CN115536288A - Antibacterial ceramic and preparation method thereof - Google Patents
Antibacterial ceramic and preparation method thereof Download PDFInfo
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- CN115536288A CN115536288A CN202211310198.4A CN202211310198A CN115536288A CN 115536288 A CN115536288 A CN 115536288A CN 202211310198 A CN202211310198 A CN 202211310198A CN 115536288 A CN115536288 A CN 115536288A
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- antibacterial
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- 239000000919 ceramic Substances 0.000 title claims abstract description 204
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 177
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 238000005342 ion exchange Methods 0.000 claims abstract description 85
- 238000004140 cleaning Methods 0.000 claims abstract description 37
- XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 claims abstract description 13
- 229910052709 silver Inorganic materials 0.000 claims description 47
- 239000004332 silver Substances 0.000 claims description 47
- 150000003839 salts Chemical class 0.000 claims description 41
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 39
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 238000002791 soaking Methods 0.000 claims description 35
- 238000001816 cooling Methods 0.000 claims description 30
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 24
- -1 silver ions Chemical class 0.000 claims description 18
- 230000008859 change Effects 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 13
- 235000006408 oxalic acid Nutrition 0.000 claims description 13
- 229910021645 metal ion Inorganic materials 0.000 claims description 12
- 239000012670 alkaline solution Substances 0.000 claims description 11
- 238000009826 distribution Methods 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- 230000000845 anti-microbial effect Effects 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 4
- 239000003929 acidic solution Substances 0.000 claims description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 4
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- 239000000645 desinfectant Substances 0.000 claims description 2
- 239000004599 antimicrobial Substances 0.000 claims 1
- 238000002845 discoloration Methods 0.000 abstract description 8
- 230000003213 activating effect Effects 0.000 abstract description 2
- 230000002688 persistence Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 42
- 230000000052 comparative effect Effects 0.000 description 14
- 238000005406 washing Methods 0.000 description 14
- 239000002585 base Substances 0.000 description 13
- 239000010433 feldspar Substances 0.000 description 12
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 12
- 230000008569 process Effects 0.000 description 10
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- 239000003513 alkali Substances 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
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- 238000009792 diffusion process Methods 0.000 description 6
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- 229910052708 sodium Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
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- 238000012360 testing method Methods 0.000 description 5
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- 230000003115 biocidal effect Effects 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
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- 229910001414 potassium ion Inorganic materials 0.000 description 4
- 238000007673 x-ray photoluminescence spectroscopy Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 229910001579 aluminosilicate mineral Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000002513 implantation Methods 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 241000191070 Escherichia coli ATCC 8739 Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 229910052656 albite Inorganic materials 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- DLHONNLASJQAHX-UHFFFAOYSA-N aluminum;potassium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Si+4].[Si+4].[Si+4].[K+] DLHONNLASJQAHX-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052664 nepheline Inorganic materials 0.000 description 1
- 239000010434 nepheline Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- ZDYUUBIMAGBMPY-UHFFFAOYSA-N oxalic acid;hydrate Chemical compound O.OC(=O)C(O)=O ZDYUUBIMAGBMPY-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 238000002294 plasma sputter deposition Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
- C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
- C03C21/005—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to introduce in the glass such metals or metallic ions as Ag, Cu
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
- C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
- C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
Abstract
The invention relates to the field of ceramic preparation, in particular to antibacterial ceramic and a preparation method thereof. The antibacterial ceramic extends the surface of the glaze layer to a certain depth inside the glaze layer through ion exchange and contains Ag + Region of said Ag-containing + The ratio of the depth of the area to the thickness of the glaze layer is 0.01-0.1:1, and the color difference value delta E before and after ion exchange of the antibacterial ceramic is less than or equal to 0.5. The preparation method comprises the steps of (1) cleaning, (2) activating treatment, (3) preheating treatment, (4) antibacterial treatment and (5) cleaning. The invention can improve the persistence and durability of the antibacterial effect and effectively reduce the problem of redox discoloration generated after ion exchange while meeting the requirement of antibacterial performance.
Description
Technical Field
The invention relates to the field of ceramic preparation, in particular to antibacterial ceramic and a preparation method thereof.
Background
Along with the improvement of living standard and the development of science and technology, SARS and H7N9 which appear in the period, and the importance of primary medical health is vital to individuals, countries and even the whole world, the requirements of people on health and hygiene are higher and higher, and the antibacterial ceramic product industry gradually develops from laboratories to daily life.
The development of antibacterial ceramic technology, represented by yinai corporation (ingax) and TOTO corporation (TOTO), has gradually formed two major technical genres: a metal ion doping type preparation method and a photocatalysis surface coating type preparation method. The metal ion doped type is prepared by adding metal ions such as silver, zinc and the like into glaze and then sintering at 800-1380 ℃. The key point lies in the preparation of the antibacterial glaze, and the antibacterial active ingredients in the antibacterial glaze are not destroyed after being fired at the high temperature of 800-1380 ℃ so as to ensure the realization of the antibacterial performance of the product. The mechanical and thermodynamic properties of the antibacterial glaze material are required to be matched with those of the green body, so that the fired antibacterial ceramic product is ensured not to have cracks, unsmooth and the like due to unmatched mechanical and thermodynamic properties. In addition, the use of the antibacterial glaze material is ensured not to influence the chromaticity and the appearance of the ceramic product, and the production process of the ceramic product, such as the sintering times and the like, is not increased, but the method easily causes the reduction of the volatilization of metal ions in the high-temperature firing process, and the use cost of the metal ions is increased invisibly.
The preparation method of the photocatalytic surface coating type is to coat a layer of TiO on the surface of the prepared ceramic finished product 2 Or TiO 2 Doping metal ion sol-gel film, and sintering at low temperature (about 500 deg.C). The key point is that the thin film material is firmly combined with the ceramic after heat treatment and keeps the antibacterial performance. At present, the ceramic film preparation technology is wide in range and multiple in methods, the technologies mainly comprise CVD, PVD, plasma sputtering deposition, sol-Gel (Sol-Gel) and the like, the film coating mode has a short-term antibacterial effect, and the antibacterial effect is greatly reduced after long-time use friction or steel wool wear resistance tests.
The earlier research of the invention uses the ion exchange mode to contain Na 2 O and K 2 Preheating O-based white ceramic, putting into antibacterial molten salt of molten copper sulfate, sodium sulfate and potassium sulfate for ion exchange, and coolingObtaining white antibacterial ceramic; copper ions are obtained on the surface of the ceramic, and the ceramic has antibacterial performance, wherein the antibacterial activity value R is more than or equal to 3, and the delta E before and after the antibacterial action is less than or equal to 1. The technical scheme has the advantages of high copper content in the molten salt, high requirement on ion exchange temperature and high production cost. According to the technical scheme, delta E is less than or equal to 1 before and after antibiosis under the condition that glaze is uniformly applied on the glaze, and when the antibacterial ceramic product with nonuniform glaze thickness is prepared, the discoloration problem caused by nonuniform glazing still easily occurs, such as the edge of a container opening in a ceramic container, the inner bottom of the container, and the outer bottom of the container easily occurs because of less glazing.
Disclosure of Invention
The application aims to provide the antibacterial ceramic and the preparation method thereof, and the problem of color change of the ceramic product after antibacterial ion exchange due to uneven surface glazing thickness is solved to a certain extent.
In order to achieve the purpose of the application, the technical scheme adopted by the application is as follows:
on one hand, the invention provides an antibacterial ceramic, which comprises a blank body and a glaze layer arranged on the surface of the blank body, wherein the antibacterial ceramic enables the surface of the glaze layer to extend to an Ag + containing region with a certain depth through ion exchange, the ratio of the depth of the Ag + containing region in the antibacterial ceramic to the thickness of the glaze layer on the surface of the blank body is 0.01-0.1, and the color difference value delta E of the antibacterial ceramic before and after ion exchange is less than or equal to 0.5 (the color difference value means that the color is extremely tiny and cannot be identified by naked eyes).
Further, the content of silver ions in the antibacterial ceramic is 0.001-0.3wt%.
Further, the maximum value of the silver content of the antibacterial ceramic is 1.0-1.5at%, the maximum value is distributed at the depth of 0.1-0.3% of the surface of the glaze layer (the ratio is the ratio of the depth from the surface of the glaze layer to the maximum value to the thickness of the glaze layer), and the thickness of the glaze layer is 0.1-0.3mm.
Further, the antibacterial R value of the antibacterial ceramic is more than 2.
Furthermore, the temperature difference of the anti-heat distortion temperature of the antibacterial ceramic is more than or equal to 160 ℃.
Furthermore, the surface of the antibacterial ceramic is washed for 500 times by using a sodium hypochlorite disinfectant with the concentration of 5 percent, and the antibacterial rate is more than or equal to 99 percent.
On the other hand, the invention provides a preparation method of antibacterial ceramic, which comprises the following steps:
cleaning, namely putting the basic ceramic into pure water for cleaning;
activating, namely soaking the cleaned basic ceramic in an acid solution, and then soaking the basic ceramic in an alkaline solution;
preheating treatment, namely placing the basic ceramic in a preheating furnace for preheating;
antibacterial treatment, namely placing the preheated basic ceramic into molten antibacterial molten salt for antibacterial ion exchange treatment;
and (3) cleaning, namely putting the basic ceramic subjected to antibacterial ion exchange into a muffle furnace for cooling, and cleaning with pure water after cooling.
Further, acid polishing is performed after the soaking treatment with the acid solution and before the soaking treatment with the alkaline solution.
Furthermore, the acidic solution comprises oxalic acid and water, wherein the concentration of the oxalic acid is 0.6% -1.5%.
Further, the soaking time of the acid solution is 1-5min, and the temperature is 60-80 ℃.
Further, the alkaline solution is sodium hydroxide aqueous solution, and the pH value of the alkaline solution is 11-12.
Further, the soaking time of the alkaline solution is 3-10min, and the temperature is 40-60 ℃.
Further, the antibacterial molten salt is a nitrate composition containing silver, potassium and sodium, wherein the content of silver ions is 0.1% -5%.
Further, the nitrate salt composition further includes lithium metal ions.
Furthermore, the antibacterial ion exchange temperature is controlled between the preheating temperature T1 and the molten salt temperature T2, and T2-T1 is controlled to be less than 50 ℃.
Further, the molten salt temperature T2 is 350-440 ℃, preferably 360-400 ℃.
Further, the antibacterial ion exchange time is controlled within 5-30min, preferably 5-15min.
Further, the antibacterial molten salt is a nitrate composition containing silver, potassium and sodium metal ions, wherein the content of silver nitrate can be adjusted according to the content of feldspar in the ceramic glaze layer, and the content of feldspar in the glaze layer is as follows: the mass ratio of silver nitrate is 10:1-2. The glaze is mainly prepared by mixing feldspar, quartz, talc, kaolin and the like, wherein the feldspar is further divided into potassium feldspar, albite, nepheline, lithium feldspar and the like. In the actual ion exchange process, silver ions and potassium ions in the molten salt exchange with sodium ions in the glaze layer, if the concentration of the silver ions in the molten salt bath is too high, the silver ions and the sodium ions have close radiuses due to small radiuses of the silver ions, and the silver ions exchange with the sodium ions preferentially, higher silver content can be formed at a deeper penetration depth potentially, and in some cases, the silver ions penetrate even deeper than the potassium ions, and the deeper silver ions penetrate, so that the glaze layer base material can be discolored; if the above-mentioned effect is alleviated by reducing the amount of silver ions in the molten salt bath, this means that the glaze layer has less silver in the silver-containing region, resulting in a reduction in antibacterial efficiency or performance; in order to efficiently and quickly carry out ion exchange, the content of silver nitrate in the molten salt can be adjusted by detecting the content of feldspar in the glaze layer. Therefore, by defining such a relation ratio, a preferable ion exchange effect can be obtained.
In addition, the content of sodium ions in the glaze layer is closely related to the components of the glaze feldspar, sodium, potassium and silver are mainly involved in antibacterial ion exchange, and excessive exchange of the silver and potassium ions can reduce the performance of the glaze; if the content of sodium ions in the glaze layer is too high, the mechanical properties of the ceramic glaze surface are easily reduced. If the content of sodium ions in the glaze layer is low, the replaced potassium ions are arranged in the surface layer of the glass too saturated, so that microcracks appear in the surface layer of the glass, and the glass is extremely easy to crack even under the action of external force. This application through feldspar in the glaze surface layer and the control of silver ion content in the fused salt, need not additionally add sodium nitrate in the fused salt, has realized that the glaze layer has good antibiotic and lasting wear resistance concurrently.
According to the antibacterial ceramic provided by the first aspect of the application, the maximum value of the silver content is distributed at a specific depth by adjusting and optimizing the components of the molten salt according to the components of the glaze and the process, so that the Ag + concentration distribution curve is in an upward parabolic shape, the antibacterial effect continuity and durability can be improved while the requirement on the antibacterial performance is met, and the problem of redox discoloration generated after ion exchange is effectively reduced.
According to the preparation method of the antibacterial ceramic provided by the second aspect of the application, the steps of acid washing and alkali washing activation treatment are added before the antibacterial ion exchange treatment, and heavy metal ions and inorganic salt deposition existing on the surface of the ceramic are washed away by acid washing, so that metal impurities possibly subjected to color change reaction with silver ions can be removed cleanly and quickly, organic matters and microorganisms are eliminated by alkali washing, the factor causing color change is also eliminated, and the difference of the color change of the ceramic before and after the antibacterial ion exchange can be effectively reduced by adding the step of the antibacterial pretreatment.
Drawings
FIG. 1 is a graph showing the concentration of Ag in example 9.
FIG. 2 is a graph showing the concentration of Ag in comparative example 1.
Detailed Description
In order to explain the technical contents, structural features, objects and effects of the technical means in detail, the following detailed description is given with reference to specific embodiments.
In order to explain in detail the possible application scenarios, technical principles, practical embodiments, and the like, the following detailed description is given with reference to the specific embodiments. The embodiments described herein are merely for more clearly illustrating the technical solutions of the present application, and therefore, the embodiments are only used as examples, and the scope of the present application is not limited thereby.
Reference herein to "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment can be included in at least one embodiment of the application. The appearances of the phrase "an embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or related to other embodiments specifically defined. In principle, in the present application, the technical features mentioned in the embodiments can be combined in any manner to form a corresponding implementable technical solution as long as there is no technical contradiction or conflict.
Unless defined otherwise, technical terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs; the use of relational terms herein is intended to describe specific embodiments only and is not intended to limit the present application.
In the description of the present application, the term "and/or" is a expression for describing a logical relationship between objects, meaning that three relationships may exist, for example a and/or B, meaning: there are three cases of A, B, and both A and B. In addition, the character "/" herein generally indicates that the former and latter associated objects are in a logical relationship of "or".
In this application, terms such as "first" and "second" are used merely to distinguish one entity or operation from another entity or operation without necessarily requiring or implying any actual such relationship or order between such entities or operations.
Without further limitation, in this application, the use of the phrases "comprising," "including," "having," or other similar expressions, is intended to cover a non-exclusive inclusion, and these expressions do not exclude the presence of additional elements in a process, method, or article that includes the elements, such that a process, method, or article that includes a list of elements may include not only those elements defined, but other elements not expressly listed, or may include other elements inherent to such process, method, or article.
As is understood in the "review guidelines," in this application, the terms "greater than," "less than," "more than," and the like are to be understood as excluding the number; the expressions "above", "below", "within" and the like are understood to include the present numbers. In addition, in the description of the embodiments of the present application, "a plurality" means two or more (including two), and expressions related to "a plurality" similar thereto are also understood, for example, "a plurality of groups", "a plurality of times", and the like, unless specifically defined otherwise.
The ceramic material is used as an inorganic non-metallic material, has various advantages of high temperature resistance and corrosion resistance, and is widely applied to the fields of daily household, electronics, medical treatment and the like.
The inventor finds that metal ions in molten salt can be implanted into a ceramic glaze layer through an ion exchange process to obtain the antibacterial effect, but because various ceramic glaze components, glaze layer structures, glazing process differences and glazing thickness unevenness exist in the process of preparing ceramic products, the problem of discoloration of ceramic surface forms with little or no glazing after ion exchange of the ceramic products is caused.
In order to solve the technical problem, the silver ion concentration distribution curve is in an upward parabolic shape by combining glaze components through adjusting and optimizing molten salt components and a process, the maximum value distribution of the silver content is controlled in a specific depth interval, the antibacterial performance requirement can be met, meanwhile, the continuity and durability of the antibacterial effect are improved, and the problem of redox discoloration generated after ion exchange is effectively solved.
According to the antibacterial ceramic preparation method provided by the second aspect of the application, the steps of acid washing and alkali washing activation treatment are added before the antibacterial ion exchange treatment, heavy metal ions and inorganic salt deposition existing on the surface of the ceramic are washed away by acid washing, so that metal impurities possibly subjected to color change reaction with silver ions can be removed cleanly and quickly, organic matters and microorganisms are eliminated by alkali washing, the factor causing color change is eliminated, the difference of color change of the ceramic before and after the antibacterial ion exchange can be effectively reduced by adding the step of antibacterial pretreatment, the activation treatment sequence is that the acid washing is carried out first and the alkali washing is carried out later, if the alkali washing is carried out first, the heavy metal ions are easily precipitated, and the effect of the acid washing is reduced.
Based on the technical scheme, the application provides an embodiment of an antibacterial ceramic and a preparation method thereof.
In some embodiments, the antibacterial ceramic extends the surface of the glaze layer to the Ag + containing region at a certain depth through ion exchange, the ratio of the depth of the Ag + containing region in the antibacterial ceramic to the thickness of the glaze layer on the surface of the ceramic blank is 0.01-0.1, the deeper the Ag + is, the more easily the discoloration phenomenon of the surface of the ceramic is caused, and the deeper the Ag + is, the more the antibacterial effect is influenced, and the unnecessary cost waste is caused during the ion exchange process.
In some embodiments, the antimicrobial ceramic has a color difference Δ E of 0.5 before and after ion-exchange, the ceramic is tested for L a b values according to QB/T1503-2011, and the ion-exchanged ceramic is tested for L a b values and Δ E is calculated and color difference determinations are made according to GB/T3532-1995.
In some embodiments, the surface of the glaze layer extends to a depth of an Ag + containing region in which the Ag + concentration profile formed is parabolic upward, and the Ag + concentration profile has a maximum of 1.0 to 1.5at% of silver content, and the maximum is distributed at a depth of 0.1 to 0.3% of the surface of the glaze layer. Wherein, the maximum value of the silver content is too high, and the distribution depth is too deep, which can cause the deterioration of the antibacterial performance of the ceramic and the possibility of color change; and the maximum value of the silver content is too low, and the distribution depth is too shallow, so that the antibacterial performance of the ceramic is poor, and the wear resistance and the durability of the antibacterial effect are not ideal.
In some embodiments, after the soaking treatment with the acidic solution, the acid chemical polishing is performed before the soaking treatment with the alkaline solution, so that the surface of the glaze layer is flat and uniform, the uneven texture on the surface of the ceramic is removed, and the antibacterial effect can be enhanced by keeping a certain range of pores.
Examples
In order to further clarify the explanation and explanation of the technical solutions of the present application, the following non-limiting examples are provided. The embodiments of the present application are subject to many efforts to ensure accuracy with respect to numbers, but some errors and deviations should be taken into account.
Examples 1-10 and comparative examples 1-3 methods of preparing the antibacterial ceramics:
example 1
Putting the basic ceramic into pure water for cleaning;
soaking the cleaned basic ceramic in 0.8% oxalic acid solution for 3min at 60 deg.C;
then, soaking the basic ceramic in 10% sodium hydroxide aqueous solution for 3min at 60 ℃;
preheating the base ceramic in a preheating furnace at 370 ℃ for 11min; and (3) placing the preheated basic ceramic into molten antibacterial molten salt for antibacterial ion exchange treatment at 390 ℃ for 10min, placing the ceramic subjected to antibacterial ion exchange into a muffle furnace for cooling, and cleaning with pure water after cooling to obtain the antibacterial ceramic.
Example 2
Putting the basic ceramic into pure water for cleaning;
soaking the cleaned basic ceramic in 0.6% oxalic acid solution for 5min at 70 deg.C;
then, soaking the basic ceramic in 10% sodium hydroxide aqueous solution for 8min at 40 ℃;
preheating the base ceramic in a preheating furnace at 370 ℃ for 11min; and (3) placing the preheated basic ceramic into molten antibacterial molten salt for antibacterial ion exchange treatment, wherein the ion exchange temperature is 400 ℃, the time is 15min, placing the ceramic subjected to antibacterial ion exchange into a muffle furnace for cooling, and cleaning with pure water after cooling to finally obtain the antibacterial ceramic.
Example 3
Putting the basic ceramic into pure water for cleaning;
soaking the cleaned basic ceramic in 0.8% oxalic acid solution for 1min at 80 deg.C;
then, soaking the basic ceramic in 15% sodium hydroxide aqueous solution for 6min at 50 ℃;
preheating the basic ceramic in a preheating furnace at 390 ℃ for 11min; and (3) placing the preheated basic ceramic into molten antibacterial molten salt for antibacterial ion exchange treatment, wherein the ion exchange temperature is 430 ℃ and the time is 8min, placing the ceramic subjected to antibacterial ion exchange into a muffle furnace for cooling, and cleaning with pure water after cooling to finally obtain the antibacterial ceramic.
Example 4
Putting the basic ceramic into pure water for cleaning;
soaking the cleaned basic ceramic in 0.7% oxalic acid solution for 3min at 60 deg.C;
then soaking the base ceramic in 15% sodium hydroxide water solution for 3min at 60 deg.C;
preheating the basic ceramic in a preheating furnace at 330 ℃ for 10min; and (3) placing the preheated basic ceramic into molten antibacterial molten salt for antibacterial ion exchange treatment, wherein the ion exchange temperature is 360 ℃ and the time is 30min, placing the ceramic subjected to antibacterial ion exchange into a muffle furnace for cooling, and cleaning with pure water after cooling to finally obtain the antibacterial ceramic.
Example 5
Putting the basic ceramic into pure water for cleaning;
soaking the cleaned basic ceramic in 1.5% oxalic acid solution for 1min at 60 deg.C;
then, soaking the basic ceramic in 15% sodium hydroxide aqueous solution for 10min at 50 ℃;
preheating the base ceramic in a preheating furnace at 350 ℃ for 15min; and (3) placing the preheated basic ceramic into molten antibacterial molten salt for antibacterial ion exchange treatment at 390 ℃ for 25min, placing the ceramic subjected to antibacterial ion exchange into a muffle furnace for cooling, and cleaning with pure water after cooling to finally obtain the antibacterial ceramic.
Example 6
Putting the basic ceramic into pure water for cleaning;
soaking the cleaned basic ceramic in 1.3% oxalic acid solution for 1min at 60 deg.C;
then soaking the basic ceramic in 15% sodium hydroxide aqueous solution alkaline solution for 10min at 50 ℃;
preheating the base ceramic in a preheating furnace at 360 ℃ for 15min; and (3) placing the preheated basic ceramic into molten antibacterial molten salt for antibacterial ion exchange treatment at 400 ℃ for 6min, placing the ceramic subjected to antibacterial ion exchange into a muffle furnace for cooling, and cleaning with pure water after cooling to finally obtain the antibacterial ceramic.
Example 7
Putting the basic ceramic into pure water for cleaning;
soaking the cleaned basic ceramic in 1.0% oxalic acid solution for 4min at 60 deg.C;
then soaking the basic ceramic in 15% sodium hydroxide water solution for 10min at 40 deg.C;
preheating the basic ceramic in a preheating furnace at 360 ℃ for 15min; and (3) placing the preheated basic ceramic into molten antibacterial molten salt for antibacterial ion exchange treatment at 390 ℃ for 5min, placing the ceramic subjected to antibacterial ion exchange into a muffle furnace for cooling, and cleaning with pure water after cooling to obtain the antibacterial ceramic.
Example 8
Putting the basic ceramic into pure water for cleaning;
soaking the cleaned basic ceramic in 0.9% oxalic acid solution for 5min at 60 deg.C;
then soaking the basic ceramic in 15% sodium hydroxide water solution for 10min at 40 deg.C;
preheating the basic ceramic in a preheating furnace at 380 deg.C for 15min; and (3) placing the preheated basic ceramic into molten antibacterial molten salt for antibacterial ion exchange treatment, wherein the ion exchange temperature is 410 ℃ and the time is 10min, placing the ceramic subjected to antibacterial ion exchange into a muffle furnace for cooling, and cleaning with pure water after cooling to finally obtain the antibacterial ceramic.
Example 9
Putting the basic ceramic into pure water for cleaning;
soaking the cleaned basic ceramic in 0.9% oxalic acid solution for 5min at 60 deg.C;
then, soaking the basic ceramic in 15% sodium hydroxide aqueous solution for 10min at 40 ℃;
preheating the base ceramic in a preheating furnace at 360 ℃ for 15min; and (3) placing the preheated basic ceramic into molten antibacterial molten salt for antibacterial ion exchange treatment at 390 ℃ for 6min, placing the ceramic subjected to antibacterial ion exchange into a muffle furnace for cooling, and cleaning with pure water after cooling to finally obtain the antibacterial ceramic.
Example 10
Putting the basic ceramic into pure water for cleaning;
soaking the cleaned basic ceramic in 0.9% oxalic acid solution for 5min at 60 deg.C;
then, soaking the basic ceramic in a solution containing 2% of hydrofluoric acid, 8% of nitric acid and the balance of water for 5min at the temperature of 60 ℃;
then soaking the basic ceramic in 15% sodium hydroxide water solution for 10min at 40 deg.C;
preheating the base ceramic in a preheating furnace at 340 ℃ for 5min; and (3) placing the preheated basic ceramic into molten antibacterial molten salt for antibacterial ion exchange treatment at the ion exchange temperature of 380 ℃ for 6min, placing the ceramic subjected to antibacterial ion exchange into a muffle furnace for cooling, and cleaning with pure water after cooling to finally obtain the antibacterial ceramic.
Comparative example 1
Putting the basic ceramic into pure water for cleaning;
preheating the base ceramic in a preheating furnace at 350 ℃ for 15min; and (3) placing the preheated basic ceramic into molten antibacterial molten salt for antibacterial ion exchange treatment at the ion exchange temperature of 450 ℃ for 20min, placing the ceramic subjected to antibacterial ion exchange into a muffle furnace for cooling, and cleaning with pure water after cooling to finally obtain the antibacterial ceramic.
Comparative example 2
Putting the basic ceramic into pure water for cleaning;
soaking the cleaned basic ceramic in 0.9% oxalic acid water solution for 5min at 60 deg.C;
preheating the base ceramic in a preheating furnace at 320 ℃ for 15min; and (3) placing the preheated basic ceramic into molten antibacterial molten salt for antibacterial ion exchange treatment at 400 ℃ for 30min, placing the ceramic subjected to antibacterial ion exchange into a muffle furnace for cooling, and cleaning with pure water after cooling to finally obtain the antibacterial ceramic.
Comparative example 3
Putting the basic ceramic into pure water for cleaning;
then, soaking the basic ceramic in 15% sodium hydroxide aqueous solution for 10min at 40 ℃;
preheating the base ceramic in a preheating furnace at 330 ℃ for 15min; and (3) placing the preheated basic ceramic into molten antibacterial molten salt for antibacterial ion exchange treatment at the ion exchange temperature of 420 ℃ for 25min, placing the ceramic subjected to antibacterial ion exchange into a muffle furnace for cooling, and cleaning with pure water after cooling to finally obtain the antibacterial ceramic.
Surface glaze layer composition: the measurement of the composition and content of the glaze surface layer was carried out using an ARLTM perfom' X-ray fluorescence spectrometer (XRF) manufactured by siemer feishel scientific ltd (thermo fisher scientific), with the following parameters: the voltage is 60kV, and the current is 40mA;
containing Ag + Depth of region (μm): detecting the implantation depth of the antibacterial ions by adopting an IMS 7f type Secondary Ion Mass Spectrometer (SIMS) produced by CAMECA company;
antibacterial effective value (R): using JIS Z2801: detecting escherichia coli ATCC8739 and staphylococcus aureus ATCC6538P by a detection method of 2010;
the Ag concentration: the Ag concentration at each layer depth (nanometer level) was measured using X-ray photoluminescence spectroscopy (XPS) and reported as atomic percent.
Antibacterial rate after 5% sodium hypochlorite cleaning: and testing by adopting a JC/897-2014 detection method.
Color difference Δ E after antibiosis: the base ceramic was first tested for la b according to QB/T1503-2011, the ion-exchanged antimicrobial ceramic was then tested for la b and Δ E was calculated and the color difference was determined according to GB/T3532-1995.
Temperature difference of sudden heat resistance: the test was performed with 10 cycles between 10 ℃ and 200 ℃ to see if cracks or other defects occurred.
Table 1 shows the antibacterial molten salt compositions and relevant performance parameters of each example and comparative example
The performance results show that: as can be seen from the above examples in combination with table 1, the antibacterial ceramic antibacterial ceramics prepared in examples 1 to 10 extend the surface of the glaze layer to Ag + containing regions of a certain depth by ion exchange, and the ratio of the depth of the Ag + containing region in the antibacterial ceramic to the thickness of the glaze layer on the surface of the ceramic green body is 0.01 to 0.1:1. in the ion exchange process, the deeper the Ag + diffusion, the more easily the discoloration phenomenon of the ceramic surface is caused, and the deeper the Ag + diffusion, the more the antibacterial effect is affected, and unnecessary cost waste is also caused.
The basic ceramic is subjected to ion exchange by combining activation treatment in an embodiment with optimized antibacterial molten salt, the color difference value delta E before and after the ion exchange is less than or equal to 0.5, the ceramic glaze surface keeps a little silver ion content by the technical scheme, the ceramic glaze surface has effective antibacterial performance by controlling the concentration content, and discoloration and cost waste caused by excessive silver ion deep diffusion can be avoided.
The antibacterial fused salt is a nitrate composition containing silver, potassium and sodium, wherein the content of silver nitrate can be adjusted according to the content of feldspar in the ceramic glaze layer, the feldspar is an aluminosilicate mineral containing calcium, sodium and potassium, the content of the aluminosilicate mineral has a promoting effect on the ion exchange speed and metal ion diffusion of the ceramic glaze layer, but excessive implantation diffusion has negative effects on the antibacterial performance and the color of the glaze layer, so that the content of the feldspar in the glaze layer is as follows: the mass ratio of silver nitrate is 10: preferably between 1 and 2.
The surface of the glaze surface is subjected to antibacterial ion exchange, and simultaneously the glaze surface forms a certain compression stress layer on the surface of the glaze surface through the ion exchange between K/Na or Na/Li, so that the surface strength of the ceramic product is improved, and the sudden thermal temperature change difference resistance of the ceramic is improved.
It can be seen by combining examples 9 and 10 that a certain amount of lithium nitrate is added to the antibacterial molten salt to accelerate the ion exchange, and the immersion in the lithium-containing metal salt can cause the ion exchange between sodium ions in the glaze layer and lithium ions in the metal salt, so that the lithium ions with small radius have a high displacement and diffusion speed, and are more easily implanted into the glaze layer surface layer, thereby causing the change of the surface spatial structure of the glaze layer, reducing the steric hindrance, and accelerating the exchange of the antibacterial silver ions with large radius. Meanwhile, the energy required by the antibacterial metal ions for ion exchange in the glaze layer is reduced due to the reduction of the steric hindrance. Thus, the temperature and/or time of ion exchange can be further reduced. In addition, there are many factors that affect the time and temperature of ion exchange, such as the alkali metal content of the object of ion exchange, the concentration formula of the ion-exchange molten salt, and the like.
As can be seen by combining the examples with the comparative examples, comparative examples 1 to 3 were not subjected to the activation acid-base treatment or were subjected to only one of them, and the feldspar in the glaze layer: the ratio of silver nitrate is not 10:1-2, so that the silver concentration is diffused deeply, silver ions are formed into silver gel or the silver ions and metal ions, inorganic salts or organic matters in the ceramic are subjected to oxidation-reduction reaction, the color difference delta E value of the surface is higher than 0.5, obvious uneven yellow color can be seen by naked eyes, the preheating temperature and the ion exchange temperature difference in a comparative example are large, and partial crack defects appear on the surface.
Table 2 shows the relevant performance parameters for examples 1, 3, 5, 9 and comparative example 1
Performance results show that: from the above examples and table 2, it can be seen by XPS detection that the antibacterial ceramic extends the surface of the glaze layer to an Ag + containing region of a certain depth through ion exchange, the Ag + concentration distribution curve formed in the region is in an upward parabolic shape, in the Ag + concentration distribution curve, the maximum value of the silver content is 1.0 to 1.5at%, and the maximum value is distributed at a depth of 0.1 to 0.3% of the surface of the glaze layer, according to the examples, it can be seen that the maximum value of the silver content is distributed in the range of 300 to 700nm, and the maximum concentration in the range can obtain effective antibacterial performance and abrasion resistance, and maintain the color difference Δ E < 0.5 after antibacterial ion exchange of the ceramic glaze. The maximum value of the comparative example 1 is distributed at the depth of about 5000nm, and the test tests show that the maximum value of the silver content is too high, and the distribution depth is too deep, so that the antibacterial performance of the ceramic is deteriorated, and the possibility of color change is caused; and the maximum value of the silver content is too low, and the distribution depth is too shallow, so that the antibacterial performance of the ceramic is poor, and the wear resistance and the durability of the antibacterial effect are not ideal.
Further, as can be seen by comparing with the comparative example, the comparative example has a low silver ion content on the surface (the silver ion content on the surface is detected by XPS or Secondary Ion Mass Spectrometer (SIMS) for the antibacterial ion implantation depth (the detection depth is in the range of 10-20 nm), most of the silver ion content is implanted deeply, although there is a certain silver ion content, the prepared ceramic has a poor antibacterial effect because the silver is gelatinized due to process difference, over-high temperature or high concentration of silver, and the silver gelatinization causes obvious yellow.
The ceramic of the embodiment is subjected to activation treatment before ion exchange, wherein the acid washing enables the deposition of heavy metal ions and inorganic salts on the surfaces of a glaze layer and a ceramic blank to be reduced, so that metal impurities which can generate color change reaction with silver ions can be removed cleanly and quickly, organic matters and microorganisms are eliminated by alkali washing, the factor causing color change is also eliminated, further, the color change of the ceramic surface caused by uneven glazing thickness can be effectively prevented by controlling the concentration of the silver ions in the ion exchange, and the color difference delta E after antibiosis is controlled to be less than 0.5.
The ceramic glaze surface of the embodiment keeps effective silver concentration within a certain depth range on the surface, and still keeps more than or equal to 99.9 of antibacterial rate after being washed for 500 times by using a sodium hypochlorite solution containing 5 percent, and the comparative example has poor surface antibacterial performance due to over-deep silver concentration distribution.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes performed by the present specification and drawings, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (14)
1. The antibacterial ceramic comprises a blank body and a glaze layer arranged on the surface of the blank body, and is characterized in that the antibacterial ceramic enables the surface of the glaze layer to extend to a certain depth inside the glaze layer through ion exchange and contains Ag + Region of said Ag + The ratio of the depth of the region to the thickness of the glaze layer is 0.01-0.1:1, and the color difference value delta E before and after ion exchange of the antibacterial ceramic is less than or equal to 0.5.
2. The antibacterial ceramic of claim 1, wherein the content of silver ions in the antibacterial ceramic is 0.001-0.3wt% based on the total weight of the glaze layer.
3. The antimicrobial ceramic of claim 1, wherein the Ag is present + The distribution of the silver content in the area is in the shape of an upward parabola, the maximum value of which is 1.0-1.5at%, and the maximum value is distributed on the surface of the glaze layer to the depth of 0.1-0.3%.
4. The antimicrobial ceramic of claim 1, wherein the antimicrobial ceramic has an antimicrobial R value > 2.
5. The antibacterial ceramic of claim 1, wherein the temperature difference of the antibacterial ceramic with respect to rapid thermal change is not less than 160 ℃.
6. The antibacterial ceramic of claim 1, wherein the antibacterial ceramic surface is washed 500 times with 5% sodium hypochlorite disinfectant to achieve an antibacterial rate of 99% or more.
7. A method for preparing the antibacterial ceramic according to any one of claims 1 to 6, comprising the steps of:
(1) Cleaning: putting the basic ceramic into pure water for cleaning;
(2) Activation treatment: soaking the cleaned basic ceramic in an acid solution, and then soaking the basic ceramic in an alkaline solution;
(3) Preheating treatment: placing the basic ceramic in a preheating furnace for preheating;
(4) And (3) antibacterial treatment: placing the preheated basic ceramic into molten antibacterial molten salt for antibacterial ion exchange treatment;
(5) Cleaning: and (3) placing the ceramic subjected to the antibacterial ion exchange into a muffle furnace for cooling, and cleaning with pure water after cooling.
8. The method for preparing an antibacterial ceramic according to claim 7, characterized in that: in the step (2), the acidic solution is oxalic acid aqueous solution, and the mass concentration is 0.6-1.5%.
9. The method for preparing an antibacterial ceramic according to claim 7, characterized in that: the soaking time of the acidic solution in the step (2) is 1-5min, and the temperature is 60-80 ℃.
10. The method for preparing an antibacterial ceramic according to claim 7, characterized in that: in the step (2), the alkaline solution is sodium hydroxide aqueous solution, and the pH value of the alkaline solution is 11-12.
11. The method for preparing an antibacterial ceramic according to claim 7, characterized in that: the soaking time of the alkaline solution in the step (2) is 3-10min, and the temperature is 40-60 ℃.
12. The method for preparing an antibacterial ceramic according to claim 7, characterized in that: the antibacterial molten salt in the step (4) is a nitrate composition containing silver, potassium and sodium metal ions, wherein the content of the silver ions is 0.1-5 wt%.
13. The method for preparing an antibacterial ceramic according to claim 7, characterized in that: the relationship between the preheated temperature T1 in the step (3) and the temperature T2 of the antibacterial molten salt in the step (4) is as follows: T2-T1 is less than 50 ℃.
14. The method for preparing an antibacterial ceramic according to claim 7, characterized in that: and (4) controlling the time of the antibacterial ion exchange in the step (4) to be 5-30min.
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