A non-slip protective glaze, non-slip ceramic tiles and their preparation method

Abstract

This invention discloses an anti-slip protective glaze, an anti-slip ceramic tile, and a method for preparing the same, relating to the field of ceramic technology. The chemical composition of the anti-slip protective glaze, by weight percentage, includes: SiO2 45%–50%, TiO2 0.1%–0.2%, Al2O3 14%–17%, Fe2O3 0.2%–0.4%, Mn3O4 0.01%–0.02%, MgO 1.5%–2.5%, CaO 3.5%–5.5%, Na2O 0.65%–0.85%, K2O 3%–4%, P2O5 0.1%–0.3%, SrO 0.03%–1%, ZrO2 0.01%–0.03%, HfO2 0–0.01%, BaO 15.5%–17.5%, ZnO 2.5%–3.5%, with a loss on ignition of 5.5%–6.5%. The anti-slip protective glaze has good anti-slip properties and stain resistance, as well as low gloss and good wear resistance, resulting in good overall performance.

Description

Technical Field

[0001] This invention relates to the field of ceramic technology, and in particular to an anti-slip protective glaze, an anti-slip ceramic tile, and a method for preparing the same. Background Technology

[0002] Matte ceramic tiles mainly consist of ordinary antique-style tiles and semi-polished tiles, all of which have poor anti-slip properties. Currently, the coefficient of friction for polished tiles can only reach a maximum of 0.4, with the lowest being only 0.2, while domestic and international safety standards require a minimum coefficient of friction of 0.5 to be considered safe. Existing polished tiles fall far short of these safety requirements, and their anti-slip performance worsens when exposed to water or oil.

[0003] There are currently a small number of matte non-slip tiles on the market, but they have been difficult to promote. The main reason is that existing matte non-slip tiles often have the problem of absorbing dirt, and when cleaning the tile surface with a mop or towel, they have a strong resistance. Not only is it difficult to clean the tile surface, but it is also easy to cause the lint of the mop or towel to fall off, damaging the mop or towel. Summary of the Invention

[0004] In view of the shortcomings of the prior art, the purpose of this invention is to provide an anti-slip protective glaze, an anti-slip ceramic tile and its preparation method, which aims to improve the anti-slip performance and stain resistance of matte anti-slip tiles.

[0005] To achieve the above objectives, the present invention adopts the following technical solution:

[0006] The first aspect of this invention provides an anti-slip protective glaze, the chemical composition of which, by weight percentage, includes: SiO2 45%–50%, TiO2 0.1%–0.2%, Al2O3 14%–17%, Fe2O3 0.2%–0.4%, Mn3O4 0.01%–0.02%, MgO 1.5%–2.5%, CaO 3.5%–5.5%, Na2O 0.65%–0.85%, K2O 3%–4%, P2O5 0.1%–0.3%, SrO 0.03%–1%, ZrO2 0.01%–0.03%, HfO2 0–0.01%, BaO 15.5%–17.5%, ZnO 2.5%–3.5%, and a loss on ignition of 5.5%–6.5%.

[0007] The aforementioned anti-slip protective glaze, by weight percentage, comprises the following raw materials: 75%–80% frit, 7%–9% potassium feldspar, 3%–5% calcined kaolin, 3%–5% wollastonite, 2%–4% alumina, and 2%–4% quartz powder; the chemical composition of the frit comprises: 50%–52% SiO2, 10%–12% Al2O3, 8%–10% CaO, 1%–2% Na2O, 4%–6% K2O, 0.01%–0.03% ZrO2, 0.1%–0.2% Fe2O3, 5.0%–7.0% ZnO, 0.01%–0.03% P2O5, 12%–14% BaO, 0.01%–1% SrO, 0.15%–0.4% MgO, and HfO2. 0.01%–0.02%, B2O3 2%–3%, the remainder being trace elements, loss on ignition 0.05%–0.2%.

[0008] A second aspect of the present invention provides an anti-slip ceramic tile, comprising a body layer, a slip layer, an anti-slip glaze layer, a pattern layer, and a protective glaze layer arranged sequentially, wherein the protective glaze layer is obtained by firing the anti-slip protective glaze described above.

[0009] A third aspect of the present invention provides an anti-slip ceramic tile, comprising a body layer, a slip layer, an anti-slip glaze layer, a pattern layer, a textured glaze layer, and a protective glaze layer arranged sequentially, wherein the protective glaze layer is obtained by firing the anti-slip protective glaze described above; and the textured glaze layer includes a plurality of hemispherical protrusions.

[0010] The aforementioned anti-slip ceramic tile, wherein the anti-slip glaze layer is obtained by firing an anti-slip glaze, and the chemical composition of the anti-slip glaze, by weight percentage, includes: SiO2 55%–60%, TiO2 0.05%–0.15%, Al2O3 22%–26%, Fe2O3 0.15%–0.3%, Mn3O4 0.01%–0.02%, MgO 2%–3%, CaO 0.5%–1.5%, Na2O 1.5%–2.5%, K2O 3%–5%, P2O5 0.1%–0.3%, SO3 0.01%–0.03%, ZrO2 4.5%–5.5%, HfO2 0.1%–0.3%, BaO 0.02%–0.04%, ZnO 1%–3%, ignition reduction 1.5%–3%.

[0011] The anti-slip ceramic tile, wherein, by weight percentage, the raw materials for preparing the anti-slip glaze include: 37%–39% potassium feldspar, 5%–7% sodium feldspar, 7%–9% kaolin, 4%–6% calcined talc, 7%–9% zirconium silicate, 15%–17% quartz, 1%–3% zinc oxide, 6%–8% calcined clay, and 9%–11% alumina.

[0012] The aforementioned anti-slip ceramic tile, wherein the slip layer is obtained by firing a base glaze, and the chemical composition of the base glaze, by weight percentage, includes: SiO2 60%–62%, TiO2 0.05%–0.15%, Al2O3 22%–26%, Fe2O3 0.1%–0.2%, Mn3O4 0.01%–0.02%, MgO 1.5%–2.5%, CaO 1%–2%, Na2O 1.5%–3.5%, K2O 0.5%–1.5%, V2O5 0.01%–0.02%, NiO 0.01%–0.02%, ZrO2 5%–7%, HfO2 0.1%–0.2%, BaO 0.01%–0.02%, P2O5 0.1%–0.3%, loss on ignition 1.5%–2.5%.

[0013] The anti-slip ceramic tile, wherein, by weight percentage, the raw materials for preparing the base glaze include: 9%–11% air-knife clay, 14%–16% calcined kaolin, 19%–21% potassium feldspar, 27%–29% sodium feldspar, 5%–7% calcined talc, 2%–4% wollastonite, 7%–9% quartz, and 9%–11% zirconium silicate.

[0014] The anti-slip ceramic tile, wherein the height of the raised structure is 200-300 micrometers; the ratio of the diameter to the height of the raised structure is 10-20; the surface contact angle of the raised structure is 10-25 degrees; and the distance between two adjacent raised structures is 6-11 micrometers.

[0015] A fourth aspect of the present invention provides a method for preparing ceramic tiles, the method being used to prepare the aforementioned anti-slip ceramic tiles, comprising the following steps: applying a base glaze to a body layer to form a slip layer; applying an anti-slip surface glaze to the slip layer to form an anti-slip surface glaze layer; printing a pattern on the anti-slip surface glaze to form a pattern layer; printing a texture on the pattern layer to form a texture glaze layer; applying an anti-slip protective glaze to the texture glaze layer to form an anti-slip protective glaze layer; and firing to obtain the anti-slip ceramic tiles.

[0016] Beneficial effects:

[0017] The first aspect of this invention provides an anti-slip protective glaze containing a high content of Al2O3 and using a large amount of alkaline earth metal oxides and alkali metal oxides to allow the anti-slip protective glaze to crystallize as a whole during the firing process, so that the glaze surface is covered with small bumps formed by fine grains, giving the glaze surface not only a matte effect, but also good anti-slip, anti-fouling and wear-resistant properties.

[0018] A second aspect of the present invention provides an anti-slip ceramic tile, which includes a body layer, a slip layer, an anti-slip glaze layer, a pattern layer, and a protective glaze layer arranged sequentially; the anti-slip ceramic tile, by providing a protective glaze layer, gives it good anti-slip, stain-resistant, and wear-resistant properties.

[0019] A third aspect of the present invention also provides an anti-slip ceramic tile, which includes a body layer, a slip layer, an anti-slip glaze layer, a pattern layer, a textured glaze layer, and a protective glaze layer arranged sequentially. The anti-slip ceramic tile, through the combination of the protective glaze layer and the textured glaze layer, not only has good stain resistance and wear resistance, but also further improves its anti-slip performance.

[0020] The fourth aspect of this invention provides a method for preparing ceramic tiles, which is used to prepare the anti-slip ceramic tiles described above. The preparation method is mature, highly feasible, and can ensure a high product yield. Attached Figure Description

[0021] Figure 1 This is a schematic diagram of the layered structure of the anti-slip ceramic tile of the present invention.

[0022] Figure 2 This is a schematic diagram showing the distribution of protruding structures in the texture layer.

[0023] Figure 3 This is a cross-sectional view of the raised structures in the texture layer in the vertical direction.

[0024] Figure 4 The image shown is a scanning electron microscope (SEM) image of the glaze surface of Example 1 at a magnification of 1000x.

[0025] Figure 5 The image shown is a scanning electron microscope (SEM) image of the glaze surface of Example 1 at a magnification of 7000x.

[0026] Figure 6 The image shown is a scanning electron microscope image of the glaze surface of Comparative Example 5 at a magnification of 1000x.

[0027] Figure 7 The image shown is a scanning electron microscope (SEM) image of the glaze surface of Comparative Example 5 at a magnification of 7000x.

[0028] Explanation of main component symbols: 1-body layer, 2-slip layer, 3-non-slip glaze layer, 4-pattern layer, 5-textured glaze layer, 6-protective glaze layer. Detailed Implementation

[0029] This invention provides an anti-slip protective glaze, an anti-slip ceramic tile, and a method for preparing the same. To make the objectives, technical solutions, and effects of this invention clearer and more explicit, the invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only for explaining the invention and are not intended to limit the invention.

[0030] This invention provides an anti-slip protective glaze, whose chemical composition, by weight percentage, includes: SiO2 45%–50%, TiO2 0.1%–0.2%, Al2O3 14%–17%, Fe2O3 0.2%–0.4%, Mn3O4 0.01%–0.02%, MgO 1.5%–2.5%, CaO 3.5%–5.5%, Na2O 0.65%–0.85%, K2O 3%–4%, P2O5 0.1%–0.3%, SrO 0.03%–1%, ZrO2 0.01%–0.03%, HfO2 0–0.01%, BaO 15.5%–17.5%, ZnO 2.5%–3.5%, with a loss on ignition of 5.5%–6.5%. The anti-slip protective glaze contains a high content of Al2O3. When combined with other solvents such as alkaline earth metal oxides CaO, BaO, ZnO, and SrO, as well as alkali metal oxides K2O and Na2O, it can "crystallize as a whole" during firing. The resulting glaze surface not only has excellent anti-slip, wear-resistant, and stain-resistant properties, but also a certain degree of light transmittance. In addition, the anorthite, barium feldspar, zirconium silicate, and zinc aluminum spinel crystals formed in the glaze layer have extremely strong diffuse reflection characteristics, giving the glaze surface a stable low-gloss effect.

[0031] Preferably, the raw materials for preparing the anti-slip protective glaze, by weight percentage, include: 75%–80% frit, 7%–9% potassium feldspar, 3%–5% calcined kaolin, 3%–5% wollastonite, 2%–4% alumina, and 2%–4% quartz powder. Compared with existing formulations that introduce large amounts of difficult-to-melt alumina raw materials, the anti-slip protective glaze of the present invention mainly introduces Al2O3 through frit. After firing, more glass phase is formed in the glaze layer, and the particles are smaller. The glaze layer has a more delicate and smooth feel, better texture, and better stain resistance, anti-slip properties, wear resistance, and clarity.

[0032] Specifically, the preparation method of the anti-slip protective glaze is as follows: add each raw material according to the formula into a ball mill, and ball mill until the fineness is 0.6% to 0.8% on a 325-mesh sieve, and control the specific gravity of the slurry at 1.45 g / ml.

[0033] Specifically, the chemical composition of the fused block includes: SiO2 50%–52%, Al2O3 10%–12%, CaO 8%–10%, Na2O 1%–2%, K2O 4%–6%, ZrO2 0.01%–0.03%, Fe2O3 0.1%–0.2%, ZnO 5.0%–7.0%, P2O5 0.01%–0.03%, BaO 12%–14%, SrO 0.01%–1%, MgO 0.15%–0.4%, HfO2 0.01%–0.02%, B2O3 2%–3%, with the remainder being trace elements, and a loss on ignition of 0.05%–0.2%.

[0034] Please see Figure 1 and Figure 2 The present invention also provides an anti-slip ceramic tile, which includes a body layer 1, a slip layer 2, an anti-slip glaze layer 3, a pattern layer 4, a texture glaze layer 5, and a protective glaze layer 6 arranged sequentially. The protective glaze layer is obtained by firing the anti-slip protective glaze described above. The texture glaze layer includes multiple hemispherical protrusions. Figure 2 In the middle, the circular pattern is the raised structure. Compared with other shapes, the hemispherical raised structure has better anti-slip, anti-fouling and wear-resistant properties, and will not drag the fine lint on the towel or mop when cleaning.

[0035] Depending on the required level of anti-slip performance, the textured glaze layer 5 can be selectively set, so that the anti-slip ceramic tile is composed of a body layer 1, a slip layer 2, an anti-slip glaze layer 3, a pattern layer 4, and a protective glaze layer 6 arranged in sequence.

[0036] In the protective glaze layer, the Al2O3 content is increased to 23%–26%. Then, a composite flux is formed using alkaline earth or divalent metal oxides such as CaO, BaO, ZnO, SrO, and MgO, and alkali metal oxides such as K2O and Na2O, creating a mixed alkali effect to lower the melting temperature of the glaze. On one hand, the introduction of CaO and BaO reduces the high-temperature viscosity of the glaze and promotes the formation of calcium and barium feldspar crystal phases, improving the glaze's anti-slip, stain-resistant, and wear-resistant properties. On the other hand, controlling the ratio of the molar number of aluminum ions to the sum of the molar numbers of alkali metal ions and alkaline earth metal ions in the glaze to 0.6–0.7 ensures that most aluminum ions exist as aluminum-oxygen tetrahedra in the glass phase, forming a unified and dense network structure with silicon-oxygen tetrahedra, thereby improving the glaze's anti-slip, stain-resistant, and wear-resistant properties.

[0037] Specifically, the anti-slip glaze layer is obtained by firing an anti-slip glaze. By weight percentage, the chemical composition of the anti-slip glaze includes: SiO2 55%–60%, TiO2 0.05%–0.15%, Al2O3 22%–26%, Fe2O3 0.15%–0.3%, Mn3O4 0.01%–0.02%, MgO 2%–3%, CaO 0.5%–1.5%, Na2O 1.5%–2.5%, K2O 3%–5%, P2O5 0.1%–0.3%, SO3 0.01%–0.03%, ZrO2 4.5%–5.5%, HfO2 0.1%–0.3%, BaO 0.02%–0.04%, and ZnO. The content is 1%–3%, and the loss on ignition is 1.5%–3%. The anti-slip glaze layer is rich in oxides such as calcium, barium, and zinc. These oxides mainly act as crystallizing agents, which can reduce the high-temperature viscosity of the glaze formula, making the glaze surface smoother after firing. Furthermore, during glaze firing, zinc-aluminum spinel and feldspar crystal protrusions can form around the alumina particles, giving the glaze an anti-slip structure. The complete melting and reaction of the anti-slip glaze and anti-slip protective glaze can precipitate a large number of fine crystals, while coarse crystals precipitate on the glaze surface, improving the anti-slip, stain-resistant, and wear-resistant properties of the glaze surface.

[0038] Preferably, the raw materials for preparing the anti-slip glaze, by weight percentage, include: 37%–39% potassium feldspar, 5%–7% sodium feldspar, 7%–9% kaolin, 4%–6% calcined talc, 7%–9% zirconium silicate, 15%–17% quartz, 1%–3% zinc oxide, 6%–8% calcined clay, and 9%–11% alumina.

[0039] Specifically, the preparation method of the anti-slip glaze is as follows: According to the formula design, accurately weigh all kinds of raw materials, put the raw materials into a ball mill for ball milling, wherein the ratio of material:ball:water is 1:2.6:0.9, the ball milling time is 12 hours, the obtained glaze slurry is passed through a 325-mesh sieve, the sieve residue is 0.4% to 1.0%, and then transferred to a storage tank for later use; the anti-slip glaze slurry should also be filtered through a vibrating sieve with a pore size of 200 mesh before use, the purpose of which is to filter out the mud and impurities formed later, and the specific gravity of the glaze slurry is in the range of 1.85 to 1.90 g / ml.

[0040] Specifically, the slip layer is obtained by firing a base glaze. By weight percentage, the chemical composition of the base glaze includes: SiO2 60%–62%, TiO2 0.05%–0.15%, Al2O3 22%–26%, Fe2O3 0.1%–0.2%, Mn3O4 0.01%–0.02%, MgO 1.5%–2.5%, CaO 1%–2%, Na2O 1.5%–3.5%, K2O 0.5%–1.5%, V2O5 0.01%–0.02%, NiO 0.01%–0.02%, ZrO2 5%–7%, HfO2 0.1%–0.2%, BaO 0.01%–0.02%, and P2O5. 0.1%–0.3%, loss on ignition 1.5%–2.5%. The base glaze has relatively high whiteness, which can cover the body layer and prevent iron and titanium impurities in the body layer from affecting the color.

[0041] Preferably, the raw materials for preparing the base glaze, by weight percentage, include: 9%–11% air-knife clay, 14%–16% calcined kaolin, 19%–21% potassium feldspar, 27%–29% sodium feldspar, 5%–7% calcined talc, 2%–4% wollastonite, 7%–9% quartz, and 9%–11% zirconium silicate.

[0042] Specifically, the preparation method of the base glaze includes the following steps: adding each raw material according to the formula into a ball mill, and then adding water (40% of the total mass of the formula), sodium methyl cellulose (0.15%) and sodium tripolyphosphate (0.3%), and ball milling together. The resulting slurry has a residue of 0.6% to 0.8% on a 325-mesh sieve, a specific gravity of 1.88 to 1.92 g / ml, and a flow rate of 33 to 38 s / 100 ml.

[0043] Preferably, the height of the protrusion structure is 200-300 micrometers; the diameter of the protrusion structure is 2000-6000 micrometers; the ratio of the diameter to the height of the protrusion structure is 10-20; and the surface contact angle of the protrusion structure is 10-25 degrees. Figure 3 This is a cross-sectional view of the raised structure in the texture layer in the vertical direction. In the figure, D represents the diameter, L represents the spacing, H represents the height, and a represents the surface contact angle.

[0044] Preferably, in the anti-slip ceramic tile, the distance between two adjacent protrusions is 6 to 11 micrometers.

[0045] Preferably, by weight percentage, the raw materials for preparing the green body layer include: 15% ultra-white sand, 2% high-alumina clay, 5.2% calcined talc, 5% pyrophyllite, 13% Sichuan potassium-sodium feldspar water-grinding material, 16% Guangxi potassium-sodium feldspar water-grinding material, 3.9% high-sodium feldspar, 12% ball clay, 13.2% kaolin, 8% diopside, 6% high-plasticity clay from raw ore, 0.5% ceramic waste, 0.1% sodium tripolyphosphate, and 0.1% sodium methylcellulose. Testing revealed that the chemical composition of the green body layer includes: 66.5% silicon dioxide, 18.4% alumina, 3.12% potassium oxide, 2.28% sodium oxide, 1.82% calcium oxide, 1.1% magnesium oxide, with the remainder to be reduced as needed.

[0046] Specifically, the preparation method of the green body layer is as follows: the raw materials are added to the ball mill according to the formula, and the fineness of the ball mill slurry is 0.8% to 1.2% residue on a 250-mesh sieve; then spray drying and granulation are carried out: the gradation is controlled at less than 5% residue on a 30-mesh sieve, 30% to 40% residue on a 40-mesh sieve, 70% to 80% residue on a 60-mesh sieve, and no more than 5% residue on a 100-mesh sieve, and the moisture content is controlled at 6.8% to 7.3%; pressed and shaped, and finally dried in a drying kiln.

[0047] This invention also provides a method for preparing ceramic tiles, the method being used to prepare the above-mentioned anti-slip ceramic tiles, comprising the following steps:

[0048] A base glaze is applied to the body layer to form a slip layer; the amount of base glaze applied is 400 g / m². 2 The glaze thickness is 0.1–0.15 mm;

[0049] An anti-slip glaze is applied to the slip layer to form an anti-slip glaze layer; the thickness of the anti-slip glaze is 0.1–0.3 mm.

[0050] Print patterns onto the non-slip glaze to form a pattern layer;

[0051] Texture is printed on the pattern layer to form a textured glaze layer. Fine-tipped ink can be used to create depressions in the corresponding areas of the non-slip glaze layer, resulting in a raised texture after firing. Specifically, CZN00078 ink and S015 ink can be used for printing, with CZN00078 ink (Torosys) at 30%–45% ink volume (corresponding to a printing grayscale value of 30%–45%) and S015 ink (Torosys) at 45%–55% ink volume (corresponding to a printing grayscale value of 45%–55%). A non-slip protective glaze is then applied on the textured glaze layer to form a non-slip protective glaze layer; the application amount of the non-slip protective glaze is 120 g / m². 2 The glaze thickness is 0.04 to 0.08 mm.

[0052] The non-slip ceramic tile is obtained by firing.

[0053] The present invention will be further illustrated by specific embodiments below.

[0054] Example 1

[0055] A non-slip ceramic tile, the preparation method of which includes the following steps:

[0056] S001. The body powder is dry-pressed to obtain a brick blank; by weight percentage, the body powder includes: 15% super white sand, 2% high alumina clay, 5.2% calcined talc, 5% pyrophyllite, 13% Sichuan potassium-sodium feldspar water-milling material, 16% Guangxi potassium-sodium feldspar water-milling material, 3.9% high-sodium feldspar, 12% ball clay, 13.2% kaolin, 8% diopside, 6% high-plasticity clay from raw ore, 0.5% ceramic waste, 0.1% sodium tripolyphosphate, and 0.1% sodium methylcellulose;

[0057] S002. The brick blanks are dried in a drying kiln to form a brick blank layer. The moisture content of the dried brick blanks is controlled within 0.35wt%.

[0058] S003. Apply a base glaze to the body layer to form a slip layer; the raw materials for preparing the base glaze, by weight percentage, include: 10% air knife clay, 15% calcined kaolin, 20% potassium feldspar, 28% sodium feldspar, 6% calcined talc, 3% wollastonite, 8% quartz, and 10% zirconium silicate.

[0059] Its corresponding chemical composition is as follows: SiO2 61.11%, TiO2 0.09%, Al2O3 23.80%, Fe2O3 0.16%, Mn3O4 0.01%, MgO 1.90%, CaO 1.40%, Na2O 2.45%, K2O 1.10%, V2O5 0.01%, NiO 0.01%, ZrO2 6.05%, HfO2 0.14%, BaO 0.01%, P2O5 0.21%, and loss on ignition 1.55%.

[0060] The base glaze is applied at a rate of 400 grams per cubic meter. 2 The glaze thickness is 0.1mm;

[0061] S004. Apply an anti-slip glaze to the slip layer to form an anti-slip glaze layer; the raw materials for preparing the anti-slip glaze, by weight percentage, include: 38% potassium feldspar, 6% sodium feldspar, 8% kaolin, 5% calcined talc, 8% zirconium silicate, 16% quartz, 2% zinc oxide, 7% calcined clay, and 10% alumina.

[0062] Its corresponding chemical composition is as follows: SiO2 59.09%, TiO2 0.09%, Al2O3 22.32%, Fe2O3 0.22%, Mn3O4 0.01%, MgO 2.52%, CaO 0.73%, Na2O 1.81%, K2O 3.94%, P2O5 0.22%, SO3 0.02%, ZrO2 5.36%, HfO2 0.14%, BaO 0.03%, ZnO 1.65%, with a loss on ignition of 1.85%.

[0063] The thickness of the anti-slip glaze is 0.3 mm;

[0064] S005. Print a pattern on the non-slip glaze to form a pattern layer;

[0065] S006. A textured glaze layer is formed by printing CZN00078 ink and S015 ink on the pattern layer; CZN00078 ink accounts for 45% of the ink volume, and S015 ink accounts for 55% of the ink volume, and the two inks are used in sequence; after printing, the textured glaze layer includes multiple raised structures, the height of the raised structures is 200 micrometers; the diameter of the raised structures is 2000 micrometers, the ratio of the diameter to the height of the raised structures is 10; the surface contact angle of the raised structures is 10 degrees; the spacing between two adjacent raised structures is 8 micrometers;

[0066] S007. Apply an anti-slip protective glaze to the textured glaze layer to form an anti-slip protective glaze layer; the raw materials for preparing the anti-slip protective glaze, by weight percentage, include: 78% frit, 8% potassium feldspar, 4% calcined kaolin, 4% wollastonite, 3% alumina, and 3% quartz powder.

[0067] Its corresponding chemical composition is as follows: SiO2 46.42%, TiO2 0.13%, Al2O3 15.80%, Fe2O3 0.27%, Mn3O4 0.01%, MgO 2.04%, CaO 4.15%, Na2O 0.78%, K2O 3.54%, P2O5 0.2%, SrO 0.06%, ZrO2 0.02%, HfO2 0%, BaO 16.82%, ZnO 3.3%, with a loss on ignition of 6.46%.

[0068] The anti-slip protective glaze is applied by spraying, with an application rate of 120 grams per square meter. 2 The glaze thickness is 0.06mm;

[0069] S008. The ceramic tile is fired rapidly in a roller kiln at a maximum firing temperature of 1180℃ for 60 minutes. After firing, the edges are ground and graded to obtain the non-slip ceramic tile.

[0070] Example 2

[0071] The preparation method of an anti-slip ceramic tile differs from that of Example 1 in that:

[0072] The formulation of the anti-slip glaze varies. In this embodiment, the raw materials for preparing the anti-slip glaze, by weight percentage, include: 39% potassium feldspar, 7% sodium feldspar, 7% kaolin, 4% calcined talc, 9% zirconium silicate, 15% quartz, 3% zinc oxide, 6% calcined clay, and 10% alumina.

[0073] The raised structure formed in the textured glaze layer has a height of 300 micrometers and a diameter of 6000 micrometers. The ratio of the diameter to the height of the raised structure is 20. The surface contact angle of the raised structure is 25 degrees. The distance between two adjacent raised structures is 11 micrometers.

[0074] The formulation of the anti-slip protective glaze varies. In this embodiment, the raw materials for preparing the anti-slip protective glaze, by weight percentage, include: 80% frit, 7% potassium feldspar, 4% calcined kaolin, 3% wollastonite, 3% alumina, and 3% quartz powder.

[0075] Example 3

[0076] The preparation method of an anti-slip ceramic tile differs from that of Example 1 in that:

[0077] The raised structure formed in the textured glaze layer has a height of 200 micrometers and a diameter of 3000 micrometers. The ratio of the diameter to the height of the raised structure is 15. The surface contact angle of the raised structure is 18 degrees. The distance between two adjacent raised structures is 8 micrometers.

[0078] Example 4

[0079] The preparation method of an anti-slip ceramic tile differs from that of Example 1 in that:

[0080] In the textured glaze layer, CZN00078 ink accounts for 35% of the ink content, and S015 ink accounts for 50% of the ink content.

[0081] Example 5

[0082] A non-slip ceramic tile, the difference between its preparation method and that of Example 1 is that a textured glaze layer is not formed in the pattern layer.

[0083] Comparative Example 1

[0084] A ceramic tile, the preparation method of which differs from that of Example 1, is as follows:

[0085] The formulations of anti-slip protective glazes vary. In this comparative example, the chemical composition of the anti-slip protective glaze, by weight percentage, includes: SiO2 47.42%, TiO2 0.23%, Al2O3 18%, Fe2O3 0.17%, Mn3O4 0.01%, MgO 2.14%, CaO 4.15%, Na2O 0.86%, K2O 3.44%, P2O5 0.15%, SrO 0.11%, ZrO2 0.01%, HfO2 0%, BaO 16.72%, ZnO 4.3%, with a loss on ignition of 2.29%.

[0086] Comparative Example 2

[0087] A ceramic tile, the preparation method of which differs from that of Example 1, is as follows:

[0088] The formulations of anti-slip protective glazes vary. In this comparative example, the chemical composition of the anti-slip protective glaze, by weight percentage, includes: SiO2 47.42%, TiO2 0.23%, Al2O3 13%, Fe2O3 0.17%, Mn3O4 0.01%, MgO 2.04%, CaO 4.65%, Na2O 0.98%, K2O 3.94%, P2O5 0.2%, SrO 0.06%, ZrO2 0.02%, HfO2 0%, BaO 16.92%, ZnO 3.6%, with a loss on ignition of 6.76%.

[0089] Comparative Example 3

[0090] A type of soft-polished glazed ceramic tile, the glaze layer of which consists of a base glaze and a top glaze, is prepared as follows:

[0091] S001. Clean the surface of the billet and spray 12 grams of water on the surface of the billet to moisten the surface of the billet;

[0092] S002. Apply a base glaze to the body; the chemical composition of the base glaze, by weight percentage, is as follows: SiO2 59%, Al2O3 14%, MgO 2%, CaO 2%, Na2O 4%, K2O 3%, ZrO2 10%, ZnO 4%; loss on ignition 2%;

[0093] S003. Inkjet printed pattern;

[0094] S004. After drying at 150℃ for 8 minutes, a protective glaze with a specific gravity of 1.25 g / ml is sprayed, and finally a top coat glaze is applied. The chemical composition of the top coat glaze is as follows: 68.61% thick polishing glaze powder, 0.15% sodium carboxymethyl cellulose, 0.26% sodium tripolyphosphate, and 30.98% water. The thick polishing glaze powder is composed of frit and raw material, with a frit:raw material mass ratio of 10:100. The chemical composition of the frit is as follows: 55% SiO2, 14% Al2O3, 7% MgO, 12% CaO, 7% B2O3, and 5% K2O. The chemical composition of the raw material is as follows: 51% SiO2, 4% Al2O3, 7% MgO, 10% CaO, 1% Na2O, 7% K2O, 8% ZnO, and 9% BaO, with the remainder being loss on ignition.

[0095] S005. Calcine at a firing temperature of 1200℃ for 50 minutes;

[0096] S006. After firing, the ceramic tile is lightly polished and its edges are ground to obtain a lightly polished glazed ceramic tile.

[0097] Comparative Example 4

[0098] A type of glaze-free ceramic tile is prepared as follows:

[0099] S001. Preparation of non-polishing glaze: by weight percentage, the raw materials for preparing non-polishing glaze include: 26% potassium feldspar, 21% sodium feldspar, 12% kaolin, 9% talc, 17% calcite, 4% zinc oxide, 6% barium carbonate, and 5% wollastonite.

[0100] Specifically, the chemical composition of the non-polishing glaze is as follows: SiO2 42.7%, Al2O3 20%, MgO 6%, CaO 8%, Na2O 2.5%, K2O 4%, ZrO2 0.1%, Fe2O3 0.2%, ZnO 2.43%, P2O5 3.3%, BaO 7.2%, with a loss on ignition of 3.57%.

[0101] Crush and mix the raw materials according to the above formula;

[0102] S002. Based on the total weight of the raw materials, add 50% water by weight to the uniformly mixed raw materials, and ball mill for 10 hours to obtain glaze slurry. Then, use a sedimentation separation method to separate and remove the coarse particles in the glaze slurry, and control the fineness (325 mesh sieve residue) to 0.3%.

[0103] S003. After aging for 24 hours, the glaze slurry after aging is applied evenly to the surface of the body using a straight drop glazing method.

[0104] S004. Calcine at a firing temperature of 1200℃ for 50 minutes to obtain the non-polished glaze ceramic tile.

[0105] Comparative Example 5

[0106] A ceramic tile comprising a body layer, a base glaze layer, and a pattern layer arranged sequentially;

[0107] The base glaze layer is prepared from a high-temperature matte glaze, and its chemical composition by weight percentage is: silicon dioxide 59%, aluminum oxide 27%, magnesium oxide 0.6%, calcium oxide 0.3%, sodium oxide 3.8%, potassium oxide 1.1%, zinc oxide 0.2%, barium oxide 0.3%, hafnium dioxide 0.2%, zirconium dioxide 5.5%, and loss on ignition 2.0%.

[0108] The pattern layer is made by inkjet printing using conventional ceramic color inks;

[0109] The ceramic tile was fired at a temperature of 1200℃ for 60 minutes.

[0110] Comparative Example 6

[0111] The preparation method of an anti-slip ceramic tile differs from that of Example 1 in that:

[0112] The formulation of the anti-slip protective glaze varies. In this embodiment, the chemical composition of the anti-slip protective glaze, by weight percentage, is as follows: SiO2 45.42%, TiO2 0.13%, Al2O3 19%, Fe2O3 0.20%, Mn3O4 0.01%, MgO 1.84%, CaO 3.95%, Na2O 0.85%, K2O 3.2%, P2O5 0.15%, SrO 0.05%, ZrO2 0.02%, HfO2 0%, BaO 15.72%, ZnO 3.0%, with a loss on ignition of 6.46%.

[0113] The corresponding raw materials for preparation are: 68% frit, 10% potassium feldspar, 7% calcined kaolin, 6% wollastonite, 5% alumina, and 4% quartz powder.

[0114] Comparative Example 7

[0115] The preparation method of an anti-slip ceramic tile differs from that of Example 1 in that:

[0116] The formulation of the anti-slip protective glaze varies. In this embodiment, the chemical composition of the anti-slip protective glaze, by weight percentage, is as follows: SiO2 49.82%, TiO2 0.15%, Al2O3 12%, Fe2O3 0.25%, Mn3O4 0.01%, MgO 2.34%, CaO 4.35%, Na2O 0.75%, K2O 3.74%, P2O5 0.2%, SrO 0.07%, ZrO2 0.02%, HfO2 0%, BaO 16.82%, ZnO 3.2%, with a loss on ignition of 6.28%.

[0117] The corresponding raw materials for its preparation are: 85% frit, 6% potassium feldspar, 3% calcined kaolin, 3% wollastonite, 1% alumina, and 2% quartz powder.

[0118] Comparative Example 8

[0119] The preparation method of an anti-slip ceramic tile differs from that of Example 1 in that:

[0120] The raised structure formed in the textured glaze layer has a height of 100 micrometers and a diameter of 1000 micrometers. The ratio of the diameter to the height of the raised structure is 10. The surface contact angle of the raised structure is 35 degrees.

[0121] Comparative Example 9

[0122] The preparation method of an anti-slip ceramic tile differs from that of Example 1 in that:

[0123] The raised structure formed in the textured glaze layer has a height of 100 micrometers and a diameter of 6000 micrometers. The ratio of the diameter to the height of the raised structure is 60. The surface contact angle of the raised structure is 5 degrees.

[0124] Comparative Example 10

[0125] The preparation method of an anti-slip ceramic tile differs from that of Example 1 in that the formula of the anti-slip glaze is different.

[0126] The chemical composition of the anti-slip glaze, by weight percentage, includes: SiO2 56.13%, TiO2 0.06%, Al2O3 28%, Fe2O3 0.20%, Mn3O4 0.01%, MgO 2.32%, CaO 0.63%, Na2O 1.61%, K2O 3.14%, P2O5 0.12%, SO3 0.02%, ZrO2 4.6%, HfO2 0.13%, BaO 0.03%, ZnO 1.45%, with a loss on ignition of 1.55%.

[0127] Comparative Example 11

[0128] The preparation method of an anti-slip ceramic tile differs from that of Example 1 in that the formula of the anti-slip glaze is different.

[0129] The chemical composition of the anti-slip glaze, by weight percentage, includes: SiO2 59.03%, TiO2 0.08%, Al2O3 20%, Fe2O3 0.20%, Mn3O4 0.01%, MgO 2.62%, CaO 0.73%, Na2O 2.31%, K2O 4.5%, P2O5 0.22%, SO3 0.02%, ZrO2 5.46%, HfO2 0.14%, BaO 0.03%, ZnO 2.65%, with a loss on ignition of 2.0%.

[0130] The various properties of the ceramic tiles in the above embodiments and comparative examples were determined. The test method for the static friction coefficient was carried out in accordance with GB / T 4100-2006.

[0131] The stain resistance test was conducted in accordance with GB / T 3810.14-2006; the test contaminants included: light oil containing chrome green, light oil containing red contaminants, iodine solution, and olive oil;

[0132] The determination of gloss was carried out in accordance with GB / T 13891-2006;

[0133] The determination of flexural strength shall be carried out in accordance with GB / T 4100-2015;

[0134] The abrasion resistance was determined in accordance with GB / T 3810.2-2016.

[0135] The test results are as follows:

[0136]

[0137]

[0138]

[0139] Based on the above results, the ceramic tiles of Examples 1-4 have the best overall performance, with a static friction coefficient / wet method greater than 0.8, wear resistance greater than level 4, good stain resistance, and good color development ability.

[0140] Figure 4 This is a scanning electron microscope image of the glaze surface of Example 1 at 1000x magnification. Figure 5The image shows a scanning electron microscope (SEM) image of the glaze surface in Example 1 at 7000x magnification. As can be seen from the image, after firing, the anti-slip protective glaze forms a large number of micron-sized calcium and barium feldspar solid solution crystals, as well as nano-sized zirconium silicate crystals. These crystals grow on the surface of the anti-slip glaze, giving it excellent anti-slip and wear-resistant properties. Furthermore, these crystals scatter light entering the glaze layer, resulting in a low-gloss effect. Fine grains reduce microcracks caused by the difference in expansion coefficients between the glaze and the glass phase, thereby improving the glaze's stain and wear resistance. It can be seen that the glaze layer precipitates numerous fine particles, including dot-like, columnar, and elongated potassium, sodium, barium, and calcium feldspar crystals, as well as zinc aluminum spinel crystals. These crystals have a strong diffuse reflection effect on light, giving the glaze a stable low-gloss finish.

[0141] Example 5, without a textured layer, showed significantly lower wear resistance and static friction coefficient / wet process performance compared to Examples 1-4. This demonstrates that a textured layer effectively improves the wear resistance and static friction coefficient / wet process of ceramic tiles. The textured layer design creates a slightly uneven texture after inkjet printing and firing, resulting in better wear resistance and friction performance. Simultaneously, the base glaze, anti-slip top glaze, and anti-slip protective glaze fully melt and react, precipitating a large number of fine crystals, particularly with controlled growth of nano-sized crystals. The precipitation of coarse crystals on the glaze surface enhances the anti-slip, stain-resistant, and wear-resistant properties of the glaze surface.

[0142] In Comparative Example 1, the aluminum content of the anti-slip protective glaze exceeded the protection scope of this invention. Test results showed a significant decrease in its stain resistance and weaker color development. This indicates that excessive aluminum content is detrimental to improving the stain resistance of the glaze.

[0143] In Comparative Example 2, the aluminum content of the anti-slip protective glaze is less than the protection range of the present invention. The test results show that its wear resistance is significantly reduced, and the static friction coefficient / wet method is also not as good as in Examples 1-5, indicating that too little aluminum content is not conducive to improving the wear resistance of the glaze.

[0144] Comparative Example 3 is a traditional soft-polished brick. In terms of its performance, whether it is stain resistance, wear resistance or static friction coefficient / wet process, Comparative Example 3 is not as good as Examples 1-5.

[0145] Comparative Example 4 is a non-polished glazed ceramic tile. In terms of its performance, its stain resistance, wear resistance and static friction coefficient / wet process are better than Comparative Example 3, but overall it is still not as good as Examples 1-5.

[0146] Comparative Example 5 is an antique-style ceramic tile. In terms of its performance, its stain resistance, wear resistance, and static friction coefficient / wet method are also inferior to those of Examples 1-5. Figure 6 This is a scanning electron microscope image of the glaze surface of Comparative Example 5 at a magnification of 1000x. Figure 7The image shows a scanning electron microscope (SEM) image of the glaze surface of Comparative Example 5 at a magnification of 7000. As can be seen from the image, the number of crystals in the glaze layer is small and the crystals are large, resulting in a smooth glaze surface and reduced anti-slip and wear-resistant properties.

[0147] In the ceramic tile of Comparative Example 6, the amount of frit used in the anti-slip protective glaze is less than the scope of protection of this application. From the perspective of its performance, the color development of Comparative Example 6 is weaker and the stain resistance is reduced. This indicates that the insufficient amount of frit is not conducive to the color development of the glaze layer and is not conducive to the stain resistance of the glaze layer.

[0148] In the ceramic tile of Comparative Example 7, the amount of frit used in the anti-slip protective glaze is greater than the scope of protection of this application. The melting temperature of the anti-slip protective glaze in Comparative Example 7 is relatively low. From its performance, the stain resistance and wear resistance of Comparative Example 7 have both decreased significantly, indicating that excessive frit usage is also not conducive to improving the stain resistance and wear resistance of the glaze layer.

[0149] In the ceramic tile of Comparative Example 8, the diameter of the raised structure of the textured glaze is smaller than the protection scope of this application, the surface contact angle of the raised structure is 35 degrees, and the undulation of its glaze surface is obvious. According to the test results, its stain resistance is significantly reduced.

[0150] In the ceramic tile of Comparative Example 9, the diameter of the raised structure of the textured glaze is larger than the protection scope of this application, the surface contact angle of the raised structure is 5 degrees, and the undulation of its glaze surface is obvious. From the test results, its anti-slip performance has been significantly reduced.

[0151] In the ceramic tile of Comparative Example 10, the amount of Al2O3 in the anti-slip glaze exceeds the protection scope of this application. The melting temperature of the adjusted anti-slip glaze is too high, which will result in more large particles. After melting with the anti-slip protective glaze, it will affect the glaze surface of the anti-slip protective glaze. According to the test results, the ceramic tile of Comparative Example 10 has serious stain absorption.

[0152] In the ceramic tile of Comparative Example 11, the amount of Al2O3 in the anti-slip glaze is less than the scope of protection of this application. According to the test results, the anti-slip coefficient of the ceramic tile of Comparative Example 11 is low. The reason is that too little Al2O3 in the anti-slip glaze will lead to a low melting temperature, which is not conducive to the formation of particles. Therefore, the anti-slip coefficient will be reduced. A low melting temperature will also cause pores to form on the glaze surface.

[0153] It is understood that those skilled in the art can make equivalent substitutions or modifications to the technical solution and inventive concept of the present invention, and all such substitutions or modifications should fall within the protection scope of the appended claims.

Claims

1. A non-slip protective glaze, characterized in that, By weight percentage, its chemical composition includes: SiO2 45%–50%, TiO2 0.1%–0.2%, Al2O3 14%–17%, Fe2O3 0.2%–0.4%, Mn3O4 0.01%–0.02%, MgO 1.5%–2.5%, CaO 3.5%–5.5%, Na2O 0.65%–0.85%, K2O 3%–4%, P2O5 0.1%–0.3%, SrO 0.03%–1%, ZrO2 0.01%–0.03%, HfO2 0–0.01%, BaO 15.5%–17.5%, ZnO 2.5%–3.5%, loss on ignition 5.5%–6.5%; by weight percentage, the raw materials for preparation include: 75%–80% frit, 7%–9% potassium feldspar, 3%–5% calcined kaolin, 3%–5% wollastonite, 2%–4% alumina, and 2%–4% quartz powder; the chemical composition of the frit includes: 50%–52% SiO2, 10%–12% Al2O3, 8%–10% CaO, 1%–2% Na2O, 4%–6% K2O, 0.01%–0.03% ZrO2, 0.1%–0.2% Fe2O3, 5.0%–7.0% ZnO, 0.01%–0.03% P2O5, 12%–14% BaO, 0.01%–1% SrO, and MgO. 0.15%–0.4%, HfO2 0.01%–0.02%, B2O3 2%–3%, the remainder being trace elements, with a loss on ignition of 0.05%–0.2%.

2. A non-slip ceramic tile, characterized in that, It includes a body layer, a slip layer, an anti-slip glaze layer, a pattern layer, and a protective glaze layer arranged in sequence, wherein the protective glaze layer is obtained by firing the anti-slip protective glaze as described in claim 1.

3. A non-slip ceramic tile, characterized in that, It includes a body layer, a slip layer, an anti-slip glaze layer, a pattern layer, a texture glaze layer, and a protective glaze layer arranged sequentially. The protective glaze layer is obtained by firing the anti-slip protective glaze as described in claim 1. The texture glaze layer includes multiple hemispherical protrusions.

4. The anti-slip ceramic tile according to claim 3, characterized in that, The anti-slip glaze layer is obtained by firing an anti-slip glaze. By weight percentage, the chemical composition of the anti-slip glaze includes: SiO2 55%–60%, TiO2 0.05%–0.15%, Al2O3 22%–26%, Fe2O3 0.15%–0.3%, Mn3O4 0.01%–0.02%, MgO 2%–3%, CaO 0.5%–1.5%, Na2O 1.5%–2.5%, K2O 3%–5%, P2O5 0.1%–0.3%, SO3 0.01%–0.03%, ZrO2 4.5%–5.5%, HfO2 0.1%–0.3%, BaO 0.02%–0.04%, ZnO 1%–3%, with a loss on ignition of 1.5%–3%.

5. The anti-slip ceramic tile according to claim 4, characterized in that, The raw materials for preparing the anti-slip glaze, by weight percentage, include: 37%–39% potassium feldspar, 5%–7% sodium feldspar, 7%–9% kaolin, 4%–6% calcined talc, 7%–9% zirconium silicate, 15%–17% quartz, 1%–3% zinc oxide, 6%–8% calcined clay, and 9%–11% alumina.

6. The anti-slip ceramic tile according to claim 3, characterized in that, The slip layer is obtained by firing a base glaze. The chemical composition of the base glaze, by weight percentage, includes: SiO2 60%–62%, TiO2 0.05%–0.15%, Al2O3 22%–26%, Fe2O3 0.1%–0.2%, Mn3O4 0.01%–0.02%, MgO 1.5%–2.5%, CaO 1%–2%, Na2O 1.5%–3.5%, K2O 0.5%–1.5%, V2O5 0.01%–0.02%, NiO 0.01%–0.02%, ZrO2 5%–7%, HfO2 0.1%–0.2%, BaO 0.01%–0.02%, P2O5 0.1%–0.3%, with a loss on ignition of 1.5%–2.5%.

7. The anti-slip ceramic tile according to claim 6, characterized in that, The raw materials for preparing the base glaze, by weight percentage, include: 9%–11% air-knife clay, 14%–16% calcined kaolin, 19%–21% potassium feldspar, 27%–29% sodium feldspar, 5%–7% calcined talc, 2%–4% wollastonite, 7%–9% quartz, and 9%–11% zirconium silicate.

8. The anti-slip ceramic tile according to claim 3, characterized in that, The height of the protrusion is 200–300 micrometers; the ratio of the diameter to the height of the protrusion is 10–20; the surface contact angle of the protrusion is 10–25 degrees; and the distance between two adjacent protrusions is 6–11 micrometers.

9. A method for preparing ceramic bricks, characterized in that, The method for preparing the anti-slip ceramic tile according to any one of claims 3-8 comprises the following steps: Apply a base glaze to the body layer to form a slip layer; Apply a non-slip glaze to the slip layer to form a non-slip glaze layer; Print patterns onto the non-slip glaze to form a pattern layer; Print the texture on the pattern layer to form a textured glaze layer; Apply a non-slip protective glaze to the textured glaze layer to form a non-slip protective glaze layer; The non-slip ceramic tile is obtained by firing.

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