Wear-resistant glazed ceramic tile and method for manufacturing the same

Abstract

This invention belongs to the field of building ceramics technology and discloses a wear-resistant glazed ceramic tile and its preparation method. First, N and / or Nb ions are implanted into the protective glaze layer of the glazed ceramic tile via ion implantation. This forms new highly wear-resistant substances or new bonds on the surface of the protective glaze layer, making the glaze network structure more compact and thus improving the wear resistance of the glaze. Then, the ion-implanted ceramic tile undergoes alkali metal molten salt surface treatment to fill the vacancy defects and interatomic gaps generated during ion implantation, further improving the glaze quality and wear resistance. Finally, the molten metal-treated ceramic tile is annealed to repair the crystal structure of the glaze layer, further reducing glaze defects and improving wear resistance. This invention allows for precise control of the ion implantation amount, maintaining the wear resistance of the glazed ceramic tile for a long time, achieving the highest wear resistance level of 5.

Description

Technical Field

[0001] This invention belongs to the field of building ceramics technology, and in particular relates to a wear-resistant glazed ceramic tile and its preparation method. Background Technology

[0002] Ceramic tiles are an important material in modern construction and interior / exterior decoration, and are closely related to people's lives. However, due to long-term exposure and contact with hard objects, the surface of ceramic tiles is easily worn, damaging their aesthetic appeal; especially glazed ceramic tiles, whose wear resistance is generally worse than that of unglazed ceramic tiles. Therefore, it is particularly necessary to develop a type of glazed ceramic tile with good wear resistance.

[0003] In existing technologies, the main methods for enhancing the surface wear resistance of glazed ceramic tiles are as follows: The first method involves adding wear-resistant media such as ultrafine alumina or aluminum hydroxide to the glaze to improve its wear resistance. However, this method has a very complex preparation process: firstly, the particle size of the wear-resistant media must be controlled; if it is too fine, it easily dissolves in the glass phase, while if it is too coarse, it will form protrusions on the glaze surface; secondly, the cooling regime must be controlled, as it affects crystallization; and thirdly, the proportions of the various components in the glaze must be considered to ensure that the required wear-resistant crystalline phase precipitates during cooling. The second method involves adding wear-resistant frit to the glaze to improve its wear resistance. This method requires high-quality frit, as its quality significantly affects the melting temperature range, gloss, and whiteness of the glaze, thus presenting a technical challenge in control.

[0004] Therefore, there is an urgent need to develop a method to improve the wear resistance of glazed ceramic tiles, so as to further enhance their wear resistance while ensuring the quality of the glaze. Summary of the Invention

[0005] The present invention aims to solve at least one of the technical problems existing in the prior art. To this end, the present invention proposes a wear-resistant glazed ceramic tile and a method for preparing the same. The ceramic tile prepared using the described method can effectively improve its wear resistance without affecting the quality of the glaze.

[0006] The inventive concept of this invention is as follows: This invention improves the wear resistance of glazed ceramic tiles through ion implantation. Specifically, wear-resistant materials are implanted into the glaze surface layer via ion implantation, followed by annealing to enhance the wear resistance of the glaze. However, during ion implantation, high-energy ions collide with the glaze surface, generating numerous vacancy defects and interstitial atoms. If annealing is performed directly after ion implantation, these vacancy defects easily accumulate, forming bubbles. Consequently, during annealing, pinholes and bubbles, among other glaze surface defects, are generated on the glaze layer surface.

[0007] To address this issue, this invention first employs N ions and / or Nb ions as wear-resistant materials, injecting them into the protective glaze layer of ceramic tiles. This forms new substances or new bonds on the surface of the protective glaze layer, thereby improving the wear resistance of the glaze. Specifically, N ions react with silicon ions in the protective glaze to generate highly wear-resistant Si3N4; Nb ions form new Nb-O-Si bonds and Nb=O bonds with the protective glaze, making the glaze network structure more compact and effectively improving the wear resistance of the glaze. Then, the ion-injected ceramic tiles undergo alkali metal molten salt surface treatment. Due to the small ionic radius of alkali metals, the molten salt treatment process fills the vacancy defects and interatomic gaps generated during ion implantation, increasing the density of the glaze network structure. This helps reduce glaze defects such as pinholes and bubbles, improving glaze quality, and further enhancing the wear resistance of the glaze. Finally, the molten salt-treated ceramic tiles undergo annealing to repair the glaze lattice structure, further reducing glaze defects and improving the wear resistance of the glaze. Therefore, by sequentially performing ion implantation, alkali metal molten salt surface treatment, and annealing treatment on ceramic tiles, the present invention significantly improves the wear resistance of the glaze surface while ensuring the quality of the ceramic tile glaze surface.

[0008] To solve the above-mentioned technical problems, the first aspect of the present invention provides a method for preparing wear-resistant glazed ceramic tiles, comprising the following steps:

[0009] (1) Ions are implanted into the protective glaze layer of glazed ceramic tiles to obtain ion-implanted ceramic tiles; the ions include nitrogen ions.

[0010] and / or Nb ions;

[0011] (2) The ion-implanted ceramic brick is immersed in molten metal salt and surface treated to obtain a surface-modified ceramic brick;

[0012] The molten metal salt includes alkali metal salts;

[0013] (3) The surface-modified ceramic brick is annealed to obtain the wear-resistant glazed ceramic brick.

[0014] In some embodiments of the present invention, in step (1), the protective glaze layer is formed by firing a protective glaze, and the chemical composition of the protective glaze by weight percentage includes: SiO2 55-70%, Al2O3 10-15%, CaO 4-7%, MgO 3-5%, K2O 3-5%, Na2O 2-4%, B2O3 3-5%, ZrO2 3-5%.

[0015] Specifically, the protective glaze of the present invention adopts a high-silicon transparent glaze system, which facilitates the reaction of N ions and Nb ions with silicon ions in the protective glaze to generate new wear-resistant materials (Si3N4) or new bonds (Nb-O-Si bonds and Nb=O bonds), thereby improving the wear resistance of the glaze surface.

[0016] In some embodiments of the present invention, in step (1), the ion implantation parameters are: implantation energy 30-40 keV, and implantation amount 1×10⁻⁶. 16 -1×10 17 ions / m 2 .

[0017] Specifically, the implantation energy mainly affects the ion implantation depth. To ensure the wear resistance of the glaze, the ion implantation depth should not be too deep. An appropriate ion implantation amount is beneficial to simultaneously ensuring the wear resistance and surface quality of the glaze; too little ion implantation will not significantly improve the wear resistance; too much ion implantation will affect the glaze quality.

[0018] In some embodiments of the present invention, in step (2), the alkali metal salt comprises, by weight, 7.5-8.5 parts of potassium salt, 1-1.5 parts of sodium salt, and 0.5-1 parts of lithium salt.

[0019] Specifically, different alkali metal ions have different radii. By using a mixture of molten metal salts with different alkali metal ion radii, vacancy-type defects and interatomic gaps of non-void size can be filled to improve the density of the glaze layer, thereby improving the wear resistance and quality of the glaze surface.

[0020] In some embodiments of the present invention, the potassium salt is selected from at least one of potassium chloride, potassium nitrate, and potassium sulfate.

[0021] In some embodiments of the present invention, the sodium salt is selected from at least one of sodium chloride, sodium nitrate, and sodium sulfate.

[0022] In some embodiments of the present invention, the lithium salt is selected from at least one of lithium chloride, lithium nitrate, and lithium sulfate.

[0023] In some embodiments of the present invention, the molten metal salt further includes aluminum chloride, and the mass ratio of the potassium salt to aluminum chloride is (97-99):(1-3). Aluminum chloride is primarily used as an activator in the present invention to eliminate the passivation of the potassium salt during the ion exchange process, thereby increasing the ion exchange rate.

[0024] In some embodiments of the present invention, in step (2), the melting temperature of the molten metal salt is 390-420°C.

[0025] In some embodiments of the present invention, the surface treatment time in step (2) is 4-6 hours.

[0026] In some embodiments of the present invention, in step (3), the annealing temperature is 450-600°C.

[0027] In some embodiments of the present invention, in step (3), the annealing process takes 40-60 minutes.

[0028] A second aspect of the present invention provides a wear-resistant glazed ceramic tile, which is prepared by the above-described method for preparing wear-resistant glazed ceramic tiles. The wear-resistant glazed ceramic tile includes a protective glaze layer, and the raw material components for preparing the protective glaze layer include N ions and / or Nb ions.

[0029] Specifically, the present invention improves the wear resistance of ceramic tiles by injecting N ions and / or Nb ions into the protective glaze layer. The N ions react with silicon ions in the protective glaze to generate highly wear-resistant Si3N4, while the Nb ions readily form new Nb-O-Si bonds and Nb=O bonds with the protective glaze, making the glaze network structure more compact.

[0030] Compared with the prior art, the above-described technical solution of the present invention has at least the following technical effects or advantages:

[0031] (1) In the preparation process of the glazed ceramic tile of the present invention, the protective glaze layer is subjected to ion implantation, alkali metal molten salt surface treatment and annealing treatment in sequence. The three processes work together to greatly improve the wear resistance of the glaze while ensuring the quality of the ceramic tile glaze. First, N ions and / or Nb ions are implanted into the protective glaze layer by ion implantation, forming new high wear-resistant materials (Si3N4) or new bonds (Nb-O-Si bonds and Nb=O bonds) on the surface of the protective glaze layer, making the glaze network structure more compact, thereby improving the wear resistance of the glaze. Then, the ceramic tile after ion implantation is subjected to alkali metal molten salt surface treatment to fill the vacancy defects and interatomic gaps generated during ion implantation, improve the density of the glaze network structure, and further improve the wear resistance of the glaze while improving the quality of the glaze. Finally, the ceramic tile after metal molten salt surface treatment is annealed to repair the crystal structure of the glaze layer, further reduce glaze defects and improve the wear resistance of the glaze.

[0032] (2) The present invention can precisely control the amount of ion implantation by adjusting the dosage of ion implantation, and the ion distribution is uniform, which can maintain the wear resistance of ceramic tiles for a long time and achieve the highest wear resistance level of 5 for ceramic tiles. Detailed Implementation

[0033] The present invention will now be described in detail with reference to embodiments to facilitate understanding of the invention by those skilled in the art. It is particularly important to note that the embodiments are merely illustrative of the invention and should not be construed as limiting the scope of protection of the invention. Non-essential improvements and adjustments made to the invention by those skilled in the art based on the above description should still fall within the scope of protection of the invention. Furthermore, all raw materials mentioned below, unless otherwise specified, are commercially available products; all process steps or preparation methods not mentioned in detail are process steps or preparation methods known to those skilled in the art.

[0034] Example 1

[0035] A method for preparing a wear-resistant glazed ceramic tile includes the following steps:

[0036] (1) Place the glazed ceramic tile into an ion implanter and inject N ions into the protective glaze layer of the glazed ceramic tile at an implantation energy of 35 keV. 16 ions / m 2 Ion implantation ceramic bricks are obtained;

[0037] The protective glaze layer is made by firing a protective glaze. The chemical composition of the protective glaze, by weight percentage, includes: SiO2 61.6%, Al2O3 12.5%, CaO 6.3%, MgO 4.4%, K2O 4.5%, Na2O 3%, B2O3 3.7%, and ZrO2 4%.

[0038] (2) Weigh the raw materials for preparing the molten metal salt, which include, by weight: 80 parts potassium chloride, 12 parts sodium chloride, 8 parts lithium chloride, and 2 parts aluminum chloride; then heat each raw material at 400°C to obtain a molten metal salt mixture; then immerse the ion-implanted ceramic brick obtained in step (1) in the molten metal salt, perform surface treatment for 5 hours, cool to room temperature, clean the surface, and obtain a surface-modified ceramic brick.

[0039] (3) The surface-modified ceramic bricks obtained in step (2) are annealed at 500°C for 40 minutes to obtain the wear-resistant glazed ceramic bricks of this embodiment.

[0040] Example 2

[0041] A method for preparing a wear-resistant glazed ceramic tile includes the following steps:

[0042] (1) Place the glazed ceramic tile into an ion implanter and inject N ions at an implantation energy of 30 keV into the protective glaze layer of the glazed ceramic tile, 1×10 16 ions / m 2 Ion implantation ceramic bricks are obtained;

[0043] Among them: the protective glaze layer is made by firing the protective glaze. The chemical composition of the protective glaze, by weight percentage, includes: SiO2 59.7%, Al2O3 14.9%, CaO 4.8%, MgO 4%, K2O 3.5%, Na2O 3.1%, B2O 35%, ZrO 25%.

[0044] (2) Weigh the raw materials for preparing the molten metal salt, which include, by weight: 75 parts potassium nitrate, 15 parts sodium nitrate, 10 parts lithium nitrate, and 1.5 parts aluminum chloride; then melt each raw material at 390°C to obtain a molten metal salt mixture; then immerse the ion-implanted ceramic brick obtained in step (1) in the molten metal salt, perform surface treatment for 6 hours, cool to room temperature, clean the surface, and obtain a surface-modified ceramic brick.

[0045] (3) The surface-modified ceramic bricks obtained in step (2) are annealed at 450°C for 60 minutes to obtain the wear-resistant glazed ceramic bricks of this embodiment.

[0046] Example 3

[0047] A method for preparing a wear-resistant glazed ceramic tile includes the following steps:

[0048] (1) Place the glazed ceramic tile into an ion implanter and inject N ions into the protective glaze layer of the glazed ceramic tile at an implantation energy of 40 keV, 5 × 10⁻⁶ kilometres per cubic meter. 16 ions / m 2 and Nb ions 5×10 16 ions / m 2 Ion implantation ceramic bricks are obtained;

[0049] The protective glaze layer is formed by firing a protective glaze. The chemical composition of the protective glaze, by weight percentage, includes: SiO2 68.6%, Al2O3 10.9%, CaO 5.2%, MgO 3.5%, K2O 3.7%, Na2O 2%, B2O3 3.1%, and ZrO2 3%.

[0050] (2) Weigh the raw materials for preparing the molten metal salt, which include, by weight: 85 parts potassium sulfate, 10 parts sodium sulfate, 5 parts lithium sulfate, and 2 parts aluminum chloride; then melt each raw material at 420°C to obtain a molten metal salt mixture; then immerse the ion-implanted ceramic brick obtained in step (1) in the molten metal salt, perform surface treatment for 4 hours, cool to room temperature, clean the surface, and obtain a surface-modified ceramic brick.

[0051] (3) The surface-modified ceramic bricks obtained in step (2) are annealed at 600°C for 30 minutes to obtain the wear-resistant glazed ceramic bricks of this embodiment.

[0052] Comparative Example 1

[0053] A method for preparing a wear-resistant glazed ceramic tile includes the following steps:

[0054] (1) Weigh the raw materials for preparing the molten metal salt, which include, by weight: 80 parts potassium chloride, 12 parts sodium chloride, 8 parts lithium chloride, and 2 parts aluminum chloride; then melt each raw material at 400°C to obtain a molten metal salt mixture; then immerse the glazed ceramic brick in the molten metal salt, perform surface treatment for 5 hours, cool to room temperature, clean the surface, and obtain a surface-modified ceramic brick.

[0055] Among them: the protective glaze layer of glazed ceramic tiles is made by firing a protective glaze. The chemical composition of the protective glaze, by weight percentage, includes: SiO2 61.6%, Al2O3 12.5%, CaO 6.3%, MgO 4.4%, K2O 4.5%, Na2O 3%, B2O3 3.7%, ZrO2 4%.

[0056] (2) The surface-modified ceramic bricks obtained in step (1) are annealed at 500°C for 40 minutes to obtain the wear-resistant glazed ceramic bricks of this comparative example.

[0057] The difference between Comparative Example 1 and Example 1 is that N ions were not injected into the protective glaze layer.

[0058] Comparative Example 2

[0059] A method for preparing a wear-resistant glazed ceramic tile includes the following steps:

[0060] (1) Place the glazed ceramic tile into an ion implanter and inject N ions into the protective glaze layer of the glazed ceramic tile at an implantation energy of 35 keV. 16 ions / m 2 Ion implantation ceramic bricks are obtained;

[0061] The protective glaze layer is made by firing a protective glaze. The chemical composition of the protective glaze, by weight percentage, includes: SiO2 61.6%, Al2O3 12.5%, CaO 6.3%, MgO 4.4%, K2O 4.5%, Na2O 3%, B2O3 3.7%, and ZrO2 4%.

[0062] (2) The ion-implanted ceramic bricks obtained in step (1) are annealed at 500°C for 40 minutes to obtain the wear-resistant glazed ceramic bricks of this comparative example.

[0063] The difference between Comparative Example 2 and Example 1 is that the ion-implanted ceramic bricks were not subjected to molten metal salt surface treatment.

[0064] Comparative Example 3

[0065] A method for preparing a wear-resistant glazed ceramic tile includes the following steps:

[0066] (1) Place the glazed ceramic tile into an ion implanter and inject N ions into the protective glaze layer of the glazed ceramic tile at an implantation energy of 35 keV. 16 ions / m 2 Ion implantation ceramic bricks are obtained;

[0067] The protective glaze layer is made by firing a protective glaze. The chemical composition of the protective glaze, by weight percentage, includes: SiO2 61.6%, Al2O3 12.5%, CaO 6.3%, MgO 4.4%, K2O 4.5%, Na2O 3%, B2O3 3.7%, and ZrO2 4%.

[0068] (2) Weigh the raw materials for preparing the molten metal salt, which include, by weight: 80 parts potassium chloride, 12 parts sodium chloride, 8 parts lithium chloride, and 2 parts aluminum chloride; then melt each raw material at 400°C to obtain a molten metal salt mixture; then immerse the ion-implanted ceramic brick obtained in step (1) in the molten metal salt, perform surface treatment for 5 hours, cool to room temperature, clean the surface, and obtain the wear-resistant glazed ceramic brick of this comparative example.

[0069] The difference between Comparative Example 3 and Example 1 is that the ceramic tiles with the molten metal salt surface treatment were not annealed.

[0070] Comparative Example 4

[0071] A method for preparing a wear-resistant glazed ceramic tile includes the following steps:

[0072] (1) Place the glazed ceramic tile into an ion implanter and inject 5 × 10 F ions into the protective glaze layer of the glazed ceramic tile at an implantation energy of 35 keV. 16 ions / m 2 Ion implantation ceramic bricks are obtained;

[0073] The protective glaze layer is made by firing a protective glaze. The chemical composition of the protective glaze, by weight percentage, includes: SiO2 61.6%, Al2O3 12.5%, CaO 6.3%, MgO 4.4%, K2O 4.5%, Na2O 3%, B2O3 3.7%, and ZrO2 4%.

[0074] (2) Weigh the raw materials for preparing the molten metal salt, which include, by weight: 80 parts potassium chloride, 12 parts sodium chloride, 8 parts lithium chloride, and 2 parts aluminum chloride; then melt each raw material at 400°C to obtain a molten metal salt mixture; then immerse the ion-implanted ceramic brick obtained in step (1) in the molten metal salt, perform surface treatment for 5 hours, cool to room temperature, clean the surface, and obtain a surface-modified ceramic brick.

[0075] (3) The surface-modified ceramic bricks obtained in step (2) are annealed at 500°C for 40 minutes to obtain the wear-resistant glazed ceramic bricks of this comparative example.

[0076] The difference between Comparative Example 4 and Example 1 is that an equal dose of F ions was used instead of N ions in Example 1.

[0077] Comparative Example 5

[0078] A method for preparing a wear-resistant glazed ceramic tile includes the following steps:

[0079] (1) Place the glazed ceramic tile into an ion implanter and inject N ions into the protective glaze layer of the glazed ceramic tile at an implantation energy of 35 keV. 16 ions / m 2 Ion implantation ceramic bricks are obtained;

[0080] Among them: the protective glaze layer is made by firing the protective glaze. The chemical composition of the protective glaze, by weight percentage, includes: SiO2 51.6%, Al2O3 14.5%, CaO 8.3%, MgO 5.4%, K2O 6.5%, Na2O 4%, B2O3 4.7%, ZrO 25%.

[0081] (2) Weigh the raw materials for preparing the molten metal salt, which include, by weight: 80 parts potassium chloride, 12 parts sodium chloride, 8 parts lithium chloride, and 2 parts aluminum chloride; then melt each raw material at 400°C to obtain a molten metal salt mixture; then immerse the ion-implanted ceramic brick obtained in step (1) in the molten metal salt, perform surface treatment for 5 hours, cool to room temperature, clean the surface, and obtain a surface-modified ceramic brick.

[0082] (3) The surface-modified ceramic bricks obtained in step (2) are annealed at 500°C for 40 minutes to obtain the wear-resistant glazed ceramic bricks of this comparative example.

[0083] The difference between Comparative Example 5 and Example 1 is that the surface protective glaze of the glazed ceramic tile has a lower SiO2 content in its chemical composition.

[0084] Performance testing

[0085] The wear-resistant glazed ceramic tile samples obtained in Examples 1-3 and Comparative Examples 1-5 were subjected to wear resistance tests, and their glaze effects were observed. The wear resistance was tested according to the ceramic tile standard GB / T 4100-2015, and the glaze effect was visually inspected. The test results are shown in Table 1 below.

[0086] Table 1:

[0087]

[0088] As shown in Table 1, the wear-resistant glazed ceramic tile samples prepared in Examples 1-3, due to the implantation of N ions into the protective glaze layer, showed a one-level improvement in wear resistance compared to Comparative Example 1 (which did not have N ion implantation). Furthermore, the glaze surface was smooth and flat, without obvious pinholes or bubbles. Comparative Example 2, compared to Example 1, showed a significant decrease in wear resistance due to the lack of metal molten salt surface treatment on the ion-implanted ceramic tile, and the presence of obvious bubbles on the glaze surface. Comparative Examples 3-5, compared to Example 1, showed a decrease in wear resistance due to the absence of annealing treatment on the metal molten salt-treated ceramic tile, the use of other implanted ions, and the adoption of different protective glazes, respectively.

[0089] For those skilled in the art, several simple deductions or substitutions can be made without departing from the inventive concept, without requiring creative effort. Therefore, any simple improvements made to this invention by those skilled in the art based on the disclosure of this invention should be within the scope of protection of this invention. The above embodiments are preferred embodiments of this invention, and all processes similar to this invention and equivalent changes should fall within the scope of protection of this invention.

Claims

1. A method for preparing a wear-resistant glazed ceramic tile, characterized in that, Includes the following steps: (1) Ions are injected into the protective glaze layer of glazed ceramic tiles to obtain ion-implanted ceramic tiles; The ions include N ions and / or Nb ions; The protective glaze layer is formed by firing a protective glaze, and the chemical composition of the protective glaze by weight percentage includes: SiO2 55-70%, Al2O3 10-15%, CaO 4-7%, MgO 3-5%, K2O 3-5%, Na2O 2-4%, B2O3 3-5%, ZrO2 3-5%; (2) The ion-implanted ceramic brick is immersed in a molten metal salt and surface treated to obtain a surface-modified ceramic brick; the molten metal salt includes an alkali metal salt. (3) The surface-modified ceramic brick is annealed at a temperature of 450-600℃ to obtain the wear-resistant glazed ceramic brick.

2. The method for preparing wear-resistant glazed ceramic tiles according to claim 1, characterized in that, In step (1), the ion implantation parameters are: implantation energy of 30-40 keV and implantation amount of 1×10⁻⁶. 16 -1×10 17 ions / m 2 .

3. The method for preparing wear-resistant glazed ceramic tiles according to claim 1, characterized in that, In step (2), the alkali metal salts include, by weight, 7.5-8.5 parts of potassium salt, 1-1.5 parts of sodium salt, and 0.5-1 parts of lithium salt.

4. The method for preparing wear-resistant glazed ceramic tiles according to claim 3, characterized in that, The molten metal salt also includes aluminum chloride, and the mass ratio of the potassium salt to aluminum chloride is (97-99):(1-3).

5. The method for preparing wear-resistant glazed ceramic tiles according to claim 1, characterized in that, In step (2), the melting temperature of the molten metal salt is 390-420℃.

6. The method for preparing wear-resistant glazed ceramic tiles according to claim 5, characterized in that, In step (2), the surface treatment takes 4-6 hours.

7. The method for preparing wear-resistant glazed ceramic tiles according to claim 1, characterized in that, In step (3), the annealing process takes 40-60 minutes.

8. A wear-resistant glazed ceramic tile, characterized in that, The wear-resistant glazed ceramic tile is prepared by the method of any one of claims 1-7, wherein the wear-resistant glazed ceramic tile includes a protective glaze layer, and the raw material components for preparing the protective glaze layer include N ions and / or Nb ions.

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