CN116425418A - Antibacterial sanitary ceramic - Google Patents
Antibacterial sanitary ceramic Download PDFInfo
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- CN116425418A CN116425418A CN202310651494.9A CN202310651494A CN116425418A CN 116425418 A CN116425418 A CN 116425418A CN 202310651494 A CN202310651494 A CN 202310651494A CN 116425418 A CN116425418 A CN 116425418A
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- antibacterial
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 95
- 239000000919 ceramic Substances 0.000 title claims abstract description 75
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 38
- 239000002002 slurry Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims description 60
- 239000000243 solution Substances 0.000 claims description 51
- 238000002156 mixing Methods 0.000 claims description 50
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 32
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 29
- 238000001354 calcination Methods 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- 239000011259 mixed solution Substances 0.000 claims description 25
- 238000002360 preparation method Methods 0.000 claims description 22
- QWDJLDTYWNBUKE-UHFFFAOYSA-L magnesium bicarbonate Chemical compound [Mg+2].OC([O-])=O.OC([O-])=O QWDJLDTYWNBUKE-UHFFFAOYSA-L 0.000 claims description 21
- 229910000022 magnesium bicarbonate Inorganic materials 0.000 claims description 21
- 235000014824 magnesium bicarbonate Nutrition 0.000 claims description 21
- 239000002370 magnesium bicarbonate Substances 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 18
- 239000004115 Sodium Silicate Substances 0.000 claims description 16
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 16
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 16
- 238000000137 annealing Methods 0.000 claims description 15
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 15
- 238000000227 grinding Methods 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 229960000583 acetic acid Drugs 0.000 claims description 10
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 10
- 239000012362 glacial acetic acid Substances 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000012535 impurity Substances 0.000 claims description 10
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 10
- 239000011812 mixed powder Substances 0.000 claims description 10
- 238000005507 spraying Methods 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 6
- 230000009471 action Effects 0.000 claims description 5
- 230000003213 activating effect Effects 0.000 claims description 5
- 230000004913 activation Effects 0.000 claims description 5
- 239000003085 diluting agent Substances 0.000 claims description 5
- 238000011068 loading method Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000000889 atomisation Methods 0.000 claims description 2
- 230000000845 anti-microbial effect Effects 0.000 claims 7
- 239000004599 antimicrobial Substances 0.000 claims 7
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 7
- 230000001580 bacterial effect Effects 0.000 abstract description 2
- 229910010293 ceramic material Inorganic materials 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 30
- 241000894006 Bacteria Species 0.000 description 8
- 230000001954 sterilising effect Effects 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 230000036541 health Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 241000588724 Escherichia coli Species 0.000 description 3
- -1 cerium ion Chemical class 0.000 description 3
- 238000005034 decoration Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 210000002421 cell wall Anatomy 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 239000000645 desinfectant Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 208000035473 Communicable disease Diseases 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000030833 cell death Effects 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 230000019522 cellular metabolic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000009545 invasion Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- OSWZKPPDZLEVGX-UHFFFAOYSA-N lanthanum(3+) oxygen(2-) titanium(4+) Chemical compound [O-2].[O-2].[Ti+4].[La+3] OSWZKPPDZLEVGX-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005406 washing 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
- 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
- C04B41/45—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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Inorganic Chemistry (AREA)
- Structural Engineering (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention relates to an antibacterial sanitary ceramic, belonging to the technical field of ceramic materials. According to the invention, by adding the antibacterial agent, the ceramic surface has an excellent antibacterial effect, bacterial reproduction can be effectively reduced, the antibacterial effect is durable, the surface can be kept clean and sanitary for a long time, the frequency and the workload of disinfection are reduced, the comfort and the quality of the household environment are improved, the antibacterial sanitary ceramic comprises a ceramic body and antibacterial glaze slurry, the antibacterial glaze slurry is arranged on the outer surface of the ceramic body, the antibacterial glaze slurry comprises basic glaze slurry and antibacterial agent, and the addition amount of the antibacterial agent is 0.5-1.2% of the mass of the basic glaze slurry.
Description
Technical Field
The invention belongs to the technical field of ceramic materials, and relates to an antibacterial sanitary ceramic.
Background
Along with the improvement of the living standard and the improvement of the working environment of people, the requirements of people on the building ceramic exceed the simple building decoration function, and the functional application of the building ceramic is more and more focused. The functional building ceramic is endowed with new application functions on the premise of ensuring the decoration effect.
The ceramic with antibacterial function can effectively reduce and avoid the invasion of various infectious diseases to human health, so that the ceramic is widely focused by people and has wide market application prospect. Japan is in the leading position in the field of antibacterial materials, where it is very early at the start of the day. The antibacterial function of the ceramic tile is realized by adding an antibacterial agent into glaze slip or sintering on the glaze. Due to the characteristic of high-temperature firing in the ceramic field, the application of the antibacterial material has a certain difficulty, but the application field of the antibacterial ceramic is very wide, so that the ceramic antibacterial product has extremely great market potential. Meanwhile, the building ceramic is a decoration material with the largest occupied area of the household space, the application space of the building ceramic is widely related to the ground and the wall surface, and the rapid development of the ceramic large plate in recent years leads the application field of the building ceramic to gradually extend to the fields of the table top plate and the like, and the antibacterial property of the building ceramic is directly related to the health of the household environment. Therefore, research and development of the building ceramic with high-efficiency and durable antibacterial property has important significance for improving the safety and health of the household environment.
Disclosure of Invention
The invention aims to provide the antibacterial sanitary ceramic, and by adding the antibacterial agent, the ceramic surface has excellent antibacterial effect, so that the bacterial reproduction can be effectively reduced, the antibacterial effect is durable, the surface can be kept clean and sanitary for a long time, the frequency and the workload of disinfection are reduced, and the comfort and the quality of the household environment are improved.
The aim of the invention can be achieved by the following technical scheme:
an antibacterial sanitary ceramic comprises a ceramic body and antibacterial glaze slip, wherein the antibacterial glaze slip is arranged on the outer surface of the ceramic body and comprises basic glaze slip and antibacterial agent, and the addition amount of the antibacterial agent is 0.5-1.2% of the mass of the basic glaze slip;
the preparation method of the antibacterial agent comprises the following steps:
1) Adding cerium nitrate, sodium silicate and copper chloride into the magnesium bicarbonate solution, and uniformly stirring to obtain a mixed solution;
2) Placing the mixed solution in a flash tank, atomizing, flash drying to obtain mixed powder;
3) Calcining the mixed powder, adding the modified titanium dioxide, and grinding to obtain the antibacterial agent.
As a preferable technical scheme of the invention, the mass ratio of cerium nitrate, sodium silicate, copper chloride, modified titanium dioxide and magnesium bicarbonate solution is 1.5-5.2:1-2.3:0.5-1.2:2.1-2.5:100, wherein the concentration of the magnesium bicarbonate solution is 30g/L.
As a preferable technical scheme of the invention, in the step 2), the conditions of atomization and flash evaporation drying are that the mixed solution is atomized under the action of high-speed rotation, and is reversely contacted with hot air heated to 200 ℃ to be quickly dried.
As a preferred technical scheme of the invention, in the step 3), the calcination condition is that the calcination is carried out for 2-2.5 hours at 550-600 ℃; the grinding condition is that the grinding is carried out for 2-2.5 hours at the rotating speed of 400-450r/min, and the grain diameter of the antibacterial agent is less than 50 nanometers.
The invention discloses a preparation method of modified titanium dioxide, which comprises the following steps:
(1) Adding tetrabutyl titanate into absolute ethyl alcohol, heating, stirring and mixing to obtain solution A;
(2) Uniformly mixing anhydrous ethanol and glacial acetic acid, adding the solution A, and stirring and mixing to obtain a solution B;
(3) Dissolving lanthanum nitrate in deionized water, and stirring and mixing to obtain a diluent;
(4) Dripping the diluted solution into the solution B, and stirring and mixing to obtain a mixed solution;
(5) And volatilizing the solvent of the mixed solution, calcining, removing impurities, activating, and annealing to obtain the modified titanium dioxide.
As a preferable technical scheme of the invention, in the step (1), the heating temperature is 70-75 ℃, the stirring condition is that the rotating speed is 100-200r/min, and the stirring time is 2-3h; in the step (2), stirring and mixing conditions are that stirring time is 0.5-1h until the solution is uniform and transparent; in the step (3), stirring and mixing time is 0.5-1h; in the step (4), stirring and mixing conditions are that the rotating speed is 200-300r/min, and stirring and mixing are carried out for 0.5-1h; in the step (5), the volatilizing condition is that heating is carried out for 1-2h at the temperature of 120-130 ℃; calcining at 750-850 ℃ for 1-1.5h; the annealing condition is that annealing is carried out in a furnace at 130-140 ℃ for 2h.
As a preferable technical scheme of the invention, the impurity removal and activation treatment step in the step (5) is to place the calcined solid in a hydrogen furnace, heat the calcined solid to 550-600 ℃, keep the temperature for 1-1.5h, heat the calcined solid to 620-650 ℃, keep the temperature for 1-1.5h under the hydrogen atmosphere, cool the calcined solid to room temperature, then move the calcined solid into a high-temperature furnace, heat the calcined solid to 450 ℃ and keep the calcined solid at the temperature for 1-1.2h under the oxygen atmosphere with the flow of 10 mL/min.
As a preferable technical scheme of the invention, the dosage ratio of absolute ethyl alcohol, tetrabutyl titanate, glacial acetic acid, lanthanum nitrate and deionized water is 1000mL:8-10g:6-7mL:5g:50mL; the dosage of the absolute ethyl alcohol in the step (2) is 1/2 of that of the absolute ethyl alcohol in the step (1).
As a preferable technical scheme of the invention, the water content of the basic glaze slip is 28-40%, and the spraying thickness of the antibacterial glaze slip is 0.8-1.0mm.
The scheme of the invention discloses a preparation method of antibacterial sanitary ceramic, which comprises the following steps:
s1, uniformly mixing basic glaze slip and the antibacterial agent to obtain antibacterial glaze slip;
s2, spraying the antibacterial glaze slurry on the outer surface of the ceramic body, drying at 90-98 ℃, loading into a kiln, and sintering at 1100-1300 ℃ for 12-16 hours to obtain the antibacterial sanitary ceramic.
The invention has the beneficial effects that:
according to the scheme, the antibacterial agent is added into the basic glaze slip, and the antibacterial glaze slip formed through interaction with the basic glaze slip enables the ceramic to form a compact antibacterial surface, so that the antibacterial capability of the ceramic surface is improved; the copper ion in the antibacterial agent has strong bactericidal effect, can destroy cell membranes and cell walls on cell walls, causes cell death, and can effectively inhibit the growth of pathogenic bacteria by synergistic effect with cerium ion and silicon ion to improve antibacterial effect.
Detailed Description
In order to further describe the technical means and effects adopted by the present invention for achieving the intended purpose, the following detailed description is given below with reference to the embodiments, structures, features and effects according to the present invention.
Example 1
An antibacterial sanitary ceramic comprises a ceramic body and antibacterial glaze slip, wherein the antibacterial glaze slip is arranged on the outer surface of the ceramic body, and is characterized in that: the antibacterial glaze slip comprises basic glaze slip and an antibacterial agent, wherein the addition amount of the antibacterial agent is 0.5% of the mass of the basic glaze slip; the water content of the basic glaze slip is 28%, and the spraying thickness of the antibacterial glaze slip is 0.8mm;
the preparation method of the antibacterial agent comprises the following steps:
1) Adding cerium nitrate, sodium silicate and copper chloride into the magnesium bicarbonate solution, and uniformly stirring to obtain a mixed solution; wherein, the mass ratio of cerium nitrate, sodium silicate, copper chloride, modified titanium dioxide and magnesium bicarbonate solution is 1.5:1:0.5:2.1:100, wherein the concentration of the magnesium bicarbonate solution is 30g/L;
2) Placing the mixed solution in a flash tank, atomizing the mixed solution under the action of high-speed rotation, reversely contacting with hot air heated to 200 ℃, and rapidly drying to obtain mixed powder;
3) Calcining the mixed powder, adding modified titanium dioxide, and grinding to obtain an antibacterial agent; wherein the calcination condition is calcination for 2 hours at 550 ℃; the grinding condition is that the grinding is carried out for 2 hours at the rotating speed of 400r/min, and the grain diameter of the antibacterial agent is 30 nanometers.
The preparation method of the modified titanium dioxide comprises the following steps:
(1) Adding tetrabutyl titanate into absolute ethyl alcohol, heating, stirring and mixing to obtain solution A; wherein the heating temperature is 70 ℃, the stirring condition is that the rotating speed is 100r/min, and the stirring time is 2h;
(2) Uniformly mixing anhydrous ethanol and glacial acetic acid, adding the solution A, and stirring and mixing to obtain a solution B; wherein, the stirring and mixing conditions are that the stirring time is 0.5h until the solution is uniform and transparent;
(3) Dissolving lanthanum nitrate in deionized water, and stirring and mixing to obtain a diluent; wherein the stirring and mixing time is 0.5h;
(4) Dripping the diluted solution into the solution B, and stirring and mixing to obtain a mixed solution; wherein, the stirring and mixing conditions are that stirring and mixing are carried out for 0.5h at the rotating speed of 200 r/min;
(5) Volatilizing the solvent of the mixed solution, calcining, removing impurities, activating, and annealing to obtain modified titanium dioxide; wherein the volatilizing condition is heating for 1h at 120 ℃; the calcination condition is that the mixture is calcined for 1h at 750 ℃; the annealing conditions were annealing in a 130 ℃ oven for 2 hours.
The impurity removal and activation treatment steps are that calcined solids are placed in a hydrogen furnace, the heating temperature is increased to 550 ℃, the temperature is kept for 1h, the temperature is increased to 620 ℃, the temperature is kept for 1h under the hydrogen atmosphere, after the calcined solids are cooled to room temperature, the calcined solids are moved into a high-temperature furnace, the temperature is increased to 450 ℃, and the calcined solids are kept for 1h in the oxygen atmosphere with the flow of 10 mL/min.
In the preparation method of the modified titanium dioxide, the dosage ratio of absolute ethyl alcohol, tetrabutyl titanate, glacial acetic acid, lanthanum nitrate and deionized water is 1000mL:8g:6mL:5g:50mL; the dosage of the absolute ethyl alcohol in the step (2) is 1/2 of that of the absolute ethyl alcohol in the step (1).
The preparation method of the antibacterial sanitary ceramic comprises the following steps:
s1, uniformly mixing basic glaze slip and the antibacterial agent to obtain antibacterial glaze slip;
s2, spraying the antibacterial glaze slurry on the outer surface of the ceramic body, drying at 90 ℃, loading into a kiln, and sintering at 1100 ℃ for 12 hours to obtain the antibacterial sanitary ceramic.
Example 2
An antibacterial sanitary ceramic comprises a ceramic body and antibacterial glaze slip, wherein the antibacterial glaze slip is arranged on the outer surface of the ceramic body, and is characterized in that: the antibacterial glaze slip comprises basic glaze slip and an antibacterial agent, wherein the addition amount of the antibacterial agent is 0.8% of the mass of the basic glaze slip; the water content of the basic glaze slip is 34%, and the spraying thickness of the antibacterial glaze slip is 0.9mm;
the preparation method of the antibacterial agent comprises the following steps:
1) Adding cerium nitrate, sodium silicate and copper chloride into the magnesium bicarbonate solution, and uniformly stirring to obtain a mixed solution; wherein, the mass ratio of cerium nitrate, sodium silicate, copper chloride, modified titanium dioxide and magnesium bicarbonate solution is 3.3:1.7:0.8:2.3:100, wherein the concentration of the magnesium bicarbonate solution is 30g/L;
2) Placing the mixed solution in a flash tank, atomizing the mixed solution under the action of high-speed rotation, reversely contacting with hot air heated to 200 ℃, and rapidly drying to obtain mixed powder;
3) Calcining the mixed powder, adding modified titanium dioxide, and grinding to obtain an antibacterial agent; wherein the calcination condition is calcination at 580 ℃ for 2.2h; the grinding condition is that the grinding is carried out for 2.2 hours at the rotating speed of 420r/min, and the grain diameter of the antibacterial agent is 30 nanometers.
The preparation method of the modified titanium dioxide comprises the following steps:
(1) Adding tetrabutyl titanate into absolute ethyl alcohol, heating, stirring and mixing to obtain solution A; wherein the heating temperature is 72 ℃, the stirring condition is that the stirring time is 2.5h at the rotating speed of 150 r/min;
(2) Uniformly mixing anhydrous ethanol and glacial acetic acid, adding the solution A, and stirring and mixing to obtain a solution B; wherein, the stirring and mixing conditions are that the stirring time is 0.8h until the solution is uniform and transparent;
(3) Dissolving lanthanum nitrate in deionized water, and stirring and mixing to obtain a diluent; wherein the stirring and mixing time is 0.8h;
(4) Dripping the diluted solution into the solution B, and stirring and mixing to obtain a mixed solution; wherein, the stirring and mixing conditions are that stirring and mixing are carried out for 0.8h at the rotating speed of 250 r/min;
(5) Volatilizing the solvent of the mixed solution, calcining, removing impurities, activating, and annealing to obtain modified titanium dioxide; wherein the volatilizing condition is heating at 125 ℃ for 1.5h; the calcination condition is that the calcination is carried out for 1.2 hours at 700 ℃; the annealing conditions were annealing in a 135 ℃ oven for 2 hours.
The impurity removal and activation treatment steps are that calcined solids are placed in a hydrogen furnace, the heating temperature is increased to 580 ℃, the temperature is kept for 1.2h, the temperature is increased to 630 ℃, the temperature is kept for 1.2h under the hydrogen atmosphere, after cooling to room temperature, the calcined solids are moved into a high-temperature furnace, the temperature is increased to 450 ℃, and the temperature is kept for 1.1h under the oxygen atmosphere with the flow of 10 mL/min.
In the preparation method of the modified titanium dioxide, the dosage ratio of absolute ethyl alcohol, tetrabutyl titanate, glacial acetic acid, lanthanum nitrate and deionized water is 1000mL:9g:6.5mL:5g:50mL; the dosage of the absolute ethyl alcohol in the step (2) is 1/2 of that of the absolute ethyl alcohol in the step (1).
The preparation method of the antibacterial sanitary ceramic comprises the following steps:
s1, uniformly mixing basic glaze slip and the antibacterial agent to obtain antibacterial glaze slip;
s2, spraying the antibacterial glaze slurry on the outer surface of the ceramic body, drying at 95 ℃, loading into a kiln, and sintering at 1200 ℃ for 14 hours to obtain the antibacterial sanitary ceramic.
Example 3
An antibacterial sanitary ceramic comprises a ceramic body and antibacterial glaze slip, wherein the antibacterial glaze slip is arranged on the outer surface of the ceramic body, and is characterized in that: the antibacterial glaze slip comprises basic glaze slip and an antibacterial agent, wherein the addition amount of the antibacterial agent is 1.2% of the mass of the basic glaze slip; the water content of the basic glaze slip is 40%, and the spraying thickness of the antibacterial glaze slip is 1.0mm;
the preparation method of the antibacterial agent comprises the following steps:
1) Adding cerium nitrate, sodium silicate and copper chloride into the magnesium bicarbonate solution, and uniformly stirring to obtain a mixed solution; wherein, the mass ratio of cerium nitrate, sodium silicate, copper chloride, modified titanium dioxide and magnesium bicarbonate solution is 5.2:2.3:1.2:2.5:100, wherein the concentration of the magnesium bicarbonate solution is 30g/L;
2) Placing the mixed solution in a flash tank, atomizing the mixed solution under the action of high-speed rotation, reversely contacting with hot air heated to 200 ℃, and rapidly drying to obtain mixed powder;
3) Calcining the mixed powder, adding modified titanium dioxide, and grinding to obtain an antibacterial agent; wherein the calcination condition is calcination at 600 ℃ for 2.5 hours; the grinding condition is that the grinding is carried out for 2.5 hours at the rotating speed of 450r/min, and the grain diameter of the antibacterial agent is 30 nanometers.
The preparation method of the modified titanium dioxide comprises the following steps:
(1) Adding tetrabutyl titanate into absolute ethyl alcohol, heating, stirring and mixing to obtain solution A; wherein the heating temperature is 75 ℃, the stirring condition is that the rotating speed is 200r/min, and the stirring time is 3h;
(2) Uniformly mixing anhydrous ethanol and glacial acetic acid, adding the solution A, and stirring and mixing to obtain a solution B; wherein, the stirring and mixing conditions are stirring time of 1h until the solution is uniform and transparent;
(3) Dissolving lanthanum nitrate in deionized water, and stirring and mixing to obtain a diluent; wherein the stirring and mixing time is 1h;
(4) Dripping the diluted solution into the solution B, and stirring and mixing to obtain a mixed solution; wherein, the stirring and mixing conditions are that stirring and mixing are carried out for 1h at the rotating speed of 300 r/min;
(5) Volatilizing the solvent of the mixed solution, calcining, removing impurities, activating, and annealing to obtain modified titanium dioxide; wherein the volatilizing condition is heating at 130 ℃ for 2 hours; the calcination condition is that the calcination is carried out for 1.5 hours at 850 ℃; the annealing conditions were annealing in a furnace at 140℃for 2h.
The impurity removal and activation treatment steps are that calcined solids are placed in a hydrogen furnace, the heating temperature is increased to 600 ℃, the temperature is kept for 1.5h, the temperature is increased to 650 ℃, the temperature is kept for 1.5h under the hydrogen atmosphere, after cooling to room temperature, the calcined solids are moved into a high-temperature furnace, the temperature is increased to 450 ℃, and the temperature is kept for 1.2h under the oxygen atmosphere with the flow of 10 mL/min.
In the preparation method of the modified titanium dioxide, the dosage ratio of absolute ethyl alcohol, tetrabutyl titanate, glacial acetic acid, lanthanum nitrate and deionized water is 1000mL:10g:7mL:5g:50mL; the dosage of the absolute ethyl alcohol in the step (2) is 1/2 of that of the absolute ethyl alcohol in the step (1).
The preparation method of the antibacterial sanitary ceramic comprises the following steps:
s1, uniformly mixing basic glaze slip and the antibacterial agent to obtain antibacterial glaze slip;
s2, spraying the antibacterial glaze slurry on the outer surface of the ceramic body, drying at 98 ℃, loading into a kiln, and sintering at 1300 ℃ for 16 hours to obtain the antibacterial sanitary ceramic.
Comparative examples 1 to 4
The difference compared with example 3 is that cerium nitrate, sodium silicate, copper chloride, magnesium bicarbonate solution, and modified titanium dioxide used in comparative examples 1 to 3 are shown in Table 1, and the addition amounts of the remaining raw materials, the preparation steps and the parameters are the same.
TABLE 1
| Cerium nitrate (weight portions) | Sodium silicate (weight portions) | Copper chloride (weight portion) | Magnesium bicarbonate solution (weight portions) | Modified titanium dioxide (weight portion) | |
| Comparative example 1 | 0 | 2.3 | 1.2 | 100 | 2.5 |
| Comparative example 2 | 5.2 | 0 | 1.2 | 100 | 2.5 |
| Comparative example 3 | 5.2 | 2.3 | 0 | 100 | 2.5 |
| Comparative example 4 | 5.2 | 2.3 | 1.2 | 100 | 0 |
Comparative example 5
In comparison with example 3, comparative example 5 was a solution in which deionized water was used instead of magnesium bicarbonate, wherein the mass ratio of cerium nitrate, sodium silicate, copper chloride, modified titanium dioxide to deionized water was 5.2:2.3:1.2:2.5:100, and the addition amount, the preparation steps and the parameters of the rest raw materials are the same.
Comparative example 6
In comparison with example 3, comparative example 6 was conducted in such a manner that titanium dioxide was used instead of modified titanium dioxide, and the addition amounts of the remaining raw materials, the preparation steps and the parameters were the same.
Performance test
Antibacterial performance test:
according to GB15979-2002, E.coli was subjected to sterilization experiments, examples 1-3, comparative examples were performed with sterile deionized water1-6 preparation examples of antibacterial ceramics sanitary after cleaning, drying, then adding 100mL of deionized water to the antibacterial ceramics, then adding 1mL of 1X 10 concentration to the mixture 3 After CFU/g of E.coli was allowed to stand at room temperature for 4 hours, the E.coli content in deionized water in examples 1 to 3 and comparative examples 1 to 6 was measured, and the sterilization rate was measured.
Antibacterial durability test: the antibacterial sanitary ceramics prepared in examples 1 to 3 and comparative examples 1 to 6 were uniformly washed with 84 disinfectant for 30 times, and after washing, the sterilization rate was measured according to the antibacterial property test method.
The antibacterial property test results are shown in table 2.
TABLE 2
| Antibacterial properties: sterilization rate (%) | Antibacterial durability: sterilization rate (%) | |
| Example 1 | 99.8 | 99.1 |
| Example 2 | 99.9 | 99.5 |
| Example 3 | 99.9 | 99.8 |
| Comparative example 1 | 72.3 | 73.9 |
| Comparative example 2 | 75.8 | 77.6 |
| Comparative example 3 | 62.7 | 65.2 |
| Comparative example 4 | 52.6 | 54.8 |
| Comparative example 5 | 69.5 | 71.5 |
| Comparative example 6 | 87.2 | 88.3 |
As can be seen from the test results in Table 2, the antibacterial rates of the antibacterial sanitary ceramics in the embodiments of the invention are significantly improved to more than 99.8% after the antibacterial agents are added in comparison with the comparative examples 1 to 6. In addition, after the sanitary ware is uniformly cleaned by 84 disinfectant for 30 times, the antibacterial rate is still more than 99.1%, which shows that the antibacterial sanitary ware in the application has excellent antibacterial effect, and can effectively reduce the condition that bacteria grow on the surface, thereby reducing the influence on the health of users.
Comparative example 1 as compared with example 3, comparative example 1 lacks cerium nitrate, and the antibacterial principle of cerium nitrate for preparing ceramic is to inhibit the growth and reproduction of bacteria by releasing ions, and to kill some bacteria; comparative example 2 in comparison with example 3, comparative example 2 lacks sodium silicate, and the antibacterial principle of sodium silicate for preparing ceramic is to inhibit the propagation and growth of bacteria by increasing the basicity of the medium to change the growth environment of bacteria; comparative example 3 in comparison with example 3, comparative example 3 lacks copper chloride, which is used for preparing ceramic according to the antibacterial principle that the metabolism of cells is inhibited by releasing copper ions, thereby preventing the growth and reproduction of cells; comparative example 5 in comparison with example 3, comparative example 5 lacks a magnesium bicarbonate solution, and the antibacterial principle of the magnesium bicarbonate solution for preparing ceramic is to change the growth environment of bacteria by increasing the acidity of a medium, thereby inhibiting the proliferation and growth of bacteria; comparative example 4 and comparative example 6 lack modified titanium dioxide, and the antibacterial principle of lanthanum-titanium dioxide for preparing ceramics is to generate active oxygen and destroy cell structure by sterilizing action of lanthanum ions and photocatalytic action of titanium dioxide, thereby inhibiting growth and reproduction of bacteria.
According to the scheme, by adding five materials, namely cerium nitrate, sodium silicate, copper chloride, magnesium bicarbonate solution and modified titanium dioxide, through different antibacterial mechanisms and mutual synergistic effects, the more effective antibacterial effect is achieved, the antibacterial spectrum is enlarged, and the long-term antibacterial effect is enhanced.
The present invention is not limited to the above embodiments, but is capable of modification and variation in detail, and other modifications and variations can be made by those skilled in the art without departing from the scope of the present invention.
Claims (10)
1. An antibacterial sanitary ceramic comprises a ceramic body and antibacterial glaze slip, wherein the antibacterial glaze slip is arranged on the outer surface of the ceramic body, and is characterized in that: the antibacterial glaze slip comprises basic glaze slip and an antibacterial agent, wherein the addition amount of the antibacterial agent is 0.5-1.2% of the mass of the basic glaze slip;
the preparation method of the antibacterial agent comprises the following steps:
1) Adding cerium nitrate, sodium silicate and copper chloride into the magnesium bicarbonate solution, and uniformly stirring to obtain a mixed solution;
2) Placing the mixed solution in a flash tank, atomizing, flash drying to obtain mixed powder;
3) Calcining the mixed powder, adding the modified titanium dioxide, and grinding to obtain the antibacterial agent.
2. An antimicrobial sanitary ceramic according to claim 1, wherein: the mass ratio of the cerium nitrate, the sodium silicate, the copper chloride, the modified titanium dioxide and the magnesium bicarbonate solution is 1.5-5.2:1-2.3:0.5-1.2:2.1-2.5:100, wherein the concentration of the magnesium bicarbonate solution is 30g/L.
3. An antimicrobial sanitary ceramic according to claim 1, wherein: in the step 2), the conditions of atomization and flash drying are that the mixed solution is atomized under the action of high-speed rotation, and is reversely contacted with hot air heated to 200 ℃ to be quickly dried.
4. An antimicrobial sanitary ceramic according to claim 1, wherein: in step 3), the calcination conditions are calcination at 550-600 ℃ for 2-2.5h; the grinding condition is that the grinding is carried out for 2-2.5 hours at the rotating speed of 400-450r/min, and the grain diameter of the antibacterial agent is less than 50 nanometers.
5. The antibacterial sanitary ceramic according to claim 1, wherein the preparation method of the modified titanium dioxide comprises the following steps:
(1) Adding tetrabutyl titanate into absolute ethyl alcohol, heating, stirring and mixing to obtain solution A;
(2) Uniformly mixing anhydrous ethanol and glacial acetic acid, adding the solution A, and stirring and mixing to obtain a solution B;
(3) Dissolving lanthanum nitrate in deionized water, and stirring and mixing to obtain a diluent;
(4) Dripping the diluted solution into the solution B, and stirring and mixing to obtain a mixed solution;
(5) And volatilizing the solvent of the mixed solution, calcining, removing impurities, activating, and annealing to obtain the modified titanium dioxide.
6. An antimicrobial sanitary ceramic according to claim 5, wherein:
in the step (1), the heating temperature is 70-75 ℃, the stirring condition is that the rotating speed is 100-200r/min, and the stirring time is 2-3h;
in the step (2), stirring and mixing conditions are that stirring time is 0.5-1h until the solution is uniform and transparent;
in the step (3), stirring and mixing time is 0.5-1h;
in the step (4), stirring and mixing conditions are that the rotating speed is 200-300r/min, and stirring and mixing are carried out for 0.5-1h;
in the step (5), the volatilizing condition is that heating is carried out for 1-2h at the temperature of 120-130 ℃; calcining at 750-850 ℃ for 1-1.5h; the annealing condition is that annealing is carried out in a furnace at 130-140 ℃ for 2h.
7. An antimicrobial sanitary ceramic according to claim 5, wherein: the impurity removal and activation treatment step in the step (5) is to place the calcined solid in a hydrogen furnace, heat the calcined solid to 550-600 ℃, keep the temperature for 1-1.5h, heat the calcined solid to 620-650 ℃, keep the temperature for 1-1.5h under the hydrogen atmosphere, cool the calcined solid to room temperature, then transfer the calcined solid into a high-temperature furnace, heat the calcined solid to 450 ℃ and keep the temperature for 1-1.2h under the oxygen atmosphere with the flow of 10 mL/min.
8. An antimicrobial sanitary ceramic according to claim 5, wherein: the dosage ratio of the absolute ethyl alcohol, the tetrabutyl titanate, the glacial acetic acid, the lanthanum nitrate and the deionized water is 1000mL:8-10g:6-7mL:5g:50mL; the dosage of the absolute ethyl alcohol in the step (2) is 1/2 of that of the absolute ethyl alcohol in the step (1).
9. An antimicrobial sanitary ceramic according to claim 1, wherein: the water content of the basic glaze slip is 28-40%, and the spraying thickness of the antibacterial glaze slip is 0.8-1.0mm.
10. The antibacterial sanitary ceramic according to claim 1, wherein the preparation method of the antibacterial sanitary ceramic comprises the following steps:
s1, uniformly mixing basic glaze slip and the antibacterial agent to obtain antibacterial glaze slip;
s2, spraying the antibacterial glaze slurry on the outer surface of the ceramic body, drying at 90-98 ℃, loading into a kiln, and sintering at 1100-1300 ℃ for 12-16 hours to obtain the antibacterial sanitary ceramic.
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