CN113998996A - Mildew-proof antibacterial ceramic material and preparation method and application thereof - Google Patents
Mildew-proof antibacterial ceramic material and preparation method and application thereof Download PDFInfo
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 85
- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 40
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 36
- -1 rare earth ions Chemical class 0.000 claims abstract description 34
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000011787 zinc oxide Substances 0.000 claims abstract description 18
- 229940104869 fluorosilicate Drugs 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 13
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 10
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 9
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 9
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000010453 quartz Substances 0.000 claims abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011232 storage material Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 21
- 239000000919 ceramic Substances 0.000 claims description 18
- 238000000137 annealing Methods 0.000 claims description 17
- 238000001354 calcination Methods 0.000 claims description 13
- 239000000440 bentonite Substances 0.000 claims description 7
- 229910000278 bentonite Inorganic materials 0.000 claims description 7
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000010456 wollastonite Substances 0.000 claims description 7
- 229910052882 wollastonite Inorganic materials 0.000 claims description 7
- 229910004725 CaSiF6 Inorganic materials 0.000 claims description 6
- 239000005084 Strontium aluminate Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 5
- 229910052758 niobium Inorganic materials 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 229910003669 SrAl2O4 Inorganic materials 0.000 claims description 3
- UGTZMIPZNRIWHX-UHFFFAOYSA-K sodium trimetaphosphate Chemical compound [Na+].[Na+].[Na+].[O-]P1(=O)OP([O-])(=O)OP([O-])(=O)O1 UGTZMIPZNRIWHX-UHFFFAOYSA-K 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 230000000845 anti-microbial effect Effects 0.000 claims 1
- 241000894006 Bacteria Species 0.000 abstract description 7
- 230000001699 photocatalysis Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 230000001580 bacterial effect Effects 0.000 abstract 1
- 230000001954 sterilising effect Effects 0.000 abstract 1
- 238000004659 sterilization and disinfection Methods 0.000 abstract 1
- 230000008569 process Effects 0.000 description 11
- 239000003242 anti bacterial agent Substances 0.000 description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 150000002910 rare earth metals Chemical class 0.000 description 6
- 238000005286 illumination Methods 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002068 microbial inoculum Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
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- C04B2235/3427—Silicates other than clay, e.g. water glass
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Abstract
The invention provides a mildew-proof antibacterial ceramic material and a preparation method and application thereof, wherein the mildew-proof antibacterial ceramic material comprises the following components: fluorosilicate doped with at least four kinds of rare earth ions, nano titanium oxide, zinc oxide, long-afterglow light-storing material, kaolin, water reducing agent, reinforcing agent and quartz. The mildew-proof antibacterial ceramic material can realize a light storage function in the daytime or under the light condition by cooperatively adopting the fluosilicate doped with at least four rare earth ions and the long-afterglow light storage material, the fluosilicate doped with at least four rare earth ions can improve the effect of light on the nano titanium oxide, so that the mildew-proof antibacterial effect is improved, the long-afterglow light storage material emits light at night or in a dark environment to continuously promote the photocatalytic sterilization effect of the nano titanium oxide, the growth of bacterial mildew at night or in the dark condition is avoided, and the mildew-proof antibacterial ceramic material can be better applied to hospitals and other environments with higher requirements on mildew resistance and bacteria resistance.
Description
Technical Field
The invention relates to the technical field of ceramics, in particular to a mildew-proof antibacterial ceramic material and a preparation method and application thereof.
Background
The ceramic tile is generally applied to the environment of people, the surface of the ceramic tile always has dead angles for pollution and bacteria breeding, particularly, bacteria are easy to breed in places such as hospitals, micro pinholes which cannot be seen by naked eyes are formed in the surface of the ceramic tile, and when the ceramic tile is used for a long time, the bacteria are easy to accumulate and breed and even infect, so that the body health is seriously affected.
Therefore, the development of an antibacterial and mildewproof ceramic tile is particularly important.
The traditional antibacterial ceramic tile is prepared by directly adding an antibacterial agent into glaze and endowing the ceramic glaze with an antibacterial function, and most of the antibacterial agents are silver-series antibacterial agents.
CN110818261A discloses an antibacterial ceramic glaze, which comprises ceramic glaze, an antibacterial agent, a suspending agent and a debonding agent, wherein the antibacterial agent is a mixture of nano zirconium silicate silver and nano zinc oxide. The existing silver-based antibacterial agent exists in the form of nano silver particles in the antibacterial ceramic tile, however, the silver-based antibacterial agent is easy to cluster after being added into the ceramic raw material, and the antibacterial effect is poor.
CN106242525A discloses a nano-antibacterial ceramic tile and a preparation method thereof, wherein an antibacterial agent, a nano-silica sol, nano-silver, nano-titanium dioxide, a silane coupling agent, neodymium oxide, and cerium oxide are added in a formula, wherein the nano-silica sol is used as a carrier, and the silane coupling agent is used as a vector, so that the clustering phenomenon between the nano-silver and the nano-titanium dioxide is effectively reduced, but the problem that the nano-titanium oxide is difficult to realize antibacterial effect in a dark environment is not recognized.
CN112939458A discloses an antibacterial glaze for wall and floor tiles and a method for using the glaze, which is characterized in that titanium dioxide is modified and doped with relevant metal elements to make the titanium dioxide have antibacterial property in a visible light region, but the problem of the antibacterial property reduction of titanium dioxide in a dark environment is not recognized.
Therefore, there is a need to develop a new mildew-proof antibacterial ceramic material and related process.
Disclosure of Invention
In order to solve the technical problems, the invention provides a mildew-proof antibacterial ceramic material and a preparation method and application thereof, and solves the problem of poor antibacterial effect of nano-titanium oxide in a dark environment by compounding fluosilicate doped with at least four rare earth ions, nano-titanium oxide, zinc oxide and a long-afterglow light-storing material.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a mildew-proof antibacterial ceramic material, comprising: fluorosilicate doped with at least four kinds of RE ions, nanometer titania, zinc oxide and long afterglow light accumulating material.
The nano titanium dioxide antibacterial agent generally needs illumination condition to carry out photocatalysis antibacterial and mildew prevention, but bacteria and mildew are more easily bred in a dark environment, the problems of agglomeration and higher cost exist when the silver antibacterial agent is adopted, the mildew-proof antibacterial ceramic material provided by the invention can realize the light-storing and photocatalytic mildew-proof antibacterial effects under the illumination condition by compounding the materials, under the condition of darkness, the long afterglow light storage material releases the stored light and the nanometer titanium oxide generates mildew-proof and antibacterial action under photocatalysis when continuing, the fluosilicate doped with at least four rare earth ions can promote the photocatalysis effect of the nano titanium oxide in the dark environment, improve the antibacterial effect, and the addition of zinc oxide can improve the catalytic activity of the nano titanium oxide, and the components have synergistic effect with each other, so that the mildew-proof and antibacterial effects are improved, and the problem of mildew growth in a dark environment is solved.
Preferably, the mildew-proof antibacterial ceramic material comprises the following components in parts by weight:
the invention preferably selects the mass ratio of the mildew-proof antibacterial ceramic material as shown above, which is more favorable for exerting the synergistic effect of the four materials and improving the mildew-proof antibacterial effect under the dark condition.
Preferably, the rare earth ions comprise La3+、Eu3+、Tb3+、Y3+、Ce4+、Ho3+、Tb4+Or Nd3+In a typical but non-limiting combination of at least four of the above, wherein the combination is Tb3+、Y3+、La3+And Eu3+Combination of (1), Ho3+、Y3+、La3+And Eu3+Combination of (1), Tb3+、Ho3+、Tb4+And Eu3+Combination of (1), Tb3+、Y3+、La3+And Tb4+Combination of (1), Tb3+、Ho3+、Nd3+And Eu3+Combination of (1), Nd3+、Ho3+、Y3+、La3+And Eu3+Combinations of (a) and (b).
Preferably, the rare earth ions are 0.1 to 0.8% of the fluorosilicate in terms of oxide, for example, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, or 0.8%, but not limited to the recited values, and other values not recited in this range are also applicable.
Preferably, the fluorosilicate salt comprises CaSiF6。
The nano titanium oxide preferably has a particle size of 1 to 70nm, and may be, for example, 1nm, 10nm, 18nm, 25nm, 30nm, 40nm, 45nm, 55nm, 60nm or 70nm, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
Preferably, the long-afterglow light-storing material comprises Dy and Nb activated CaAl3O4、Sr4Al14O25Or SrAl2O4Any one or a combination of at least two of them. The long-afterglow light-storing material disclosed by the invention preferably adopts a silicate material activated by Dy and Nb, and the silicate material interacts with fluosilicate doped with at least four rare earth ions, so that the photocatalysis function of titanium dioxide can be realized in a dark environment, the growth of mould in the dark environment is avoided from the source, and the difficulty of mould prevention and antibiosis in the daytime is reduced.
Preferably, the mildew-proof antibacterial ceramic material further comprises kaolin, a water reducing agent, a reinforcing agent and quartz.
Preferably, the water reducing agent comprises sodium humate and/or sodium trimetaphosphate.
Preferably, the reinforcing agent comprises acicular wollastonite and bentonite. The combination of the reinforcing agent is preferable, so that better toughness can be provided for the ceramic, and the strength of the ceramic material can be better improved.
The mass ratio of the needle-like wollastonite to the bentonite is preferably 1:0.5 to 0.8, and may be, for example, 1:0.5, 1:0.65, 1:0.7, 1:0.75, 1:0.78 or 1:0.8, but is not limited to the above-mentioned values, and other values not mentioned in this range are also applicable. The proportion of the reinforcing agent is optimized, so that the strength of the ceramic material can be improved better.
Preferably, the mildew-proof antibacterial ceramic material comprises the following components in parts by weight:
in the present invention, the amount of the fluorosilicate doped with at least four rare earth ions is 1 to 15 parts, for example, 1 part, 3 parts, 5 parts, 6 parts, 8 parts, 9 parts, 11 parts, 12 parts, 14 parts, or 15 parts, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
The amount of the nano titanium oxide is, for example, 0.15 to 0.3 parts, and may be, for example, 0.15 parts, 0.17 parts, 0.19 parts, 0.2 parts, 0.22 parts, 0.24 parts, 0.25 parts, 0.27 parts, 0.29 parts, or 0.3 parts, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
The zinc oxide may be 2.3 to 10 parts, for example, 2.3 parts, 3.2 parts, 4.1 parts, 4.9 parts, 5.8 parts, 6.6 parts, 7.5 parts, 8.3 parts, 9.2 parts, or 10 parts, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
The amount of the long-afterglow light-storing material is, for example, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts or 15 parts, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
The kaolin is 10 to 25 parts, for example, 10 parts, 12 parts, 14 parts, 15 parts, 17 parts, 19 parts, 20 parts, 22 parts, 24 parts or 25 parts, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
The amount of the water reducing agent is 2 to 5 parts, for example, 2 parts, 2.4 parts, 2.7 parts, 3 parts, 3.4 parts, 3.7 parts, 4 parts, 4.4 parts, 4.7 parts or 5 parts, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
The amount of the reinforcing agent is 5 to 10 parts, for example, 5 parts, 5.6 parts, 6.2 parts, 6.7 parts, 7.3 parts, 7.8 parts, 8.4 parts, 8.9 parts, 9.5 parts or 10 parts, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
The quartz may be, for example, 50 parts, 52 parts, 53 parts, 54 parts, 55 parts, 56 parts, 57 parts, 58 parts, 59 parts or 60 parts, but is not limited to the above-mentioned values, and other values not shown in the above range are also applicable.
In a second aspect, the present invention provides a method for preparing the mildewproof and antibacterial ceramic material according to the first aspect, comprising:
(1) mixing oxide doped with at least four rare earth ions and fluorosilicate, melting, granulating, primary annealing and cooling to obtain the fluorosilicate doped with at least four rare earth ions;
(2) and mixing the fluosilicate doped with at least four rare earth ions, nano titanium oxide, zinc oxide, the long afterglow light storage material, kaolin, a water reducing agent, a reinforcing agent and quartz, calcining and carrying out secondary annealing to obtain the mildew-proof antibacterial ceramic material.
The mildew-proof antibacterial ceramic material provided by the invention is simple in preparation process and easy for industrial production, and the obtained mildew-proof antibacterial ceramic material is excellent in antibacterial effect.
The granulation in the above process is not particularly limited in the present invention, and any apparatus and method for granulation known to those skilled in the art may be used, and may be adjusted according to the actual process.
Preferably, the melting temperature in step (1) is 1300 to 1600 ℃, and may be 1300 ℃, 1334 ℃, 1367 ℃, 1400 ℃, 1434 ℃, 1467 ℃, 1500 ℃, 1534 ℃, 1567 ℃ or 1600 ℃, for example, but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the temperature of the primary annealing is 700 to 800 ℃, for example 700 ℃, 710 ℃, 720 ℃, 735 ℃, 745 ℃, 755 ℃, 760 ℃, 770 ℃, 780 ℃, or 800 ℃, but is not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the time of the primary annealing is 20 to 40min, for example, 20min, 23min, 25min, 27min, 29min, 32min, 34min, 36min, 38min or 40min, but is not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the cooling is to room temperature.
Preferably, the calcination in step (2) is a temperature programmed calcination.
Preferably, the final temperature of the calcination is 1000 to 1300 ℃, for example, 1000 ℃, 1030 ℃, 1060 ℃, 1100 ℃, 1130 ℃, 1160 ℃, 1200 ℃, 1230 ℃, 1260 ℃, 1300 ℃ or the like, but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the heating rate of the calcination is 3 to 5 ℃/min, for example, 3 ℃/min, 3.3 ℃/min, 3.5 ℃/min, 3.7 ℃/min, 3.9 ℃/min, 4.2 ℃/min, 4.4 ℃/min, 4.6 ℃/min, 4.8 ℃/min, or 5 ℃/min, etc., but is not limited to the values listed, and other values not listed in the range are also applicable.
Preferably, the temperature of the secondary annealing is 500 to 600 ℃, for example, 500 ℃, 510 ℃, 520 ℃, 530 ℃, 540 ℃, 550 ℃, 560 ℃, 570 ℃, 580 ℃ or 600 ℃, but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the time of the secondary annealing is 30 to 90min, for example, 30min, 35min, 45min, 50min, 55min, 60min, 70min, 75min, 80min or 90min, but not limited to the recited values, and other values not recited in the range are also applicable. The invention further optimizes the process parameters and has better effects on the aspects of mechanical strength, antibiosis and mildew resistance.
In a third aspect, the present invention provides a use of the mould-proof antibacterial ceramic material according to the first aspect in medical ceramics.
The mildew-proof antibacterial ceramic material provided by the first aspect of the invention can be better applied to medical environment due to the fact that the problem of germ growth at night or in a dark environment can be solved.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) the mildew-proof antibacterial ceramic material provided by the invention combines nano titanium oxide and zinc oxide to improve the catalytic effect of titanium oxide, and utilizes fluorosilicate doped with at least four rare earth ions and a long afterglow light storage material to realize the mildew-proof antibacterial effect of a titanium oxide microbial inoculum in a dark or dark environment, and can be better applied to a medical environment, and a test result of placing the material in the dark environment for 12 hours after 6 hours under an illumination condition shows that the antibacterial rate of escherichia coli is more than 90%, preferably more than 99%, and the antibacterial rate of staphylococcus aureus is more than 93%, preferably more than 99%;
(2) the preparation method of the mildew-proof antibacterial ceramic material provided by the invention is simple in process flow and easy for industrial production.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a mildew-proof antibacterial ceramic material, which comprises the following components in parts by mass:
the particle size of the nano titanium oxide is 20-70 nm, and the CaSiF is doped with rare earth ions6The medium rare earth ion is La3+、Eu3+、Tb3+And Y3+(the molar ratio is 1:1:1:1), and the total amount of rare earth ions accounts for 0.5 percent of the fluosilicate according to the oxide.
The embodiment also provides a preparation method of the mildew-proof antibacterial ceramic material, which comprises the following steps:
(1) mixed oxide doped with four rare earth ions and CaSiF6Melting at 1400 deg.C, granulatingAnnealing for 30min at 750 ℃ for one time and cooling to room temperature to obtain the fluosilicate doped with the four rare earth ions;
(2) and mixing the fluosilicate doped with the four rare earth ions, the nano titanium oxide, the zinc oxide, the long afterglow light storage material, the kaolin, the sodium trimetaphosphate, the needle-shaped wollastonite, the bentonite and the quartz, heating to 1200 ℃ at the speed of 3.5 ℃/min, calcining for 80min, and carrying out secondary annealing at the temperature of 550 ℃ for 60min to obtain the mildew-proof antibacterial ceramic material.
Example 2
The embodiment provides a mildew-proof antibacterial ceramic material, which comprises the following components in parts by mass:
the particle size of the nano titanium oxide is 20-65 nm, and the CaSiF is doped with rare earth ions6The medium rare earth ion is La3+、Ho3+、Ce4+And Eu3+(the molar ratio is 1:1:1:1), and the total amount of rare earth ions accounts for 0.8% of the fluosilicate according to the oxide.
The embodiment also provides a preparation method of the mildew-proof antibacterial ceramic material, which comprises the following steps:
(1) mixed oxide doped with four rare earth ions and CaSiF6Melting at 1600 ℃, granulating, annealing for 40min at 800 ℃ for one time, and cooling to room temperature to obtain the fluosilicate doped with four rare earth ions;
(2) mixing the four rare earth ion doped fluorosilicate, nano titanium oxide, zinc oxide, Dy and Nb activated Sr4Al14O25The mildew-proof antibacterial ceramic material is prepared by the steps of heating powder, kaolin, sodium humate, needle-shaped wollastonite, bentonite and quartz at the temperature of 5 ℃/min to 1300 ℃, calcining for 120min and secondarily annealing at the temperature of 500 ℃ for 30 min.
Example 3
The embodiment provides a mildew-proof antibacterial ceramic material, which comprises the following components in parts by mass:
the particle size of the nano titanium oxide is 10-55 nm, and the CaSiF is doped with rare earth ions6The medium rare earth ion is La3+、Eu3+、Ho3+、Tb3+And Nd3+(the molar ratio is 1:1:1:1:1), and the total amount of rare earth ions accounts for 0.1% of the fluosilicate in terms of oxides.
The embodiment also provides a preparation method of the mildew-proof antibacterial ceramic material, which comprises the following steps:
(1) mixed oxide doped with four rare earth ions and CaSiF6Melting at 1300 ℃, granulating, annealing for 20min at 700 ℃ for one time, and cooling to room temperature to obtain the fluosilicate doped with four rare earth ions;
(2) mixing the four rare earth ion doped fluosilicate, nano titanium oxide, zinc oxide, Dy and Nb activated SrAl2O4The mildew-proof antibacterial ceramic material is prepared from powder, kaolin, sodium humate, needle-shaped wollastonite, bentonite and quartz, wherein the temperature is increased to 1000 ℃ at a rate of 3 ℃/min, the calcination is carried out for 60min, and the secondary annealing is carried out for 90min at a temperature of 600 ℃ to obtain the mildew-proof antibacterial ceramic material.
Example 4
This example provides a mildew-resistant antibacterial ceramic material, which is prepared by removing CaSiF doped with four rare earth ions6The procedure was as in example 1 except that the amount was 0.5 part.
Example 5
This example provides a mildew-resistant antibacterial ceramic material doped withFour rare earth ions of CaSiF6The procedure was as in example 1 except that the amount was 20 parts.
Example 6
This example provides a mildew-proof and antibacterial ceramic material, which is the same as that in example 1 except that 1 part of zinc oxide is used.
Example 7
This example provides a mildew-proof and antibacterial ceramic material, which is the same as that in example 1 except that 12 parts of zinc oxide is used.
Comparative example 1
The comparative example provides a mildew-proof antibacterial ceramic material, which is prepared by removing CaAl activated without Dy and Nb3O4The procedure of example 1 was repeated except for the powder.
Comparative example 2
This comparative example provides a mold-proof and antibacterial ceramic material, which is the same as example 1 except that zinc oxide is not added.
Comparative example 3
The comparative example provides a mildew-resistant antibacterial ceramic material without adding CaSiF doped with four rare earth ions6Otherwise, the same procedure as in example 1 was repeated.
The test method comprises the following steps: the detection is carried out according to JC/T897-2014 antibacterial performance of antibacterial ceramic products, the difference is that the antibacterial ceramic products are placed under the illumination condition for 6 hours and then placed in the dark environment for 12 hours, and finally, the antibacterial rate is counted, and the result is shown in Table 1.
TABLE 1
From table 1, the following points can be seen:
(1) the comprehensive examples 1-3 show that the mildew-proof antibacterial ceramic material provided by the invention still has excellent antibacterial effect in dark environment, and the antibacterial rate is over 99%;
(2) as can be seen by combining examples 1 and 4 to 5, CaSiF doped with four rare earth ions6The addition amount of (A) has a great influence on the antibacterial performance of the final product, and the antibacterial effect is further improved by optimizing a specific range;
(3) it can be seen from the comprehensive examples 1 and 6 to 7 that the addition amount of the zinc oxide in example 1 is 5 parts, and compared with 1 part and 12 parts of examples 6 to 7, the antibacterial effect of example 1 is better than that of examples 6 to 7, thereby showing that the antibacterial effect is further improved by preferably selecting the proportion of the zinc oxide and other components;
(4) it can be seen from the comprehensive examples 1 and comparative examples 1 to 3 that the components have a synergistic antibacterial effect, and the synergistic cooperation of the components achieves an excellent antibacterial effect in a dark environment.
In conclusion, the mildew-proof antibacterial ceramic material provided by the invention can effectively avoid the growth of bacteria and mold at night or under dark conditions, and can be better applied to environments with higher requirements on mildew resistance and bacteria resistance, such as hospitals and the like.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A mold-proof and antibacterial ceramic material, comprising: fluorosilicate doped with at least four kinds of RE ions, nanometer titania, zinc oxide and long afterglow light accumulating material.
2. The mold-proof, antimicrobial ceramic material of claim 1, wherein the rare earth ions comprise La3+、Eu3+、Tb3+、Y3+、Ce4+、Ho3+、Tb4+Or Nd3+Combinations of at least four of the above.
3. A mould-proof and antibacterial ceramic material as claimed in claim 1 or 2, wherein the rare earth ions account for 0.1-0.8% of the fluorosilicate calculated as oxide;
preferably, the fluorosilicate salt comprises CaSiF6。
4. The mildew-proof and antibacterial ceramic material as claimed in any one of claims 1 to 3, wherein the nano titanium oxide has a particle size of 1 to 70 nm.
5. The mildew-proof and antibacterial ceramic material as claimed in any one of claims 1 to 4, wherein the long-afterglow light-storing material comprises Dy and Nb activated CaAl3O4、Sr4Al14O25Or SrAl2O4Any one or a combination of at least two of them.
6. The mildew-proof and antibacterial ceramic material as claimed in any one of claims 1 to 5, further comprising kaolin, a water reducing agent, a reinforcing agent and quartz;
preferably, the water reducing agent comprises sodium humate and/or sodium trimetaphosphate;
preferably, the reinforcing agent comprises acicular wollastonite and bentonite;
preferably, the mass ratio of the needle-shaped wollastonite to the bentonite is 1: 0.5-0.8.
7. The mildew-proof antibacterial ceramic material of claim 6, which comprises the following components in parts by weight:
8. a method for preparing the mildew-proof and antibacterial ceramic material according to any one of claims 1 to 7, wherein the method comprises the following steps:
(1) mixing oxide doped with at least four rare earth ions and fluorosilicate, melting, granulating, primary annealing and cooling to obtain the fluorosilicate doped with at least four rare earth ions;
(2) and mixing the fluosilicate doped with at least four rare earth ions, nano titanium oxide, zinc oxide, the long afterglow light storage material, kaolin, a water reducing agent, a reinforcing agent and quartz, calcining and carrying out secondary annealing to obtain the mildew-proof antibacterial ceramic material.
9. The method according to claim 9, wherein the melting temperature in the step (1) is 1300-1600 ℃;
preferably, the temperature of the primary annealing is 700-800 ℃;
preferably, the time of the primary annealing is 20-40 min;
preferably, the cooling is to room temperature;
preferably, the calcination in step (2) is temperature programmed calcination;
preferably, the final temperature of the calcination is 1000-1300 ℃;
preferably, the temperature rise rate of the calcination is 3-5 ℃/min;
preferably, the temperature of the secondary annealing is 500-600 ℃;
preferably, the time of the secondary annealing is 30-90 min.
10. Use of the mildew-resistant antibacterial ceramic material according to any one of claims 1 to 7 in medical ceramics.
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