Sanitary ceramic product with antibacterial function
By uniformly dispersing copper oxide-nickel oxide nanocomposite antibacterial agent units on the surface of sanitary ceramic products and generating reactive oxygen free radicals by visible light excitation, the problems of poor antibacterial effect and complex preparation process of sanitary ceramic products are solved, achieving efficient antibacterial effect and easy production.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Utility models(China)
- Current Assignee / Owner
- CHINA AGRI UNIV
- Filing Date
- 2025-05-12
- Publication Date
- 2026-04-21
AI Technical Summary
Existing sanitary ceramic products have poor antibacterial effects and complex manufacturing processes, making them difficult to industrialize.
A copper oxide-nickel oxide nanocomposite antibacterial agent unit is uniformly dispersed on the surface of the sanitary ceramic body. It forms a pn heterojunction through visible light excitation, generating active oxygen free radicals to achieve efficient antibacterial effect. The preparation process is simple.
It achieves efficient and broad-spectrum antibacterial effects, has a self-cleaning function that responds to visible light, has a good glaze quality, is easy to produce, and is suitable for industrialization.
Smart Images
Figure CN224147959U_ABST
Abstract
Description
[0001] Technical Field
[0002] This utility model relates to the field of sanitary ceramic products technology, and in particular to a sanitary ceramic product with antibacterial function. Background Technology
[0003] Adding antibacterial and self-cleaning functions to sanitary ceramic products will inevitably increase their brand value. Currently, antibacterial ceramic technology in sanitary ware is mainly applied in the fields of sanitary ware and building tiles, inhibiting the growth of surface microorganisms by adding antibacterial ingredients such as silver and zinc. However, the antibacterial effect of sanitary ceramic products with antibacterial functions still needs improvement, and the manufacturing process is complex and difficult to produce. Utility Model Content
[0004] The purpose of this invention is to provide a sanitary ceramic product with antibacterial function, which has good antibacterial effect, good glaze quality, simple preparation process, and is easy to produce.
[0005] According to an embodiment of the present invention, a sanitary ceramic product with antibacterial function includes: a sanitary ceramic body and a copper oxide-nickel oxide nanocomposite antibacterial agent unit, wherein the copper oxide-nickel oxide nanocomposite antibacterial agent unit is uniformly dispersed and embedded on the surface of the sanitary ceramic body, and the copper oxide-nickel oxide nanocomposite antibacterial agent unit is at least partially protruding and exposed on the surface of the sanitary ceramic body.
[0006] Because the copper oxide-nickel oxide nanocomposite antibacterial agent units are uniformly dispersed and embedded on the surface of the sanitary ceramic body, and at least partially protrude and are exposed on the surface of the sanitary ceramic body, the copper oxide-nickel oxide nanocomposite antibacterial agent units are easily irradiated by visible light. Under visible light irradiation, the pn heterojunction formed by copper oxide and nickel oxide can effectively promote the separation of photogenerated electron-hole pairs and generate reactive oxygen free radicals (ROS). These highly reactive free radicals can destroy the bacterial cell structure and achieve a highly efficient and broad-spectrum antibacterial effect.
[0007] The antibacterial sanitary ceramic product of this utility model embodiment can be prepared by the following method: Pure glaze and a composite glaze consisting of a uniform mixture of the copper oxide-nickel oxide nanocomposite antibacterial agent unit and the sanitary glaze are sequentially applied layer by layer to the sanitary ceramic body. The mixture is then calcined at 1200-1250℃ for 100-120 minutes. Specifically, after applying the pure glaze to the sanitary ceramic body, the composite glaze consisting of a uniform mixture of the copper oxide-nickel oxide nanocomposite antibacterial agent unit and the sanitary glaze can be applied by spraying, dipping, or brushing. In the composite glaze applied to the sanitary ceramic body, the mass percentage of the copper oxide-nickel oxide nanocomposite antibacterial agent unit is 0.5%-5.0%, and the mass percentage of the sanitary glaze is 95.0%-99.5%. The copper oxide-nickel oxide nanocomposite antibacterial agent unit is uniformly dispersed and suspended on the surface of the sanitary glaze.
[0008] The sanitary ceramic product with antibacterial function according to the present invention has the following advantages: On the one hand, the copper oxide-nickel oxide nanocomposite antibacterial agent unit is uniformly dispersed and embedded on the surface of the sanitary ceramic body, and the copper oxide-nickel oxide nanocomposite antibacterial agent unit is at least partially protruding and exposed on the surface of the sanitary ceramic body. The copper oxide-nickel oxide nanocomposite antibacterial agent unit is easily irradiated by visible light. By doping copper oxide in the copper oxide-nickel oxide nanocomposite antibacterial agent unit, the band gap is reduced, hindering the recombination of electron / hole (e- / h+) pairs, prolonging the lifetime of charge carriers, allowing electrons to move freely at the interface, generating an additional electric field, making it easier for photo-excited electrons and holes to migrate at the heterojunction, effectively promoting the separation of photogenerated electron-hole pairs, generating reactive oxygen free radicals (ROS). These highly reactive free radicals can destroy the bacterial cell structure, achieving a highly efficient and broad-spectrum antibacterial effect, and giving the product a self-cleaning function that responds to visible light; the sanitary ceramic product with antibacterial function according to the present invention can provide long-lasting antibacterial protection. On the other hand, the synergistic effect allows for a sterilization rate of over 99% with only a low dose of the copper oxide-nickel oxide nanocomposite antibacterial agent unit. More importantly, the copper oxide-nickel oxide nanocomposite antibacterial agent unit, while exerting its antibacterial function, does not affect the original appearance and properties of the sanitary ceramics, resulting in a high-quality glaze. Furthermore, the preparation process is simple, with the product being fired only once after glazing, making it easy to produce. The sanitary ceramic products with antibacterial function according to this embodiment provide a new technical path for the functional upgrading and industrial promotion of sanitary ceramics, and are expected to lead the development of sanitary ceramic products towards health and intelligence.
[0009] In some embodiments, the copper oxide-nickel oxide nanocomposite antibacterial agent unit includes a copper oxide core and a nickel oxide shell covering the copper oxide core, wherein the nickel oxide shell and the copper oxide core form a heterogeneous nodule-shell structure; the nickel oxide shell is a flower-like shell structure.
[0010] In some embodiments, the outer diameter of the copper oxide-nickel oxide nanocomposite antibacterial agent unit is 1~4μm.
[0011] In some embodiments, the radial dimension of the copper oxide core is 500~1900 nm, and the thickness of the nickel oxide shell is 100~1500 nm.
[0012] In some embodiments, the sanitary ceramic body includes a sanitary ceramic body layer, a glaze bonding layer, and a sanitary ceramic glaze surface layer; the glaze bonding layer is connected between the sanitary ceramic body layer and the sanitary ceramic glaze surface layer, and the copper oxide-nickel oxide nanocomposite antibacterial agent units are uniformly dispersed and embedded on the outer surface of the sanitary ceramic glaze surface layer.
[0013] In some embodiments, the thickness of the composite glaze layer consisting of the sanitary enamel surface layer and the copper oxide-nickel oxide nanocomposite antibacterial agent unit is 10~150μm.
[0014] In some embodiments, the sanitary ceramic product with antibacterial function is a sanitary ceramic product made by applying pure glaze and a composite glaze uniformly mixed by the copper oxide-nickel oxide nanocomposite antibacterial agent unit to the sanitary ceramic body layer in sequence, and then firing it at a temperature of 1200~1250℃ for 100~120min.
[0015] Additional aspects and advantages of this invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. Attached Figure Description
[0016] The above and / or additional aspects and advantages of this utility model will become apparent and readily understood from the description of the embodiments taken in conjunction with the following drawings, in which:
[0017] Figure 1 This is a schematic diagram of the structure of a sanitary ceramic product with antibacterial function according to an embodiment of the present invention;
[0018] Figure 2 This is a scanning electron microscope image of the surface of a sanitary ceramic product with antibacterial function according to an embodiment of the present invention, in which the copper oxide-nickel oxide nanocomposite antibacterial agent unit is shown.
[0019] Figure 3 This is a scanning electron microscope image of a cross-section of a sanitary ceramic with antibacterial function according to an embodiment of this utility model.
[0020] Figure label:
[0021] Sanitary ceramic products with antibacterial function 1000; sanitary ceramic body 1; sanitary ceramic body layer 101; glaze bonding layer 102; sanitary ceramic glaze surface layer 103; copper oxide-nickel oxide nanocomposite antibacterial agent unit 2. Detailed Implementation
[0022] The embodiments of this utility model are described in detail below. Examples of these embodiments are shown in the accompanying drawings, wherein the same or similar reference numerals denote the same or similar elements or elements having the same or similar functions throughout. The embodiments described below with reference to the accompanying drawings are exemplary and are only used to explain this utility model, and should not be construed as limiting this utility model.
[0023] The following is combined with Figures 1 to 3 This invention describes a sanitary ceramic product 1000 with antibacterial function according to an embodiment of the present invention.
[0024] like Figures 1 to 3 As shown, the sanitary ceramic product 1000 with antibacterial function according to an embodiment of the present utility model includes: a sanitary ceramic body 1 and a copper oxide-nickel oxide nanocomposite antibacterial agent unit 2. The copper oxide-nickel oxide nanocomposite antibacterial agent unit 2 is uniformly dispersed and embedded on the surface of the sanitary ceramic body 1, and the copper oxide-nickel oxide nanocomposite antibacterial agent unit 2 is at least partially protruding and exposed on the surface of the sanitary ceramic body 1.
[0025] Because the copper oxide-nickel oxide nanocomposite antibacterial agent unit 2 is uniformly dispersed and embedded on the surface of the sanitary ceramic body 1, and the copper oxide-nickel oxide nanocomposite antibacterial agent unit 2 is at least partially protruding and exposed on the surface of the sanitary ceramic body 1, the copper oxide-nickel oxide nanocomposite antibacterial agent unit 2 is easily directly irradiated by visible light. Under visible light irradiation, the pn heterojunction formed by copper oxide and nickel oxide can effectively promote the separation of photogenerated electron-hole pairs and generate reactive oxygen free radicals (ROS). These highly active free radicals can destroy the bacterial cell structure and achieve a highly efficient and broad-spectrum antibacterial effect.
[0026] The following is a comparison of the antibacterial effects of the sanitary ceramic product 1000 with antibacterial function in this embodiment with other ceramics containing different antibacterial agents in a durability antibacterial test. The samples are as follows: (a) ceramics with La-TiO2 antibacterial agent added, where La-TiO2 is TiO2 doped with the rare earth element lanthanum; (b) ceramics with ZnO antibacterial agent added; (c) ceramics with Ce-TiO2 antibacterial agent added, where Ce-TiO2 is TiO2 doped with the rare earth element cerium; and (d) a sample of the sanitary ceramic product 1000 with antibacterial function in this embodiment containing copper oxide-nickel oxide nanocomposite antibacterial agent units.
[0027] Regarding the antibacterial effect of the first antibacterial test on the above samples, Escherichia coli colonies were still present on the petri dishes of ceramic samples (a), (b), and (c), while E. coli were almost absent on the antibacterial sanitary ceramic product of sample (d). Therefore, it can be concluded that the antibacterial sanitary ceramic product of this embodiment has a very good bactericidal effect.
[0028] Regarding the antibacterial effect of the second antibacterial test conducted some time after the first antibacterial test on the above samples, Escherichia coli colonies were still present on the petri dishes of ceramic samples (a), (b), and (c), while E. coli were almost absent on the antibacterial sanitary ceramic product of sample (d). Therefore, it can be concluded that the antibacterial sanitary ceramic product of this embodiment still has a very good bactericidal effect.
[0029] Therefore, the sanitary ceramic products with antibacterial function of this utility model embodiment can kill bacteria for a long time and with high efficiency.
[0030] The antibacterial sanitary ceramic product 1000 of this utility model embodiment can be prepared by the following method: Pure glaze and a composite glaze consisting of a copper oxide-nickel oxide nanocomposite antibacterial agent unit 2 uniformly mixed with the sanitary ceramic glaze are sequentially applied layer by layer to the sanitary ceramic body layer 101, followed by calcination at 1200~1250℃ for 100~120 minutes. Specifically, after applying the pure glaze to the sanitary ceramic body layer 101, the composite glaze consisting of the copper oxide-nickel oxide nanocomposite antibacterial agent unit 2 uniformly mixed with the sanitary ceramic glaze can be applied by spraying, dipping, or brushing. In the composite glaze applied to the sanitary ceramic body layer 101, the mass percentage of the copper oxide-nickel oxide nanocomposite antibacterial agent unit 2 is 0.5%~5.0%, and the mass percentage of the sanitary ceramic glaze is 95.0%~99.5%. The copper oxide-nickel oxide nanocomposite antibacterial agent unit 2 is uniformly dispersed and suspended on the surface of the sanitary ceramic glaze.
[0031] The sanitary ceramic product 1000 with antibacterial function according to this embodiment of the present invention has the following advantages: On the one hand, since the copper oxide-nickel oxide nanocomposite antibacterial agent unit 2 is uniformly dispersed and embedded on the surface of the sanitary ceramic body 1 and at least partially protrudes and is exposed on the surface of the sanitary ceramic body 1, the copper oxide-nickel oxide nanocomposite antibacterial agent unit 2 is easily directly irradiated by visible light. By doping copper oxide in the copper oxide-nickel oxide nanocomposite antibacterial agent unit 2, the band gap is reduced, hindering the recombination of electron / hole (e- / h+) pairs, prolonging the lifetime of charge carriers, allowing electrons to move freely at the interface, generating an additional electric field, making it easier for photo-excited electrons and holes to migrate at the heterojunction, effectively promoting the separation of photogenerated electron-hole pairs, generating reactive oxygen free radicals (ROS). These highly active oxidative free radicals can destroy the bacterial cell structure, achieving a highly efficient and broad-spectrum antibacterial effect, and giving the product a self-cleaning function that responds to visible light; the sanitary ceramic product 1000 with antibacterial function according to this embodiment of the present invention can provide long-lasting antibacterial protection. On the other hand, the synergistic effect allows for a sterilization rate of over 99% with only a low dose of copper oxide-nickel oxide nanocomposite antibacterial agent unit 2. More importantly, while exerting its antibacterial function, the copper oxide-nickel oxide nanocomposite antibacterial agent unit 2 does not affect the original appearance and performance of the sanitary ceramics, resulting in a high-quality glaze. Furthermore, the preparation process is simple, with the product being fired only once after glazing, making it easy to produce. The sanitary ceramic product 1000 with antibacterial function according to this embodiment provides a new technical path for the functional upgrading and industrial promotion of sanitary ceramics, and is expected to lead the development of sanitary ceramic products towards health and intelligence.
[0032] In some embodiments, the copper oxide-nickel oxide nanocomposite antibacterial agent unit 2 includes a copper oxide core and a nickel oxide shell covering the copper oxide core, the nickel oxide shell and the copper oxide core forming a heterogeneous nodular shell structure; the nickel oxide shell has a flower-like shell structure. Because the nickel oxide shell has a flower-like shell structure, the specific surface area of the copper oxide-nickel oxide nanocomposite antibacterial agent unit 2 is increased, which helps the copper oxide-nickel oxide nanocomposite antibacterial agent unit 2 to float on the outer surface of the sanitary ceramic body during the preparation of the antibacterial sanitary ceramic product 1000 of this invention. Specifically, it floats on... Figure 1 On the outer surface of the sanitary ceramic glaze 103 shown, this arrangement facilitates the copper oxide-nickel oxide nanocomposite antibacterial agent unit 2 to protrude at least partially from the surface of the sanitary ceramic body 1, thereby making the copper oxide-nickel oxide nanocomposite antibacterial agent unit 2 more easily irradiated by visible light. The heterojunction formed between the nickel oxide shell and the copper oxide core is a pn heterojunction, which can effectively promote the separation of photogenerated electron-hole pairs and generate reactive oxygen free radicals. These highly reactive oxygen free radicals can destroy the bacterial cell structure and achieve a highly efficient and broad-spectrum antibacterial effect.
[0033] In some embodiments, the outer diameter of the copper oxide-nickel oxide nanocomposite antibacterial agent unit 2 is 1~4 μm. For example, Figure 2 This is a scanning electron microscope (SEM) image of the copper oxide-nickel oxide nanocomposite antibacterial agent unit 2, where the outer diameter of the unit is approximately 2 μm. When a composite glaze containing the copper oxide-nickel oxide nanocomposite antibacterial agent unit 2 (with an outer diameter of 1-4 μm) and sanitary ware glaze is prepared, it facilitates thorough mixing of the unit 2 and the glaze. Furthermore, when the composite glaze is sprayed, dipped, or brushed to form a composite glaze layer, this ensures that the copper oxide-nickel oxide nanocomposite antibacterial agent unit 2 is uniformly dispersed and suspended on the outer surface of the glaze, thereby increasing the specific surface area of the unit 2. The agent unit 2 is more likely to float on the outer surface of the sanitary ware glaze and at least partially protrude and be exposed on the surface of the sanitary ware glaze, thus finally forming a structure of sanitary ware glaze surface layer 103 and copper oxide-nickel oxide nanocomposite antibacterial agent unit 2 dispersed and embedded on the outer surface of sanitary ware glaze surface layer 103 and at least protruding and exposed on the outer surface of sanitary ware glaze surface layer 103. This allows the copper oxide-nickel oxide nanocomposite antibacterial agent unit 2 to exert its antibacterial function under visible light irradiation without affecting the original appearance performance of the sanitary ceramic, resulting in good glaze quality.
[0034] In some embodiments, the radial dimension of the copper oxide core is 500-1900 nm, and the thickness of the nickel oxide shell is 100-1500 nm. This facilitates the utilization of the heterojunction properties of the copper oxide-nickel oxide nanocomposite antibacterial agent unit 2, more effectively promoting the separation of photogenerated electron-hole pairs and generating more reactive oxygen species (ROS). These highly reactive ROS can disrupt bacterial cell structures, achieving a highly efficient and broad-spectrum antibacterial effect with significant antibacterial efficacy.
[0035] In some embodiments, such as Figure 1 As shown, the sanitary ceramic body 1 includes a sanitary ceramic body layer 101, a glaze bonding layer 102, and a sanitary ceramic glaze surface layer 103. The glaze bonding layer 102 connects the sanitary ceramic body layer 101 and the sanitary ceramic glaze surface layer 103. The copper oxide-nickel oxide nanocomposite antibacterial agent unit 2 is uniformly dispersed and embedded on the outer surface of the sanitary ceramic glaze surface layer 103. Therefore, the sanitary ceramic product 1000 with antibacterial function in this embodiment has a simple structure. The copper oxide-nickel oxide nanocomposite antibacterial agent unit 2 exerts its antibacterial function without affecting the original appearance performance of the sanitary ceramic, resulting in good glaze quality.
[0036] In some embodiments, the thickness of the composite glaze layer consisting of the sanitary ware glaze surface layer 103 and the copper oxide-nickel oxide nanocomposite antibacterial agent unit 2 is 10~150μm. Therefore, the copper oxide-nickel oxide nanocomposite antibacterial agent unit 2 can exert its antibacterial function without affecting the original appearance and properties of the sanitary ware, resulting in a high-quality glaze surface.
[0037] In some implementations, the antibacterial sanitary ceramic product 1000 is a sanitary ceramic product made by sequentially applying pure glaze and a composite glaze consisting of a copper oxide-nickel oxide nanocomposite antibacterial agent unit 2 uniformly mixed with the sanitary glaze to the sanitary ceramic body layer 101, followed by firing at a temperature of 1200~1250℃ for 100~120 minutes. Specifically, after applying the pure glaze to the sanitary ceramic body layer 101, the composite glaze consisting of the copper oxide-nickel oxide nanocomposite antibacterial agent unit 2 uniformly mixed with the sanitary glaze can be applied by spraying, dipping, or brushing. In the composite glaze applied to the sanitary ceramic body layer 101, the mass percentage of the copper oxide-nickel oxide nanocomposite antibacterial agent unit 2 is 0.5%~5.0%, and the mass percentage of the sanitary glaze is 95.0%~99.5%. The copper oxide-nickel oxide nanocomposite antibacterial agent unit 2 is uniformly dispersed and suspended on the surface of the sanitary glaze. Therefore, the manufacturing process of the antibacterial sanitary ceramic product 1000 in this embodiment is simple. The sanitary ceramic body layer 101 is glazed and fired once, making it easy to produce. Furthermore, the copper oxide-nickel oxide nanocomposite antibacterial agent unit 2, through copper oxide doping, narrows the band gap, hinders the recombination of electron / hole (e- / h+) pairs, and prolongs the carrier lifetime. This allows electrons to move freely at the interface, generating an additional electric field, making it easier for photo-excited electrons and holes to migrate at the heterojunction. This effectively promotes the separation of photogenerated electron-hole pairs, generating reactive oxygen species (ROS). These highly reactive ROS can destroy bacterial cell structures, achieving a highly efficient and broad-spectrum antibacterial effect, and endowing the product with a visible light-responsive self-cleaning function. The synergistic effect allows for a sterilization rate of over 99% with only a low dose of the copper oxide-nickel oxide nanocomposite antibacterial agent unit 2. More importantly, while exerting its antibacterial function, the copper oxide-nickel oxide nanocomposite antibacterial agent unit 2 does not affect the original appearance and performance of the sanitary ceramic, resulting in a high-quality glaze.
[0038] In the description of this specification, the references to terms such as "one embodiment," "some embodiments," "illustrative embodiment," "example," "specific example," or "some examples," etc., indicate that a specific feature, structure, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.
[0039] Although embodiments of the present invention have been shown and described, those skilled in the art will understand that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the present invention, the scope of which is defined by the claims and their equivalents.
Claims
1. A sanitary ceramic article having an antibacterial function, characterized by, include: The sanitary ceramic body and the copper oxide-nickel oxide nanocomposite antibacterial agent unit are uniformly dispersed and embedded on the surface of the sanitary ceramic body, and the copper oxide-nickel oxide nanocomposite antibacterial agent unit is at least partially protruding and exposed on the surface of the sanitary ceramic body.
2. The sanitary ceramic article with antibacterial function according to claim 1, characterized in that, The copper oxide-nickel oxide nanocomposite antibacterial agent unit includes a copper oxide core and a nickel oxide shell covering the copper oxide core, wherein the nickel oxide shell and the copper oxide core form a heterogeneous nodule-shell structure; the nickel oxide shell has a flower-like shell structure.
3. The sanitary ceramic article with antibacterial function according to claim 2, characterized in that, The outer diameter of the copper oxide-nickel oxide nanocomposite antibacterial agent unit is 1~4μm.
4. The sanitary ceramic article with antibacterial function according to claim 3, characterized in that, The radial dimension of the copper oxide core is 500~1900nm, and the thickness of the nickel oxide shell is 100~1500nm.
5. The sanitary ceramic article with antibacterial function according to any one of claims 1-4, characterized in that, The sanitary ceramic body includes a sanitary ceramic body layer, a glaze bonding layer, and a sanitary ceramic glaze surface layer; the glaze bonding layer connects the sanitary ceramic body layer and the sanitary ceramic glaze surface layer, and the copper oxide-nickel oxide nanocomposite antibacterial agent units are uniformly dispersed and embedded on the outer surface of the sanitary ceramic glaze surface layer.
6. The sanitary ceramic article with antibacterial function according to claim 5, characterized in that, The thickness of the composite glaze layer, which consists of the surface layer of the sanitary ware glaze and the copper oxide-nickel oxide nanocomposite antibacterial agent unit, is 10~150μm.
7. The sanitary ceramic article with antibacterial function according to claim 5, characterized in that, The sanitary ceramic product with antibacterial function is made by applying pure glaze and a composite glaze consisting of copper oxide-nickel oxide nanocomposite antibacterial agent unit uniformly mixed with the sanitary ceramic glaze in layers sequentially on the sanitary ceramic body, and then firing it at a temperature of 1200~1250℃ for 100~120min.