Composite corundum protective glaze, high-wear-resistance, stain-resistant and anti-slip ceramic tile and preparation method thereof

Abstract

The application belongs to the field of building ceramics, and discloses a composite corundum protective glaze, high-wear-resistance, stain-resistance and anti-slip ceramic tile and a preparation method. The raw materials of the composite corundum protective glaze include, by weight, 30-50 parts of sodium feldspar, 3-8 parts of potassium feldspar, 10-20 parts of calcined kaolin, 5-10 parts of corundum, 5-10 parts of calcined alumina, 3-5 parts of zinc oxide, 10-20 parts of calcite, 8-15 parts of dolomite, 4-8 parts of air-knife soil and 2-5 parts of barium carbonate. The corundum is tabular corundum. The firing temperature of the composite corundum protective glaze is 1180-1230 DEG C. The high-wear-resistance, stain-resistance and anti-slip ceramic tile is obtained by forming a glaze layer on the surface of the ceramic tile through the composite corundum protective glaze. The composite corundum protective glaze of the application achieves the core performance target of high wear resistance, strong stain resistance and excellent slip resistance while ensuring smooth glaze surface, non-irritating hand feeling and high-grade matte texture through the synergistic effect of the raw materials.

Description

Technical Field

[0001] This invention belongs to the field of building ceramics technology, and specifically relates to a composite corundum protective glaze, a highly wear-resistant, stain-resistant, and anti-slip ceramic tile, and its preparation method. Background Technology

[0002] With the upgrading of consumption and the significant increase in people's awareness of safety in living spaces, the market demand for high-end anti-slip tiles is rapidly expanding from traditional kitchen and bathroom spaces to the entire home space (such as living room, bedroom, and balcony) and high-end commercial venues (such as hotel lobbies, restaurants, hospitals, and nursing homes). The market is no longer satisfied with products that are "only anti-slip," but has an urgent need for tile products that combine ultimate anti-slip performance, high wear resistance and durability, excellent antibacterial and easy-to-clean properties, and advanced aesthetic effects.

[0003] Traditional anti-slip tiles mainly achieve anti-slip properties by creating an uneven surface using molds or by adding materials such as ordinary alumina. However, they have obvious shortcomings: uneven surfaces are prone to accumulating dirt and are difficult to clean; ordinary anti-slip glazes often lack wear resistance, and their anti-slip performance decreases significantly after a period of use; and the surface texture is inconsistent with the requirements of high-end design. Summary of the Invention

[0004] The present invention aims to improve at least one technical problem in the prior art.

[0005] The first aspect of this invention provides a composite corundum protective glaze, the raw materials of which, by weight, include: 30-50 parts of sodium feldspar, 3-8 parts of potassium feldspar, 10-20 parts of calcined kaolin, 5-10 parts of corundum, 5-10 parts of calcined alumina, 3-5 parts of zinc oxide, 10-20 parts of calcite, 8-15 parts of dolomite, 4-8 parts of air-knife clay, and 2-5 parts of barium carbonate.

[0006] Among them, the above-mentioned corundum is tabular corundum, and the aspect ratio of tabular corundum is (2-4):1.

[0007] The firing temperature of the aforementioned composite corundum protective glaze is 1180℃-1230℃.

[0008] In the composite corundum protective glaze provided in this application, the corundum is tabular corundum, which is sintered from α-Al2O3 near its melting point. The crystals develop into a coarse and complete tabular structure, which has high density, high strength and excellent thermal shock stability. In addition, the tabular corundum in this application has a specific aspect ratio of (2-4):1. This specific aspect ratio allows its tabular crystals to fully interlock and form a stable skeleton, which continuously plays a role in strengthening, toughening and stabilizing the volume as an inert skeleton. With its high hardness and toughness, it directly forms a hard "microscopic anchor point" protrusion structure on the glaze surface, providing the glaze surface with durable and effective anti-slip and anti-wear capabilities.

[0009] In the composite corundum protective glaze provided in this application, the calcined alumina is obtained by calcining industrial alumina at medium and low temperatures. Its crystal type is γ-Al2O3, which has small crystal size, loose and porous structure, and large specific surface area, thus exhibiting high reactivity. Although calcined alumina itself has low strength and wear resistance compared to tabular corundum, at the specific firing temperature of 1180℃-1230℃ specified in this application, γ-Al2O3 is in the critical range of transformation to stable α-Al2O3. This temperature is neither too high, causing the transformation rate to be too fast, nor too low, causing the transformation to be insufficient. It can enhance the atomic migration ability of the γ-Al2O3 particle surface, achieving synergistic effects with other raw materials through solid-phase reaction rather than melting. This not only helps to disperse and sinter in the glaze melt, ensuring a stable glaze texture, but also promotes the precipitation of microcrystals in the glaze melt, working together with tabular corundum to construct an anti-slip surface.

[0010] In this application, calcined alumina plays a crucial role in promoting the formation of a dense "microscopic anchor point" protrusion structure in tabular corundum. The firing temperature of 1180℃-1230℃ is the core prerequisite for achieving this synergistic effect. The high reactivity of calcined alumina (derived from the transformation characteristics of γ-Al2O3 to α-Al2O3) is fully utilized at this temperature, which can effectively promote the overall densification and sintering of the glaze melt, providing an ideal matrix environment for the stable existence and structural formation of tabular corundum. During the transformation process, calcined alumina forms a stable phase on the surface of tabular corundum particles through solid-phase reaction. This phase can precisely fill the tiny gaps between the interlocking tabular corundum particles that form the skeleton, and at the same time form a partial solid solution with the α-Al2O3 lattice of the tabular corundum itself, ultimately allowing the originally independent tabular corundum particles to be firmly combined into one, preventing the "microscopic anchor point" protrusion structure from loosening and falling off. Meanwhile, calcined alumina, as an effective crystallization inducer, can promote the precipitation of more microcrystals in the glaze melt during the temperature control transition process. These microcrystals interact with the tabular corundum particles, like building "cement" around the tabular crystals, further strengthening their interlocking skeleton. The aspect ratio design of the tabular corundum optimizes the adhesion and interlocking space of the microcrystals. Ultimately, the tabular corundum, with its morphological advantages and temperature adaptability, tightly interlocks with the microcrystal network promoted by calcined alumina, jointly constructing a more robust and interlocking "microscopic anchor point" protrusion reinforcement structure, significantly improving the anti-slip and wear resistance of the glaze surface. In addition, calcined alumina can moderately increase the high-temperature viscosity of the glaze melt during the transformation process. This moderate viscosity can prevent the tabular corundum from settling due to excessive fluidity of the glaze melt during firing at 1180℃-1230℃, while ensuring that the glaze melt fully coats the tabular corundum, resulting in a uniform distribution of the tabular corundum. At the same time, the calcined alumina interspersed between the tabular corundum skeletons acts as a physical spacer and a "ball" lubricant. Combined with the aspect ratio design of the tabular corundum, it further reduces its tendency to agglomerate during slurry preparation and glazing, thereby promoting its three-dimensional uniform distribution in the glaze layer.

[0011] In summary, the composite corundum protective glaze provided in this application, through the synergistic combination of tabular corundum and calcined alumina and the reasonable matching of various raw materials, constructs a solid "microscopic anchor point" raised reinforcement structure, achieving a durable and effective anti-slip and anti-wear capability of the glaze surface, while also possessing a stable glaze texture and good wear resistance and stain resistance.

[0012] The aforementioned composite corundum protective glaze comprises, by mass percentage: 48%-55% SiO2, 18%-25% Al2O3, 0%-1% K2O, 1%-4% Na2O, 8%-15% CaO, 1%-4% MgO, 3%-6% ZnO, 0%-1% BaO, with the remainder being trace impurities and loss on ignition.

[0013] In some preferred embodiments, the particle size D50 of the corundum is 5μm-15μm.

[0014] In some preferred embodiments, the particle size D50 of the calcined alumina is 1μm-5μm.

[0015] In some preferred embodiments, the raw materials of the above-mentioned composite corundum protective glaze include, by weight: 34 parts of sodium feldspar, 5 parts of potassium feldspar, 10 parts of calcined kaolin, 6 parts of corundum, 9 parts of calcined alumina, 4 parts of zinc oxide, 12 parts of calcite, 11 parts of dolomite, 6 parts of air-knife clay, and 3 parts of barium carbonate.

[0016] The preparation method of the above-mentioned composite corundum protective glaze includes the following steps:

[0017] The above raw materials are ball-milled with water until the glaze slurry has a fineness of 0.1%-0.5% residue on a 10,000-mesh sieve. After passing through a 325-mesh sieve to remove iron, the glaze is aged for more than 24 hours to obtain a composite corundum protective glaze.

[0018] The total mass of the above-mentioned raw materials is in the mass ratio of water to 1:(0.3-0.45).

[0019] The ball milling time mentioned above is 2h-4h.

[0020] The second aspect of the present invention provides a highly wear-resistant, stain-resistant, and anti-slip ceramic tile, comprising, in sequence: a body layer, a surface glaze layer, a pattern layer, and an anti-slip protective glaze layer;

[0021] The anti-slip protective glaze layer is formed by the aforementioned composite corundum protective glaze.

[0022] The high wear-resistant, stain-resistant, and anti-slip ceramic tile provided in this application has an anti-slip protective glaze layer on the outermost surface formed by the aforementioned composite corundum protective glaze. This glaze can not only tightly cover the surface of the pattern layer, protecting the underlying structure and pattern and preventing wear or contamination of the pattern during use, but also, relying on the properties of the composite corundum protective glaze itself, endow the ceramic tile surface with excellent wear resistance, stain resistance, and anti-slip properties, enabling the ceramic tile to maintain a beautiful decorative effect while possessing long-lasting and stable practical performance.

[0023] A third aspect of this invention provides a method for preparing the above-mentioned high wear-resistant, stain-resistant, and anti-slip ceramic tile, wherein the surface glaze layer is formed by a surface glaze, and the pattern layer is formed by a first ink; the preparation method includes the following steps:

[0024] A surface glaze is applied to the surface of the body layer, then the first ink is printed, followed by the application of a composite corundum protective glaze and firing, resulting in a highly wear-resistant, stain-resistant, and slip-resistant ceramic tile.

[0025] The specific gravity of the aforementioned glaze is 1.85 g / mL to 1.98 g / mL, and the application amount is 395 g / mL. 2 -485g / m 2 The flow rate of the glaze is 32s-45s, and the application method is bell-shaped glaze application.

[0026] The specific gravity of the aforementioned composite corundum protective glaze is 1.25 g / mL-1.35 g / mL, and the application amount is 152 g / mL. 2 -303g / m 2 .

[0027] The firing temperature is 1180℃-1230℃, and the firing time is 35min-60min.

[0028] The edges are ground after firing.

[0029] The beneficial effects of this invention are as follows: The composite corundum protective glaze of this application achieves the core performance goals of high wear resistance, strong stain resistance, and excellent anti-slip properties by ensuring a smooth, non-irritating feel and a high-grade matte texture through the synergistic effect of raw materials. Its simple and efficient preparation method for high wear resistance, stain resistance, and anti-slip ceramic tiles is suitable for the needs of large-scale industrial production and provides a comprehensive solution for high-durability ceramic application scenarios. Attached Figure Description

[0030] 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.

[0031] Figure 1 This is a structural diagram of a high wear-resistant, stain-resistant, and slip-resistant ceramic tile.

[0032] Figure 2 This is a scanning electron microscope (SEM) image of the tabular corundum from Example 1.

[0033] Figure 3 The XRD phase analysis diagram of the high wear-resistant, stain-resistant, and anti-slip ceramic tile prepared in Example 1 is shown below.

[0034] Figure 4 This is a scanning electron microscope (SEM) image of the highly wear-resistant, stain-resistant, and anti-slip ceramic tile prepared in Example 1.

[0035] Figure 5 A picture of the high wear-resistant, stain-resistant, and anti-slip ceramic tile prepared in Example 1 after a grinding test of 6000 revolutions;

[0036] Figure 6 This is a picture of the ceramic tile prepared in Comparative Example 1 after grinding for 6000 revolutions. Detailed Implementation

[0037] 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.

[0038] Example 1

[0039] A composite corundum protective glaze comprises, by weight, the following raw materials: 34 parts albite, 5 parts potassium feldspar, 10 parts calcined kaolin, 6 parts tabular corundum (length-to-diameter ratio 2:1, particle size D50 8 μm), 9 parts calcined alumina (particle size D50 2 μm), 4 parts zinc oxide, 12 parts calcite, 11 parts dolomite, 6 parts air-knife clay, and 3 parts barium carbonate. The SEM image of the tabular corundum is shown below. Figure 2 As shown.

[0040] The composite corundum protective glaze comprises, by weight percentage: 51.13% SiO2, 21.20% Al2O3, 0.82% K2O, 2.54% Na2O, 13.40% CaO, 2.61% MgO, 4.23% ZnO, 0.18% BaO, with the remainder being trace impurities and a loss on ignition of 3.85%.

[0041] The preparation method of this composite corundum protective glaze includes the following steps:

[0042] The above raw materials and water (the total mass of raw materials to the mass ratio of water is 1:0.3) are put into a ball mill and ball milled for 2 hours until the fineness of the glaze slurry is 0.1% residue on a 10,000-mesh sieve. After passing through a 325-mesh sieve to remove iron, the slurry is aged in a storage tank for more than 24 hours to obtain a composite corundum protective glaze.

[0043] This embodiment provides a highly wear-resistant, stain-resistant, and anti-slip ceramic tile, which sequentially comprises: a body layer, a glaze layer, a pattern layer, and an anti-slip protective glaze layer; its structural schematic diagram is shown below. Figure 1 As shown ( Figure 1 In the middle: 1-body layer; 2-glaze layer; 3-pattern layer; 4-anti-slip protective glaze layer).

[0044] The anti-slip protective glaze layer is formed by the composite corundum protective glaze of this embodiment;

[0045] The green body layer, by mass percentage, comprises: SiO2 66.41%, Al2O3 21.29%, K2O 2.62%, Na2O 2.68%, CaO 1.5%, MgO 0.99%, Fe2O3 0.59%, TiO2 0.2%, with the remainder being trace impurities and loss on ignition;

[0046] The surface glaze layer is formed by the surface glaze, and the raw materials of the surface glaze, by weight, include: 22 parts potassium feldspar, 17 parts sodium feldspar, 11 parts high-white nepheline, 3 parts calcined kaolin, 9 parts air-knife clay, 7 parts calcined alumina, 5 parts wollastonite, 13 parts quartz powder, 3 parts zinc oxide, 2 parts matte frit, and 9 parts zirconium silicate. The surface glaze slurry is obtained by mixing and grinding the above-mentioned surface glaze raw materials with 0.2 parts methylcellulose, 0.3 parts sodium tripolyphosphate, and 40 parts water. The fineness of the surface glaze slurry is controlled at 0.25g / 100g slurry (passing through a 325-mesh standard sieve).

[0047] The pattern layer features a stone-like texture, formed by inkjet printing of the first ink pattern using the following components: (Torrexit) CXN-11012 blue ink 0.12ml / m 2 (Taolixi) CXN-55166 Dark Brown Ink 1.06ml / m 2 (Yangtze) NGY82012 packaged yellow ink 1.15ml / m 2 (Taolixi) CXN-40118 Black Ink 0.16ml / m 2 (Taolixi) CXN-31929 Beige Ink 1.23ml / m 2 (Yangtze) NGY82016 packaged red ink 0.56ml / m 2 .

[0048] The preparation method of the high wear-resistant, stain-resistant, and anti-slip ceramic tile in this embodiment includes the following steps:

[0049] The green body layer is fed into the glaze spraying equipment, and the glaze is applied to the surface of the green body layer using the bell jar glazing method (the specific gravity of the glaze is 1.85 g / mL, and the application amount is 395 g / mL). 2 (The flow rate of the applied glaze is 32s).

[0050] Enter the printing device and print the first ink according to the preset stone texture;

[0051] The composite corundum protective glaze is applied using a high-pressure spray gun in the glaze spraying equipment (the specific gravity of the composite corundum protective glaze is 1.25 g / mL, and the application rate is 180 g / mL). 2 );

[0052] The ceramic tiles are fired in a roller kiln (firing temperature is 1180℃, time is 60min), and then the edges are ground in a grinding machine to obtain highly wear-resistant, stain-resistant and slip-resistant ceramic tiles.

[0053] The XRD phase analysis diagram of the high wear-resistant, stain-resistant, and anti-slip ceramic tile prepared in Example 1 is shown below. Figure 3 As shown, the SEM (Scanning Electron Microscope) image is as follows: Figure 4 As shown.

[0054] Example 2

[0055] This embodiment provides a composite corundum protective glaze and the resulting highly wear-resistant, stain-resistant, and anti-slip ceramic tile, which differs from Embodiment 1 in that: (1) the raw materials of the composite corundum protective glaze, by weight, include: 34 parts of sodium feldspar, 5 parts of potassium feldspar, 10 parts of calcined kaolin, 5 parts of corundum, 10 parts of calcined alumina, 4 parts of zinc oxide, 12 parts of calcite, 11 parts of dolomite, 6 parts of air-knife clay, and 3 parts of barium carbonate; (2) the firing temperature is 1200℃. Other aspects are the same as in Embodiment 1.

[0056] Example 3

[0057] This embodiment provides a composite corundum protective glaze and the resulting highly wear-resistant, stain-resistant, and anti-slip ceramic tile, which differs from Embodiment 1 in that: (1) the raw materials of the composite corundum protective glaze, by weight, include: 34 parts of sodium feldspar, 5 parts of potassium feldspar, 10 parts of calcined kaolin, 10 parts of corundum, 5 parts of calcined alumina, 4 parts of zinc oxide, 12 parts of calcite, 11 parts of dolomite, 6 parts of air-knife clay, and 3 parts of barium carbonate; (2) the firing temperature is 1230℃. Other aspects are the same as in Embodiment 1.

[0058] Comparative Example 1

[0059] This comparative example provides a protective glaze and the ceramic tile formed therefrom, which differs from Example 1 in that the raw materials of the protective glaze, by weight, include: 34 parts sodium feldspar, 5 parts potassium feldspar, 10 parts calcined kaolin, 4 parts corundum, 11 parts calcined alumina, 4 parts zinc oxide, 12 parts calcite, 11 parts dolomite, 6 parts air-knife clay, and 3 parts barium carbonate. All other aspects are the same as in Example 1.

[0060] Comparative Example 2

[0061] This comparative example provides a protective glaze and the ceramic tile formed therefrom, which differs from Example 1 in that the raw materials of the protective glaze, by weight, include: 34 parts sodium feldspar, 5 parts potassium feldspar, 10 parts calcined kaolin, 11 parts corundum, 4 parts calcined alumina, 4 parts zinc oxide, 12 parts calcite, 11 parts dolomite, 6 parts air-knife clay, and 3 parts barium carbonate. All other aspects are the same as in Example 1.

[0062] Comparative Example 3

[0063] This comparative example provides a protective glaze and the ceramic tile formed therefrom, which differs from Example 1 in that the raw materials of the protective glaze, by weight, include: 34 parts sodium feldspar, 5 parts potassium feldspar, 10 parts calcined kaolin, 0 parts corundum, 15 parts calcined alumina, 4 parts zinc oxide, 12 parts calcite, 11 parts dolomite, 6 parts air-knife clay, and 3 parts barium carbonate. All other aspects are the same as in Example 1.

[0064] Comparative Example 4

[0065] This comparative example provides a protective glaze and the ceramic tile formed therefrom, which differs from Example 1 in that the raw materials of the protective glaze, by weight, include: 34 parts of sodium feldspar, 5 parts of potassium feldspar, 10 parts of calcined kaolin, 15 parts of corundum, 0 parts of calcined alumina, 4 parts of zinc oxide, 12 parts of calcite, 11 parts of dolomite, 6 parts of air-knife clay, and 3 parts of barium carbonate. All other aspects are the same as in Example 1.

[0066] Comparative Example 5

[0067] This comparative example provides a protective glaze and the ceramic tile formed therefrom, which differs from Example 1 in that the aspect ratio of the tabular corundum is 1:1. Everything else is the same as in Example 1.

[0068] Comparative Example 6

[0069] This comparative example provides a protective glaze and the ceramic tile formed therefrom, which differs from Example 1 in that the aspect ratio of the tabular corundum is 6:1. Everything else is the same as in Example 1.

[0070] Comparative Example 7

[0071] This comparative example provides a protective glaze and the ceramic tile formed therefrom, which differs from Example 1 in that the firing temperature is 1050°C. Everything else is the same as Example 1.

[0072] Comparative Example 8

[0073] This comparative example provides a protective glaze and the ceramic tile formed therefrom, which differs from Example 1 in that the firing temperature is 1350°C. Everything else is the same as Example 1.

[0074] Performance testing

[0075] The high wear-resistant, stain-resistant, and slip-resistant ceramic tiles prepared in Examples 1-3 and the ceramic tiles prepared in Comparative Examples 1-8 were subjected to relevant tests, including: gloss, glaze texture evaluation, wear resistance, stain resistance, and slip resistance.

[0076] Among them, (1) Gloss: The gloss was tested using a Sanlian Scientific Gloss Meter (WGG60-E4), and the calibrated gloss value was 24.5 GU. (2) Evaluation of the glaze texture of the ceramic tile: The evaluation group was formed by the R&D personnel and sales personnel of matte anti-slip ceramic tiles in the industry to evaluate the surface of the sample. The evaluation results were given by the evaluation group after discussion. The evaluation group members observed the glaze texture with their eyes and touched it with their hands, and divided it into three grades: excellent, medium and inferior. ① Excellent is the smooth and non-rough glaze; ② Medium is the smooth and rough glaze; ③ Inferior is the uneven and rough glaze. (3) Abrasion resistance: The test shall be conducted in accordance with GB / T3810.7-2016 (released on April 25, 2016, and implemented on March 1, 2017): The abrasion resistance of the glaze surface is determined by placing abrasive media on the glaze surface and rotating it, and then observing and comparing the worn sample with the unworn sample to evaluate the abrasion resistance of ceramic tiles. The abrasion resistance is divided into grades 0, 1, 2, 3, 4, and 5. The abrasive media for each sample includes: ① 70.0g of steel balls with a diameter of 5mm; ② 52.5g of steel balls with a diameter of 3mm; ③ 43.75g of steel balls with a diameter of 2mm; ④ 8.75g of steel balls with a diameter of 1mm; ⑤ 3.0g of corundum abrasive with a particle size of F80 as specified in ISO 8486-1:1996; ⑥ 20mL of deionized water or distilled water. (4) Stain resistance: The test is conducted in accordance with GB / T 3810.14-2016. The staining agent is brought into contact with the glaze surface of the sample and allowed to act for a certain period of time. Then, the sample is cleaned according to the specified cleaning method, and the visible changes on the glaze surface of the sample are observed to determine the stain resistance of the sample. The staining agents are: ① staining agents that easily leave marks (paste-like substances): green staining agents and red staining agents in light oil; ② staining agents that can undergo oxidation reactions: iodine tincture with a concentration of 13g / L; ③ staining agents that can form a film: olive oil. (5) Anti-slip property: Static friction coefficient test method, using the specified slider assembly. The relative motion tendency between the slider assembly and the horizontal surface of the specimen is generated by dragging the slider assembly with a tension gauge, and the static friction coefficient of the specimen surface is measured.

[0077] The test results are shown in Table 1.

[0078] Table 1 Performance Test Results

[0079]

[0080] As shown in Table 1, the high wear-resistant, stain-resistant, and anti-slip ceramic tiles prepared in Examples 1-3 have a surface gloss of 2.5-3 GU, a smooth and non-prickly tactile texture, a wear resistance rating of 6000 revolutions at level 4, a stain resistance rating of level 5 (the highest level), and a static friction coefficient (dry state) of 0.73-0.78, exhibiting high wear resistance, high stain resistance, and high anti-slip capability. A photograph of the high wear-resistant, stain-resistant, and anti-slip ceramic tile prepared in Example 1 after a grinding test of 6000 revolutions is shown below. Figure 5 As shown, after 6000 revolutions of grinding test, no obvious wear "circular" marks were seen on the surface, and the wear resistance was judged to reach level 4 of 6000 revolutions.

[0081] Compared to Example 1, Comparative Example 1 used less tabular corundum and more calcined alumina. The tabular corundum, as a "microscopic anchor" framework for wear resistance and slip resistance, was insufficient to form an effective interlocking support structure, resulting in a smooth and rough glaze surface and lower wear resistance in the fired ceramic tile. Conversely, the excessive calcined alumina caused abnormal viscosity in the glaze melt, making it difficult to evenly coat the small amount of corundum. This resulted in an uneven glaze structure, increased porosity, and ultimately a smooth and rough glaze surface with lower stain resistance. The ceramic tile obtained in Comparative Example 1 after a grinding test of 6000 revolutions is shown in the image below. Figure 6 As shown, its surface has obvious wear and abrasion "circular" marks, indicating that its wear resistance reaches level 4 at 2100 revolutions.

[0082] Compared with Example 1, Comparative Example 2 used more tabular corundum and less calcined alumina. The tabular corundum "skeleton" was too dense. Although the sufficient "skeleton" made the glaze of the fired ceramic tile uneven and rough, and the wear resistance and anti-slip properties were very high, the lack of sufficient calcined alumina to fill the gaps between particles and promote the densification of the glaze melt resulted in low stain resistance and was unqualified.

[0083] Compared with Example 1, Comparative Example 3 did not use tabular corundum and had more calcined alumina. Although the high activity of calcined alumina can improve the overall hardness of the glaze and make the wear resistance and anti-slip properties of the glaze high, it lacks the "microscopic anchor points" support of tabular corundum. The glaze structure has no stable skeleton, resulting in an uneven and rough surface. Although the wear resistance and anti-slip properties are very high, the excessive amount of alumina can easily cause over-sintering, forming micro-cracks on the glaze surface, which allows stains to easily penetrate, resulting in low stain resistance and failing the test.

[0084] Compared with Example 1, Comparative Example 4 used more tabular corundum and no calcined alumina. The tabular corundum had a dense "skeleton", so the ceramic tile had high wear resistance and anti-slip properties. However, without the filling of gaps and densification effect of calcined alumina, the gaps between corundum particles could not be closed, the glaze surface was loose, porous and uneven and rough, and stains were easy to adhere and penetrate. In the end, the stain resistance was low and unqualified.

[0085] Compared to Example 1, the aspect ratio of the tabular corundum in Comparative Example 5 is smaller (1:1). While a smaller aspect ratio allows for closer packing and a denser surface structure, reducing surface porosity and making it difficult for dirt and liquid to penetrate, achieving a stain resistance level of 5, and the stable packing structure of near-spherical particles with an aspect ratio of 1:1 can evenly distribute stress and reduce local damage, resulting in more durable and stable wear resistance (wear resistance up to 2100 revolutions, level 4), a gloss level of 3GU, and excellent glaze texture, its anti-slip performance mainly depends on the surface micro-roughness. With a smaller aspect ratio of 1:1, the macro-texture of the near-spherical particles (high roundness) is not sharp enough to form effective protrusions. Especially in humid or oily environments, the friction and drainage channels provided are not as good as those of angular particles. The static friction coefficient (dry state) is low at 0.46, far from achieving the ideal anti-slip effect.

[0086] Compared to Example 1, the tabular corundum in Comparative Example 6 has a larger aspect ratio of 6:1. Although its interlaced tabular crystals form a strong and wear-resistant skeleton, achieving a wear resistance of 6000 revolutions at level 4, and the prominent tabular crystals can increase the micro-roughness of the glaze surface and improve friction, with a static friction coefficient (dry state) of 0.72, the excessive aspect ratio and improper orientation lead to a looser microstructure, increased open pores, and easier adhesion and penetration of stains, resulting in a stain resistance level of 1 (unqualified). Furthermore, the large aspect ratio crystals cause an increase in the micro-roughness of the glaze surface, resulting in diffuse reflection of light and a matte finish with a gloss level of 1. At the same time, it also makes the glaze surface rougher, with a rougher feel and the appearance of defects such as pinholes and burrs, affecting the aesthetics and tactile experience.

[0087] Compared with Example 1, the firing temperature of Comparative Example 7 is too low. At this temperature, the γ-Al2O3 of calcined alumina is difficult to fully transform into α-Al2O3, resulting in weak surface atomic migration ability. This makes it impossible to effectively promote the densification of the glaze melt, nor can it form a stable solid solution with the α-Al2O3 lattice of tabular corundum. Consequently, the gaps between the "microscopic anchor points" of the tabular corundum cannot be filled, resulting in a loose structure that is easy to fall off and low wear resistance. At the same time, the low firing temperature makes the glaze melt less fluid, the tabular corundum unevenly distributed, the glaze porosity high, stains easy to penetrate, and the surface micro-roughness insufficient, resulting in poor anti-slip effect.

[0088] Compared with Example 1, the firing temperature of Comparative Example 8 was too high. The excessively high temperature caused the γ-Al2O3 of the calcined alumina to transform into α-Al2O3 too quickly. It did not have enough time to fully fill the gaps between the tabular corundum particles and build a microcrystalline network before the phase transformation was completed. As a result, the glaze surface formed micro-cracks and a large number of open pores, making it easy for stains to adhere and penetrate. Although the tabular corundum remained stable at high temperatures and still had a certain degree of wear resistance, the excessively high firing temperature caused the viscosity of the glaze melt to decrease abnormally. The tabular corundum was prone to sedimentation and agglomeration, and the glaze surface showed pinholes and local deformation defects. The wear resistance and anti-slip performance were easily reduced, and the texture was greatly reduced.

[0089] 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.

[0090] 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 composite corundum protective glaze, characterized by, The raw materials of the composite corundum protective glaze include, by weight fraction: 30-50 parts of sodium feldspar, 3-8 parts of potassium feldspar, 10-20 parts of calcined kaolin, 5-10 parts of corundum, 5-10 parts of calcined alumina, 3-5 parts of zinc oxide, 10-20 parts of calcite, 8-15 parts of dolomite, 4-8 parts of air-knife clay, and 2-5 parts of barium carbonate; The corundum is plate-shaped corundum, and the aspect ratio of the plate-shaped corundum is (2-4):1; The particle size D50 of the corundum is 5-15 μm; The crystal type of the calcined alumina is γ-Al2O3; The particle size D50 of the calcined alumina is 1-5 μm; The firing temperature of the composite corundum protective glaze is 1180-1230 °C.

2. The composite corundum protective glaze according to claim 1, characterized in that, The raw materials of the composite corundum protective glaze include, by weight fraction: 34 parts of sodium feldspar, 5 parts of potassium feldspar, 10 parts of calcined kaolin, 6 parts of corundum, 9 parts of calcined alumina, 4 parts of zinc oxide, 12 parts of calcite, 11 parts of dolomite, 6 parts of air-knife clay, and 3 parts of barium carbonate.

3. The composite corundum protective glaze according to claim 1, characterized in that, The preparation method of the composite corundum protective glaze includes the following steps: The raw materials are ball milled with water to a glaze pulp fineness of 0.1-0.5% on a 20-mesh sieve, and then passed through a 325-mesh sieve, iron is removed, and the mixture is aged for 24 hours or more to obtain the composite corundum protective glaze.

4. A high wear, stain and slip resistant ceramic tile, characterized in that, In order, the following are included: A body layer, a surface glaze layer, a pattern layer, and an anti-slip protective glaze layer; The anti-slip protective glaze layer is formed from the composite corundum protective glaze of any one of claims 1-3.

5. The method of manufacturing the high wear, stain and slip resistant ceramic tile according to claim 4, wherein, The surface glaze layer is formed from a surface glaze, and the pattern layer is formed from a first ink; the preparation method includes the following steps: The surface glaze is applied to the surface of the body layer, then the first ink is printed, and then the composite corundum protective glaze is applied, and fired to obtain the high-wear-resistant, stain-resistant, and anti-slip ceramic tile; The firing temperature is 1180-1230 °C.

6. The method for preparing high wear-resistant, stain-resistant, and anti-slip ceramic tiles according to claim 5, characterized in that, The face glaze has a specific gravity of 1.85 g / mL to 1.98 g / mL, and an application amount of 395 g / m 2 -485 g / m 2 .

7. The method for preparing high wear-resistant, stain-resistant, and anti-slip ceramic tiles according to claim 5, characterized in that, The specific gravity of the composite corundum protective glaze is 1.25 g / mL-1.35 g / mL, and the application amount is 152 g / m 2 -303 g / m 2 .

8. The method for preparing high wear-resistant, stain-resistant, and anti-slip ceramic tiles according to claim 5, characterized in that, The firing time is 35-60 minutes.

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