CN113877452B - Centrifugal dispersing instrument and method for preparing inorganic nano antibacterial mildew-proof spray by using same - Google Patents
Centrifugal dispersing instrument and method for preparing inorganic nano antibacterial mildew-proof spray by using same Download PDFInfo
- Publication number
- CN113877452B CN113877452B CN202111401601.XA CN202111401601A CN113877452B CN 113877452 B CN113877452 B CN 113877452B CN 202111401601 A CN202111401601 A CN 202111401601A CN 113877452 B CN113877452 B CN 113877452B
- Authority
- CN
- China
- Prior art keywords
- nano
- dispersing
- centrifugal
- pipeline
- particles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 230000000844 anti-bacterial effect Effects 0.000 title abstract description 83
- 239000007921 spray Substances 0.000 title abstract description 39
- 238000000034 method Methods 0.000 title abstract description 27
- 239000002105 nanoparticle Substances 0.000 abstract description 143
- 239000002245 particle Substances 0.000 abstract description 67
- 238000002360 preparation method Methods 0.000 abstract description 19
- 230000008569 process Effects 0.000 abstract description 13
- 238000009826 distribution Methods 0.000 abstract description 11
- 230000001954 sterilising effect Effects 0.000 abstract description 10
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 10
- 238000005054 agglomeration Methods 0.000 abstract description 8
- 230000002776 aggregation Effects 0.000 abstract description 8
- 239000012752 auxiliary agent Substances 0.000 abstract description 8
- 230000005012 migration Effects 0.000 abstract description 5
- 238000013508 migration Methods 0.000 abstract description 5
- 230000007774 longterm Effects 0.000 abstract description 4
- 230000001186 cumulative effect Effects 0.000 abstract description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 142
- 239000011787 zinc oxide Substances 0.000 description 66
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 41
- 239000011259 mixed solution Substances 0.000 description 34
- 239000002270 dispersing agent Substances 0.000 description 33
- 239000006185 dispersion Substances 0.000 description 33
- 239000007788 liquid Substances 0.000 description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 29
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 24
- 230000009471 action Effects 0.000 description 20
- 239000008367 deionised water Substances 0.000 description 19
- 229910021641 deionized water Inorganic materials 0.000 description 19
- 239000000463 material Substances 0.000 description 19
- 238000010008 shearing Methods 0.000 description 18
- 239000000243 solution Substances 0.000 description 17
- 230000000694 effects Effects 0.000 description 16
- 239000011701 zinc Substances 0.000 description 16
- 239000002086 nanomaterial Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 12
- 235000005074 zinc chloride Nutrition 0.000 description 12
- 239000011592 zinc chloride Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 239000003242 anti bacterial agent Substances 0.000 description 10
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 9
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 9
- 238000000518 rheometry Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 238000002156 mixing Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 241000894006 Bacteria Species 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 238000005286 illumination Methods 0.000 description 6
- 239000003380 propellant Substances 0.000 description 6
- 239000002202 Polyethylene glycol Substances 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 230000001580 bacterial effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- -1 iron ions Chemical class 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 241000588724 Escherichia coli Species 0.000 description 3
- 241000191967 Staphylococcus aureus Species 0.000 description 3
- 239000000443 aerosol Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 229920002873 Polyethylenimine Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical group 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 description 2
- AUZONCFQVSMFAP-UHFFFAOYSA-N disulfiram Chemical compound CCN(CC)C(=S)SSC(=S)N(CC)CC AUZONCFQVSMFAP-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Chemical group 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- HDLBOHGQTWKFRG-CVBJKYQLSA-N 3-azaniumylpropylazanium;(z)-octadec-9-enoate Chemical compound NCCCN.CCCCCCCC\C=C/CCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCC(O)=O HDLBOHGQTWKFRG-CVBJKYQLSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 244000063299 Bacillus subtilis Species 0.000 description 1
- 235000014469 Bacillus subtilis Nutrition 0.000 description 1
- 241000222122 Candida albicans Species 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 241000192125 Firmicutes Species 0.000 description 1
- 241000589517 Pseudomonas aeruginosa Species 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 241000456688 Sarika Species 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- SFEWMGIPBBLNJX-KTKRTIGZSA-N amino (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)ON SFEWMGIPBBLNJX-KTKRTIGZSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000000843 anti-fungal effect Effects 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229940095731 candida albicans Drugs 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000005911 diet Nutrition 0.000 description 1
- 230000037213 diet Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000002158 endotoxin Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 230000035558 fertility Effects 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000003053 toxin Substances 0.000 description 1
- 231100000765 toxin Toxicity 0.000 description 1
- 108700012359 toxins Proteins 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- 229940029284 trichlorofluoromethane Drugs 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
- A01N25/06—Aerosols
-
- 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
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/26—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests in coated particulate form
-
- 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
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
-
- 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
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D21/00—Separation of suspended solid particles from liquids by sedimentation
- B01D21/26—Separation of sediment aided by centrifugal force or centripetal force
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Abstract
The invention discloses a centrifugal dispersing instrument and a method for preparing an inorganic nano antibacterial and mildew-proof spray by using the same, wherein the preparation method of the inorganic nano antibacterial and mildew-proof spray adopts the centrifugal dispersing instrument, an auxiliary dispersing auxiliary agent and a related dispersing treatment process, so that the particle diameter D90 of doped ZnO nano particles can be realized, namely the particle cumulative distribution of the ZnO nano particles is 90 percent, the particle content of the particles smaller than the particle diameter is less than 110nm and less than 50nm, the agglomeration of the nano particles is effectively avoided, the dispersing efficiency of the doped nano particles is high, the particle diameter distribution is narrow, and the particle distribution is uniform. The inorganic nano antibacterial mildew-proof spray prepared by the preparation method can still have the characteristics of high sterilization efficiency, wide sterilization range, high safety and the like under the condition of insufficient light, and has long-term effectiveness and non-migration nano scale.
Description
Technical Field
The invention relates to the technical field of antibacterial materials, in particular to a centrifugal dispersing instrument and a method for preparing inorganic nano antibacterial mildew-proof spray by using the same.
Background
For a long time, various bacteria in life spread to cause various health problems, and microorganisms such as bacteria and mold enter human bodies through a certain mode (contact, respiration, diet, air flow and the like), so that the health is affected and diseases are spread. Along with the development and improvement of the knowledge of society, people also pay more and more attention to the sanitary problem in daily life, and the clean living environment can make human beings healthier, and the most effective way for keeping the clean living environment is sterilization and mildew removal so as to limit the spread of bacteria and microorganisms.
As such, development and application of antibacterial agents are receiving increasing attention, and existing antibacterial agents can be classified into organic antibacterial agents, inorganic antibacterial agents, natural plant antibacterial agents, etc., and inorganic antibacterial agents have been widely used in recent years due to their characteristics of durable antibacterial performance, good antibacterial effect, heat resistance, stable properties, etc.
Research shows that the effective components of the inorganic antibacterial material are thinned and dispersed into nano-sized inorganic nano antibacterial material, so that the nano-sized effect of the inorganic antibacterial material can be effectively utilized to kill bacteria. Inorganic nano antibacterial materials are generally classified into metal nano particle antibacterial materials (such as nano silver, nano copper, nano zinc and the like) and inorganic non-metal oxide nano antibacterial materials (such as nano silicon dioxide, nano zinc oxide, nano titanium dioxide, nano aluminum oxide, nano zirconium oxide, nano iron oxide and the like). The silver, copper and other components in the common metal nano particle antibacterial material can deactivate bacterial cells, but harmful substances such as internal toxins and the like can be released after bacteria are killed; the inorganic nonmetallic oxide nano antibacterial material not only can influence the bacterial fertility, but also can attack the outer layer of bacterial cells, penetrate cell membranes, thoroughly destroy bacteria and prevent secondary pollution caused by endotoxin. In contrast, the inorganic nonmetallic oxide nano antibacterial material has the characteristics of high safety, thorough sterilization, wide sources, lasting antibacterial performance and the like, and is paid attention to.
Chinese patent No. 109893539A (title of the invention: a compound antibacterial aerosol and its preparation method) is prepared by mixing chitosan bisquaternary ammonium salt, nanoscale titanium dioxide and sea salt, adding into ethanol solution, adding surfactant, stirring thoroughly, adding film forming agent and lubricant, stirring uniformly, sealing the obtained mixture with metering valve system, and pressing into propellant. The antibacterial aerosol is prepared by uniformly mixing the nano particles by a stirring and mixing method, so that the nano particles cannot be kept in nano scale, and the antibacterial aerosol is easy to agglomerate and affects the antibacterial effect; the antibacterial spray material can only play an antibacterial role under the condition of strong illumination, and the antibacterial effect is not good under the condition of weak illumination.
Chinese patent No. 1772375A (title of invention: doped nano zinc oxide, preparation method thereof, photocatalytic degradation of organic matter and antibacterial application) relates to a preparation method of nano zinc oxide doped with silver and rare earth metals, and photocatalytic degradation of organic matter and antibacterial application thereof. The photocatalyst generates higher photocatalytic activity than common zinc oxide under illumination, and improves the antibacterial capability; when no light is irradiated, the silver, zinc, rare earth metal and other antibacterial ions still have strong antibacterial effect. However, the nano zinc oxide doped antibacterial agent only adopts a mixing method to uniformly mix nano particles, and the processing technology does not perform corresponding surface treatment on the nano zinc oxide doped to achieve good nano dispersion effect, is easy to generate agglomeration phenomenon, and cannot enable the nano zinc oxide doped to always keep nano size, thereby influencing the antibacterial effect.
《M 2+ (m=cu, cd, ag, fe) -doped zinc oxide nanocrystals for antibacterial properties (Ding Yan et al, inorganic chemistry report, 2014.2,30 (2)) ZnO and M were prepared by the citric acid sol-gel method 2+ The ZnO nano powder crystal (M=Cu, cd, ag and Fe) is doped, the composition, structure and appearance of the sample are characterized by using a test technology, and the antibacterial activity of the sample under sunlight irradiation is studied by using escherichia coli, staphylococcus aureus and candida albicans as test strains. The results show that the antibacterial properties of Cu, ag and Cd doped samples are significantly enhanced compared with the parent ZnO, which is probably due to the substitution of Zn by doped metal ions 2+ Lattice defects and charge defects are generated, and photo-generated electrons and photo-generated hole pairs are preventedCompounding thereby enhancing photocatalytic activity and antibacterial activity. However, the doped zinc oxide nano powder crystal does not adopt any nano particle dispersing measure, and the processing technology does not carry out corresponding surface treatment on the doped nano zinc oxide, so that the nano dispersing effect cannot be achieved, and the doped zinc oxide nano powder crystal particles exist in an agglomerated form, cannot keep the nano size and influence the antibacterial effect.
Chinese patent No. 102417220A (title: application of tantalum doped zinc oxide nanopowder photocatalyst in water treatment antibacterial) discloses application of tantalum doped zinc oxide nanopowder photocatalyst in water treatment antibacterial. The strain comprises gram positive bacteria including bacillus subtilis, staphylococcus aureus, gram negative bacteria such as escherichia coli and pseudomonas aeruginosa, and the tantalum-doped zinc oxide nano powder can inhibit bacterial growth in dark environment and visible light, and has antibacterial property superior to that of pure zinc oxide nano powder; and the photocatalysis can effectively reduce the Minimum Inhibitory Concentration (MIC) in a dark environment, and a higher antibacterial effect can be achieved by smaller addition amount. However, the tantalum doped zinc oxide nano powder antibacterial agent does not adopt any nano particle dispersing measure, and powder particles still exist in an agglomerated form, so that nano size cannot be maintained, and the antibacterial effect is affected.
In general, even if the nanoparticles are dispersed in a matrix material, agglomeration still occurs during subsequent storage, no longer maintains the nano-sized effect, and the antibacterial effect of the antibacterial agent is affected, so that it is required to find a material capable of stably maintaining the nano-sized of the antibacterial agent for a long time.
Among a plurality of inorganic nonmetallic oxide nano-materials, zinc oxide (ZnO) has the advantages of simple preparation process, various preparation methods, easy doping and the like, and is widely concerned; znO is a direct band gap wide bandgap semiconductor with high electron mobility (115-155 cm) 2 And (V.s)), the ZnO nano material is subjected to dispersion modification, so that the nano size of the ZnO nano material can be stably maintained for a long time, and the inorganic nano antibacterial mildew-proof spray is prepared.
Disclosure of Invention
To overcome the shortcomings and drawbacks of the prior art, a primary object of the present invention is to provide a centrifugal disperser that can be used to physically disperse inorganic nonmetallic particles in a solution.
The second object of the invention is to provide a preparation method of the inorganic nano antibacterial and mildew-proof spray, wherein a centrifugal dispersing instrument is used in the preparation method, and the inorganic nano antibacterial and mildew-proof spray with excellent antibacterial and mildew-proof performances is prepared by uniformly dispersing a to-be-dispersed mixed solution in a mode of combining physical dispersion and chemical dispersion.
The specific surface area of the nano particle is large, the surface energy is high, the coordination number of surface atoms is insufficient, the activity of the surface atoms is high, the nano particle is extremely unstable, and surface electrons are easy to separate from holes. Conventional inorganic nonmetallic oxide nanoparticles achieve antibacterial effect by means of such electron-hole separation. However, the electrons and holes are often recombined, so that the antibacterial effect is reduced, and another ion is required to be introduced to prevent the combination of the electrons and the holes, so that the catalytic efficiency is improved, and a common method is transition metal doping. Studies have shown (Singh, sarika, back, et al Novel and Efficient Three Dimensional Mesoporous ZnO Nanoassemblies For Envirnomental Remediation [ J)]International Journal of Nanoscience, 2011) iron ions (Fe 3+ ) Radius is close to zinc ion (Zn) 2+ ) The catalyst is nontoxic and easy to dope, and can effectively improve the catalytic efficiency of the inorganic nano oxide. Fe (Fe) 3+ The capability of capturing electrons and the capability of capturing holes of the valence d orbit of the ZnO are basically the same, the recombination of electron-hole pairs generated on the surface of ZnO can be prevented by capturing the electrons and the holes, and the energy is released and absorbed continuously, so that the antibacterial activity of the inorganic nonmetallic oxide nano material is improved, the sterilization effect is greatly improved, and the ZnO doped with iron ions (Fe 3+ ) The inorganic nano antibacterial mildew-proof spray can effectively sterilize even under the condition of insufficient light.
The third aim of the invention is to provide the inorganic nano antibacterial mildew-proof spray prepared by the preparation method.
The primary purpose of the invention is realized by the following technical scheme:
a centrifugal dispersing instrument, as shown in figure 1, consists of a feed inlet, a pressure build-up bin, a high-pressure pump and a centrifugal dispersing device; the charging port and the high-pressure pump are connected with the pressure building bin through a valve; the centrifugal dispersing device is arranged at the lower end of the pressure building bin and is connected with the pressure building bin through a sealing valve; the centrifugal dispersing device comprises a coarse pipeline, an accelerating pipeline and a centrifugal dispersing pipeline which are connected in sequence, wherein the diameter of the coarse pipeline is the same as the maximum diameter of the accelerating pipeline, and the diameter of the centrifugal dispersing pipeline is the same as the minimum diameter of the accelerating pipeline.
Preferably, the centrifugal dispersing instrument further comprises a dispersing instrument outlet arranged at the tail end of the centrifugal dispersing pipeline.
Preferably, the accelerating pipeline is an annular accelerating pipeline with gradually reduced diameter, and the ratio of the maximum diameter to the minimum diameter of the accelerating pipeline is 4:1.
The high-pressure pump is external equipment, and can increase the pressure in the pressure building bin to 40-50MPa; the inner wall of the accelerating pipeline and the inner wall of the centrifugal dispersing pipeline are frosted pipeline walls, and the surface roughness of the frosted pipeline walls reaches 3000 meshes.
Critical dimensions of the centrifugal disperser include: the diameter of the thick pipeline is 20mm; the ratio of the maximum diameter to the minimum diameter of the accelerating pipeline is-4:1; accelerating the length of the pipeline to 40mm; the diameter of the centrifugal dispersing pipeline is-5 mm; the total length of the centrifugal dispersing pipeline is-2 m, the maximum encircling diameter is-0.3 m, and the encircling number is-4.
Preferably, the specific working process of the centrifugal dispersing instrument for dispersing the nanoparticle mixed solution is as follows:
1) Firstly, adding the nanoparticle mixed solution to be dispersed into a pressure building bin through a charging port, closing all valves connected with the pressure building bin, opening a high-pressure pump and a closed valve to start pressure building, and setting the pressure target value of the pressure building to be 40-50MPa;
2) After the pressure reaches a target set value, a valve connected between the pressure build bin and the coarse pipeline is opened, the nanoparticle mixed liquid easy to agglomerate passes through the coarse pipeline to reach an accelerating pipeline, the pipeline of the accelerating pipeline gradually tapers, and the volume flow of the nanoparticle mixed liquid easy to agglomerate is unchanged in the process of tapering through the pipeline, so that the linear speed of the nanoparticle mixed liquid easy to agglomerate in the fine pipeline is relatively higher, the linear speed of the nanoparticle mixed liquid to be dispersed in the coarse pipeline is relatively lower, and the stretching effect of the nanoparticle mixed liquid to be dispersed in the flow speed direction is caused by the speed difference under the higher speed and the pressure, so that the stretching rheology is generated; the extensional rheology leads the particles in the mixed solution of the nano particles to be dispersed to be strongly stretched, and the agglomerated particles are gradually dispersed under the action of the extensional rheology to form nano-scale particles;
3) After the nanoparticle mixed liquid easy to agglomerate enters the centrifugal dispersing pipeline after being accelerated, the nanoparticle mixed liquid is enabled to be subjected to a great centrifugal force by the annular pipeline due to the fact that the nanoparticle mixed liquid has a high speed, the centrifugal force is provided by the outer side of the inner wall of the centrifugal dispersing pipeline (the outer side a of the inner wall of the pipeline), high acting force and high-speed friction are generated between the 3000-mesh frosted wall surface of the position and the nanoparticle mixed liquid easy to agglomerate, and agglomerated nanoparticles can be further dispersed and dissociated in water.
In the whole dispersing process, the pressure applied by the high-pressure pump directly acts on the nanoparticle mixed solution easy to agglomerate, so that the nanoparticle mixed solution is always in a high-pressure state; the high flow rate of the nanoparticle mixture liquid easy to agglomerate is generated under high pressure, so that the nanoparticles easy to agglomerate at the accelerating pipeline are stretched by a high flow rate difference, and the agglomerated nanoparticles are gradually scattered and dispersed into nanoparticles; on the other hand, the annular pipeline gives a certain centrifugal force to the nanoparticle mixed liquid with high flow rate, the centrifugal force is balanced with the pressure of the nanoparticle mixed liquid acting on the pipe wall, the nanoparticle mixed liquid is subjected to high shearing action under the action of the pressure and the rough pipe wall, and the high shearing action again performs shearing and tearing actions on the agglomerated nanoparticles, so that the agglomeration phenomenon is further broken up, and the nanoscale particles are formed.
Compared with common nano dispersing equipment, the centrifugal dispersing instrument provided by the invention has the advantages of high speed, high pressure, high stretching, high shearing and the like. The dispersion equipment commonly used in the market generally relies on shearing force generated by high-speed running of the equipment to grind nano particles, such as a ball mill, a high-speed grinder and the like; in addition, there are devices such as spray-drying dispersing instruments and the like which rely on the application of high pressure to the material to disperse the particles. These devices simply disperse the agglomerated nanoparticles by creating high shear or high pressure, which is not effective. The centrifugal dispersing instrument provided by the invention combines high speed, high pressure, high stretching and high shearing to make the centrifugal dispersing instrument act on the easily agglomerated nano particles, so that the uniform dispersion of the easily agglomerated nano particles can be better carried out.
The second object of the invention is achieved by the following technical scheme:
a preparation method of an inorganic nano antibacterial mildew-proof spray comprises the following steps: the inorganic nano antibacterial and mildew-proof spray is prepared by uniformly mixing, by mass, 0.5-10 parts of inorganic nonmetallic oxide nano particles, 20-80 parts of deionized water, 1-20 parts of dispersing agents and 1-40 parts of auxiliary dispersing aids to obtain a nano particle mixed solution, adding the nano particle mixed solution into a centrifugal dispersing instrument shown in fig. 1 for centrifugal dispersion, adding a propellant into the water-soluble nano mixed solution after dispersion treatment, mixing and bottling. Wherein the propellant is used in an amount according to the situation, and the pressure in the bottle can reach 2-5Mpa during bottling.
Preferably, the nanoparticle mixed solution reaches an accelerating pipeline 6 through a coarse pipeline 5 of the centrifugal dispersing instrument, the pipeline gradually tapers, the nanoparticle mixed solution is forced to generate stretching rheology, a dispersing agent in the nanoparticle mixed solution, znO particles, auxiliary dispersing aids and the like are stretched and oriented, the agglomerated ZnO particles are gradually dispersed under the action of the stretching force, and the dispersing agent and a dispersing agent molecular chain are mixed in a solvent, so that a better dispersing effect is achieved. In addition, the inner wall of the annular pipeline in the centrifugal dispersing instrument also provides a larger centrifugal force for ZnO mixed liquid flowing at a high speed, so that the nano particles in the mixed liquid are subjected to a high shearing action, and the aim of uniform dispersion is fulfilled.
Preferably, the inorganic nonmetallic oxide nanoparticles have the molecular formula Zn 1-x Fe x O 1+0.5x Wherein x is more than or equal to 0.05 and less than or equal to 0.15.
Preferably, the inorganic nonmetallic oxide nanoparticles have the molecular formula Zn 0.95 Fe 0.05 O 1.025 。
Preferably, the inorganic nonmetallic oxide nanoparticles have the molecular formula Zn 0.85 Fe 0.15 O 1.075 。
Preferably, the preparation method of the inorganic nonmetallic oxide nano-particles comprises the following steps:
(1) Zinc chloride (ZnCl) 2 ) Dissolving in hydrochloric acid (HCl) solution, adding ammonia water (NH) 3 ·H 2 O), regulating pH to 1-4, stirring uniformly to obtain mixed solution, znCl in the mixed solution 2 The mass volume ratio of the mixed solution to the mixed solution is 1g to 80-100mL;
(2) Adding the mixed solution obtained in the step (1) into deionized water, wherein the volume ratio of the mixed solution to the deionized water is 1 (20-25), and carrying out hydrothermal reaction for 2-10h at 120-200 ℃;
(3) Adding ferric chloride hexahydrate (FeCl) to the product obtained in the step (2) 3 ·6H 2 O) stirring and mixing, microwave reacting for 1-2h, and then ultrasonic treating for 30-50min, wherein FeCl is added 3 ·6H 2 O and ZnCl 2 The mass ratio of (2) is 1:10-50;
(4) Stirring and reacting the product obtained in the step (3) for 8-12 hours at 150-160 ℃, then centrifuging, washing the precipitate with deionized water and absolute ethyl alcohol for 5 times respectively, and drying to obtain the inorganic nonmetallic oxide nano particles.
The invention uses iron ion (Fe 3+ ) Zinc oxide (ZnO) is doped to improve the antimicrobial activity of the inorganic non-metal oxide nanomaterial. The particles in the mixed solution are uniformly dispersed by a mode of combining a physical dispersion method (centrifugal dispersing instrument) and a chemical dispersion method (dispersing agent), so that the particles completely reach a nano-size state, and the inorganic nonmetallic oxide nano particles dispersed into the nano-size state have excellent antibacterial and mildew-proof effects.
The inorganic nonmetallic oxide nanoparticles (Zn) 1-x Fe x O 1+0.5x X is more than or equal to 0.05 and less than or equal to 0.15) is Fe 3+ The doped ZnO particles are subjected to preliminary grinding to obtain powdery Fe 3+ Doped ZnO particles (Zn) 1-x Fe x O 1+0.5x ) At this time, the ZnO particles do not reach the nano-sized state, and it is necessary to disperse them.
Preferably, the dispersing agent includes anionic dispersing agent, cationic dispersing agent, nonionic dispersing agent, amphoteric dispersing agent, electrically neutral dispersing agent and high molecular dispersing agent; the anionic dispersing agent is one of sodium oleate, carboxylate, sulfate salt or sulfonate, and the cationic dispersing agent is one of octadecylenamine acetate, ammonium salt, aminopropylamine dioleate, quaternary ammonium salt, polyaminoamide phosphate or pyridinium salt; the nonionic dispersing agent is one of an adduct of fatty acid ethylene oxide, a polyethyleneimine derivative glycol type or a polyol type; the amphoteric dispersant is phosphate type high molecular polymer; the electrically neutral dispersant is oil amino oleate; the high molecular type dispersing agent is one of a poly-caprolactame polyol-polyethyleneimine segmented copolymer type, an acrylic ester high molecular type or a polyurethane or polyester type high molecular dispersing agent.
Preferably, the auxiliary dispersing aid is polyethylene glycol grafted glycidyl methacrylate (PEG-g-GMA), and can be prepared by a method described in patent CN201710959226.8 (polyethylene glycol modified glycidyl methacrylate resin, preparation method and application) (polyethylene glycol diacrylate and glycidyl methacrylate are used as monomers, tetraethylthiuram disulfide is used as a precursor, azodiisobutyronitrile is used as an initiator, and a one-pot reaction system is used for reaction for 6 hours at 70 ℃).
Preferably, the propellant is at least one of compressed carbon dioxide, compressed nitrous oxide, trichlorofluoromethane, difluoromethane.
By passing Fe through 3+ Adding the mixed solution of doped ZnO particles (hereinafter referred to as ZnO particles) together with deionized water, dispersant and auxiliary dispersing aid into a centrifugal dispersing instrument shown in figure 1, enabling the mixed solution to reach an accelerating pipeline through a coarse pipeline, gradually tapering the pipeline to force the mixed solution to generate stretching rheology, stretching and orienting the dispersant in the mixed solution together with ZnO particles, auxiliary dispersing aid and the like to agglomerate ZThe nO particles are gradually dispersed under the action of the tensile force and are mixed with the molecular chains of the dispersing agent in the solvent, so that a better dispersing effect is achieved. In addition, the inner wall of the annular pipeline in the centrifugal dispersing instrument also provides a larger centrifugal force for ZnO mixed liquid flowing at a high speed, so that the nano particles in the mixed liquid are subjected to a high shearing action, and the aim of uniform dispersion is fulfilled.
The particle size of ZnO nano particles treated by the physical dispersion and chemical dispersion method provided by the invention is kept around 110nm, the minimum particle size is below 50nm, and the ZnO nano particles can be uniformly dispersed in aqueous solution for a long time through the wrapping of a dispersing auxiliary agent. Adding a propellant into the water-soluble nanometer mixed solution after the dispersion treatment, mixing and bottling to obtain the inorganic nanometer antibacterial and mildew-proof spray. The spray has good antibacterial and mildew-proof effects and lasting antibacterial performance.
In addition, fe 3+ The surface of the doped ZnO nano particle is adsorbed with a large number of hydroxyl groups, and glycidyl methacrylate (-GMA) molecules in molecular chains of the auxiliary dispersing agent which are free in water contain epoxy groups, hydrogen bonds can be formed between the two groups and partial chemical reaction can be generated to carry out modification, and the modified ZnO nano particle is connected with a dispersing aid; meanwhile, polyethylene glycol molecular chains in the dispersing aid are easy to dissolve in water, and dispersed nano particles are wrapped by the dispersing aid under the shearing and grinding effects of a centrifugal dispersing instrument and can be uniformly dispersed in the aqueous solution; on the other hand, the ZnO nano-particles are connected with the dispersing aid, which is equivalent to dragging a long molecular chain, and the migration and movement capacity of the ZnO nano-particles is blocked by the molecular chain of the dispersing agent, so that the ZnO nano-particles cannot be agglomerated again due to contact with other nano-particles for a long time after being dispersed.
The third object of the invention is achieved by the following technical scheme:
the inorganic nano antibacterial and mildew-proof spray prepared by the preparation method has the characteristics of high sterilization efficiency, wide sterilization range, high safety and the like under the condition of insufficient light rays, and has long-term effective non-migration nano scale.
Compared with the prior art, the invention has the following advantages:
(1) When the inorganic nano antibacterial mildew-proof spray is prepared, the particle diameter D90 of the doped ZnO nano particles (namely, the particle cumulative distribution of the particles is 90 percent, the particle content of the particles smaller than the particle diameter is 90 percent of the total particles) can be smaller than 110nm, and the minimum particle content can be smaller than 50nm by adopting a centrifugal disperser, an auxiliary dispersing auxiliary agent and a related dispersing treatment process, so that the agglomeration of the nano particles is effectively avoided, the dispersing efficiency of the doped nano particles is high, the particle size distribution is narrow, and the particle distribution is uniform.
(2) When the invention is used for preparing the inorganic nano antibacterial mildew-proof spray, a centrifugal dispersing instrument is used for dispersing Fe 3+ The doped ZnO particles are subjected to high-speed, high-pressure, high-tensile and high-shear dispersion treatment. The ZnO aqueous solution is subjected to extensional rheology in a centrifugal dispersing instrument, the dispersing agent, znO particles and auxiliary dispersing auxiliary agents are stretched and oriented together, and the agglomerated ZnO particles are dispersed under the action of the stretching force and mixed with molecular chains of the dispersing agent in a solvent. In addition, the accelerating pipeline is an annular pipeline, the radius of the annular pipeline is gradually reduced, so that higher pressure (centrifugal force is larger and larger) is formed between the nano solution and the outer wall of the pipeline, the wall surface of the inner wall of the accelerating pipeline collides with ZnO nano particles at high speed and high pressure, and agglomerated particles are subjected to stronger shearing force and further good dispersion. In a centrifugal dispersing instrument, through Fe 3+ The doped ZnO particles are subjected to high-speed and high-pressure actions and high-tensile and high-shear dispersing actions, and the four actions can disperse the particles to the greatest extent, so that the particles are dispersed into nano-sized particles, and the ZnO particles have the advantages which are not possessed by other dispersing equipment in the current market. This ensures uniform dispersion of the nanoparticles and excellent antibacterial and antifungal effects of the finally formed spray.
In a centrifugal disperser, fe 3+ The surface of the doped ZnO nano particle is provided with hydroxyl, and the hydroxyl and the auxiliary dispersing aid polyethylene glycol grafted glycidyl methacrylate can be connected through hydrogen bonds, and can also be connected through chemical reaction, so that the state that the auxiliary dispersing aid molecules wrap the ZnO nano particle is formed; meanwhile, as the ZnO nano-particles are connected with one or more long molecular chains,the migration movement capability of the ZnO nano-particle is hindered by a molecular chain of the dispersing agent, and the agglomeration phenomenon can not happen again due to contact with other nano-particles after the ZnO nano-particle is dispersed, so that the ZnO nano-particle after the ZnO nano-particle is dispersed can be kept in a nano-size state for a long time, and the finally prepared spray has long-term antibacterial and mildew-proof effects.
The mechanical physical dispersion of the nano particles by using a centrifugal dispersing instrument and the chemical dispersion of the nano particles by using a dispersing aid are two important characteristics of the preparation method of the antibacterial and mildew-proof spray. Only by combining the two dispersing methods, the nano particle size in the antibacterial and mildew-proof spray can be ensured to be minimized, and the nano particle can be uniformly dispersed and can be placed for a long time without agglomeration, so that the nano material can fully exert the nano size effect, the nano antibacterial mechanism is realized, and the finally prepared spray has excellent and durable antibacterial and mildew-proof effects. If one of the two important dispersing methods is absent, the antibacterial and mildew-proof effects of the spray are deteriorated.
(3) The inorganic nano antibacterial mildew-proof spray prepared by the invention can still have the characteristics of high sterilization efficiency, wide sterilization range, high safety and the like under the condition of insufficient light, and has long-term effectiveness of non-migration nano scale.
Drawings
FIG. 1 is a schematic diagram of the centrifugal disperser in example 1,
wherein, 1-a charging port; 2-high pressure pump; 3-a sealing valve; 4, building a pressure bin; 5-coarse piping; 6-accelerating pipeline;
7-centrifuging the dispersion pipeline; 8-disperser outlet (a-outside of inner wall of pipe; b-inside of inner wall of pipe);
FIG. 2 is a graph showing the particle size and distribution of ZnO particles in example 2;
FIG. 3 is a graph showing the particle size and distribution of ZnO particles in example 3;
FIG. 4 is a graph showing the particle size and distribution of ZnO particles in example 4;
FIG. 5 is a graph showing the particle size and distribution of ZnO particles in example 5;
FIG. 6 is a graph of the particle size of the abrasive particles of the comparative example.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but embodiments of the present invention are not limited thereto.
Example 1
The centrifugal dispersing instrument shown in fig. 1 consists of a feed inlet 1, a pressure building bin 4, a high-pressure pump 2 and a centrifugal dispersing device; the charging port 1 and the high-pressure pump 2 are connected with the pressure building bin 4 through valves; the centrifugal dispersing device is arranged at the lower end of the pressure building bin 4 and is connected through the sealing valve 3; the centrifugal dispersing device comprises a coarse pipeline 5, an accelerating pipeline 6 and a centrifugal dispersing pipeline 7 which are connected in sequence, wherein the diameter of the coarse pipeline 5 is the same as the maximum diameter of the accelerating pipeline 6, and the diameter of the centrifugal dispersing pipeline 7 is the same as the minimum diameter of the accelerating pipeline 6.
Further, the centrifugal dispersing instrument further comprises a dispersing instrument outlet 8 arranged at the tail end of the centrifugal dispersing pipeline 7.
Further, the accelerating pipeline 6 is an annular accelerating pipeline with gradually reduced diameter, and the ratio of the maximum diameter to the minimum diameter of the accelerating pipeline 6 is 4:1.
The high-pressure pump 2 is external equipment, and can increase the pressure in the pressure building bin to 40MPa; the inner walls of the accelerating pipeline 6 and the centrifugal dispersing pipeline 7 are frosted pipe walls, and the surface roughness of the frosted pipe walls reaches 3000 meshes.
The key dimensions of the centrifugal disperser in this embodiment include: the diameter of the thick pipeline 5 is 20mm; the ratio of the maximum diameter to the minimum diameter of the accelerating pipeline 6 is 4:1; the length of the accelerating pipeline 6 is 40mm; the diameter of the centrifugal dispersing pipeline 7 is 5mm; the centrifugal dispersing pipe 7 has an overall length of 2m, a maximum encircling diameter of 0.3m and 4 encircling turns.
In this embodiment, the specific working process of the centrifugal dispersing instrument for dispersing the nanoparticle mixture is as follows:
1) Firstly, adding a nanoparticle mixed solution to be dispersed into a pressure building bin 4 through a charging port 1, closing all valves connected with the pressure building bin 4, opening a high-pressure pump 2 and a closed valve 3 to start pressure building, and setting a pressure target value of the pressure building to 40MPa;
2) After the pressure reaches a target set value, a valve connected between the pressure build bin 4 and the coarse pipeline 5 is opened, the nanoparticle mixed liquid easy to agglomerate passes through the coarse pipeline 5 to reach an accelerating pipeline 6, the pipeline of the accelerating pipeline 6 gradually tapers, and the volume flow of the nanoparticle mixed liquid easy to agglomerate is unchanged in the process of tapering through the pipeline, so that the linear speed of the nanoparticle mixed liquid easy to agglomerate in the fine pipeline is relatively higher, the linear speed of the nanoparticle mixed liquid to be dispersed in the coarse pipeline is relatively lower, and the stretching effect of the nanoparticle mixed liquid to be dispersed in the flow speed direction is caused by the speed difference under the higher speed and the pressure, so that the stretching rheology is generated; the extensional rheology leads the particles in the mixed solution of the nano particles to be dispersed to be strongly stretched, and the agglomerated particles are gradually dispersed under the action of the extensional rheology to form nano-scale particles;
3) After being accelerated, the nanoparticle mixed liquid easy to agglomerate enters a centrifugal dispersing pipeline 7, and the nanoparticle mixed liquid is subjected to a great centrifugal force by the annular pipeline due to the fact that the nanoparticle mixed liquid has a high speed, and the centrifugal force is provided by the outer side of the inner wall of the centrifugal dispersing pipeline 7 (the outer side a of the inner wall of the pipeline), high acting force and high-speed friction are generated between a 3000-mesh frosted wall surface and the nanoparticle mixed liquid easy to agglomerate, so that the agglomerated nanoparticles can be further dispersed and dissociated in water.
In the whole dispersing process, the pressure applied by the high-pressure pump 2 directly acts on the nanoparticle mixed solution easy to agglomerate, so that the nanoparticle mixed solution is always in a high-pressure state; the easily agglomerated nanoparticle mixture generates high flow velocity under high pressure, so that the easily agglomerated nanoparticles at the accelerating pipeline 6 are stretched by high flow velocity difference, and the agglomerated nanoparticles are gradually scattered and dispersed into nanoparticles; on the other hand, the annular pipeline gives a certain centrifugal force to the nanoparticle mixed liquid with high flow rate, the centrifugal force is balanced with the pressure of the nanoparticle mixed liquid acting on the pipe wall, the nanoparticle mixed liquid is subjected to high shearing action under the action of the pressure and the rough pipe wall, and the high shearing action again performs shearing and tearing actions on the agglomerated nanoparticles, so that the agglomeration phenomenon is further broken up, and the nanoscale particles are formed.
Compared with common nano dispersing equipment, the centrifugal dispersing instrument provided by the embodiment of the invention has the advantages of high speed, high pressure, high stretching, high shearing and the like. The dispersion equipment commonly used in the market generally relies on shearing force generated by high-speed running of the equipment to grind nano particles, such as a ball mill, a high-speed grinder and the like; in addition, there are devices such as spray-drying dispersing instruments and the like which rely on the application of high pressure to the material to disperse the particles. These devices simply disperse the agglomerated nanoparticles by creating high shear or high pressure, which is not effective. The centrifugal dispersing instrument provided by the invention combines high speed, high pressure, high stretching and high shearing to make the centrifugal dispersing instrument act on the easily agglomerated nano particles, so that the uniform dispersion of the easily agglomerated nano particles can be better carried out.
Table 1 shows the main performance comparison of the centrifugal disperser provided by the invention with two dispersing devices commonly used in the market at present. It can be seen that the centrifugal disperser provided by the invention combines speed and pressure to disperse particles; the common nano dispersing device mainly depends on the action of high-speed shearing force, and the centrifugal dispersing instrument provided by the invention not only applies high-speed shearing force to particles, but also applies the action of tensile force.
Table 1 main performance comparison of each dispersing apparatus
The centrifugal disperser provided by the invention is used for physically dispersing inorganic nonmetallic oxide particles in a solution.
Example 2
1、Fe 3+ Doping ZnO nano material to prepare inorganic nonmetallic oxide nano particles, wherein the modification process comprises the following steps:
(1) ZnCl 2 (ZnCl 2 Model: the germany langsheng 1050, guangzhou pun distal chemical company, is dissolved in HCl solution (model: 0.1-1.0MOL, shenzhen Jinyi trade Co., ltd.) with an appropriate amount of NH 3 ·H 2 O (model: A801005, michelin), adjusting pH to 2, stirringHomogenizing, in this case as a mixed solution, znCl 2 The ratio of the solution to the mixed solution is 1g to 80mL;
(2) Adding the solution into deionized water, wherein the volume ratio of the solution to the deionized water is 1:20, and carrying out hydrothermal reaction for 8 hours at 150 ℃;
(3) FeCl is added into the product in the step (2) 3 ·6H 2 O (model: I809489, michelin) is stirred and mixed, reacted for 2 hours by microwave, and then treated by ultrasonic for 50 minutes, wherein FeCl is added 3 ·6H 2 O and ZnCl 2 The mass ratio of (2) is 1:50;
(4) Stirring the product obtained in the step (3) at 160 ℃ for reaction for 10 hours, centrifuging, washing the precipitate with deionized water and absolute ethyl alcohol for 5 times respectively, and drying to obtain Fe-treated product 3+ Doped ZnO nanoparticles forming Zn 0.95 Fe 0.05 O 1.025 The powder doped inorganic nonmetallic oxide nano particles can be obtained through preliminary grinding.
2. An inorganic nano-antibacterial mildew-proof spray comprises the following components in parts by mass:
the inorganic nonmetallic oxide nanoparticles after doping are added into a centrifugal disperser described in example 1 together with deionized water, a dispersing agent and an auxiliary dispersing aid for treatment, so that the average particle diameter of the nanoparticles is kept below 96nm (as shown in fig. 2, the left-hand marked arrow indicates the content percentage of each nanometer size shown in the graph and corresponds to the left scale; the right-hand arrow indicates the cumulative distribution of the sizes of the nanoparticles shown in the graph and corresponds to the right scale), and the nanoparticles are dispersed in water for a long time and uniformly. Finally, the Fe is added into 3+ And compressing and bottling (3 MPa) the doped and dispersed ZnO dispersion liquid with propellant carbon dioxide to obtain the inorganic nano antibacterial mildew-proof spray.
Example 3
Doping Fe 3+ The nano ZnO material of (2) is used for preparing inorganic nonmetallic oxide nano particles, in particularThe following operations were performed, wherein each composition ratio (mass ratio) was the same as in example 2, except that nano ZnO was subjected to Fe with different contents in step (3) 3+ Doping and modifying. Fe (Fe) 3+ The modification process of the doped ZnO nano material comprises the following steps:
(1) ZnCl 2 (ZnCl 2 Model: the germany langsheng 1050, guangzhou pun distal chemical company, is dissolved in HCl solution (model: 0.1-1.0MOL, shenzhen Jinyi trade Co., ltd.) with an appropriate amount of NH 3 ·H 2 O (model: A801005, michelin), adjusting pH to 2, stirring to obtain mixed solution, znCl 2 The ratio of the solution to the mixed solution is 1g to 80mL;
(2) Adding the solution into deionized water, wherein the volume ratio of the solution to the deionized water is 1:20, and carrying out hydrothermal reaction for 8 hours at 150 ℃;
(3) FeCl is added into the product in the step (2) 3 ·6H 2 O (model: I809489, michelin) is stirred and mixed, reacted for 2 hours by microwave, and then treated by ultrasonic for 50 minutes, wherein FeCl is added 3 ·6H 2 O and ZnCl 2 The mass ratio of (2) is 1:30;
(4) Stirring the product obtained in the step (3) at 160 ℃ for reaction for 10 hours, centrifuging, washing the precipitate with deionized water and absolute ethyl alcohol for 5 times respectively, and drying to obtain Fe-treated product 3+ Doped ZnO nanoparticles forming Zn 0.9 Fe 0.1 O 1.05 The powder doped inorganic nonmetallic oxide nano particles can be obtained through preliminary grinding.
2. The inorganic nonmetallic oxide nano particles, deionized water, a dispersing agent and an auxiliary dispersing auxiliary agent are added into a centrifugal dispersing instrument for dispersion treatment, wherein the composition ratio (mass ratio) is the same as that of the embodiment 1, and the difference is that in the step (3), the inorganic nonmetallic oxide nano particles pass through nano ZnO and have different contents of Fe 3+ Doping modification, which keeps the average particle diameter of the nano particles below 101nm (as shown in figure 3), and the nano particles are uniformly dispersed in water for a long time. Finally, the Fe is added into 3+ The doped and dispersed ZnO dispersion liquid is compressed by carbon dioxide and bottled (4 MPa) to obtain the inorganic nano antibacterial and anti-bacterial agentAnd (5) mould spray.
Example 4
1、Fe 3+ Doping ZnO nano material to prepare inorganic nonmetallic oxide nano particles, wherein the modification process comprises the following steps:
(1) ZnCl 2 (ZnCl 2 Model: the germany langsheng 1050, guangzhou pun distal chemical company, is dissolved in HCl solution (model: 0.1-1.0MOL, shenzhen Jinyi trade Co., ltd.) with an appropriate amount of NH 3 ·H 2 O (model: A801005, michelin), adjusting pH to 2, stirring to obtain mixed solution, znCl 2 The ratio of the solution to the mixed solution is 1g to 100mL;
(2) Adding the solution into deionized water, wherein the volume ratio of the solution to the deionized water is 1:25, and carrying out hydrothermal reaction for 10 hours at 190 ℃;
(3) FeCl is added into the product in the step (2) 3 ·6H 2 O (model: I809489, michelin) is stirred and mixed, reacted for 1 hour by microwave, and then treated by ultrasonic for 50 minutes, wherein FeCl is added 3 ·6H 2 O and ZnCl 2 The mass ratio of (2) is 1:10;
(4) Stirring the product obtained in the step (3) at 160 ℃ for reaction for 8 hours, centrifuging, washing the precipitate with deionized water and absolute ethyl alcohol for 5 times respectively, and drying to obtain Fe-treated product 3+ Doped ZnO nanoparticles forming Zn 0.85 Fe 0.15 O 1.075 The powder doped inorganic nonmetallic oxide nano particles can be obtained through preliminary grinding.
2. An inorganic nano-antibacterial mildew-proof spray comprises the following components in parts by mass:
the doped nano material, deionized water, a dispersing agent and an auxiliary dispersing auxiliary agent are added into a centrifugal dispersing instrument for dispersion treatment, and the average particle size of nano particles is kept below 102nm (shown in figure 4) and can be uniformly dispersed in water for a long time.Finally, the Fe is added into 3+ And compressing and bottling (3 MPa) the doped and dispersed ZnO dispersion liquid with carbon dioxide, and bottling to obtain the inorganic nano antibacterial mildew-proof spray.
Example 5
1、Fe 3+ The doped ZnO nano material is used for preparing inorganic nonmetallic oxide nano particles, and the doping process and the doping amount are the same as those of the embodiment 3, namely Zn is formed 0.85 Fe 0.15 O 1.075 。
2. An inorganic nano-antibacterial mildew-proof spray comprises the following components in parts by mass:
the doped nano material, deionized water, a dispersing agent and an auxiliary dispersing auxiliary agent are added into a centrifugal dispersing instrument for dispersion treatment, and the average particle size of nano particles is kept below 89nm (shown in figure 5) through detection, and the nano particles can be uniformly dispersed in water for a long time; finally, the Fe is added into 3+ And compressing and bottling (3 MPa) the doped and dispersed ZnO dispersion liquid with carbon dioxide to obtain the inorganic nano antibacterial mildew-proof spray.
Comparative example
1. The Fe is 3+ The doped ZnO nano material is used for preparing inorganic nonmetallic oxide nano particles, and the doping process and the doping amount are the same as those of the embodiment 2, namely Zn is formed 0.95 Fe 0.05 O 1.025 。
2. An inorganic nano-antibacterial mildew-proof spray comprises the following components in parts by mass:
the preparation method of the inorganic nano antibacterial mildew-proof spray is as follows:
the inorganic nonmetallic oxide nano particles are mixed with deionized water, a dispersing agent and an auxiliary dispersing auxiliary agent in common, and are subjected to dispersion treatment by a high-speed grinding machine. The average particle diameter of the nanoparticles was found to be 140nm or less (as shown in FIG. 6). It can be seen that the high-speed mill does not have the advantages of combining the physical dispersion of the centrifugal disperser and the chemical dispersion of the dispersant according to the invention.
Antibacterial property test
The spray obtained in the above examples and comparative examples was left at room temperature for one year, and the comparative test of sterilization rate was performed under insufficient illumination with the inorganic nano antibacterial and mildew-proof material. The test adopts the method specified by the national standard GB/T21866-2008, the main test strains are escherichia coli and staphylococcus aureus, the test results are shown in table 2, wherein the "x value" represents the doped nano material Zn 1-x Fe x O 1+0.5x The value of x in the nanometer material part refers to Zn added in the preparation of the antibacterial spray material 1-x Fe x O 1+0.5x Parts by weight of (a).
TABLE 2 antibacterial Rate of nanomaterial at different doping levels and parts (under insufficient illumination conditions)
It can be seen that, through Fe 3+ The inorganic nonmetallic oxide nano antibacterial mildew-proof spray material treated by doping and the preparation method of the invention still has excellent antibacterial performance under the condition of insufficient illumination after being placed for one year; the compared antibacterial spray product which is not treated by the preparation method provided by the invention has larger particle size of nano particles and poorer antibacterial effect after being placed for one year.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (3)
1. The centrifugal dispersing instrument is characterized by comprising a charging port, a pressure building bin, a high-pressure pump and a centrifugal dispersing device; the charging port and the high-pressure pump are respectively connected with the pressure building bin through valves; the centrifugal dispersing device is arranged at the lower end of the pressure building bin and is connected with the pressure building bin through a closed valve; the centrifugal dispersing device comprises a coarse pipeline, an accelerating pipeline and a centrifugal dispersing pipeline which are connected in sequence, wherein the diameter of the coarse pipeline is the same as the maximum diameter of the accelerating pipeline, and the diameter of the centrifugal dispersing pipeline is the same as the minimum diameter of the accelerating pipeline; the accelerating pipeline is an annular accelerating pipeline with gradually reduced diameter.
2. The centrifugal disperser according to claim 1, further comprising a disperser outlet provided at the tail end of the centrifugal dispersing pipe.
3. The centrifugal disperser according to claim 1, characterized in that the ratio of maximum diameter to minimum diameter of the accelerating tube is 4:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310320765.2A CN116530507A (en) | 2021-09-02 | 2021-11-24 | Inorganic nano antibacterial mildew-proof spray and preparation method thereof |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2021110238548 | 2021-09-02 | ||
| CN202111023854 | 2021-09-02 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310320765.2A Division CN116530507A (en) | 2021-09-02 | 2021-11-24 | Inorganic nano antibacterial mildew-proof spray and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113877452A CN113877452A (en) | 2022-01-04 |
| CN113877452B true CN113877452B (en) | 2023-06-16 |
Family
ID=79015553
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111401601.XA Active CN113877452B (en) | 2021-09-02 | 2021-11-24 | Centrifugal dispersing instrument and method for preparing inorganic nano antibacterial mildew-proof spray by using same |
| CN202310320765.2A Pending CN116530507A (en) | 2021-09-02 | 2021-11-24 | Inorganic nano antibacterial mildew-proof spray and preparation method thereof |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310320765.2A Pending CN116530507A (en) | 2021-09-02 | 2021-11-24 | Inorganic nano antibacterial mildew-proof spray and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN113877452B (en) |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB562921A (en) * | 1942-01-16 | 1944-07-21 | Du Pont | Centrifugal homogeniser |
| NL75390C (en) * | 1950-10-13 | 1900-01-01 | ||
| JP4803508B2 (en) * | 2009-12-04 | 2011-10-26 | 国立大学法人九州大学 | Method and apparatus for producing a composition in which a dispersed phase is finely dispersed in a continuous phase |
| CN109463380A (en) * | 2018-10-19 | 2019-03-15 | 东南大学 | A kind of high activity composite antibacterial spray and preparation method thereof |
| CN110280157A (en) * | 2019-05-16 | 2019-09-27 | 广州丽盈塑料有限公司 | A kind of nanoscale high molecular polymer decentralized system and its dispersing method |
| CN111569687B (en) * | 2020-04-23 | 2023-04-18 | 上海灿越化工科技有限公司 | Unpowered spiral-flow type mixing device and mixing method thereof |
| CN112853328B (en) * | 2021-01-05 | 2022-05-10 | 中国科学院上海硅酸盐研究所 | Iron ion modified zinc oxide antibacterial coating for surface of implant and preparation method thereof |
-
2021
- 2021-11-24 CN CN202111401601.XA patent/CN113877452B/en active Active
- 2021-11-24 CN CN202310320765.2A patent/CN116530507A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| CN116530507A (en) | 2023-08-04 |
| CN113877452A (en) | 2022-01-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Abebe et al. | A review on enhancing the antibacterial activity of ZnO: Mechanisms and microscopic investigation | |
| Lee et al. | Biological synthesis of copper nanoparticles using plant extract | |
| Zhang et al. | Antibacterial mechanism and activity of cerium oxide nanoparticles | |
| Yang et al. | Long-term antibacterial stable reduced graphene oxide nanocomposites loaded with cuprous oxide nanoparticles | |
| Nigussie et al. | Antibacterial activity of Ag-doped TiO 2 and Ag-doped ZnO nanoparticles | |
| Sharma | ZnO nano-flowers from Carica papaya milk: degradation of Alizarin Red-S dye and antibacterial activity against Pseudomonas aeruginosa and Staphylococcus aureus | |
| Kathiresan et al. | Analysis of antimicrobial silver nanoparticles synthesized by coastal strains of Escherichia coli and Aspergillus niger | |
| Tripathi et al. | Antibacterial applications of silver nanoparticles synthesized by aqueous extract of Azadirachta indica (Neem) leaves | |
| Ahmad et al. | Eco-benign approach to synthesize spherical iron oxide nanoparticles: A new insight in photocatalytic and biomedical applications | |
| Li et al. | Efficient antimicrobial properties of layered double hydroxide assembled with transition metals via a facile preparation method | |
| Chen et al. | Fabrication of Cu/TiO2 nanocomposite: toward an enhanced antibacterial performance in the absence of light | |
| Reshma et al. | Cerium Oxide Nanoparticles: Synthesis, Characterization and Study of Antimicrobial Activity. J Nanomater Mol Nanotechnol 6: 3 | |
| Mustajab et al. | Promising performance of polyvinylpyrrolidone-doped bismuth oxyiodide quantum dots for antibacterial and catalytic applications | |
| Kong et al. | Evaluation of copper (I)-doped zinc oxide composite nanoparticles on both gram-negative and gram-positive bacteria | |
| Chang et al. | Efficient synthesis of Ag/AgCl/W18O49 nanorods and their antibacterial activities | |
| Castro Alarcon et al. | Antibacterial activity of nanoparticles of titanium dioxide, intrinsic and doped with indium and iron | |
| CN106312089A (en) | Preparation method of carbon nanoscroll/nano-silver composite antibacterial material | |
| Janani et al. | Synthesis of carbon stabilized zinc oxide nanoparticles and evaluation of its photocatalytic, antibacterial and anti-biofilm activities | |
| Hao et al. | One-pot synthesis of vancomycin-encapsulated ZIF-8 nanoparticles as multivalent and photocatalytic antibacterial agents for selective-killing of pathogenic gram-positive bacteria | |
| Elango et al. | Investigation of structural, morphological and antimicrobial properties of polyindole/Ag doped CeO2 nanocomposites | |
| CN113877452B (en) | Centrifugal dispersing instrument and method for preparing inorganic nano antibacterial mildew-proof spray by using same | |
| Iqbal et al. | Facile synthesis of zinc oxide nanostructures and their antibacterial and antioxidant properties | |
| Saha et al. | Comparative study of synergistic effects of antibiotics with triangular shaped silver nanoparticles, synthesized using UV-light irradiation, on Staphylococcus aureus and Pseudomonas aeruginosa | |
| Abdulkadhim | Synthesis titanium dioxide nanoparticles doped with silver and Novel antibacterial activity | |
| WO2023087634A1 (en) | Silver colloid and preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |