CN117488245A - Antibacterial ceramic tile based on magnetron sputtering technology and preparation method thereof - Google Patents
Antibacterial ceramic tile based on magnetron sputtering technology and preparation method thereof Download PDFInfo
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- CN117488245A CN117488245A CN202311491105.7A CN202311491105A CN117488245A CN 117488245 A CN117488245 A CN 117488245A CN 202311491105 A CN202311491105 A CN 202311491105A CN 117488245 A CN117488245 A CN 117488245A
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- ceramic tile
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- zinc oxide
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 188
- 239000000919 ceramic Substances 0.000 title claims abstract description 111
- 238000001755 magnetron sputter deposition Methods 0.000 title claims abstract description 43
- 238000005516 engineering process Methods 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 130
- 239000011787 zinc oxide Substances 0.000 claims abstract description 54
- 239000000843 powder Substances 0.000 claims abstract description 52
- 239000003607 modifier Substances 0.000 claims abstract description 29
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims abstract description 12
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims abstract description 12
- 238000000151 deposition Methods 0.000 claims abstract description 11
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 31
- 229910001868 water Inorganic materials 0.000 claims description 17
- 238000001354 calcination Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 15
- 239000002243 precursor Substances 0.000 claims description 14
- 239000002202 Polyethylene glycol Substances 0.000 claims description 12
- 229920001223 polyethylene glycol Polymers 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 9
- 230000000845 anti-microbial effect Effects 0.000 claims description 8
- 239000002270 dispersing agent Substances 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 238000004544 sputter deposition Methods 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- 150000003751 zinc Chemical class 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000013077 target material Substances 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 239000012716 precipitator Substances 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical group [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- IPCXNCATNBAPKW-UHFFFAOYSA-N zinc;hydrate Chemical compound O.[Zn] IPCXNCATNBAPKW-UHFFFAOYSA-N 0.000 claims description 2
- 150000004677 hydrates Chemical class 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 18
- 239000000203 mixture Substances 0.000 description 16
- 238000012986 modification Methods 0.000 description 16
- 230000004048 modification Effects 0.000 description 16
- 239000008367 deionised water Substances 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- 238000003756 stirring Methods 0.000 description 14
- 230000006872 improvement Effects 0.000 description 13
- 230000018109 developmental process Effects 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 239000002244 precipitate Substances 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- 239000003242 anti bacterial agent Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 5
- 238000005054 agglomeration Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 238000001659 ion-beam spectroscopy Methods 0.000 description 5
- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- 239000011667 zinc carbonate Substances 0.000 description 5
- 235000004416 zinc carbonate Nutrition 0.000 description 5
- 229910000010 zinc carbonate Inorganic materials 0.000 description 5
- 241000588724 Escherichia coli Species 0.000 description 4
- 241000191967 Staphylococcus aureus Species 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000001788 irregular Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical group C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical compound [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
Abstract
The invention belongs to the technical field of functional ceramics, and particularly discloses an antibacterial ceramic tile based on a magnetron sputtering technology and a preparation method thereof. The antibacterial ceramic tile comprises a ceramic tile body and an antibacterial film, wherein the antibacterial film is arranged on the upper surface of the ceramic tile body and is formed by depositing antibacterial powder through a magnetron sputtering technology; the antibacterial powder is prepared from nano zinc oxide and a modifier, wherein the modifier comprises sodium polyacrylate and/or polyvinylpyrrolidone. According to the invention, the antibacterial powder is deposited on the upper surface of the ceramic tile body by utilizing the magnetron sputtering technology to form the antibacterial film, so that the antibacterial durability of the product is improved. Meanwhile, the nano zinc oxide is improved by adding a specific modifier, so that the antibacterial efficiency is greatly improved. The prepared ceramic tile has good antibacterial rate and antibacterial durability, the antibacterial rate can reach 99.99%, the antibacterial durability can reach 99.24%, and the pattern and the color development effect of the ceramic tile are not affected.
Description
Technical Field
The invention belongs to the technical field of functional ceramics, and particularly relates to an antibacterial ceramic tile based on a magnetron sputtering technology and a preparation method thereof.
Background
With the rapid development of economy and science and technology and the continuous improvement of living standard of people, people pay more attention to sanitation, environment and the like, and products such as antibacterial ceramics, glass and the like are gradually rising. The antibacterial hidden ceramic tile, also called as green ceramic tile, is a novel ecological functional material, not only maintains the high mechanical strength and chemical stability of the ceramic tile, but also endows the ceramic tile with antibacterial, bactericidal and bacteriostatic effects.
At present, the preparation methods of the antibacterial ceramic tile mainly comprise two methods, namely adding an antibacterial agent into a ceramic glaze material and grinding the ceramic glaze material together to prepare glaze slurry or preparing the antibacterial agent into glaze slurry independently, then applying the glaze slurry to a green body and firing the green body at a high temperature (about 1100-1200 ℃), wherein the added antibacterial agent is subjected to fusion reaction with other raw materials in the high-temperature firing process, so that the antibacterial ceramic tile prepared by the method has poor antibacterial effect; secondly, a layer of coating containing an antibacterial agent is coated on the surface of the ceramic tile, and the antibacterial agent is adhered to the surface of the ceramic tile through a bonding material, and the coating falls off along with the aging failure of most of the bonding material, so that the antibacterial performance of a product is reduced, and therefore, the antibacterial ceramic tile prepared by the method is poor in antibacterial durability.
The magnetron sputtering technology is one of Physical Vapor Deposition (PVD), has been widely used for surfaces of metal, semiconductor and glass materials, and has the advantages of simple equipment, easy control, large coating area, strong adhesive force and the like. However, the magnetron sputtering technology has higher requirements on plasma bombardment target materials, such as the existing antibacterial agent is directly used as the plasma bombardment target materials to be deposited by the magnetron sputtering technology, and uneven film layers exist, so that the antibacterial performance and the durability are affected, and certain influence is generated on the patterns and the color development of the ceramic tile.
Therefore, it is highly desirable to develop an antibacterial material suitable for magnetron sputtering technology, so that an antibacterial film layer formed by using the antibacterial material for magnetron sputtering technology deposition has good uniformity, and further antibacterial performance and antibacterial durability of ceramic tiles are improved, and patterns and color development of the ceramic tiles are not affected.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the prior art described above. Therefore, the invention provides the antibacterial ceramic tile based on the magnetron sputtering technology and the preparation method thereof, and the antibacterial ceramic tile utilizes the magnetron sputtering technology to deposit antibacterial powder on the upper surface of the ceramic tile body, so that the ceramic tile can have good antibacterial performance and antibacterial durability at the same time, and no influence is generated on the pattern and color development of the ceramic tile.
In order to solve the technical problems, a first aspect of the invention provides an antibacterial ceramic tile, which comprises a ceramic tile body and an antibacterial film, wherein the antibacterial film is arranged on the upper surface of the ceramic tile body, and the antibacterial film is formed by depositing antibacterial powder through a magnetron sputtering technology; the antibacterial powder is prepared from nano zinc oxide and a modifier, wherein the modifier comprises sodium polyacrylate and/or polyvinylpyrrolidone.
Specifically, the invention utilizes the magnetron sputtering technology to deposit antibacterial powder on the upper surface of the ceramic tile body so as to form an antibacterial film; compared with the traditional spraying or polishing process, the adhesive force between the antibacterial film and the ceramic tile body can be greatly improved, so that the antibacterial durability of the product is improved. Meanwhile, in order to ensure the uniformity of a film formed by the antibacterial powder in the magnetron sputtering process, improve the antibacterial efficiency and not influence the pattern and the color development of the ceramic tile body, the invention selects nano zinc oxide with high light transmittance as an antibacterial agent so as to improve the light transmittance of a thin layer; and specific modifier sodium polyacrylate and/or polyvinylpyrrolidone are added to modify the nano zinc oxide. Before modification, nano zinc oxide is seriously aggregated, the morphology of the zinc oxide is irregular, the movement of released electrons is blocked, and electrons with antibacterial effect are difficult to move to the surface of the film, so that the effective antibacterial rate is lower; after modification, the appearance of the nano zinc oxide is regular, the agglomeration phenomenon is greatly reduced, the electronic mobile circuit released by the nano zinc oxide is smooth, and a large number of electrons move to the surface of the film, so that the antibacterial efficiency of the product is greatly improved, and the antibacterial efficiency of the antibacterial film after modification is greatly improved.
As a further improvement of the scheme, the modifier is used in an amount of 5-30wt% of the nano zinc oxide. The modifier with proper dosage can effectively overcome the agglomeration phenomenon of nano zinc oxide, thereby improving the antibacterial efficiency of the antibacterial film layer.
As a further improvement of the scheme, the average particle size of the nano zinc oxide is 50-100nm.
Specifically, when the nano zinc oxide semiconductor material absorbs light, electrons acquire energy and transition from an energy band with lower energy to an energy band with higher energy, so that electron hole pairs are generated, a large number of free radicals can be activated by the holes to enable the holes to undergo a strong oxidation-reduction reaction, and when the holes are contacted with bacteria, cell membranes and cell walls of the bacteria are directly damaged, so that the nano zinc oxide semiconductor material has good sterilization and disinfection effects.
As a further improvement of the scheme, the preparation raw materials of the antibacterial powder also comprise water, and the preparation process comprises the following steps:
mixing and grinding nano zinc oxide powder, water and a modifier to prepare slurry; and (3) drying, and calcining at 750-850 ℃ to obtain the antibacterial powder.
As a further improvement of the scheme, the preparation of the nano zinc oxide adopts a uniform precipitation method, and specifically comprises the following steps:
(1) Respectively dissolving water-soluble zinc salt and a precipitator in water to obtain a solution A and a solution B;
(2) Mixing the solution A and the solution B, adding a dispersing agent, performing hydrothermal reaction, washing, suction filtering and drying to obtain precursor powder;
(3) Calcining the precursor powder to obtain the nano zinc oxide powder.
Preferably, the water-soluble zinc salt is at least one selected from zinc nitrate, zinc chloride, zinc sulfate and zinc acetate and hydrate thereof; further preferably, the water-soluble zinc salt is zinc nitrate hexahydrate.
Preferably, the precipitant is urea.
Preferably, the dispersing agent is sodium dodecyl benzene sulfonate and/or polyethylene glycol.
Preferably, the water is deionized water.
Specifically, the following chemical reactions mainly occur in the preparation process of the nano zinc oxide:
and (3) decomposition reaction: CO (NH) 2 )2+3H 2 O→CO 2 ↑+2NH 3 ·H 2 O
Precipitation reaction: zn (zinc) 2+ +2NH 3 ·H 2 O→Zn(OH) 2 ↓+2NH 4+
And (3) heat treatment: zn (OH) 2 →ZnO+H2O↑
As a further improvement of the scheme, in the step (1), the molar ratio of the water-soluble zinc salt to the precipitator is 1:2-4.
As a further improvement of the above scheme, in the step (2), the addition amount of the dispersing agent is 5-10% of the total mass of the solution A and the solution B; the temperature of the hydrothermal reaction is 85-95 ℃, and the time of the hydrothermal reaction is 2-4 hours.
As a further improvement of the scheme, in the step (2), water and absolute ethyl alcohol are adopted for washing, the drying time is 75-8 ℃, and the drying time is 10-14 hours.
As a further improvement of the above scheme, in the step (3), the temperature of the calcination is 400-500 ℃ and the time of the calcination is 1-3 hours.
As a further improvement of the above-mentioned scheme, the thickness of the antibacterial film is 0.3-5 μm. The thickness of the film layer is controlled to be in a micron level, so that the antibacterial efficiency is ensured, and meanwhile, the pattern and the color development of the ceramic tile are not affected.
The second aspect of the present invention provides a method for preparing an antibacterial ceramic tile, comprising the steps of:
and bombarding a target material by taking the ceramic tile body as a substrate and taking antibacterial powder as plasma, and depositing the antibacterial powder on the upper surface of the ceramic tile body by a magnetron sputtering technology to form an antibacterial film, thereby obtaining the antibacterial ceramic tile.
As a further improvement of the above scheme, the working temperature of the magnetron sputtering is less than 500 ℃.
Preferably, the working temperature of the magnetron sputtering is 400-500 ℃.
As a further improvement of the above scheme, the magnetron sputtering process conditions include: the sputtering gas is argon and oxygen, the frequency of the radio frequency source is 10-15MHz, and the working pressure is 1-5Pa.
As a further improvement of the above solution, the magnetron sputtering process conditions further include: the power of the radio frequency source is less than or equal to 1000W, and the limiting pressure is 8 multiplied by 10 -5 Pa。
Compared with the prior art, the technical scheme of the invention has at least the following technical effects or advantages:
(1) According to the invention, the antibacterial powder is deposited on the upper surface of the ceramic tile body by utilizing the magnetron sputtering technology to form the antibacterial film, so that the adhesion between the antibacterial film and the ceramic tile body is greatly improved, and the antibacterial durability of the product is improved. Meanwhile, nano zinc oxide with high light transmittance is selected as an antibacterial agent so as to improve the light transmittance of the thin layer; and the specific modifier sodium polyacrylate and/or polyvinylpyrrolidone is added to improve the nano zinc oxide, so that the modified nano zinc oxide has regular appearance, no agglomeration phenomenon and smooth released electronic mobile line, thereby greatly improving the antibacterial efficiency.
(2) When the antibacterial ceramic tile is prepared, the specific antibacterial powder is adopted and used as a plasma bombardment target, the magnetron sputtering technology is utilized to deposit on the surface of the ceramic tile body to form an antibacterial film, and meanwhile, the magnetron sputtering process conditions are controlled, so that the prepared ceramic tile has good antibacterial rate and antibacterial durability, the antibacterial rate of escherichia coli and staphylococcus aureus can reach 99.99%, the antibacterial durability of escherichia coli can reach 99.24%, the antibacterial durability of staphylococcus aureus can reach 99.12%, and the pattern and the color development effect of the ceramic tile are not affected.
Drawings
FIG. 1 is an SEM image of nano zinc oxide prepared in example 1;
FIG. 2 is an SEM image of the antibacterial powder prepared in example 1;
FIG. 3 shows the results of the test of the inhibition zones before and after modification of the nano zinc oxide prepared in example 1.
Detailed Description
The present invention is described in detail below with reference to examples to facilitate understanding of the present invention by those skilled in the art. It is specifically pointed out that the examples are given solely for the purpose of illustration of the invention and are not to be construed as limiting the scope of the invention, since numerous insubstantial modifications and variations of the invention will be within the scope of the invention, as described above, will become apparent to those skilled in the art. Meanwhile, the raw materials mentioned below are not specified, and are all commercial products; the process steps or preparation methods not mentioned in detail are those known to the person skilled in the art.
Example 1
An antibacterial ceramic tile comprises a ceramic tile body and an antibacterial film, wherein the antibacterial film is arranged on the upper surface of the ceramic tile body and is formed by depositing antibacterial powder through a magnetron sputtering technology; the antibacterial powder is prepared from nano zinc oxide and a modifier, wherein the modifier is sodium polyacrylate; the amount of the modifier is 5% of the nano zinc oxide.
The preparation method of the antibacterial ceramic tile comprises the following steps:
(1) The nano zinc oxide powder is prepared by adopting a uniform precipitation method: firstly, 271 and gZn (NO) 3 ) 2 ·6H 2 O, adding enough deionized water to dissolve in a beaker 1, standing for standby, and then weighing 180gCO (NH 2 ) 2 Adding enough deionized water to dissolve in the beaker 2; then placing the beaker 1 in a hot water bath at 95 ℃ for stirring, adding 27.1g of polyethylene glycol, slowly adding the mixture into the beaker 2 after the polyethylene glycol is fully dissolved, and continuously stirring the mixture by adopting a magnetic stirrer while keeping the stirring speed at 60r/min to obtain zinc carbonate precipitate; separating out precipitate by centrifugation, and washing with distilled water for 2 times to obtain basic zinc carbonate precursor; finally, the precursor is placed in an oven at 80 ℃ for drying for 12 hours, and then transferred into a crucible for calcining for 1.5 hours at 450 ℃ by a muffle furnace, so as to obtain the nano zinc oxide powder.
As shown in the SEM image of the nano zinc oxide powder prepared in the step (1) as shown in figure 1, the powder has irregular shape and serious agglomeration phenomenon as shown in figure 1.
(2) Modification of nano oxidability: weighing 50g of nano zinc oxide powder prepared in the step (1), sequentially adding 20g of deionized water and 2.5g of sodium polyacrylate, grinding into slurry, and drying at 120 ℃ to prepare powder; and then calcining the mixture in a muffle furnace at 800 ℃ for 1 hour, and cooling the mixture to obtain the modified nano zinc oxide, namely the antibacterial powder.
As shown in the SEM image of the antibacterial powder prepared in the step (2) as shown in fig. 2, the shape of the modified nano zinc oxide powder is greatly changed compared with that of the powder before modification, the particles are changed from irregular to regular hexagons, and no obvious particle agglomeration phenomenon is seen.
Meanwhile, the antibacterial effect is tested by a method for measuring the antibacterial effect by using the antibacterial effect measuring method of the polypeptide antibacterial property of the standard GB/39101-2020 according to the nano zinc oxide before and after the modification of the nano zinc oxide prepared in the step (1) and the step (2). The test result is shown in fig. 3, the Kj7 sample in fig. 3 is nano zinc oxide before modification, the size of a bacteriostasis zone is 15.5mm, and the antibacterial effect is poor; the Kj8 sample is modified nano zinc oxide, the size of a bacteriostasis ring is 28.9mm, and the antibacterial effect is greatly improved compared with that before modification, and the amplification is 86.5%.
(3) Coating by utilizing a magnetron sputtering technology: firstly, starting a magnetic control and ion beam sputtering system, and starting a mechanical pump to vacuumize to 10 -4 Pa, preheating the radio frequency source, and introducing sputtering gas Ar and O with purity of 99.999 percent 2 Maintaining the air pressure of the vacuum chamber at 1MPa; the plasma generated by the radio frequency source bombards the target (the antibacterial powder prepared in the step (2)), the particles on the surface of the target obtain energy to escape, and the energy is deposited on the upper surface of the substrate (the ceramic tile body) to form a compact zinc oxide antibacterial film, wherein the thickness of the antibacterial film is 2 mu m, and the antibacterial ceramic tile of the embodiment is obtained. Wherein: the process conditions of the magnetron sputtering are as follows: the frequency of the radio frequency source is 13.5MHz; the power of the radio frequency source is 1000W, the working pressure is 3Pa, and the limiting pressure is 8 multiplied by 10 -5 Pa, the working temperature is 450 ℃.
Example 2
An antibacterial ceramic tile comprises a ceramic tile body and an antibacterial film, wherein the antibacterial film is arranged on the upper surface of the ceramic tile body and is formed by depositing antibacterial powder through a magnetron sputtering technology; the antibacterial powder is prepared from nano zinc oxide and a modifier, wherein the modifier is PVP; the amount of the modifier is 10% of the nano zinc oxide.
The preparation method of the antibacterial ceramic tile comprises the following steps:
(1) The nano zinc oxide powder is prepared by adopting a uniform precipitation method: firstly, 271 and gZn (NO) 3 ) 2 ·6H 2 O, adding enough deionized water to dissolve in a beaker 1, standing for standby, and then weighing 180gCO (NH 2 ) 2 Adding enough deionized water to dissolve in the beaker 2; then placing the beaker 1 in a hot water bath at 95 ℃ for stirring, adding 33.6g of polyethylene glycol, slowly adding the mixture into the beaker 2 after the polyethylene glycol is fully dissolved, and continuously stirring the mixture by adopting a magnetic stirrer while keeping the stirring speed at 60r/min to obtain zinc carbonate precipitate; separating out precipitate by centrifugation, and washing with distilled water for 2 times to obtain basic zinc carbonate precursor; finally, the precursor is placed in an oven at 80 ℃ for drying for 12 hours, and then transferred into a crucible for calcining for 1.5 hours at 450 ℃ by a muffle furnace, so as to obtain the nano zinc oxide powder.
(2) Modification of nano oxidability: weighing 50g of nano zinc oxide powder prepared in the step (1), sequentially adding 20g of deionized water and 5g of sodium polyacrylate, grinding into slurry, and drying at 120 ℃ to prepare powder; and then calcining the mixture in a muffle furnace at 800 ℃ for 1 hour, and cooling the mixture to obtain the modified nano zinc oxide, namely the antibacterial powder.
(3) Coating by utilizing a magnetron sputtering technology: firstly, starting a magnetic control and ion beam sputtering system, and starting a mechanical pump to vacuumize to 10 -4 Pa, preheating the radio frequency source, and introducing sputtering gas Ar and O with purity of 99.999 percent 2 Maintaining the air pressure of the vacuum chamber at 1MPa; the plasma generated by the radio frequency source bombards the target (the antibacterial powder prepared in the step (2)), the particles on the surface of the target obtain energy to escape, and the energy is deposited on the upper surface of the substrate (the ceramic tile body) to form a compact zinc oxide antibacterial film, wherein the thickness of the antibacterial film is 1 mu m, and the antibacterial ceramic tile of the embodiment is obtained. Wherein: the process conditions of the magnetron sputtering are as follows: the frequency of the radio frequency source is 13.5MHz; the power of the radio frequency source is 1000W, the working pressure is 2Pa, and the limiting pressure is 8 multiplied by 10 -5 Pa, the working temperature is 450 ℃.
Example 3
An antibacterial ceramic tile comprises a ceramic tile body and an antibacterial film, wherein the antibacterial film is arranged on the upper surface of the ceramic tile body and is formed by depositing antibacterial powder through a magnetron sputtering technology; the antibacterial powder is prepared from nano zinc oxide and a modifier, wherein the modifier is sodium polyacrylate; the amount of the modifier is 20% of the nano zinc oxide.
The preparation method of the antibacterial ceramic tile comprises the following steps:
(1) The nano zinc oxide powder is prepared by adopting a uniform precipitation method: firstly, 271 and gZn (NO) 3 ) 2 ·6H 2 O, adding enough deionized water to dissolve in a beaker 1, standing for standby, and then weighing 180gCO (NH 2 ) 2 Adding enough deionized water to dissolve in the beaker 2; stirring beaker 1 in 95 deg.C hot water bath, adding 36.8g polyethylene glycol, dissolving, slowly adding into beaker 2, and stirring with magnetic stirrer at 60 r%min, obtaining zinc carbonate precipitate; separating out precipitate by centrifugation, and washing with distilled water for 2 times to obtain basic zinc carbonate precursor; finally, the precursor is placed in an oven at 80 ℃ for drying for 12 hours, and then transferred into a crucible for calcining for 1.5 hours at 450 ℃ by a muffle furnace, so as to obtain the nano zinc oxide powder.
(2) Modification of nano oxidability: weighing 50g of nano zinc oxide powder prepared in the step (1), sequentially adding 20g of deionized water and 10g of sodium polyacrylate, grinding into slurry, and drying at 120 ℃ to prepare powder; and then calcining the mixture in a muffle furnace at 800 ℃ for 1 hour, and cooling the mixture to obtain the modified nano zinc oxide, namely the antibacterial powder.
(3) Coating by utilizing a magnetron sputtering technology: firstly, starting a magnetic control and ion beam sputtering system, and starting a mechanical pump to vacuumize to 10 -4 Pa, preheating the radio frequency source, and introducing sputtering gas Ar and O with purity of 99.999 percent 2 Maintaining the air pressure of the vacuum chamber at 1MPa; the plasma generated by the radio frequency source bombards the target (the antibacterial powder prepared in the step (2)), the particles on the surface of the target obtain energy to escape, and the energy is deposited on the upper surface of the substrate (the ceramic tile body) to form a compact zinc oxide antibacterial film, wherein the thickness of the antibacterial film is 1.5 mu m, and the antibacterial ceramic tile of the embodiment is obtained. Wherein: the process conditions of the magnetron sputtering are as follows: the frequency of the radio frequency source is 13.5MHz; the power of the radio frequency source is 1000W, the working pressure is 3Pa, and the limiting pressure is 8 multiplied by 10 -5 Pa, the working temperature is 450 ℃.
Example 4
An antibacterial ceramic tile comprises a ceramic tile body and an antibacterial film, wherein the antibacterial film is arranged on the upper surface of the ceramic tile body and is formed by depositing antibacterial powder through a magnetron sputtering technology; the antibacterial powder is prepared from nano zinc oxide and a modifier, wherein the modifier is PVP; the amount of the modifier is 30% of the nano zinc oxide.
The preparation method of the antibacterial ceramic tile comprises the following steps:
(1) The nano zinc oxide powder is prepared by adopting a uniform precipitation method: firstly, 271 and gZn (NO) 3 ) 2 ·6H 2 O, adding enough deionized water to dissolve in a beaker 1, standing for standby, and then weighing180 and gCO (NH) 2 ) 2 Adding enough deionized water to dissolve in the beaker 2; then placing the beaker 1 in a hot water bath at 95 ℃ for stirring, adding 40g of polyethylene glycol, slowly adding the mixture into the beaker 2 after the polyethylene glycol is fully dissolved, and continuously stirring the mixture by adopting a magnetic stirrer while keeping the stirring speed at 60r/min to obtain zinc carbonate precipitate; separating out precipitate by centrifugation, and washing with distilled water for 2 times to obtain basic zinc carbonate precursor; finally, the precursor is placed in an oven at 80 ℃ for drying for 12 hours, and then transferred into a crucible for calcining for 1.5 hours at 450 ℃ by a muffle furnace, so as to obtain the nano zinc oxide powder.
(2) Modification of nano oxidability: weighing 50g of nano zinc oxide powder prepared in the step (1), sequentially adding 20g of deionized water and 15g of sodium polyacrylate, grinding into slurry, and drying at 120 ℃ to prepare powder; and then calcining the mixture in a muffle furnace at 450 ℃ for 1 hour, and cooling the mixture to obtain the modified nano zinc oxide, namely the antibacterial powder.
(3) Coating by utilizing a magnetron sputtering technology: firstly, starting a magnetic control and ion beam sputtering system, and starting a mechanical pump to vacuumize to 10 -4 Pa, preheating the radio frequency source, and introducing sputtering gas Ar and O with purity of 99.999 percent 2 Maintaining the air pressure of the vacuum chamber at 1MPa; the plasma generated by the radio frequency source bombards the target (the antibacterial powder prepared in the step (2)), the particles on the surface of the target obtain energy to escape, and the energy is deposited on the upper surface of the substrate (the ceramic tile body) to form a compact zinc oxide antibacterial film, wherein the thickness of the antibacterial film is 3 mu m, and the antibacterial ceramic tile of the embodiment is obtained. Wherein: the process conditions of the magnetron sputtering are as follows: the frequency of the radio frequency source is 13.5MHz; the power of the radio frequency source is 1000W, the working pressure is 2Pa, and the limiting pressure is 8 multiplied by 10 -5 Pa, the working temperature is 450 ℃.
Comparative example 1
An antibacterial ceramic tile comprises a ceramic tile body and an antibacterial film, wherein the antibacterial film is arranged on the upper surface of the ceramic tile body and is formed by depositing antibacterial powder through a magnetron sputtering technology; and the antibacterial powder is nano zinc oxide.
The preparation method of the antibacterial ceramic tile comprises the following steps:
(1) By using uniformityPreparing nano zinc oxide powder by a precipitation method: firstly, 271 and gZn (NO) 3 ) 2 ·6H 2 O, adding enough deionized water to dissolve in a beaker 1, standing for standby, and then weighing 180gCO (NH 2 ) 2 Adding enough deionized water to dissolve in the beaker 2; then placing the beaker 1 in a hot water bath at 95 ℃ for stirring, adding 27.1g of polyethylene glycol, slowly adding the mixture into the beaker 2 after the polyethylene glycol is fully dissolved, and continuously stirring the mixture by adopting a magnetic stirrer while keeping the stirring speed at 60r/min to obtain zinc carbonate precipitate; separating out precipitate by centrifugation, and washing with distilled water for 2 times to obtain basic zinc carbonate precursor; finally, the precursor is placed in an oven at 80 ℃ for drying for 12 hours, and then transferred into a crucible for calcining for 1.5 hours at 450 ℃ by a muffle furnace, so as to obtain the nano zinc oxide powder.
(2) Coating by utilizing a magnetron sputtering technology: firstly, starting a magnetic control and ion beam sputtering system, and starting a mechanical pump to vacuumize to 10 -4 Pa, preheating the radio frequency source, and introducing sputtering gas Ar and O with purity of 99.999 percent 2 Maintaining the air pressure of the vacuum chamber at 1MPa; the plasma generated by the radio frequency source bombards the target (nano zinc oxide powder prepared in the step (1)), the particles on the surface of the target obtain energy to escape, and the energy is deposited on the upper surface of the substrate (ceramic tile body) to form a compact zinc oxide antibacterial film, wherein the thickness of the antibacterial film is 2 mu m, and the antibacterial ceramic tile of the embodiment is obtained. Wherein: the process conditions of the magnetron sputtering are as follows: the frequency of the radio frequency source is 13.5MHz; the power of the radio frequency source is 1000W, the working pressure is 3Pa, and the limiting pressure is 8 multiplied by 10 -5 Pa, the working temperature is 450 ℃.
Comparative example 1 differs from example 1 only in that the antibacterial powder of comparative example 1 is unmodified nano zinc oxide.
Comparative example 2
Comparative example 2 differs from example 1 only in that the modifier of comparative example 2 is polyethylene glycol.
Comparative example 3
Comparative example 3 differs from example 2 only in that the modifier of comparative example 3 is polyvinyl alcohol (PVA).
Comparative example 4
Comparative example 4 differs from example only in that the antimicrobial ceramic tile of comparative example 4 was spray coated to form an antimicrobial film.
An antibacterial ceramic tile comprises a ceramic tile body and an antibacterial film, wherein the antibacterial film is arranged on the upper surface of the ceramic tile body and is formed by spraying and thermally curing antibacterial suspension; and the raw materials for preparing the antibacterial powder comprise nano zinc oxide, water-based resin and dispersing agent.
The preparation method of the antibacterial ceramic tile comprises the following steps:
(1) Preparation and modification of nano zinc oxide powder: the preparation method is the same as that of the example 1, and the modified nano zinc oxide is obtained.
(2) Forming an antibacterial film by using a spraying mode: weighing 20g of the modified nano zinc oxide prepared in the step (1), adding 100g of water, 10g of water-based acrylic resin and 1g of dispersing agent sodium polyacrylate, grinding into slurry, and adjusting the parameters as follows: the specific gravity is between 1.05 and 1.15, the flow velocity is between 12 and 15 seconds, the ceramic tile body is evenly sprayed on the surface of the ceramic tile body by a high-pressure spray gun, and the spraying amount is between 5 and 10g/m 2 After heat curing for 10min at 200 ℃, the nano zinc oxide antibacterial film is formed, and the ceramic tile of the comparative example is obtained.
Performance testing
Antibacterial rate and durability tests were performed on the antibacterial ceramic tile samples prepared in examples 1 to 4 and comparative examples 1 to 4, and the appearance of the antibacterial film was observed. Wherein: the antibacterial rate is tested according to the standard JC/T897-2014 antibacterial ceramic product antibacterial performance, and the antibacterial durability test process comprises the following steps: after the antibacterial ceramic tile is irradiated for 72 hours under the lighting condition of the lamp light, the antibacterial rate of a test sample is re-tested according to the antibacterial property of a standard JC/T897-2014 antibacterial ceramic product, and the antibacterial rate is taken as the durable antibacterial rate; the test results are shown in Table 1.
Table 1: performance table of antibacterial ceramic tile samples prepared in examples 1 to 4 and comparative examples 1 to 4
As can be seen from Table 1, the antibacterial ceramic tile samples prepared in examples 1-4 all have good antibacterial rate and antibacterial durability, the antibacterial rate of Escherichia coli and Staphylococcus aureus can reach 99.99%, the antibacterial durability against Escherichia coli can reach 99.24%, the antibacterial durability against Staphylococcus aureus can reach 99.12%, and the pattern and color development effect of the ceramic tile are not affected.
Comparative example 1 was inferior to example 1 in antibacterial efficiency and antibacterial durability, and also resulted in uneven film, inferior pattern definition of ceramic tile itself, and color development was also changed from that of the plating layer, since nano zinc oxide was not modified, as compared with example 1.
Comparative examples 2 to 3 were compared with examples 1 to 2, respectively, using other kinds of modifiers, the antibacterial property and durability of the tile were remarkably reduced, and the pattern definition of the tile after coating was reduced, and the color development was also deteriorated.
Comparative example 4 compared to example 1, the adhesion of the film layer to the ceramic tile body was poor due to the film formation using the conventional spray coating process, resulting in a significant decrease in antimicrobial durability.
It will be apparent to those skilled in the art that several simple deductions or substitutions may be made without departing from the inventive concept. Accordingly, it is intended that all such modifications as would be within the scope of this invention be included within the scope of this invention. The above embodiments are preferred embodiments of the present invention, and all similar processes and equivalent modifications are intended to fall within the scope of the present invention.
Claims (10)
1. The antibacterial ceramic tile is characterized by comprising a ceramic tile body and an antibacterial film, wherein the antibacterial film is arranged on the upper surface of the ceramic tile body and is formed by depositing antibacterial powder through a magnetron sputtering technology; the antibacterial powder is prepared from nano zinc oxide and a modifier, wherein the modifier comprises sodium polyacrylate and/or polyvinylpyrrolidone.
2. The antimicrobial ceramic tile of claim 1, wherein the modifier is present in an amount of 5-30wt% of the nano zinc oxide.
3. The antimicrobial ceramic tile of claim 1, wherein the nano zinc oxide has an average particle size of 50-100nm.
4. The antibacterial ceramic tile according to claim 1, wherein the raw materials for preparing the antibacterial powder further comprise water, and the preparation process comprises the following steps:
mixing and grinding nano zinc oxide powder, water and a modifier to prepare slurry; and (3) drying, and calcining at 750-850 ℃ to obtain the antibacterial powder.
5. The antimicrobial ceramic tile of claim 1, wherein the process of preparing the nano zinc oxide comprises the steps of:
(1) Respectively dissolving water-soluble zinc salt and a precipitator in water to obtain a solution A and a solution B;
(2) Mixing the solution A and the solution B, adding a dispersing agent, performing hydrothermal reaction, washing, suction filtering and drying to obtain precursor powder;
(3) Calcining the precursor powder to obtain the nano zinc oxide powder.
6. The antibacterial ceramic tile according to claim 5, wherein the water-soluble zinc salt is at least one selected from zinc nitrate, zinc chloride, zinc sulfate, zinc acetate and hydrates thereof, the precipitant is urea, and the dispersant is sodium dodecyl benzene sulfonate and/or polyethylene glycol;
and/or, in step (1), the molar ratio of the water-soluble zinc salt and the precipitant is 1: (2-4);
and/or in the step (2), the addition amount of the dispersing agent is 5-10% of the total mass of the solution A and the solution B, and the temperature of the hydrothermal reaction is 85-95 ℃;
and/or, in the step (3), the calcining temperature is 400-500 ℃.
7. The antimicrobial ceramic tile according to any one of claims 1 to 6, wherein the antimicrobial film has a thickness of 0.3 to 5 μm.
8. A method of producing an antibacterial ceramic tile according to any one of claims 1 to 7, comprising the steps of:
and bombarding a target material by taking the ceramic tile body as a substrate and taking antibacterial powder as plasma, and depositing the antibacterial powder on the upper surface of the ceramic tile body by a magnetron sputtering technology to form an antibacterial film, thereby obtaining the antibacterial ceramic tile.
9. The method of producing an antibacterial ceramic tile according to claim 8, wherein the magnetron sputtering has an operating temperature of less than 500 ℃.
10. The method for preparing an antibacterial ceramic tile according to claim 8, wherein the process conditions of the magnetron sputtering include: the sputtering gas is argon and oxygen, the frequency of the radio frequency source is 10-15MHz, and the working pressure is 1-5Pa.
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