CN118637827B - A modified rare earth antibacterial glaze and preparation method thereof - Google Patents
A modified rare earth antibacterial glaze and preparation method thereof Download PDFInfo
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 104
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 61
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000010433 feldspar Substances 0.000 claims abstract description 8
- 239000010453 quartz Substances 0.000 claims abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004927 clay Substances 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 45
- -1 rare earth nitrate Chemical class 0.000 claims description 43
- 229910002651 NO3 Inorganic materials 0.000 claims description 36
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- 229920001661 Chitosan Polymers 0.000 claims description 23
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical class [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 22
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 238000000227 grinding Methods 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 13
- 239000011787 zinc oxide Chemical class 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 8
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 8
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 239000004576 sand Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 abstract description 17
- 244000005700 microbiome Species 0.000 abstract description 10
- 230000005764 inhibitory process Effects 0.000 abstract description 3
- 241000588724 Escherichia coli Species 0.000 description 19
- 241000191967 Staphylococcus aureus Species 0.000 description 18
- 239000000463 material Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 230000001580 bacterial effect Effects 0.000 description 5
- 230000003385 bacteriostatic effect Effects 0.000 description 5
- 210000004027 cell Anatomy 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 241000894006 Bacteria Species 0.000 description 4
- 210000000170 cell membrane Anatomy 0.000 description 4
- 230000036541 health Effects 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 230000003115 biocidal effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 239000001963 growth medium Substances 0.000 description 2
- 208000015181 infectious disease Diseases 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 210000000056 organ Anatomy 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 208000031729 Bacteremia Diseases 0.000 description 1
- 208000035473 Communicable disease Diseases 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- 239000006142 Luria-Bertani Agar Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 206010040047 Sepsis Diseases 0.000 description 1
- 206010040070 Septic Shock Diseases 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 244000037640 animal pathogen Species 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 230000037358 bacterial metabolism Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical group O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 206010014665 endocarditis Diseases 0.000 description 1
- 230000000688 enterotoxigenic effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003834 intracellular effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 230000036542 oxidative stress Effects 0.000 description 1
- 230000001717 pathogenic effect Effects 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000028327 secretion Effects 0.000 description 1
- 230000036303 septic shock Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 208000011580 syndromic disease Diseases 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- QBAZWXKSCUESGU-UHFFFAOYSA-N yttrium(3+);trinitrate;hexahydrate Chemical group O.O.O.O.O.O.[Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QBAZWXKSCUESGU-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
-
- 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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/02—Pretreated ingredients
- C03C1/026—Pelletisation or prereacting of powdered raw materials
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/86—Glazes; Cold glazes
-
- 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
- C03C2204/00—Glasses, glazes or enamels with special properties
- C03C2204/02—Antibacterial glass, glaze or enamel
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/60—Production of ceramic materials or ceramic elements, e.g. substitution of clay or shale by alternative raw materials, e.g. ashes
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Structural Engineering (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
本发明提供了一种改性稀土抗菌釉料及其制备方法，改性稀土抗菌釉料，该釉料由包括如下重量份的原料制成：石英3‑5份，长石9‑11份，粘土4‑6份，改性稀土配合物1‑2份。本发明所述的改性稀土抗菌釉料采用了改性稀土配合物，对陶瓷制品日常使用时残留的微生物具有良好杀灭或抑制能力。
The present invention provides a modified rare earth antibacterial glaze and a preparation method thereof, wherein the modified rare earth antibacterial glaze is made of the following raw materials in parts by weight: 3-5 parts of quartz, 9-11 parts of feldspar, 4-6 parts of clay, and 1-2 parts of a modified rare earth complex. The modified rare earth antibacterial glaze of the present invention uses a modified rare earth complex and has good killing or inhibition capabilities for microorganisms remaining in ceramic products during daily use.
Description
Technical Field
The invention belongs to the field of antibiosis, and particularly relates to a modified rare earth antibacterial glaze and a preparation method thereof.
Background
With the development of economy, the requirements of people on life quality are also increased, and the main performance is that people pay more attention to the functionality of daily necessities in life rather than other factors such as appearance, wherein the antibacterial function of daily necessities is widely concerned, and in the daily necessities, an antibacterial ceramic cup is a big hot spot in current research because the ceramic cup can be closely contacted with drinking water entering a human body and is closely related to the health of the human body. The common ceramic cup with common antibacterial property is easy to remain some microorganisms which are pathogenic to human body, and the microorganisms are mainly escherichia coli and staphylococcus aureus, so that the antibacterial ceramic cup can kill or inhibit the two microorganisms, and can have positive influence on the health of the human body. Under normal conditions, the escherichia coli can not bring any harm to the health of people, is in symbiotic relation with the human body, but breaks the microecological balance of the 'invaded' organs after the living environment of the escherichia coli changes, such as entering other organs, so that part infection is caused, systemic disseminated infection can be caused when serious, even life is endangered, and five typical bacteria harmful to people such as enterotoxigenic escherichia coli are classified at present. Staphylococcus aureus is also a typical animal pathogen that can cause a variety of infectious diseases in humans, such as bacteremia, endocarditis, sepsis and septic shock syndrome.
The capability of rare earth elements to kill or inhibit microorganisms has been widely verified, especially for colibacillus and staphylococcus aureus, while rare earth nano-examples further strengthen the antibacterial effect by small molecular effect on the basis, the antibacterial mechanism of rare earth nano-materials mainly consists of three types of oxidative stress, ion release and contact antibacterial, and besides, rare earth nano-ions can combine nano-particles with bacterial cell membranes through electrostatic interaction, thereby affecting the transportation and exchange of nutrient substances between bacteria and cell fluid and inhibiting bacterial growth. In addition to rare earth, zinc oxide is also a typical antimicrobial material that can kill or inhibit microorganisms by mechanisms such as ion elution, inhibition of bacterial metabolism, photocatalysis, electron transfer, and the like. In addition, researches show that the rare earth lanthanum element-zinc oxide composite can generate a synergistic effect to further strengthen the antibacterial effect, and meanwhile, although the rare earth cerium element-zinc oxide composite material also has good antibacterial performance, due to frequent change of rare earth price in the international market, a rare earth compound with higher cost performance is also required to be found to ensure the possibility of future amplified production.
Disclosure of Invention
In view of the above, the invention aims to overcome the defects in the prior art, and provides a modified rare earth antibacterial glaze and a preparation method thereof.
In order to achieve the above purpose, the technical scheme of the invention is realized as follows:
the modified rare earth antibacterial glaze is prepared from the following raw materials, by weight, 3-5 parts of quartz, 9-11 parts of feldspar, 4-6 parts of clay and 1-2 parts of modified rare earth complex;
The modified rare earth complex is prepared by adding ammonia water, absolute ethyl alcohol, modified rare earth nitrate and zinc oxide into deionized water, uniformly mixing to obtain a mixed solution, drying the mixed solution to obtain a solid sample, calcining, grinding and sanding the solid sample to obtain nano slurry, and drying and grinding the nano slurry to obtain the modified rare earth complex.
Further, the solid-to-liquid ratio of the ammonia water, the absolute ethyl alcohol, the modified rare earth nitrate, the zinc oxide and the deionized water is 4-6:4-6:4-5:1-2:23-25, and the mass concentration of the ammonia water is 25-28%.
Further, the temperature of the drying step is 80-150 ℃ for 12-18 hours, the temperature of the calcining step is 1200-1450 ℃ for 3-4.5 hours, the sand grinding speed is 2500-3500 r/min for 3-4 hours, and the particle size of the modified rare earth complex is 80-100 nm.
Further, the modified rare earth nitrate is prepared by a method comprising the following steps:
step 1, adding rare earth nitrate into deionized water, and dissolving to obtain rare earth nitrate solution;
Step 2, adding chitosan into a citric acid solution, and dissolving to obtain a chitosan solution;
And 3, mixing the chitosan solution with the rare earth nitrate solution, regulating the pH value of the solution, adding sodium bicarbonate solution into the solution, and carrying out suction filtration, washing, drying and grinding on the white precipitate after the reaction is finished to obtain the modified rare earth nitrate.
Further, the concentration of the rare earth nitrate solution in the step 1 is 0.5-0.7 mol/L, the mass concentration of the citric acid solution in the step 2 is 0.7-1.5%, and the solid-liquid ratio of the chitosan and the citric acid solution in the step 2 is 1-1.5g:40-45 mL.
Further, the rare earth nitrate is at least one of cerium, lanthanum or yttrium nitrate.
Further, the volume ratio of the chitosan solution, the rare earth nitrate solution and the sodium bicarbonate solution in the step 3 is 3.5-4.5:0.5-1.5:2.0-3.0, and the mass concentration of the sodium bicarbonate solution in the step 3 is 30-40%.
Further, the pH value in the step 3 is 6.5-7.5, the temperature in the drying step in the step 3 is 80-120 ℃ and the time is 10-15 hours.
The preparation method of the modified rare earth antibacterial glaze comprises the following steps of adding quartz, feldspar and sticky modified rare earth complex into deionized water with the amount of 1.5-2.0 times, and uniformly mixing to obtain the modified rare earth antibacterial glaze.
The modified rare earth nitrate can take chitosan as a carrier, provide a stable space structure for rare earth ions with antibacterial effect, wrap the rare earth ions, enable the material structure to be more stable, enable the chitosan to penetrate cell membranes and enter the inside of cells, inhibit secretion of intracellular enzymes through catalysis of the rare earth ions after the rare earth ions with antibacterial effect are carried, and enable the chitosan entering the cells to chelate metal ions with promotion effect on bacterial growth, and enable the chitosan entering the cells to interact with the metal ions, so that the proliferation of microorganisms is more effectively inhibited.
Compared with the prior art, the invention has the following advantages:
The modified rare earth nitrate can penetrate through the cell membrane on the surface of the microorganism more efficiently through the electrostatic action of the chitosan, and after entering the cell, the modified rare earth nitrate utilizes the chelation of the chitosan and the catalysis of the rare earth ions to cooperatively resist bacteria, and finally has obvious inhibition effect on escherichia coli and staphylococcus aureus.
The modified rare earth complex is a nanoscale material, and the modified rare earth nitrate and zinc oxide are compounded, so that the modified rare earth complex not only has a special small-size antibacterial effect of the nanomaterial, but also is easier to cause the change and cracking of the membrane permeability, and finally has a very prominent effect of inhibiting microorganisms.
The modified rare earth antibacterial glaze adopts the modified rare earth complex, and has good capability of killing or inhibiting residual microorganisms in daily use of ceramic products.
Drawings
FIG. 1 is a graph showing the antibacterial effect of the modified rare earth antibacterial glaze material of example 1 of the present invention on Escherichia coli;
FIG. 2 is a graph showing the antibacterial effect of the modified rare earth antibacterial glaze material according to the embodiment 2 of the invention on Escherichia coli;
FIG. 3 is a graph showing the antibacterial effect of the modified rare earth antibacterial glaze material of example 3 of the present invention on Escherichia coli;
FIG. 4 is a graph showing the antibacterial effect of the modified rare earth antibacterial glaze material according to comparative example 1 on Escherichia coli;
FIG. 5 is a graph showing the antibacterial effect of the modified rare earth antibacterial glaze material according to comparative example 2 on Escherichia coli;
FIG. 6 is a blank of E.coli according to the present invention;
FIG. 7 is a graph showing the antibacterial effect of the modified rare earth antibacterial glaze material of example 1 of the present invention against Staphylococcus aureus;
FIG. 8 is a graph showing the antibacterial effect of the modified rare earth antibacterial glaze material according to example 2 of the present invention on Staphylococcus aureus;
FIG. 9 is a graph showing the antibacterial effect of the modified rare earth antibacterial glaze material of example 3 of the present invention on Staphylococcus aureus;
FIG. 10 is a graph showing the antibacterial effect of the modified rare earth antibacterial glaze according to comparative example 1 on Staphylococcus aureus;
FIG. 11 is a graph showing the antibacterial effect of the modified rare earth antibacterial glaze according to comparative example 2 on Staphylococcus aureus;
FIG. 12 is a blank of Staphylococcus aureus according to the present invention.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention pertains. The test reagents used in the following examples are all conventional biochemical reagents unless otherwise specified, and the test methods are all conventional methods unless otherwise specified.
The present invention will be described in detail with reference to examples.
Example 1
A preparation method of a modified rare earth antibacterial glaze comprises the following steps:
(1) Adding lanthanum nitrate hexahydrate into deionized water, dissolving to obtain 0.6 mol/L rare earth nitrate solution, adding 5 g chitosan into 200mL of 1% citric acid solution, dissolving to obtain chitosan solution, mixing 200mL of chitosan solution with 50mL rare earth nitrate solution, regulating the pH value of the solution to about 7.0 by using 5% ammonia water, adding 100mL of 35% sodium bicarbonate solution, carrying out suction filtration, flushing for 3 times, drying at 80 ℃ for 12h, and grinding to obtain the modified rare earth nitrate La-CHI;
(2) Adding 10 mL ammonia water, 10 mL absolute ethyl alcohol, 10 g modified rare earth nitrate and 2g zinc oxide into 50mL deionized water, uniformly mixing to obtain a mixed solution, drying the mixed solution at 150 ℃ for 18 hours to obtain a solid sample, calcining the solid sample at 1400 ℃ for 5 hours, grinding for one time, grinding at 3000 r/min for 4 hours to obtain nano slurry with Dv (90) of 80-100 nm, drying the nano slurry at 0.01 Mpa and 80 ℃ for 24 hours, and grinding again to obtain the modified rare earth complex La@YH;
(3) Quartz, feldspar and sticky modified rare earth complex with the mass ratio of 4:10:5:1 are added into deionized water with the amount of 2 times, and the modified rare earth antibacterial glaze is obtained after uniform mixing.
Example 2
The only difference from example 1 is that the rare earth nitrate is cerium nitrate hexahydrate.
Example 3
The only difference from example 1 is that the rare earth nitrate is yttrium nitrate hexahydrate.
Comparative example 1
The preparation process of RE antibiotic glaze includes the following steps:
(1) Adding 10 mL ammonia water, 10 mL absolute ethyl alcohol, 10 g modified rare earth nitrate and 2 g zinc oxide into 50 mL deionized water, uniformly mixing to obtain a mixed solution, drying the mixed solution at 150 ℃ for 18 hours to obtain a solid sample, calcining the solid sample at 1400 ℃ for 5 hours, grinding for one time, grinding at 3000 r/min for 4 hours to obtain nano slurry with Dv (90) of 80-100 nm, drying the nano slurry at 0.01 Mpa and 80 ℃ for 24 hours, and grinding again to obtain the modified rare earth complex La@YH;
(2) Quartz, feldspar and adhesion modified rare earth complex with the mass ratio of 4:10:5:1 are added into deionized water with the amount of 2 times, and the rare earth antibacterial glaze is obtained after uniform mixing.
Comparative example 2
A preparation method of a modified rare earth antibacterial glaze comprises the following steps:
(1) Adding lanthanum nitrate hexahydrate into deionized water, dissolving to obtain 0.6 mol/L rare earth nitrate solution, adding 5 g chitosan into 200mL of 1% citric acid solution, dissolving to obtain chitosan solution, mixing 200mL of chitosan solution with 50mL rare earth nitrate solution, regulating the pH value of the solution to about 7.0 by using 5% ammonia water, adding 100mL of 35% sodium bicarbonate solution, carrying out suction filtration, flushing for 3 times, drying at 80 ℃ for 12h, and grinding to obtain the modified rare earth nitrate La-CHI;
(2) Quartz, feldspar and sticky modified rare earth nitrate with the mass ratio of 4:10:5:1 are added into deionized water with the amount of 2 times, and the modified rare earth antibacterial glaze is obtained after uniform mixing.
The rare earth ceramic cups prepared from the glaze products prepared in examples 1-3 and comparative examples 1-2 were tested for resistance to Escherichia coli and Staphylococcus aureus by the following method:
Activating escherichia coli and staphylococcus aureus to 1X 10 9 cfu/mL by using an LB culture medium, sucking 0.3: 0.3mL, dripping the activated escherichia coli and staphylococcus aureus into the bottom of an antibacterial ceramic cup containing different rare earth complexes ((RE@YH)), uniformly covering the bacteria liquid by using a sterile polyethylene film with the length of 40mm (length) and the width of 40mm (width) and the thickness of 10mm, transferring the ceramic cup into an incubator at 37 ℃ and 24: 24h after no air holes exist on the surface of the film. The film was then removed, repeatedly rinsed with 10 mLpH to 7.2 of 0.9% NaCl solution as eluent, and finally diluted 10 and 100 times with PBS buffer, each of which was aspirated 1: 1mL in a blank dish, poured into 20: 20mL of LB agar medium which was sterilized and cooled to 58℃and placed in an incubator after shaking uniformly at 37℃and 24: 24 h. After the culture is finished, colony counting is carried out, and a control group is LB solid culture medium plates which are respectively mixed with 10mL eluent and then poured for counting, wherein the temperature of the control group is 37 ℃ in an incubator, and the temperature of 0.3mL escherichia coli bacterial liquid and staphylococcus aureus bacterial liquid after 24h culture are respectively carried out. Antibacterial ratio = experimental colony count/control colony count.
As shown in fig. 1-12, the ceramic cups prepared from the glaze in example 1 had a bacteriostatic rate of 99.99% for both escherichia coli and staphylococcus aureus, and the ceramic cups prepared from the glazes in example 2 and example 3 had a bacteriostatic rate of 99.99% for both staphylococcus aureus, but had a bacteriostatic rate of less than 99% for escherichia coli. The ceramic cup prepared from the glaze in comparative example 1 has a bacteriostatic rate of less than 97% for escherichia coli and staphylococcus aureus, and the ceramic cup prepared from the antibacterial glaze prepared from the rare earth nitrate without chitosan modification lacks the effect of penetrating cell membranes efficiently, so that the bacteriostatic ability is lower than that of the ceramic cup prepared from the glaze in example 1. The ceramic cup prepared by the glaze in the comparative example 2 has the antibacterial rate of less than 97% on escherichia coli and staphylococcus aureus, and the obtained glaze cannot be synergistically reacted with zinc oxide without adding zinc oxide in the preparation process of the glaze, so that the antibacterial capability of the ceramic cup prepared by the glaze is lower than that of the ceramic cup prepared by the glaze in the example 1.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (7)
1. The modified rare earth antibacterial glaze is characterized by comprising the following raw materials, by weight, 3-5 parts of quartz, 9-11 parts of feldspar, 4-6 parts of clay and 1-2 parts of modified rare earth complex;
Adding ammonia water, absolute ethyl alcohol, modified rare earth nitrate and zinc oxide into deionized water, uniformly mixing to obtain a mixed solution, drying the mixed solution to obtain a solid sample, calcining, grinding and sanding the solid sample to obtain nano slurry, and drying and grinding the nano slurry to obtain the modified rare earth complex;
The solid-to-liquid ratio of the ammonia water, the absolute ethyl alcohol, the modified rare earth nitrate, the zinc oxide and the deionized water is 4-6:4-6:4-5:1-2:23-25, the mass concentration of the ammonia water is 25-28%, the sand grinding speed is 2500-3500 r/min, and the time is 3-4 hours;
the preparation method of the modified rare earth nitrate comprises the following steps:
step 1, adding rare earth nitrate into deionized water, and dissolving to obtain rare earth nitrate solution;
Step 2, adding chitosan into a citric acid solution, and dissolving to obtain a chitosan solution;
And 3, mixing the chitosan solution with the rare earth nitrate solution, regulating the pH value of the solution, adding sodium bicarbonate solution into the solution, and carrying out suction filtration, washing, drying and grinding on the white precipitate after the reaction is finished to obtain the modified rare earth nitrate.
2. The modified rare earth antibacterial glaze according to claim 1, wherein the temperature of the drying step is 80-150 ℃ for 12-18 hours, the temperature of the calcining step is 1200-1450 ℃ for 3-4.5 hours, and the particle size of the modified rare earth complex is 80-100 nm.
3. The modified rare earth antibacterial glaze according to claim 1, wherein the concentration of the rare earth nitrate solution in the step 1 is 0.5-0.7 mol/L, the mass concentration of the citric acid solution in the step 2 is 0.7-1.5%, and the solid-to-liquid ratio of chitosan to the citric acid solution in the step 2 is 1-1.5g:40-45 mL.
4. The modified rare earth antibacterial glaze according to claim 1, wherein the rare earth nitrate is at least one of cerium, lanthanum or yttrium nitrate.
5. The modified rare earth antibacterial glaze according to claim 1, wherein the volume ratio of the chitosan solution, the rare earth nitrate solution and the sodium bicarbonate solution in the step 3 is 3.5-4.5:0.5-1.5:2.0-3.0, and the mass concentration of the sodium bicarbonate solution in the step 3 is 30-40%.
6. The modified rare earth antibacterial glaze according to claim 1, wherein the pH value in the step 3 is 6.5-7.5, and the temperature in the drying step in the step 3 is 80-120 ℃ for 10-15 hours.
7. The method for preparing the modified rare earth antibacterial glaze as claimed in any one of claims 1 to 6, which is characterized by comprising the following steps of adding quartz, feldspar and adhesion modified rare earth complex into deionized water with the amount of 1.5 to 2.0 times, and uniformly mixing to obtain the modified rare earth antibacterial glaze.
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