glaze of claim 1, wherein The preparation method of the matte wear-resistant glaze includes the following steps: The fused quartz powder, the frit powder, and the low-temperature glaze slurry are uniformly mixed with water and a suspending agent to obtain the matte wear-resistant glaze. The low-temperature glaze slurry is prepared from the low-temperature glaze.

7. The matte wear-resistant glaze of claim 1, wherein The frit powder includes, in mass percentage, 62.5-67.7% of SiO2, 11.0-13.0% of Al2O3, 7.5-8.5% of CaO, 1.4-1.8% of MgO, 4.0-4.8% of K2O, 2.0-2.5% of Na2O, and 6.0-7.0% of ZnO, with the remainder being ignition loss and impurities. And / or, the low-temperature glaze includes, in mass percentage, 53.0-57.0% of SiO2, 19.0-22.0% of Al2O3, 6.2-7.2% of CaO, 4.4-5.2% of MgO, 1.2-1.7% of K2O, 7.4-8.5% of Na2O, and 1.8-2.5% of BaO, with the remainder being ignition loss and impurities.

8. A matte wear-resistant ceramic tile, characterized by, comprising a body layer and a matte wear-resistant glaze layer; the matte wear-resistant glaze layer is formed by the matte wear-resistant glaze according to any one of claims 1 to 7.

9. A method of producing a matte wear-resistant ceramic tile according to claim 8, characterized in that, comprising the following steps: applying the matte wear-resistant glaze on the surface of the body layer, firing, brushing and polishing to obtain the matte wear-resistant ceramic tile.

10. The method of claim 9, wherein the matte wear-resistant ceramic tile is prepared by the steps of: The specific gravity of the matt wear-resistant glaze is 1.14 g / cm 3 ~1.18 g / cm 3 , the application amount is 260 g / m 2 ~280 g / m 2 .

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