CN112607784A - Nano-particles for antibacterial ceramics and preparation method and application thereof - Google Patents

Nano-particles for antibacterial ceramics and preparation method and application thereof Download PDF

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Publication number
CN112607784A
CN112607784A CN202011537926.6A CN202011537926A CN112607784A CN 112607784 A CN112607784 A CN 112607784A CN 202011537926 A CN202011537926 A CN 202011537926A CN 112607784 A CN112607784 A CN 112607784A
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antibacterial
precursor
nanoparticles
zinc
ceramic
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甄崇礼
廖洁娴
周理龙
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Chuangqi Times Qingdao Technology Co ltd
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Chuangqi Times Qingdao Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/0018—Mixed oxides or hydroxides
    • C01G49/0063—Mixed oxides or hydroxides containing zinc
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C01G23/08—Drying; Calcining ; After treatment of titanium oxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • C01G9/02—Oxides; Hydroxides
    • 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
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • C03C8/20—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing titanium compounds; containing zirconium compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases

Abstract

The invention belongs to the technical field of functional nano materials, and particularly relates to nano particles for antibacterial ceramics, and a preparation method and application thereof. Nanoparticles for use in antimicrobial ceramics having the following structural formula: mxZnyOzOr MxTiyOzWherein M is selected from Fe, Mn, Ni, Ag, Au, La, Ce or ZrOne or more of them. Dissolving the nanoparticle precursor in a solvent to obtain a precursor solution, injecting the precursor solution into high-pressure gas, dispersing the precursor solution into methane-oxygen flame, reacting, coagulating and cooling to obtain the nanoparticles for the antibacterial ceramic. The invention utilizes flame spray decomposition method to prepare composite metal oxide based on zinc oxide or titanium oxide, which is doped into glaze for antibacterial ceramic surface coating, and can achieve good antibacterial effect under the condition of small addition amount.

Description

Nano-particles for antibacterial ceramics and preparation method and application thereof
Technical Field
The invention belongs to the technical field of functional nano materials, and particularly relates to nano particles for antibacterial ceramics, and a preparation method and application thereof.
Background
At present, the antibacterial glaze mainly comprises nano silver, nano zinc oxide, titanium oxide and the like, and can generate free radicals with strong oxidizing property or achieve the sterilization effect by the strong oxidizing property; or some radioactive substance with trace amount, such as tourmaline, is added to generate negative ions, so as to achieve the purpose of antibiosis.
Chinese patent CN105152683A discloses a method for preparing a nano antibacterial ceramic glaze layer, the chemical components of the precursor of the superfine powder of the nano antibacterial ceramic glaze layer are: SiO 22：45～60％，Al2O3 10～14％，CaO：7～10％，ZnO：5～ 7％，CuO：2～5％，MgO：3～6％，TiO2：1～3％，Ag2O: 0.2 to 2 percent. The precursor of the nanometer antibiotic ceramic glaze layer superfine powder is prepared in proportion and is put into a graphite container, the temperature is kept for 120min to 240min under the protection of argon atmosphere and the temperature condition of 1250 ℃ to 1400 ℃, and then absolute ethyl alcohol is added into a ball mill for mechanical ball milling for 24 hours, so as to obtain the superfine precursor powder with the grain size of 30 nm to 80 nm. The metal particles of zinc, copper, magnesium and silver are more fine and evenly distributed in the glaze layer, the diameter of the metal particles is 30-80nm, and the metal particles can quickly and persistently release the antibacterial elements. In the patent, zinc oxide, titanium oxide, silver oxide and the like are added into the glaze to prepare the antibacterial ceramic, so that a better antibacterial effect is achieved; however, the nano oxide particles are prepared by ball milling, and the obtained particles have large and uneven sizes, so that the antibacterial effect is influenced.
Chinese patent CN101433209A discloses a high-temperature resistant anion antibacterial material and a preparation method thereof, the realization of the antibacterial and purifying functions of the anion and antibacterial composite functional material adopts a nano inorganic antibacterial agent and nano titanium dioxide; the realization of the negative ion function adopts polar mineral tourmaline; the composite material with high-temperature resistance, high-efficiency anion release, high-efficiency antibiosis and air purification is prepared by carrying phosphate of a high-temperature resistant material and activating rare earth oxide through the working procedures of mixing, superfine grinding and the like, can be used for buildings, ceramics, coatings, floors, plastics and the like, and has obvious removal effect on toxic and harmful gases such as formaldehyde, benzene, ammonia and the like released by various indoor decoration materials, furniture and the like. In the patent, tourmaline is added on the basis of cerium phosphate, titanium oxide and zinc oxide, so that negative ions are generated, and a good antibacterial effect is generated; however, tourmaline has a certain radioactivity, and thus may have adverse effects on human body, and thus, it is necessary to develop a new antibacterial ceramic glaze.
At present, the nanoparticles for antibacterial ceramics which have good antibacterial effect and are harmless to human bodies are needed to be provided.
Disclosure of Invention
The invention aims to provide a nano-particle for antibacterial ceramic, which has good antibacterial effect and no harm to human body, and simultaneously provides a preparation method and application of the nano-particle for antibacterial ceramic.
The nano-particles for the antibacterial ceramic have the following structural formula:
MxZnyOzor MxTiyOz，
Wherein M is the doping metal, x is the mole fraction of M, y is the mole fraction of zinc or titanium, and z is the mole fraction of oxygen;
m is one or more of iron, manganese, nickel, silver, gold, lanthanum, cerium or zirconium.
The x is 0.01-0.25, the y is 0.75-0.99, the z is 1-3, and the particle size of the nano-particles is 10-300 nm.
The preparation method of the nano-particles for the antibacterial ceramic comprises the steps of dissolving a nano-particle precursor in a solvent to obtain a precursor solution, injecting the precursor solution into high-pressure gas, dispersing the precursor solution into methane-oxygen flame, reacting, coagulating and cooling to obtain the nano-particles for the antibacterial ceramic.
The nanoparticle precursor is a precursor of M and zinc or a precursor of M and titanium.
The precursor of M and zinc is one or more of M nitrate, acetate, citrate, 2-ethylhexanoate or metal acid, the precursor of zinc is one or more of zinc nitrate, acetate, citrate or 2-ethylhexanoate, and the precursor of titanium is one or more of titanium nitrate, acetate, citrate, 2-ethylhexanoate or titanate.
The solvent is one or more of water, ethanol, toluene or xylene.
The content of the nanoparticle precursor in the precursor solution is 2.5-60 wt.%.
The high-pressure gas is oxygen or nitrogen.
The pressure of the high-pressure gas is 0.1-1 MPa.
The flow rate of the precursor solution dispersed in the methane-oxygen flame is 1-20 mL/min.
The preparation method of the nano-particles for the antibacterial ceramic specifically comprises the steps of dissolving a nano-particle precursor in a solvent to obtain a precursor solution, injecting the precursor solution into high-pressure gas (namely dispersion gas), dispersing the precursor solution into methane-oxygen flame under the protection of protective oxygen, reacting, coagulating and cooling to obtain the nano-particles for the antibacterial ceramic.
The flow rate of the methane is 0.5-3.5L/min, the flow rate of the dispersion gas is 1-3L/min, and the flow rate of the protective oxygen is 2-6L/min.
The dispersion gas is preferably oxygen; the volume ratio of methane to oxygen is 1: 2-5, wherein the oxygen is dispersed oxygen and protective oxygen.
The nano particles for the antibacterial ceramic are collected by a collector with a filter screen.
The application of the nano-particles for the antibacterial ceramic is that the nano-particles for the antibacterial ceramic are doped into ceramic glaze, and a ceramic blank is fired after glazing to obtain the antibacterial ceramic.
The content of the nano particles for the antibacterial ceramic in the glaze is 0.5-10 wt.%.
The nano-particles for antibacterial ceramics are composed of a composite oxide mainly containing zinc oxide or titanium oxide.
The grain diameter (less than 300nm, most of which is less than 20nm) of the metal-doped zinc oxide or the metal-doped titanium oxide prepared by the invention is in the nanometer level, and has more defect sites, so the activity is very high. The zinc oxide and the titanium oxide both have photocatalytic activity, and after being doped with metal, the zinc oxide and the titanium oxide can obviously improve the activity, can generate photoproduction electrons and holes under illumination and can react with O in the air2And H2And O reaction to generate free radicals with strong oxidability, wherein the free radicals can kill toxic and harmful bacteria and fungi, thereby achieving the antibacterial effect.
The metal oxides added in the invention are nontoxic, so the metal oxides have no toxic or harmful effect on human bodies.
The invention has the following beneficial effects:
the invention disperses the nanometer particle precursor dissolved in the solvent into methane-oxygen flame by a flame spray decomposition method for combustion, reaction and coagulation to obtain nanometer particles with antibacterial function, and the nanometer particles are mixed in the ceramic glaze to achieve the aim of ceramic antibacterial.
Aiming at the problems that the antibacterial effect of the prepared antibacterial ceramic surface glaze is not ideal enough or potential harm is caused to human bodies at present, the invention prepares the composite metal oxide based on zinc oxide or titanium oxide by using a flame spray decomposition method, and the composite metal oxide is doped into the glaze for the antibacterial ceramic surface coating, and can achieve good antibacterial effect under the condition of small addition amount.
Drawings
FIG. 1 is a schematic diagram of a process for preparing nanoparticles of the present invention.
Detailed Description
The present invention is further described below with reference to examples.
Example 1
5g of zinc nitrate, 1g of ferrous nitrate and 0.05g of zirconium nitrate were dissolved in 50mL of deionized water using a micro syringe pumpInjecting the mixture into dispersed oxygen at a flow rate of 4mL/min, dispersing the mixture into methane-oxygen flame under the protection of oxygen around a spray head, reacting, coagulating and cooling, wherein the flow rate of methane is 2.1L/min, the flow rate of protected oxygen is 4.2L/min, the flow rate of dispersed oxygen is 2.2L/min, and the pressure of dispersed oxygen is 0.17 MPa. The nanoparticles generated in the flame were collected by a collector with a glass screen. The prepared nano particles (Zn) are measured by XRD0.822Fe0.173Zr0.005O1.005) The particle size was 15.3 nm.
The prepared nanoparticles were incorporated into a glaze in an amount of 0.5 wt.%, and the ceramic tile was glazed to obtain an antibacterial ceramic, which was subjected to an antibacterial test.
The ceramic tile antibacterial performance test is carried out according to the national standard JC/T897-2014 antibacterial ceramic product antibacterial performance, staphylococcus aureus and Escherichia coli are used for detection, firstly, 12 ceramic tiles with 5 x 5cm added with antibacterial nano particles and 2 ceramic tiles without the antibacterial nano particles are taken and sterilized at high temperature by a steam boiler, then, after further sterilization by 70 percent alcohol, the glaze faces upwards, the blank is placed downwards and soaked in sterile water for 24 hours, and the blank is ensured to fully absorb water. Then, the strains are evenly inoculated on the surfaces of the porcelain slices by a film method, the strains are cultured for 24 hours in a constant temperature incubator at 37 ℃, the colonies on the porcelain slices in the experimental group and the control group are eluted by washing liquid, then the strains in the eluent are inoculated in plate counting agar, the strains are cultured for 24 hours in the constant temperature incubator at 37 ℃, and then viable bacteria counting is carried out. The antibacterial rate calculation method comprises the following steps:
R＝(B-C)/B×100％
r is antibacterial rate, B is the number of average colony count after blank control sample is cultured for 24h, and the unit is colony count; c is the value of the average colony count of the antibacterial ceramic sample after 24h of culture, and the unit is the colony count.
The antibacterial test shows that the antibacterial rate is 95%.
Example 2
5g of tetraethyl titanate, 0.8g of ferrous nitrate and 0.05g of cerium nitrate were dissolved in 50mL of deionized water, and then injected into dispersed oxygen gas at a flow rate of 4mL/min using a microinjection pump, thenAnd then dispersing the mixture into methane-oxygen flame under the protection of oxygen around the spray head, reacting, condensing and cooling, wherein the flow rate of methane is 1.1L/min, the flow rate of protective oxygen is 3.2L/min, the flow rate of dispersed oxygen is 1.2L/min, and the pressure of the dispersed oxygen is 0.2 MPa. The nanoparticles generated in the flame were collected by a collector with a glass screen. XRD determination shows that the prepared nano particles (Ti)0.762Fe0.231Ce0.007O1.769) The particle size was 56.7 nm.
The prepared nanoparticles were incorporated into glaze in an amount of 0.5 wt.% and glazed on a ceramic tile to obtain an antibacterial ceramic, which was subjected to an antibacterial test using the same antibacterial test method as in example 1, with an antibacterial rate of 95.3%.
Example 3
5g of 2-zinc ethyl hexanoate, 0.2g of lanthanum citrate and 0.01g of chloroauric acid are dissolved in 50mL of xylene, then the solution is injected into dispersed oxygen at the flow rate of 5mL/min by a micro injection pump, and then the dispersed oxygen is dispersed into methane-oxygen flame under the protection of oxygen around a spray head to react, coagulate and cool, the flow rate of methane is 3L/min, the flow rate of protected oxygen is 5.2L/min, the flow rate of dispersed oxygen is 2.5L/min, and the pressure of dispersed oxygen is 0.5 MPa. The nanoparticles generated in the flame were collected by a collector with a glass screen. The prepared nano particles (Zn) are measured by XRD0.951La0.041Au0.008O1.012) The particle size was 132.6 nm.
The prepared nanoparticles were incorporated into glaze in an amount of 1 wt.% and glazed on a ceramic tile to obtain an antibacterial ceramic, which was subjected to an antibacterial test using the same antibacterial test method as in example 1, and the antibacterial rate was 97.8%.
Comparative example 1
The ceramic tile without the antibacterial nano-particles is subjected to an antibacterial test, the antibacterial test method is the same as that of the example 1, and the antibacterial rate is 5.6%.
Comparative example 2
Commercially available zinc oxide (ZnO) having a particle size of 50nm was added to the glaze in an amount of 1 wt.%, and the ceramic tile was glazed and subjected to an antibacterial test in the same manner as in example 1, wherein the antibacterial ratio was 65.4%.
Comparative example 3
Commercially available titanium dioxide (TiO) with the particle size of P252) The ceramic tile is mixed into glaze with the content of 1 wt%, glazed and subjected to an antibacterial test according to the same method as that of example 1, wherein the antibacterial rate is 36.7%.

Claims (10)

1. A nanoparticle for antimicrobial ceramics, characterized by the structural formula:
MxZnyOzor MxTiyOz，
Wherein M is the doping metal, x is the mole fraction of M, y is the mole fraction of zinc or titanium, and z is the mole fraction of oxygen;
m is one or more of iron, manganese, nickel, silver, gold, lanthanum, cerium or zirconium.
2. The nanoparticle for antibacterial ceramic of claim 1, wherein x is 0.01 to 0.25, y is 0.75 to 0.99, z is 1 to 3, and the particle size of the nanoparticle is 10 to 300 nm.
3. A method for preparing nanoparticles for antibacterial ceramics according to claim 1 or 2, characterized in that the nanoparticles precursor is dissolved in a solvent to obtain a precursor solution, the precursor solution is injected into a high-pressure gas, and then dispersed in a methane-oxygen flame to undergo reaction, coagulation and cooling, to obtain nanoparticles for antibacterial ceramics.
4. The method of claim 3, wherein the nanoparticle precursor is a precursor of M and zinc or a precursor of M and titanium.
5. The method according to claim 4, wherein the M and zinc precursors are M and zinc precursors, the M and titanium precursors are M and titanium precursors, the M precursor is one or more of M nitrate, acetate, citrate, 2-ethylhexanoate and metal acid, the zinc precursor is one or more of zinc nitrate, acetate, citrate and 2-ethylhexanoate, and the titanium precursor is one or more of titanium nitrate, acetate, citrate, 2-ethylhexanoate and titanate.
6. The method of claim 3, wherein the solvent is one or more selected from water, ethanol, toluene, and xylene.
7. The method of claim 3, wherein the nanoparticle precursor is present in the precursor solution in an amount of 2.5-60 wt.%.
8. The method of claim 3, wherein the high pressure gas is oxygen or nitrogen, the pressure of the high pressure gas is 0.1 to 1MPa, the flow rate of the precursor solution dispersed in the methane-oxygen flame is 1 to 20mL/min, and the nanoparticles for the antibacterial ceramic are collected by a collector having a screen.
9. The use of the nanoparticles for antimicrobial ceramics according to claim 1 or 2, characterized in that the nanoparticles for antimicrobial ceramics are incorporated into ceramic glaze, and the ceramic body is fired after glazing to obtain the antimicrobial ceramics.
10. Use of nanoparticles for antimicrobial ceramics according to claim 9, characterized in that the content of nanoparticles for antimicrobial ceramics in the glaze is 0.5-10 wt.%.
CN202011537926.6A 2020-12-23 2020-12-23 Nano-particles for antibacterial ceramics and preparation method and application thereof Pending CN112607784A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113287635A (en) * 2021-05-12 2021-08-24 湘潭大学 Preparation method of doped metal oxide nano-particles, dispersion or powder for resisting bacteria and preventing mildew

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1772375A (en) * 2005-10-27 2006-05-17 南京大学 Nanometer doped zinc oxide and its prepn and application in photocatalysis to degrade organic matter and kill bacteria
CN101565300A (en) * 2008-04-25 2009-10-28 浙江大学 Low-loss microwave dielectric ceramics
CN105152683A (en) * 2015-08-25 2015-12-16 山东建筑大学 Method for manufacturing nanometer antibacterial ceramic glaze layers

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1772375A (en) * 2005-10-27 2006-05-17 南京大学 Nanometer doped zinc oxide and its prepn and application in photocatalysis to degrade organic matter and kill bacteria
CN101565300A (en) * 2008-04-25 2009-10-28 浙江大学 Low-loss microwave dielectric ceramics
CN105152683A (en) * 2015-08-25 2015-12-16 山东建筑大学 Method for manufacturing nanometer antibacterial ceramic glaze layers

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
LINGQUAN MENG ET: "Low-temperature complete removal of toluene over highly active nanoparticles CuO-TiO2 synthesized via flame spray pyrolysis", 《APPLIED CATALYSIS B: ENVIRONMENTAL》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113287635A (en) * 2021-05-12 2021-08-24 湘潭大学 Preparation method of doped metal oxide nano-particles, dispersion or powder for resisting bacteria and preventing mildew

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