CN116639876A - Antibacterial ceramic glaze and preparation method and application thereof - Google Patents
Antibacterial ceramic glaze and preparation method and application thereof Download PDFInfo
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- CN116639876A CN116639876A CN202310710602.5A CN202310710602A CN116639876A CN 116639876 A CN116639876 A CN 116639876A CN 202310710602 A CN202310710602 A CN 202310710602A CN 116639876 A CN116639876 A CN 116639876A
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- 239000000919 ceramic Substances 0.000 title claims abstract description 94
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 76
- ZZBBCSFCMKWYQR-UHFFFAOYSA-N copper;dioxido(oxo)silane Chemical compound [Cu+2].[O-][Si]([O-])=O ZZBBCSFCMKWYQR-UHFFFAOYSA-N 0.000 claims abstract description 53
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 44
- 239000000654 additive Substances 0.000 claims abstract description 41
- 230000000996 additive effect Effects 0.000 claims abstract description 41
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 29
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000004005 microsphere Substances 0.000 claims abstract description 26
- 229910052623 talc Inorganic materials 0.000 claims abstract description 14
- 239000004927 clay Substances 0.000 claims abstract description 13
- 239000010433 feldspar Substances 0.000 claims abstract description 13
- 235000012222 talc Nutrition 0.000 claims abstract description 13
- 239000000454 talc Substances 0.000 claims abstract description 13
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 12
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 12
- 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 12
- 239000010453 quartz Substances 0.000 claims abstract description 12
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 82
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 58
- 238000006243 chemical reaction Methods 0.000 claims description 41
- 239000008367 deionised water Substances 0.000 claims description 41
- 229910021641 deionized water Inorganic materials 0.000 claims description 41
- 238000002156 mixing Methods 0.000 claims description 41
- 239000000203 mixture Substances 0.000 claims description 41
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 238000000498 ball milling Methods 0.000 claims description 22
- 238000005303 weighing Methods 0.000 claims description 22
- 239000000377 silicon dioxide Substances 0.000 claims description 20
- FTXJFNVGIDRLEM-UHFFFAOYSA-N copper;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O FTXJFNVGIDRLEM-UHFFFAOYSA-N 0.000 claims description 19
- 238000005245 sintering Methods 0.000 claims description 19
- 230000000845 anti-microbial effect Effects 0.000 claims description 18
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 17
- 238000000576 coating method Methods 0.000 claims description 16
- 239000011248 coating agent Substances 0.000 claims description 15
- 239000012265 solid product Substances 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 14
- FQERWQCDIIMLHB-UHFFFAOYSA-N 1-ethyl-3-methyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].CC[NH+]1CN(C)C=C1 FQERWQCDIIMLHB-UHFFFAOYSA-N 0.000 claims description 12
- 239000005543 nano-size silicon particle Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 10
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 10
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 10
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 10
- 239000004599 antimicrobial Substances 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 239000007791 liquid phase Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000007872 degassing Methods 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 238000000265 homogenisation Methods 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 239000002585 base Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims 14
- 239000007864 aqueous solution Substances 0.000 claims 3
- 238000009832 plasma treatment Methods 0.000 claims 1
- 229910010293 ceramic material Inorganic materials 0.000 abstract description 6
- 230000007774 longterm Effects 0.000 abstract description 2
- 230000001681 protective effect Effects 0.000 abstract description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 239000003242 anti bacterial agent Substances 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 230000001580 bacterial effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 229910052656 albite Inorganic materials 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- -1 silver ions Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
-
- 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
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5022—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with vitreous 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Structural Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention relates to an antibacterial ceramic glaze and a preparation method and application thereof, wherein the antibacterial ceramic glaze comprises a basic glaze and an antibacterial additive in a mass ratio of 100:3-8; the basic glaze comprises the following components in parts by weight: 28-35 parts of feldspar, 14-20 parts of quartz, 1.2-6.8 parts of talcum, 8-12 parts of kaolin and 2.5-5 parts of clay; the antibacterial additive is aluminum diboride and porous copper silicate microspheres. The invention designs a novel antibacterial ceramic glaze, which comprises a basic glaze and an antibacterial additive, wherein the basic glaze is feldspar quartz, talcum, kaolin and clay, the antibacterial additive is aluminum diboride and porous copper silicate, and the ceramic glaze finally obtained by reasonable component proportion has strong antibacterial property and high surface strength and can play a long-term protective role on ceramic materials.
Description
Technical Field
The invention relates to the field of ceramic materials, in particular to an antibacterial ceramic glaze and a preparation method and application thereof.
Background
Ceramic art has been a major consideration in thousands of years of brilliant art culture in china. In ceramic art, the glaze is a key part of the ceramic art. In general, a so-called ceramic frit is a thin, uniform layer of glass that covers the surface of a ceramic body. For ceramic products, the ceramic glaze can improve the service performance, play a decorative role and the like. In the existing building decoration materials such as wall bricks, ceramic glaze with stable antibacterial function, which has better uniformity, is reported, if antibacterial agent is simply added, the antibacterial stability is weakened and even the antibacterial effect is possibly lost due to the high-temperature melting process.
At present, metal ions with the function of inhibiting bacterial growth and reproduction or destroying bacterial cell tissue structure are added into ceramic materials, and silver ions, copper ions, zinc ions and rare earth metals are commonly used, or a coating with the function of sterilizing under the action of ultraviolet rays is added on the surface of the materials. However, the components of the metal ion antibacterial agents are complex, the structural damage is easy to occur in the high-temperature sintering process, so that the antibacterial capability of the metal ion antibacterial agents is reduced, the original properties of the products are affected, and the common silver ion antibacterial agents are easy to oxidize and change color; titanium dioxide is often used in photosensitive ultraviolet coatings, the materials are greatly limited by illumination, and particularly titanium dioxide distributed on the surface of the antibacterial ceramic of the titanium-doped glaze is relatively less, and most of titanium dioxide is converted into rutile type with poor photocatalytic activity after high-temperature firing, so that the antibacterial effect is greatly affected.
Therefore, there is a need for a ceramic glaze that has a good antimicrobial effect and can protect ceramic materials well.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention aims to provide an antibacterial ceramic glaze and a preparation method and application thereof.
The aim of the invention is realized by adopting the following technical scheme:
in a first aspect, the invention provides an antibacterial ceramic glaze, which comprises a basic glaze and an antibacterial additive in parts by weight, wherein the mass ratio of the basic glaze to the antibacterial additive is 100:3-8; the basic glaze comprises the following components in parts by weight:
28-35 parts of feldspar, 14-20 parts of quartz, 1.2-6.8 parts of talcum, 8-12 parts of kaolin and 2.5-5 parts of clay.
Preferably, the particle size of the base glaze is 50-100 μm.
Preferably, the antibacterial additive is aluminum diboride & porous copper silicate microsphere with particle size of 1-5 μm.
Preferably, the preparation method of the antibacterial additive comprises the following steps:
(1) Preparing porous copper silicate microspheres:
s1, weighing copper nitrate hexahydrate and deionized water, mixing, and completely dissolving the copper nitrate hexahydrate and the deionized water, wherein the copper nitrate solution; wherein the mass ratio of the copper nitrate hexahydrate to the deionized water is 3.2-4.8:30-50;
weighing nano silicon dioxide and deionized water, mixing, and forming a silicon dioxide solution after ultrasonic treatment is uniform; wherein the mass ratio of the nano silicon dioxide to the deionized water is 1:20-40;
s2, dropwise adding ammonia water into a copper nitrate solution to adjust the pH value of the reaction solution to be 11-12, then mixing the reaction solution with a silicon dioxide solution, stirring the mixture at room temperature for 1-2 hours, pouring the reaction solution into a reaction kettle, performing constant temperature treatment at 110-150 ℃ for 10-15 hours, filtering out solids, washing the solids to be neutral by using pure water, washing the solids by using ethanol for three times, and performing vacuum drying to obtain porous copper silicate microspheres; wherein the mass ratio of the copper nitrate solution to the silicon dioxide solution is 1.2-1.4:1;
(2) Preparing aluminum diboride & porous copper silicate microspheres:
s3, weighing aluminum chloride, mixing the aluminum chloride with 1-ethyl-3-methylimidazole chloride salt, and uniformly stirring under the protection effect to form an aluminum chloride solution;
wherein the mass ratio of the aluminum chloride to the 1-ethyl-3-methylimidazole chloride salt is 0.52-0.78:17-23;
s4, adding porous copper silicate into the aluminum chloride solution, introducing inert gas as a shielding gas, introducing diborane, and pouring into a reaction kettle after ultrasonic homogenization;
wherein the mass ratio of the porous copper silicate to the aluminum chloride solution is 1:10-15; the mass ratio of diborane to aluminum chloride in the aluminum chloride solution is 1.1-1.2:1;
s5, treating the reaction kettle with liquid phase microwave discharge plasma at room temperature, wherein the treatment power is 500-600W, the treatment time is 30-50min, centrifuging and collecting solid products after the reaction is finished, washing the solid products sequentially with distilled water and ethanol, and drying the solid products in vacuum to obtain pretreated products;
s6, placing the pretreated product into a tube furnace for sintering treatment, wherein the sintering temperature is 700-800 ℃, and naturally cooling to obtain aluminum diboride and porous copper silicate.
In a second aspect, the invention provides a method for preparing an antimicrobial ceramic glaze, comprising:
firstly, weighing all components of a basic glaze according to parts by weight, mixing the components into deionized water, adding sodium carboxymethyl cellulose, and fully mixing to form a first ceramic mixture;
secondly, adding the antibacterial additive into the first ceramic mixture, fully mixing again, and then placing the mixture in a ball mill for ball milling treatment to obtain a second ceramic mixture;
and thirdly, coating the second ceramic mixture on the ceramic blank, and performing high-temperature sintering to form the antibacterial ceramic glaze on the ceramic blank.
Preferably, in the first step, the addition amount of deionized water is 50% -80% of the total weight of the basic glaze, and the addition amount of sodium carboxymethyl cellulose is 0.5% -1% of the total weight of the basic glaze.
Preferably, in the second step, during the ball milling treatment, the ball material ratio is 6-8:1, the ball milling speed is 400-600rpm, the ball milling time is 4-6h, and the water content of the second ceramic mixture is adjusted to be 35-40% after the ball milling is finished.
Preferably, in the third step, a degassing treatment is required before the second ceramic mixture is coated, and the coating thickness is 200-500 μm.
Preferably, in the third step, the high temperature sintering temperature is raised to 350-400 ℃ for sintering for 5-10min, then raised to 700-800 ℃ for sintering for 10-20min, and then raised to 1100-1200 ℃ for sintering for 3-5min.
In a third aspect, the present invention provides the use of an antimicrobial ceramic glaze in an antimicrobial ceramic tile or antimicrobial ceramic ware.
The beneficial effects of the invention are as follows:
1. the invention designs a novel antibacterial ceramic glaze, which comprises a basic glaze and an antibacterial additive, wherein the basic glaze is feldspar quartz, talcum, kaolin and clay, the antibacterial additive is aluminum diboride and porous copper silicate, and the ceramic glaze finally obtained by reasonable component proportion has strong antibacterial property and high surface strength and can play a long-term protective role on ceramic materials.
2. According to the invention, the antibacterial additive is prepared by self, copper silicate with a porous structure is obtained by hydrothermal reaction of copper salt and silicon dioxide under the action of ammonia water, and then aluminum salt and diborane are reacted under the action of ionic liquid 1-ethyl-3-methylimidazole chloride salt in a mode of utilizing liquid phase microwave discharge plasma to generate aluminum diboride with a two-dimensional structure in situ on the surface and in a pore canal of the porous copper silicate, so that the porous copper silicate coated with the aluminum diboride is obtained.
3. In the antibacterial additive prepared by the invention, the substrate copper silicate or the coating aluminum diboride has a good antibacterial effect, and the aluminum diboride is formed on the surface or in a pore canal of the copper silicate, so that the high temperature resistance of the copper silicate is improved, and the antibacterial effect of the copper silicate is enhanced. The invention detects that compared with the single addition of aluminum diboride, copper silicate or the mixture of the aluminum diboride and the copper silicate, the composite microsphere not only has better antibacterial property, but also has better improvement on the strength and the wear resistance of ceramic glaze, can protect ceramic materials for a long time,
Detailed Description
The technical features, objects and advantages of the present invention will be more clearly understood from the following detailed description of the technical aspects of the present invention, but should not be construed as limiting the scope of the invention.
Clay is
The invention is further described with reference to the following examples.
Example 1
The antibacterial ceramic glaze comprises a basic glaze and an antibacterial additive in a mass ratio of 100:5, wherein the basic glaze comprises a base glaze and the antibacterial additive in parts by weight; the basic glaze comprises the following components in parts by weight:
32 parts of feldspar, 18 parts of quartz, 3.4 parts of talcum, 10 parts of kaolin and 3.5 parts of clay.
The feldspar is albite, and the content (weight) of the feldspar comprises: siO (SiO) 2 :64.8％，Al 2 O 3 :18.4％，Na 2 O:16.6% and the balance of impurities.
The purity of quartz is more than 98%; the talcum is ordinary silicate talcum and comprises Mg 3 Si 4 O 10 (OH) 2 The method comprises the steps of carrying out a first treatment on the surface of the The purity of the kaolin is more than 98 percent.
The clay has a composition (by weight) of SiO 2 :48.1％、A1 2 O 3 :22.4％、K 2 O2.4% and TiO 2 1.1 percent of water and impurities in balance.
The grain size of the basic glaze is 50-100 mu m, the antibacterial additive is aluminum diboride and porous copper silicate microsphere, and the grain size is 1-5 mu m.
The preparation method of the antibacterial additive comprises the following steps:
s1, weighing copper nitrate hexahydrate and deionized water, mixing, and completely dissolving the copper nitrate hexahydrate and the deionized water, wherein the copper nitrate solution; wherein, the mass ratio of the hexahydrate copper nitrate to the deionized water is 3.6:40;
weighing nano silicon dioxide and deionized water, mixing, and forming a silicon dioxide solution after ultrasonic treatment is uniform; wherein the mass ratio of the nano silicon dioxide to the deionized water is 1:30;
s2, dropwise adding ammonia water into a copper nitrate solution to adjust the pH value of the reaction solution to be 11-12, then mixing the reaction solution with a silicon dioxide solution, stirring the mixture at room temperature for 1.5 hours, pouring the reaction solution into a reaction kettle, performing constant temperature treatment at 120 ℃ for 12 hours, filtering out solids, washing the solids to be neutral by using pure water, washing the solids by using ethanol for three times, and performing vacuum drying to obtain porous copper silicate microspheres; wherein the mass ratio of the copper nitrate solution to the silicon dioxide solution is 1.3:1;
s3, weighing aluminum chloride, mixing the aluminum chloride with 1-ethyl-3-methylimidazole chloride salt, and uniformly stirring under the protection effect to form an aluminum chloride solution;
wherein the mass ratio of the aluminum chloride to the 1-ethyl-3-methylimidazole chloride salt is 0.63:20;
s4, adding porous copper silicate into the aluminum chloride solution, introducing inert gas as a shielding gas, introducing diborane, and pouring into a reaction kettle after ultrasonic homogenization;
wherein the mass ratio of the porous copper silicate to the aluminum chloride solution is 1:12; the mass ratio of diborane to aluminum chloride in the aluminum chloride solution is 1.1:1;
s5, treating the reaction kettle with liquid phase microwave discharge plasma at room temperature, wherein the treatment power is 550W, the treatment time is 40min, centrifuging and collecting solid products after the reaction is finished, washing the solid products sequentially with distilled water and ethanol, and drying the solid products in vacuum to obtain a pretreated product;
s6, placing the pretreated product into a tube furnace for sintering treatment, wherein the sintering temperature is 750 ℃, and naturally cooling to obtain aluminum diboride and porous copper silicate.
The preparation method of the antibacterial ceramic glaze comprises the following steps:
firstly, weighing all components of a basic glaze according to parts by weight, mixing the components into deionized water, adding sodium carboxymethyl cellulose, and fully mixing to form a first ceramic mixture; the addition amount of deionized water is 60% of the total weight of the basic glaze, and the addition amount of sodium carboxymethyl cellulose is 0.8% of the total weight of the basic glaze.
Secondly, adding the antibacterial additive into the first ceramic mixture, fully mixing again, and then placing the mixture in a ball mill for ball milling treatment, wherein the ball material ratio is 7:1, the ball milling speed is 500rpm, the ball milling time is 5 hours, and the water content is adjusted to 40% after ball milling is finished to obtain a second ceramic mixture;
thirdly, coating the second ceramic mixture on a ceramic blank, wherein degassing treatment is needed before coating, the coating thickness is 350 mu m, and the ceramic blank is sintered at high temperature, namely, the ceramic blank is heated to 350 ℃ for 8min, then heated to 750 ℃ for 15min, and finally heated to 1150 ℃ for 4min, so that the antibacterial ceramic glaze is formed on the ceramic blank.
Example 2
The antibacterial ceramic glaze comprises a basic glaze and an antibacterial additive in a mass ratio of 100:3; the basic glaze comprises the following components in parts by weight:
28 parts of feldspar, 14 parts of quartz, 1.2 parts of talcum, 8 parts of kaolin and 2.5 parts of clay.
The grain size of the basic glaze is 50-100 mu m, the antibacterial additive is aluminum diboride and porous copper silicate microsphere, and the grain size is 1-5 mu m.
The preparation method of the antibacterial additive comprises the following steps:
s1, weighing copper nitrate hexahydrate and deionized water, mixing, and completely dissolving the copper nitrate hexahydrate and the deionized water, wherein the copper nitrate solution; wherein, the mass ratio of the hexahydrate copper nitrate to the deionized water is 3.2:30;
weighing nano silicon dioxide and deionized water, mixing, and forming a silicon dioxide solution after ultrasonic treatment is uniform; wherein the mass ratio of the nano silicon dioxide to the deionized water is 1:20;
s2, dropwise adding ammonia water into a copper nitrate solution to adjust the pH value of the reaction solution to be 11-12, then mixing the reaction solution with a silicon dioxide solution, stirring the mixture at room temperature for 1h, pouring the reaction solution into a reaction kettle, performing constant temperature treatment at 110 ℃ for 10h, filtering out solids, washing the solids to be neutral by using pure water, washing the solids by using ethanol for three times, and performing vacuum drying to obtain porous copper silicate microspheres; wherein the mass ratio of the copper nitrate solution to the silicon dioxide solution is 1.2:1;
s3, weighing aluminum chloride, mixing the aluminum chloride with 1-ethyl-3-methylimidazole chloride salt, and uniformly stirring under the protection effect to form an aluminum chloride solution;
wherein the mass ratio of the aluminum chloride to the 1-ethyl-3-methylimidazole chloride salt is 0.52:17;
s4, adding porous copper silicate into the aluminum chloride solution, introducing inert gas as a shielding gas, introducing diborane, and pouring into a reaction kettle after ultrasonic homogenization;
wherein the mass ratio of the porous copper silicate to the aluminum chloride solution is 1:10; the mass ratio of diborane to aluminum chloride in the aluminum chloride solution is 1.1:1;
s5, treating the reaction kettle with liquid phase microwave discharge plasma at room temperature, wherein the treatment power is 500W, the treatment time is 30min, centrifuging and collecting solid products after the reaction is finished, washing the solid products sequentially with distilled water and ethanol, and drying the solid products in vacuum to obtain a pretreated product;
s6, placing the pretreated product into a tube furnace for sintering treatment, wherein the sintering temperature is 700 ℃, and naturally cooling to obtain aluminum diboride and porous copper silicate.
The preparation method of the antibacterial ceramic glaze comprises the following steps:
firstly, weighing all components of a basic glaze according to parts by weight, mixing the components into deionized water, adding sodium carboxymethyl cellulose, and fully mixing to form a first ceramic mixture; the addition amount of deionized water is 50% of the total weight of the basic glaze, and the addition amount of sodium carboxymethyl cellulose is 0.5% of the total weight of the basic glaze.
Secondly, adding the antibacterial additive into the first ceramic mixture, fully mixing again, and then placing the mixture in a ball mill for ball milling treatment, wherein the ball material ratio is 6:1, the ball milling speed is 400rpm, the ball milling time is 4 hours, and the water content is adjusted to be 35% after ball milling is finished to obtain a second ceramic mixture;
thirdly, coating the second ceramic mixture on a ceramic blank, wherein degassing treatment is needed before coating, the coating thickness is 200 mu m, and the ceramic blank is sintered at high temperature, namely, the ceramic blank is heated to 350 ℃ for 5min, then heated to 700 ℃ for 10min, and finally heated to 1100 ℃ for 3min, so that the antibacterial ceramic glaze is formed on the ceramic blank.
Example 3
The antibacterial ceramic glaze comprises a basic glaze and an antibacterial additive in a mass ratio of 100:8; the basic glaze comprises the following components in parts by weight:
35 parts of feldspar, 20 parts of quartz, 6.8 parts of talcum, 12 parts of kaolin and 5 parts of clay.
The grain size of the basic glaze is 50-100 mu m, the antibacterial additive is aluminum diboride and porous copper silicate microsphere, and the grain size is 1-5 mu m.
The preparation method of the antibacterial additive comprises the following steps:
s1, weighing copper nitrate hexahydrate and deionized water, mixing, and completely dissolving the copper nitrate hexahydrate and the deionized water, wherein the copper nitrate solution; wherein, the mass ratio of the hexahydrate copper nitrate to the deionized water is 4.8:50;
weighing nano silicon dioxide and deionized water, mixing, and forming a silicon dioxide solution after ultrasonic treatment is uniform; wherein the mass ratio of the nano silicon dioxide to the deionized water is 1:40;
s2, dropwise adding ammonia water into a copper nitrate solution to adjust the pH value of the reaction solution to be 11-12, then mixing the reaction solution with a silicon dioxide solution, stirring the mixture at room temperature for 2 hours, pouring the reaction solution into a reaction kettle, performing constant temperature treatment at 150 ℃ for 15 hours, filtering out solids, washing the solids to be neutral by using pure water, washing the solids by using ethanol for three times, and performing vacuum drying to obtain porous copper silicate microspheres; wherein the mass ratio of the copper nitrate solution to the silicon dioxide solution is 1.4:1;
s3, weighing aluminum chloride, mixing the aluminum chloride with 1-ethyl-3-methylimidazole chloride salt, and uniformly stirring under the protection effect to form an aluminum chloride solution;
wherein the mass ratio of the aluminum chloride to the 1-ethyl-3-methylimidazole chloride salt is 0.78:23;
s4, adding porous copper silicate into the aluminum chloride solution, introducing inert gas as a shielding gas, introducing diborane, and pouring into a reaction kettle after ultrasonic homogenization;
wherein the mass ratio of the porous copper silicate to the aluminum chloride solution is 1:15; the mass ratio of diborane to aluminum chloride in the aluminum chloride solution is 1.2:1;
s5, treating the reaction kettle with liquid phase microwave discharge plasma at room temperature, wherein the treatment power is 600W, the treatment time is 50min, centrifuging and collecting solid products after the reaction is finished, washing the solid products sequentially with distilled water and ethanol, and drying the solid products in vacuum to obtain a pretreated product;
s6, placing the pretreated product into a tube furnace for sintering treatment, wherein the sintering temperature is 800 ℃, and naturally cooling to obtain aluminum diboride and porous copper silicate.
The preparation method of the antibacterial ceramic glaze comprises the following steps:
firstly, weighing all components of a basic glaze according to parts by weight, mixing the components into deionized water, adding sodium carboxymethyl cellulose, and fully mixing to form a first ceramic mixture; the addition amount of deionized water is 80% of the total weight of the basic glaze, and the addition amount of sodium carboxymethyl cellulose is 1% of the total weight of the basic glaze.
Secondly, adding the antibacterial additive into the first ceramic mixture, fully mixing again, and then placing the mixture in a ball mill for ball milling treatment, wherein the ball material ratio is 8:1, the ball milling speed is 600rpm, the ball milling time is 6 hours, and the water content is adjusted to 40% after ball milling is finished to obtain a second ceramic mixture;
thirdly, coating the second ceramic mixture on a ceramic blank, wherein degassing treatment is needed before coating, the coating thickness is 500 mu m, and the ceramic blank is sintered at high temperature, namely, the ceramic blank is heated to 400 ℃ for 10min, then heated to 800 ℃ for 20min, and finally heated to 1200 ℃ for 5min, so that the antibacterial ceramic glaze is formed on the ceramic blank.
Comparative example 1
An antimicrobial ceramic glaze differs from example 1 in that the antimicrobial additive is copper silicate microspheres.
The antibacterial glaze comprises a basic glaze and an antibacterial additive in a mass ratio of 100:5; the basic glaze comprises the following components in parts by weight:
32 parts of feldspar, 18 parts of quartz, 3.4 parts of talcum, 10 parts of kaolin and 3.5 parts of clay.
The antibacterial additive is copper silicate microsphere with particle diameter of 1-5 μm.
The preparation method of the antibacterial additive comprises the following steps:
s1, weighing copper nitrate hexahydrate and deionized water, mixing, and completely dissolving the copper nitrate hexahydrate and the deionized water, wherein the copper nitrate solution; wherein, the mass ratio of the hexahydrate copper nitrate to the deionized water is 3.6:40;
weighing nano silicon dioxide and deionized water, mixing, and forming a silicon dioxide solution after ultrasonic treatment is uniform; wherein the mass ratio of the nano silicon dioxide to the deionized water is 1:30;
s2, dropwise adding ammonia water into a copper nitrate solution to adjust the pH value of the reaction solution to be 11-12, then mixing the reaction solution with a silicon dioxide solution, stirring the mixture at room temperature for 1.5 hours, pouring the reaction solution into a reaction kettle, performing constant temperature treatment at 120 ℃ for 12 hours, filtering out solids, washing the solids to be neutral by using pure water, washing the solids by using ethanol for three times, and performing vacuum drying to obtain porous copper silicate microspheres; wherein the mass ratio of the copper nitrate solution to the silicon dioxide solution is 1.3:1.
Comparative example 2
An antimicrobial ceramic glaze differs from example 1 in that the antimicrobial additive is aluminum diboride powder.
The antibacterial glaze comprises a basic glaze and an antibacterial additive in a mass ratio of 100:5; the basic glaze comprises the following components in parts by weight:
32 parts of feldspar, 18 parts of quartz, 3.4 parts of talcum, 10 parts of kaolin and 3.5 parts of clay.
The antibiotic additive is aluminum diboride powder (directly purchased from market) with a particle size of 1-5 μm.
Comparative example 3
An antimicrobial ceramic glaze differs from example 1 in that the antimicrobial additive is a mixture of aluminum diboride powder and copper silicate microspheres.
The antibacterial glaze comprises a basic glaze and an antibacterial additive in a mass ratio of 100:5; the basic glaze comprises the following components in parts by weight:
32 parts of feldspar, 18 parts of quartz, 3.4 parts of talcum, 10 parts of kaolin and 3.5 parts of clay.
The antibacterial additive is a mixture of aluminum diboride powder and copper silicate microspheres, and the particle size is 1-5 mu m.
The preparation method of the copper silicate microspheres is the same as that of comparative example 1, aluminum diboride powder is directly purchased from the market, and the mass ratio of the aluminum diboride powder to the copper silicate microspheres is 0.51:1.
Experimental example
The performance of the antibacterial ceramic glaze prepared in the example 1 and the comparative examples 1-3 is tested, and the test of the friction coefficient is referred to GB/T3810.4-2016 ceramic tile test method: determination of modulus of rupture and breaking Strength (antibacterial detection reference JC/T897-2014 (antibacterial ceramic product antibacterial Performance), and the detection results are shown in Table 1.
TABLE 1 results of Performance detection of antibacterial ceramic glaze
As can be seen from Table 1, the ceramic glaze prepared in the manner of example 1 of the present invention has the highest breaking strength, breaking modulus and Rockwell hardness, indicating that the strength and wear resistance are better; and the antibacterial property of the composition to escherichia coli and staphylococcus aureus is better improved than that of other comparative examples, so that the composition shows more excellent antibacterial property.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. The antibacterial ceramic glaze is characterized by comprising a basic glaze and an antibacterial additive in parts by weight, wherein the mass ratio of the basic glaze to the antibacterial additive is 100:3-8; the basic glaze comprises the following components in parts by weight:
28-35 parts of feldspar, 14-20 parts of quartz, 1.2-6.8 parts of talcum, 8-12 parts of kaolin and 2.5-5 parts of clay;
the antibacterial additive is aluminum diboride and porous copper silicate microspheres.
2. An antimicrobial ceramic glaze according to claim 2 wherein the antimicrobial additive is prepared by a process comprising:
(1) Preparing porous copper silicate microspheres:
firstly mixing hexahydrate copper nitrate with deionized water to form an aqueous solution, then adjusting the pH value of the reaction solution to be 11-12 by using ammonia water, then mixing the aqueous solution with the aqueous solution of silicon dioxide, and reacting in a reaction kettle to obtain porous copper silicate microspheres;
(2) Preparing aluminum diboride & porous copper silicate microspheres:
firstly mixing aluminum chloride with 1-ethyl-3-methylimidazole chloride, then adding porous copper silicate, carrying out liquid phase microwave discharge plasma treatment under the condition of introducing diborane to obtain a pretreatment product, and then sintering in a tube furnace to obtain aluminum diboride and porous copper silicate.
3. The antibacterial ceramic glaze according to claim 2, wherein the preparation method of the porous copper silicate microspheres comprises the following steps:
s1, weighing copper nitrate hexahydrate and deionized water, mixing, and completely dissolving the copper nitrate hexahydrate and the deionized water, wherein the copper nitrate solution; wherein the mass ratio of the copper nitrate hexahydrate to the deionized water is 3.2-4.8:30-50;
weighing nano silicon dioxide and deionized water, mixing, and forming a silicon dioxide solution after ultrasonic treatment is uniform; wherein the mass ratio of the nano silicon dioxide to the deionized water is 1:20-40;
s2, dropwise adding ammonia water into a copper nitrate solution to adjust the pH value of the reaction solution to be 11-12, then mixing the reaction solution with a silicon dioxide solution, stirring the mixture at room temperature for 1-2 hours, pouring the reaction solution into a reaction kettle, performing constant temperature treatment at 110-150 ℃ for 10-15 hours, filtering out solids, washing the solids to be neutral by using pure water, washing the solids by using ethanol for three times, and performing vacuum drying to obtain porous copper silicate microspheres; wherein the mass ratio of the copper nitrate solution to the silicon dioxide solution is 1.2-1.4:1.
4. An antimicrobial ceramic glaze according to claim 2 wherein said aluminum diboride & porous copper silicate microspheres are prepared by a process comprising:
s3, weighing aluminum chloride, mixing the aluminum chloride with 1-ethyl-3-methylimidazole chloride salt, and uniformly stirring under the protection effect to form an aluminum chloride solution;
wherein the mass ratio of the aluminum chloride to the 1-ethyl-3-methylimidazole chloride salt is 0.52-0.78:17-23;
s4, adding porous copper silicate into the aluminum chloride solution, introducing inert gas as a shielding gas, introducing diborane, and pouring into a reaction kettle after ultrasonic homogenization;
wherein the mass ratio of the porous copper silicate to the aluminum chloride solution is 1:10-15; the mass ratio of diborane to aluminum chloride in the aluminum chloride solution is 1.1-1.2:1;
s5, treating the reaction kettle with liquid phase microwave discharge plasma at room temperature, wherein the treatment power is 500-600W, the treatment time is 30-50min, centrifuging and collecting solid products after the reaction is finished, washing the solid products sequentially with distilled water and ethanol, and drying the solid products in vacuum to obtain pretreated products;
s6, placing the pretreated product into a tube furnace for sintering treatment, wherein the sintering temperature is 700-800 ℃, and naturally cooling to obtain aluminum diboride and porous copper silicate.
5. A method of preparing the antimicrobial ceramic glaze of claim 1, comprising:
firstly, weighing all components of a basic glaze according to parts by weight, mixing the components into deionized water, adding sodium carboxymethyl cellulose, and fully mixing to form a first ceramic mixture;
secondly, adding the antibacterial additive into the first ceramic mixture, fully mixing again, and then placing the mixture in a ball mill for ball milling treatment to obtain a second ceramic mixture;
and thirdly, coating the second ceramic mixture on the ceramic blank, and performing high-temperature sintering to form the antibacterial ceramic glaze on the ceramic blank.
6. The method according to claim 5, wherein the deionized water is added in an amount of 50 to 80% of the total weight of the base glaze and the sodium carboxymethyl cellulose is added in an amount of 0.5 to 1% of the total weight of the base glaze in the first step.
7. The method according to claim 5, wherein in the second step, during the ball milling process, the ball-to-material ratio is 6-8:1, the ball milling speed is 400-600rpm, the ball milling time is 4-6h, and the water content of the second ceramic mixture is adjusted to 35% -40% after the ball milling is finished.
8. The method for preparing an antibacterial ceramic glaze according to claim 5, wherein in the third step, degassing treatment is required before the second ceramic mixture is coated, and the coating thickness is 200-500 μm.
9. The method according to claim 5, wherein in the third step, the high temperature sintering temperature is raised to 350-400 ℃ for 5-10min, then raised to 700-800 ℃ for 10-20min, and then raised to 1100-1200 ℃ for 3-5min.
10. Use of the antimicrobial ceramic glaze of claim 1 in an antimicrobial ceramic tile or antimicrobial ceramic ware.
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