Ceramic product, preparation method thereof and closestool

Abstract

The invention relates to the field of bathroom accessories, in particular to a ceramic product and a preparation method thereof. The ceramic product comprises a ceramic substrate, a transition layer is arranged on the ceramic substrate, a photocatalytic layer is arranged on the side, away from the ceramic substrate, of the transition layer, the photocatalytic layer comprises titanium oxide, zirconium oxide and doping elements, and the doping elements comprise the iron element and the nitrogen element. The photocatalytic layer has strong adhesive force, wide spectral response and corrosion resistance, can be adapted to a working system of the ceramic product, and solves the self-cleaning problem of the ceramic product.

Description

Technical Field

[0001] This application relates to the sanitary ware industry, and in particular to ceramic products and their preparation methods, and toilets. Background Technology

[0002] As core equipment in modern bathroom spaces, ceramic products directly impact users' daily experience through their materials, design, and functionality. With continuous advancements in materials science, the Internet of Things, and artificial intelligence, smart ceramic products (such as smart toilets and smart sensor sinks) are rapidly gaining popularity and increasingly entering homes, bringing users a more comfortable, convenient, and personalized bathroom experience. However, surface hygiene maintenance remains a key challenge for both ordinary and smart ceramic products. Taking smart toilets as an example, their inner walls, water traps, and nozzles are constantly exposed to a damp environment, making them prone to the growth of pathogens such as E. coli and Staphylococcus aureus. Furthermore, residual urine and fecal matter during use can produce unpleasant odors such as ammonia and hydrogen sulfide, severely affecting the user experience.

[0003] Titanium dioxide is a semiconductor material. When exposed to light, the titanium dioxide photocatalytic layer can be excited to produce a strong oxidant that attacks and decomposes organic matter such as bacteria and odor molecules. The industry has tried to apply the titanium dioxide photocatalytic layer to toilets to play a self-cleaning role. However, in actual production, it has been found that the catalytic efficiency of the titanium dioxide photocatalytic layer is limited, and it is easily damaged and detached, resulting in a short service life. Summary of the Invention

[0004] Based on this, the first aspect of this application provides a ceramic product, the technical solution of which is as follows:

[0005] A ceramic product includes a ceramic substrate, a transition layer disposed on the ceramic substrate, and a photocatalytic layer disposed on the side of the transition layer away from the ceramic substrate. The photocatalytic layer includes titanium oxide, zirconium oxide, and doping elements, wherein the doping elements include iron and nitrogen.

[0006] The second aspect of this application provides a method for preparing ceramic articles, the technical solution of which is as follows:

[0007] A method for preparing a ceramic product includes the following steps:

[0008] The ceramic substrate is dried at a temperature of 300℃ to 500℃ for 1 to 3 hours.

[0009] A transition layer is deposited on the dried ceramic substrate;

[0010] A photocatalytic layer is deposited on the side of the transition layer away from the ceramic substrate. The photocatalytic layer includes titanium oxide, zirconium oxide, and doping elements, including iron and nitrogen.

[0011] A third aspect of this application provides a toilet comprising a ceramic article as described above or a ceramic article prepared by a method for preparing a ceramic article as described above.

[0012] Compared with traditional solutions, this application has the following advantages:

[0013] The photocatalytic layer of this application comprises titanium dioxide, zirconium oxide, and doping elements, including iron and nitrogen. The co-doping of iron and nitrogen helps to reduce the band gap of titanium dioxide from 3.2 eV to 2.4 eV–2.8 eV, expanding the visible light response range and improving photocatalytic efficiency. Simultaneously, the addition of zirconium oxide improves the acid and alkali corrosion resistance of the photocatalytic layer, making it adaptable to the chemical environment of the ceramic product and mitigating the problem of damage after long-term use. Furthermore, this application adds a transition layer between the photocatalytic layer and the ceramic product. This transition layer enhances the adhesion between the photocatalytic layer and the glaze of the ceramic product, reducing the risk of the photocatalytic layer detaching during use. Through these methods, the photocatalytic layer possesses strong adhesion, a broad spectral response, and corrosion resistance, making it suitable for the working system of ceramic products and solving the self-cleaning problem of ceramic products. Attached Figure Description

[0014] To more clearly illustrate the technical solutions in the embodiments of this application and to more completely understand this application and its beneficial effects, the drawings used in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0015] Figure 1 A partial structural schematic diagram of a ceramic product according to one embodiment;

[0016] Figure 2 SEM image of the photocatalytic layer in Example 1;

[0017] Figure 3 Here is a SEM image of the photocatalytic layer in Comparative Example 2;

[0018] Figure 4 The image shown is of the ceramic product from Example 1.

[0019] Figure 5 This is a photograph of the ceramic product from Example 2;

[0020] Figure 6 The decomposition of methylene blue solution in Example 1 at different times is shown. Detailed Implementation

[0021] The present application will be further described in detail below with reference to specific embodiments. The present application can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a more thorough and complete understanding of the disclosure of this application.

[0022] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of this application.

[0023] Unless otherwise stated or in case of contradiction, the terms or phrases used herein shall have the following meanings:

[0024] In this application, the terms "multiple", "various", "multiple times", "multi-dimensional", etc., unless otherwise specified, refer to a quantity greater than or equal to 2. For example, "one or more" means one or more than or equal to two.

[0025] In this application, "several" means at least one, such as one, two, etc., unless otherwise expressly and specifically defined.

[0026] In this application, the terms "optionally," "optionally," and "optional" refer to options that are optional, meaning they can be selected from either "with" or "without." If multiple "optional" options appear in a technical solution, unless otherwise specified and there are no contradictions or mutual constraints, each "optional" option is independent.

[0027] In this application, the terms "first aspect," "second aspect," "third aspect," and "fourth aspect," etc., are used for descriptive purposes only and should not be construed as indicating or implying relative importance or quantity, nor should they be construed as implicitly indicating the importance or quantity of the indicated technical features. Moreover, "first," "second," "third," and "fourth," etc., serve only a non-exhaustive enumeration purpose and should be understood not to constitute a closed limitation on quantity.

[0028] In this application, numerical intervals (i.e. numerical ranges) are involved. Unless otherwise specified, the selected numerical distributions within the above-mentioned numerical intervals are considered continuous, and include the two numerical endpoints (i.e., the minimum value and the maximum value) of the numerical range, as well as every value between the two numerical endpoints.

[0029] The first aspect of this application provides a ceramic article, in one embodiment of which see [reference needed]. Figure 1The ceramic product 100 includes a ceramic substrate 10, a transition layer 20 is disposed on the ceramic substrate 10, and a photocatalytic layer 30 is disposed on the side of the transition layer 20 away from the ceramic substrate. The photocatalytic layer 30 includes titanium oxide, zirconium oxide and doping elements, including iron and nitrogen.

[0030] The photocatalytic layer in the above-described embodiment comprises titanium oxide, zirconium oxide, and doping elements, including iron and nitrogen. The co-doping of iron and nitrogen helps to reduce the band gap of titanium oxide from 3.2 eV to 2.4 eV–2.8 eV, expanding the visible light response range and improving photocatalytic efficiency. Simultaneously, the addition of zirconium oxide improves the acid and alkali corrosion resistance of the photocatalytic layer, making it adaptable to the chemical environment of the ceramic product and mitigating the problem of damage after long-term use. Furthermore, this application adds a transition layer between the photocatalytic layer and the ceramic product. This transition layer enhances the adhesion between the photocatalytic layer and the glaze of the ceramic product, reducing the risk of the photocatalytic layer detaching during use. Through these methods, the photocatalytic layer possesses strong adhesion, a broad spectral response, and corrosion resistance, making it suitable for the working system of ceramic products and solving the self-cleaning problem of ceramic products.

[0031] The ceramic product in this embodiment can be an ordinary ceramic product or a smart ceramic product. The ceramic product can be a toilet or a basin. When the ceramic product is a toilet, the ceramic substrate is the basin body, and the transition layer is located on the inner wall of the basin body. Understandably, the surface of the ceramic substrate is a ceramic glaze. In this embodiment, the photocatalytic layer is formed by physical vapor deposition (PVD). The thermal expansion coefficient of the photocatalytic layer formed by PVD does not match the thermal expansion coefficient of the ceramic glaze, which easily leads to interface cracking. By setting a transition layer, it is beneficial to match the thermal expansion coefficient of the ceramic glaze, reduce interfacial stress, and improve the adhesion between the photocatalytic layer and the ceramic glaze. Optionally, the transition layer includes TiAlN. Adjusting the N content in the transition layer to 15wt%~25wt% can match the thermal expansion coefficient of the ceramic glaze. The transition layer can be formed by physical vapor deposition. Optionally, the thickness of the transition layer is 60nm~200nm.

[0032] Optionally, the surface roughness of the photocatalytic layer on the side away from the transition layer is ≤50nm. The photocatalytic layer formed by PVD has a smaller roughness and better photocatalytic efficiency compared to the photocatalytic layer formed by the sol-gel method.

[0033] Optionally, the titanium oxide accounts for 82% to 92% of the mass of the photocatalytic layer. The zirconium oxide accounts for 1% to 5% of the mass of the photocatalytic layer. The iron element accounts for 2% to 7% of the mass of the photocatalytic layer. The nitrogen element accounts for 2% to 6% of the mass of the photocatalytic layer.

[0034] Optionally, the photocatalytic layer further includes alumina. Adding alumina helps to increase the refractive index of the photocatalytic layer and enhance its whiteness. Optionally, the alumina accounts for 1% to 3% of the mass of the photocatalytic layer.

[0035] Optionally, the thickness of the photocatalytic layer is 300nm~1000nm.

[0036] Traditional ceramic products struggle to achieve a comprehensive, sustainable, and maintenance-free cleanliness experience, exhibiting passivity and limitations, including temporary effects, material aging, and diminishing effectiveness. This solution overcomes the shortcomings of traditional ceramic products, such as incomplete sterilization, easy coating failure, and poor functional synergy, providing a photocatalytic intelligent ceramic coating with strong adhesion, chemical corrosion resistance, and highly efficient sterilization. It offers the following advantages:

[0037] 1. Breakthrough in interface bonding performance: The adhesion between the photocatalytic layer and the ceramic substrate is enhanced through the gradient stress buffering effect of the TiAlN transition layer.

[0038] 2. Significantly improved photocatalytic efficiency: Fe-N co-doping achieves high-efficiency photoresponse, enabling the photocatalytic layer to achieve higher sterilization and deodorization efficiency than pure TiO2 coating with the assistance of intelligent ceramic product supplementary lighting system.

[0039] 3. Co-optimization of corrosion resistance and function: The introduction of Al2O3 and ZrO2 enables the photocatalytic layer to withstand the acid and alkaline environment and cleaning agent corrosion of ceramic products, solving the defect of poor chemical stability of traditional photocatalytic materials.

[0040] A second aspect of this application provides a method for preparing a ceramic article. In one embodiment, the method for preparing a ceramic article includes the following steps:

[0041] S1. Dry the ceramic substrate.

[0042] The ceramic substrate is dried to remove surface impurities. Optionally, the drying temperature is 300℃~500℃, and the drying time is 1h~3h.

[0043] S2. Deposit a transition layer on the dried ceramic substrate.

[0044] Optionally, a transition layer is deposited on a ceramic substrate, including the following steps:

[0045] S21. Provide a first target material, the first target material comprising a titanium-aluminum (TiAl) alloy.

[0046] The purity of the TiAl alloy is ≥99.9%, and the molar ratio of Ti to Al is (2~4):1.

[0047] S22. Provide a first reaction gas, the first reaction gas including nitrogen (N2).

[0048] S23. The first target material is bombarded to sputter target atoms, which react with the first reactive gas, and the reactants are deposited on the ceramic substrate to form the transition layer.

[0049] In this embodiment, Ar is used as the sputtering gas to bombard the first target material to sputter target atoms, wherein the flow rate ratio of N2 to Ar is 1:(4~6).

[0050] Optionally, the deposition parameters include: a vacuum degree of 1×10⁻⁶. -3 Pa~5×10 -3 Pa, sputtering power of 200W~350W, substrate bias of -100~-250V, deposition temperature of 180~250℃, and deposition time of 15 minutes~30 minutes.

[0051] S3. A photocatalytic layer is deposited on the side of the transition layer away from the ceramic substrate. The photocatalytic layer includes titanium oxide, zirconium oxide, and doping elements, including iron and nitrogen.

[0052] Optionally, depositing a photocatalytic layer on the transition layer includes the following steps:

[0053] S31. Provide a second target material, the second target material including a titanium oxide (TiO2) target, a zirconium oxide (ZrO2) target and an iron target (Fe).

[0054] The TiO2 target is the primary target with a purity ≥99.9% and a power of 300W~500W. ZrO2 and Fe targets are auxiliary targets, both with a purity ≥99.9%, with the Fe target power at 40W~80W and the ZrO2 target power at 30W~60W. Optionally, the second target material may also include an alumina (Al2O3) target, with the Al2O3 target as an auxiliary target, a purity ≥99.9%, and a power of 20W~50W.

[0055] S32. Provide a second reaction gas, the second reaction gas comprising nitrogen (N2) and oxygen (O2).

[0056] Optionally, the volume ratio of N2 to O2 is 1:(7~10). The total flow rate of the second reaction gas is 25 sccm~60 sccm.

[0057] S33. The second target material is bombarded to sputter target atoms, which react with the second reactive gas, and the reactants are deposited on the transition layer to form the photocatalytic layer.

[0058] In this embodiment, Ar is used as the sputtering gas to bombard the second target material to sputter target atoms, wherein the flow rate ratio of the second reaction gas to Ar is 1:(4~6).

[0059] Optionally, the deposition parameters include: a vacuum degree of 5 × 10⁻⁶. -4 Pa~2×10 -3 Pa, substrate bias voltage -50V~-100V, temperature 200~300℃, deposition time 30 minutes~90 minutes.

[0060] PVD technology, due to its advantages of strong coating adhesion and controllable composition, has been validated in the field of medical antibacterial coatings. However, its application to ceramic substrates still faces technical obstacles: firstly, the thermal expansion coefficients of the PVD coating and the ceramic substrate glaze are mismatched, easily leading to interface cracking; secondly, the PVD coating is difficult to adapt to the chemical environment of ceramic products. The above-described implementation method forms a transition layer and a photocatalytic layer through PVD, with multi-target magnetron sputtering technology used during the deposition of the photocatalytic layer. On the one hand, the transition layer overcomes the problem of the thermal expansion coefficient mismatch between the photocatalytic layer and the ceramic glaze, improving the adhesion between the photocatalytic layer and the ceramic glaze. On the other hand, through multi-component design, it takes into account broad spectral response, corrosion resistance, and mechanical strength, and can work in conjunction with the supplementary lighting and rinsing systems of smart ceramic products, adapting to the working system of smart ceramic products and fully utilizing photocatalytic efficiency. At the same time, PVD technology is a green coating process with no waste liquid discharge, and the low-temperature deposition process (≤300℃) will not damage the ceramic substrate, making it suitable for various models of smart ceramic products.

[0061] A third aspect of this application provides a toilet comprising a ceramic article as described above or a ceramic article prepared by a method for preparing a ceramic article as described above.

[0062] The following description is further illustrated with specific embodiments and comparative examples. Unless otherwise specified, the raw materials involved in the following specific embodiments and comparative examples are all commercially available. Unless otherwise specified, the instruments used are all commercially available. Unless otherwise specified, the processes involved are conventionally selected by those skilled in the art.

[0063] Example 1

[0064] This embodiment provides a ceramic product and its preparation method, the steps of which are as follows:

[0065] Step 1: Provide a ceramic substrate with a ceramic glaze on the inner wall. Dry the ceramic substrate at 400℃ for 2 hours.

[0066] Step 2: Using TiAl alloy as the target material (Ti:Al = 3:1 in molar ratio), N2 as the reactant gas, and Ar as the sputtering gas, the target material is bombarded to sputter target atoms, which react with the reactant gas. The reactants are deposited on the inner wall of the ceramic substrate to form a TiAlN transition layer. The flow ratio of the reactant gas to Ar is 1:5, and the vacuum degree is 3 × 10⁻⁶. -3 The sputtering power was 300W, the substrate bias was -200, the deposition temperature was 220℃, the deposition time was 20 minutes, and the thickness of the TiAlN transition layer was 120nm.

[0067] Step 3: Using TiO2 as the main target with a power of 400W, and Fe, Al2O3, and ZrO2 as auxiliary targets, with Fe target power of 60W, Al2O3 target power of 30W, and ZrO2 target power of 40W, N2 and O2 are used as reactant gases at a volume ratio of 1:8 and a total flow rate of 40 sccm. Ar is used as the sputtering gas to bombard the target material, causing target atoms to be sputtered and react with the reactant gases. The reactants are deposited on the TiAlN transition layer to form a photocatalytic layer. The flow rate ratio of reactant gas to Ar is 1:5, and the vacuum degree is 1×10⁻⁶. -3 Pa, substrate bias voltage -100V, temperature 250℃, deposition time 60 minutes, photocatalytic layer thickness 600nm.

[0068] Example 2

[0069] This embodiment provides a ceramic product and its preparation method, which is basically the same as that in Example 1, except that an Al2O3 target is not used. The steps are as follows:

[0070] Step 1, same as in Example 1.

[0071] Step 2, same as in Example 1.

[0072] Step 3: Using a TiO2 target as the main target with a power of 400W, and Fe and ZrO2 targets as auxiliary targets (Fe target power 60W, ZrO2 target power 40W), N2 and O2 are used as reactant gases with a volume ratio of 1:8 and a total flow rate of 40 sccm. Ar is used as the sputtering gas to bombard the target material, causing target atoms to be sputtered and react with the reactant gases. The reactants are deposited on the TiAlN transition layer, forming a photocatalytic layer. The flow rate ratio of the reactant gas to Ar is 1:5, and the vacuum level is 1×10⁻⁶. -3 Pa, substrate bias voltage -100V, temperature 250℃, deposition time 60 minutes, photocatalytic layer thickness 600nm.

[0073] Comparative Example 1

[0074] This comparative example provides a ceramic product and its preparation method, which is basically the same as that in Example 1, except that a transition layer and a photocatalytic layer are not formed. The steps are as follows:

[0075] Step 1, same as in Example 1.

[0076] Comparative Example 2

[0077] This comparative example provides a ceramic product and its preparation method, which are basically the same as those in Example 1, except that: no transition layer is formed, and the photocatalytic layer is prepared by the sol-gel method, with the following steps:

[0078] Step 1, same as in Example 1.

[0079] Step 2: Mix 400 mL of anhydrous ethanol with 40 g of rosin powder and heat to dissolve to prepare an alcohol rosin solution; slowly add 15 mL of tetrabutyl titanate (Ti(OC4H9)4) and stir until a deep yellow precipitate appears; wash the precipitate, dry it, and dissolve it in a mixed solvent to prepare a solution containing 3 wt%~5 wt% titanium oxide; adjust the viscosity with turpentine (to prevent dripping during coating), stir evenly, and let it stand for 24 hours to remove air bubbles; then spray it onto the inner wall of the ceramic substrate and fire at 750℃ for 2 hours to form a photocatalytic layer with a thickness of 600 nm.

[0080] Comparative Example 3

[0081] This comparative example provides a ceramic product and its preparation method, which is basically the same as that in Example 1, except that a transition layer is not formed. The steps are as follows:

[0082] Step 1, same as in Example 1.

[0083] Step 2: Using TiO2 as the main target with a power of 400W, and Fe, Al2O3, and ZrO2 as auxiliary targets, with power of 60W for Fe, 30W for Al2O3, and 40W for ZrO2, N2 and O2 are used as reactant gases at a volume ratio of 1:8 and a total flow rate of 40 sccm. Ar is used as the sputtering gas to bombard the target material, causing target atoms to be sputtered and react with the reactant gases. The reactants are deposited on the inner wall of the ceramic substrate, forming a photocatalytic layer. The flow rate ratio of reactant gas to Ar is 1:5, and the vacuum level is 1×10⁻⁶. -3 Pa, substrate bias voltage -100V, temperature 250℃, deposition time 60 minutes, photocatalytic layer thickness 600nm.

[0084] Comparative Example 4

[0085] This comparative example provides a ceramic product and its preparation method, which is basically the same as that in Example 1, except that an F target is not used. The steps are as follows:

[0086] Step 1, same as in Example 1.

[0087] Step 2, same as in Example 1.

[0088] Step 3: Using TiO2 as the main target with a power of 400W, and Al2O3 and ZrO2 as auxiliary targets (30W for Al2O3 and 40W for ZrO2), N2 and O2 are used as reactant gases at a volume ratio of 1:8 and a total flow rate of 40 sccm. Ar is used as the sputtering gas to bombard the target material, causing target atoms to be sputtered and react with the reactant gases. The reactants are deposited on the TiAlN transition layer to form a photocatalytic layer. The flow rate ratio of reactant gases to Ar is 1:5, and the vacuum level is 1×10⁻⁶. -3 Pa, substrate bias voltage -100V, temperature 250℃, deposition time 60 minutes, photocatalytic layer thickness 600nm.

[0089] Comparative Example 5

[0090] This comparative example provides a ceramic product and its preparation method, which is basically the same as that in Example 1, except that a ZrO2 target is not used. The steps are as follows:

[0091] Step 1, same as in Example 1.

[0092] Step 2, same as in Example 1.

[0093] Step 3: Using TiO2 as the main target with a power of 400W, and Fe and Al2O3 as auxiliary targets (Fe target power 60W, Al2O3 target power 30W), N2 and O2 are used as reactant gases with a volume ratio of 1:8 and a total flow rate of 40 sccm. Ar is used as the sputtering gas to bombard the target material, causing target atoms to be sputtered and react with the reactant gases. The reactants are deposited on the TiAlN transition layer, forming a photocatalytic layer. The flow rate ratio of reactant gases to Ar is 1:5, and the vacuum level is 1×10⁻⁶. -3 Pa, substrate bias voltage -100V, temperature 250℃, deposition time 60 minutes, photocatalytic layer thickness 600nm.

[0094] The ceramic products of each embodiment and comparative example were tested, and the test items and methods are as follows:

[0095] SEM images of the photocatalytic layer on the side away from the ceramic substrate in Project 1 and Example 1 are shown below. Figure 2 SEM images of the photocatalytic layer on the side away from the ceramic substrate in Comparative Example 2 are shown below. Figure 3It can be seen that the photocatalytic layer prepared by the sol-gel method contains large and uneven particles, resulting in many defects, while the photocatalytic layer prepared by physical vapor deposition has good particle size consistency and uniform distribution.

[0096] Project 2: Using a roughness tester, the roughness of the surface of the photocatalytic layer away from the ceramic substrate in Example 1, Comparative Example 1 and Comparative Example 2 was tested. The results are shown in Table 1.

[0097] Project 3: X-ray photoelectron spectroscopy (XPS) was used to analyze the composition and content of the photocatalytic layers in each example and comparative example. The results are shown in Table 1.

[0098] Table 1

[0099]

[0100] For a physical image of the ceramic product in Project 4 and Example 1, please refer to [link / reference]. Figure 4 For a physical image of the ceramic product in Example 2, please refer to... Figure 5 As can be seen, the photocatalytic layer is yellow when Al2O3 is not used, while it has a silvery-white luster when Al2O3 is used.

[0101] Project 5: A methylene blue solution was dotted onto the ceramic substrate of the photocatalytic layer in Example 1 and irradiated with ultraviolet light. The decomposition of the methylene blue solution was recorded after irradiation for 0 min, 20 min, 40 min, 60 min, 80 min, and 100 min, respectively. (See attached document). Figure 6 As can be seen, under ultraviolet light irradiation, the photocatalytic layer of Example 1 can decompose methylene blue molecules, causing the methylene blue solution to change from blue to colorless.

[0102] Project 6: Testing the catalytic efficiency of the photocatalytic layers in each embodiment and comparative example. The specific method was as follows: Following GB / T23764-2009, "Test Method for Performance of Photocatalytic Self-Cleaning Materials," oleic acid with a purity >60% was loaded onto the sample surface and irradiated with ultraviolet light. The water contact angle of the samples was recorded after irradiation for 0 min, 30 min, 60 min, 90 min, and 120 min, respectively. The results are shown in Table 2. A smaller water contact angle indicates stronger surface hydrophilicity, better photocatalytic decomposition of oleic acid, and stronger self-cleaning ability.

[0103] Table 2

[0104]

[0105] The results showed that the contact angle of Comparative Example 1 remained almost unchanged over time, indicating that Comparative Example 1 had no photocatalytic activity. Examples 1 and 2 both decreased from an initial large contact angle to below 20° within 120 minutes, indicating high catalytic efficiency. However, the photocatalytic efficiency of the photocatalytic layers in Comparative Examples 2, 4, and 5 was relatively low. While Comparative Example 3 exhibited high catalytic efficiency, the adhesion between the photocatalytic layer and the glaze of the ceramic substrate was poor, posing a risk of photocatalytic layer detachment and potential failure.

[0106] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0107] The embodiments described above are merely illustrative of several implementation methods of this application, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these all fall within the protection scope of this application. Therefore, the protection scope of this patent application should be determined by the appended claims.

Claims

1. A ceramic product, characterized in that, The invention includes a ceramic substrate, a transition layer disposed on the ceramic substrate, and a photocatalytic layer disposed on the side of the transition layer away from the ceramic substrate. The photocatalytic layer includes titanium oxide, zirconium oxide, and doping elements, including iron and nitrogen.

2. The ceramic product according to claim 1, characterized in that, The surface roughness of the photocatalytic layer on the side away from the transition layer is ≤50nm.

3. The ceramic product according to claim 1, characterized in that, Includes at least one of the following features: (1) The titanium oxide accounts for 82% to 92% of the mass of the photocatalytic layer; (2) The zirconium oxide accounts for 1% to 5% of the mass of the photocatalytic layer; (3) The iron element accounts for 2% to 7% of the mass of the photocatalytic layer; (4) The nitrogen element accounts for 2% to 6% of the mass of the photocatalytic layer.

4. The ceramic product according to claim 1, characterized in that, The photocatalytic layer also includes aluminum oxide.

5. The ceramic product according to claim 4, characterized in that, The alumina accounts for 1% to 3% of the mass of the photocatalytic layer.

6. The ceramic article according to any one of claims 1 to 5, characterized in that, The transition layer comprises TiAlN.

7. The ceramic article according to any one of claims 1 to 5, characterized in that, Includes at least one of the following features: (1) The thickness of the photocatalytic layer is 300 nm to 1000 nm; (2) The thickness of the transition layer is 60nm~200nm.

8. A method for preparing a ceramic product, characterized in that, Includes the following steps: The ceramic substrate is dried at a temperature of 300℃ to 500℃ for 1 to 3 hours. A transition layer is deposited on the dried ceramic substrate; A photocatalytic layer is deposited on the side of the transition layer away from the ceramic substrate. The photocatalytic layer includes titanium oxide, zirconium oxide, and doping elements, including iron and nitrogen.

9. The method for preparing ceramic products according to claim 8, characterized in that, Depositing a photocatalytic layer on the transition layer includes the following steps: A second target is provided, the second target comprising a titanium oxide target, a zirconium oxide target, and an iron target; A second reactant gas is provided, the second reactant gas comprising nitrogen and oxygen; The second target is bombarded to sputter target atoms, which react with the second reactive gas, and the reactants are deposited on the transition layer to form the photocatalytic layer.

10. The method for preparing ceramic products according to claim 8, characterized in that, Depositing a transition layer on a ceramic substrate includes the following steps: A first target material is provided, the first target material comprising a titanium-aluminum alloy; A first reaction gas is provided, the first reaction gas comprising nitrogen; The first target material is bombarded to sputter target atoms, which react with the first reactive gas, and the reactants are deposited on the ceramic substrate to form the transition layer.

11. A toilet, characterized in that, The ceramics include the ceramic articles according to any one of claims 1 to 7, or the ceramics prepared by the method of preparing the ceramic articles according to any one of claims 8 to 10.

Images