CN114847279B - Inorganic antibacterial agent and preparation method thereof - Google Patents
Inorganic antibacterial agent and preparation method thereof Download PDFInfo
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- CN114847279B CN114847279B CN202210654363.1A CN202210654363A CN114847279B CN 114847279 B CN114847279 B CN 114847279B CN 202210654363 A CN202210654363 A CN 202210654363A CN 114847279 B CN114847279 B CN 114847279B
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- 239000003242 anti bacterial agent Substances 0.000 title claims abstract description 104
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000011521 glass Substances 0.000 claims abstract description 203
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 76
- 239000002245 particle Substances 0.000 claims abstract description 44
- 239000000843 powder Substances 0.000 claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 18
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 13
- 238000012360 testing method Methods 0.000 claims abstract description 13
- 229910052709 silver Inorganic materials 0.000 claims abstract description 12
- 239000004332 silver Substances 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 11
- 238000005342 ion exchange Methods 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 8
- 229910001413 alkali metal ion Inorganic materials 0.000 claims abstract description 5
- 238000001514 detection method Methods 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims description 41
- 239000000203 mixture Substances 0.000 claims description 35
- 239000002904 solvent Substances 0.000 claims description 34
- 239000006063 cullet Substances 0.000 claims description 30
- 238000000227 grinding Methods 0.000 claims description 29
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 22
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 22
- 238000004140 cleaning Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- 239000011734 sodium Substances 0.000 claims description 12
- 235000010333 potassium nitrate Nutrition 0.000 claims description 11
- 239000004323 potassium nitrate Substances 0.000 claims description 11
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 11
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 9
- 230000000845 anti-microbial effect Effects 0.000 claims description 8
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 7
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- 239000005749 Copper compound Substances 0.000 claims description 4
- 239000004599 antimicrobial Substances 0.000 claims description 4
- 150000001880 copper compounds Chemical class 0.000 claims description 4
- 229940100890 silver compound Drugs 0.000 claims description 4
- 150000003379 silver compounds Chemical class 0.000 claims description 4
- 239000005358 alkali aluminosilicate glass Substances 0.000 claims description 3
- 239000005407 aluminoborosilicate glass Substances 0.000 claims description 3
- 239000005388 borosilicate glass Substances 0.000 claims description 3
- 239000002241 glass-ceramic Substances 0.000 claims description 3
- 230000007246 mechanism Effects 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000005361 soda-lime glass Substances 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 150000003752 zinc compounds Chemical class 0.000 claims description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims 2
- 230000001788 irregular Effects 0.000 claims 1
- 235000010344 sodium nitrate Nutrition 0.000 claims 1
- 239000004317 sodium nitrate Substances 0.000 claims 1
- 150000002500 ions Chemical class 0.000 abstract description 13
- 150000003839 salts Chemical class 0.000 abstract description 8
- 230000002829 reductive effect Effects 0.000 abstract description 6
- 230000001954 sterilising effect Effects 0.000 abstract description 6
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 238000011068 loading method Methods 0.000 abstract description 5
- -1 silver ions Chemical class 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract 1
- 239000006121 base glass Substances 0.000 description 25
- 239000002131 composite material Substances 0.000 description 12
- 238000012216 screening Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- 239000000292 calcium oxide Substances 0.000 description 6
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 6
- 229910052939 potassium sulfate Inorganic materials 0.000 description 6
- 235000011151 potassium sulphates Nutrition 0.000 description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 description 6
- 235000011152 sodium sulphate Nutrition 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000002401 inhibitory effect Effects 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 241000588724 Escherichia coli Species 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 3
- 241000191967 Staphylococcus aureus Species 0.000 description 3
- 230000001580 bacterial effect Effects 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000014509 gene expression Effects 0.000 description 3
- 238000007496 glass forming Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 241000589517 Pseudomonas aeruginosa Species 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000009512 pharmaceutical packaging Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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
- A01N25/08—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 solids as carriers or diluents
-
- 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
-
- 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
- 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
- A01N59/20—Copper
-
- 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
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Environmental Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Zoology (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Dentistry (AREA)
- Agronomy & Crop Science (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Toxicology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Glass Compositions (AREA)
Abstract
The application relates to the field of antibacterial materials, in particular to an inorganic antibacterial agent and a preparation method thereof, which can realize the loading of higher antibacterial ion content, have simple process, are suitable for mass production and reduce the production cost. The inorganic antibacterial agent is in a powder shape, the average particle size of the inorganic antibacterial agent is 10-50 mu m, broken glass is used as a carrier, antibacterial metal ions are implanted into the glass carrier through a low-temperature alkali metal ion exchange method, and the content of the antibacterial metal ions is 3-8.5 wt% through XRF detection. The inorganic antibacterial agent provided by the application can enable the antibacterial agent to rapidly release silver ions and/or cuprous ions, has high-concentration uniform load capacity, and improves the distance of an antibacterial effective range, so that the use amount of the antibacterial agent is reduced, and the strong sterilization and bacteriostasis effects are still maintained after the durability test is passed. The broken glass powder is used as an antibacterial agent carrier, so that recycling can be effectively performed, the problem of molten salt waste caused by traditional molten salt ion exchange can be effectively solved, and the method is environment-friendly and low in cost.
Description
Technical Field
The application relates to the field of antibacterial materials, in particular to an inorganic antibacterial agent and a preparation method thereof.
Background
In recent years, with the improvement of the living standard of people in China and the further improvement of the requirements for health and hygiene, the application of the antibacterial material has important significance for public health industry in China.
Most of the existing antibacterial materials are prepared by adding antibacterial components into the materials. For example, CN112042669a is an inorganic powder material with disinfection and sterilization functions, which comprises the following components in parts by weight: 48-58 parts of quartz powder, 25-35 parts of borax powder, 15-20 parts of zinc oxide powder and 2-4 parts of cerium oxide powder; is prepared through proportioning, smelting, cooling, grinding, inspection and packing, and features that the antibacterial component is added to glass component for smelting to obtain antibacterial effect, and the smelting temp. is 1100-1650 deg.C, but when silver raw material is used, ag is used + The silver material is obviously volatilized at about 961 ℃, so that the effective silver content is reduced, the expensive silver material is not effectively applied, and the problem of uneven silver load is easily caused.
The inventor studies application CN112913839A in advance, which adds a certain concentration of erosion liquid into waste glass to erode, damages the original silicate network structure in the glass, forms a network structure body structure which is favorable for effectively adsorbing rare earth and antibacterial ions, and enhances the antibacterial effect. The above application adopts the mode of eroding and adsorbing the cullet, and the mode has the problems of uneven silver load and complicated working procedure. There are also problems of waste of molten salt and limited silver content load caused by ion exchange of molten salt by directly adding cullet into molten antibacterial bath salt, environmental protection and low cost.
Disclosure of Invention
The application aims to solve the technical problems of providing an inorganic antibacterial agent and a preparation method thereof, which can realize the loading of higher antibacterial ion content, have simple process, are suitable for mass production and reduce the production cost.
The application is realized in the following way:
the application firstly provides an inorganic antibacterial agent which is in a powder shape and has an average particle diameter of 10-50 mu m, wherein broken glass is used as a carrier, antibacterial metal ions are exchanged to the carrier through a low-temperature alkali metal ion exchange method, and the content of the metal ions detected by XRF is 3-8.5 wt%, and further 5-8.5 wt%.
Further, the effective antibacterial range of the inorganic antibacterial agent is 10-26mm.
Further, the antimicrobial metal ion comprises at least one of silver, copper, or zinc.
Further, the glass component of the carrier comprises SiO 2 、Al 2 O 3 、B 2 O 3 、P 2 O 5 、RO、R 2 O; wherein 80wt% is more than or equal to P 2 O 5 +RO is more than or equal to 60wt%; and 0.9 is more than or equal to CaO/R 2 O≥0.7。
R 2 R in O can be Na, K and other elements.
R in RO may be Mg, ca or other elements.
Further, the antibacterial effective value of the inorganic antibacterial agent is more than or equal to 3 after passing the durability test.
The application also provides a preparation method of the inorganic antibacterial agent, which comprises the following steps:
step one: the crushed glass particles are screened by a filter screen.
Step two: and cleaning and drying the screened broken glass.
Step three: mixing the cleaned and dried cullet, the antibacterial agent and the solvable agent to form a uniform antibacterial mixture.
Step four: performing low-temperature alkali metal ion exchange treatment on the antibacterial mixture, wherein the treatment heating temperature is 350-450 ℃; heating for 10min-60min.
Step five: and (5) cleaning and drying the crushed glass after the extraction and heating treatment.
Step six: grinding the dried broken glass to obtain the inorganic antibacterial agent.
Preferably, in the first step, the size of the screened glass cullet particles is controlled to be 100-200 microns, and the glass cullet particles can be in a regular geometric shape or a random shape and can be screened by using a laser particle sizer or a screen. The purpose of controlling the size is to control the load of antibacterial ions, and the smaller the load of the particles is when the size of the glass cullet particles is too large, the antibacterial performance is reduced, and the smaller the size of the glass cullet particles is, the further influence on the cleaning and drying in the step five is brought, so that the operation difficulty is increased.
Preferably, the cullet size/(antimicrobial+solvent blend weight) relationship ratio is defined to be 1-3.5. For example: the particle size of the cullet is 100 micrometers, wherein the content of the cullet is 45 weight percent, the content of the copper sulfate powder is 35 weight percent, the content of the potassium sulfate is 15 weight percent, the content of the sodium sulfate is 5 weight percent, the relation ratio of the size of the cullet/(the antibacterial agent+the solvable) is 100/(35+15+5) =1.8, and the silver ions and/or the cuprous ions can be rapidly released by the antibacterial agent by limiting the ratio of the size of the cullet to the mixed weight of the (antibacterial agent+the solvable), so that the cullet has uniform antibacterial ion loading with high concentration, the distance of an antibacterial effective range is increased, the use amount of the antibacterial agent is reduced, and the strong sterilization and bacteriostasis effects are still maintained after the durability test.
The glass cullet suitable for the preparation method can comprise tempered or unreinforced glass, and the glass cullet also comprises soda lime glass, alkali-free glass, alkali aluminosilicate glass, alkali-containing borosilicate glass and alkali aluminoborosilicate glass. Glass ceramic or single crystal mechanism materials may also be included.
In some embodiments, the cullet component in step one is P 2 O 5 50-70wt％；Na 2 O5-15wt％； B 2 O 3 1-10wt％；CaO5-10wt％；Al 2 O 3 5-15wt％；SiO 2 5-15wt%, and the total mass ratio is 100%.
In some embodiments, the cullet content in step three is 40 to 70wt%, more preferably 50 to 60wt%.
In some embodiments, the antimicrobial agent in step three is at least one of a silver compound, a copper compound, or a zinc compound.
Further, the silver compound is silver nitrate powder in an amount of 4 to 10wt%, more preferably 5 to 8wt%. The copper compound is copper sulfate powder, and the content is 35-45wt%, and more preferably 35-40 wt%.
In some embodiments, the solvent in the third step is at least one of powdery potassium nitrate and lithium nitrate, and the solvent content is 30-55wt%, and more preferably 40-55wt%.
In some embodiments, the solvent in the third step is at least one of powdery sodium sulfate and potassium sulfate, and the content of the solvent is 20-30wt%.
Note that: the above contents are mass ratio of the antibacterial mixture.
In some embodiments, the washed and dried cullet is ground in step five to obtain inorganic antimicrobial particles having a size of 10 to 25 μm. The size is more preferably 15 to 20. Mu.m.
The application has the following advantages: according to the inorganic antibacterial agent provided by the application, through optimizing and adjusting the relation ratio of the size of cullet/(the antibacterial agent+the solvable), silver ions and/or cuprous ions can be rapidly released by the antibacterial agent, the uniform loading capacity with high concentration is realized, the distance of an antibacterial effective range is increased, the usage amount of the antibacterial agent is reduced, and the strong sterilization and bacteriostasis effects are still maintained after the durability test is passed. The broken glass powder is used as an antibacterial agent carrier, so that the broken glass powder can be effectively recycled, the broken glass and the antibacterial composition are firstly mixed and then subjected to heating treatment in a preferable proportion, the problem of molten salt waste caused by traditional molten salt ion exchange is effectively solved, and the method is environment-friendly and low in cost.
Drawings
The application will be further described with reference to examples of embodiments with reference to the accompanying drawings.
FIG. 1 shows the antibacterial cultures of example 1 and comparative example 1.
FIG. 2 shows the bacteriostatic cultures of example 2 and comparative example 2.
FIG. 3 shows the antibacterial cultures of example 3 and comparative example 3.
Detailed Description
In order to describe the technical content, constructional features, achieved objects and effects of the technical solution in detail, the following description is made in detail with reference to specific embodiments.
In order to describe the possible application scenarios, technical principles, practical embodiments, and the like of the present application in detail, the following description is made with reference to the specific embodiments. The embodiments described in the present application are only for more clearly illustrating the technical aspects of the present application, and thus are only examples, and are not intended to limit the scope of the present application.
Reference in the specification to "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment may be included in at least one embodiment of the application. The appearances of the phrase "in various places in the specification are not necessarily all referring to the same embodiment, nor are they particularly limited to independence or relevance from other embodiments. In principle, in the present application, as long as there is no technical contradiction or conflict, the technical features mentioned in each embodiment may be combined in any manner to form a corresponding implementable technical solution.
Unless defined otherwise, technical terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present application pertains; the use of related terms in the present application is only for the purpose of describing particular embodiments and is not intended to limit the present application.
In the description of the present application, the term "and/or" is a representation for describing a logical relationship between objects, which means that three relationships may exist, for example a and/or B, representing: there are three cases, a, B, and both a and B. In addition, the character "/" in the present application generally indicates that the front-rear association object is an or logical relationship.
In the present application, terms such as "first" and "second" are used merely to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual number, order, or sequence of such entities or operations.
Without further limitation, the use of the terms "comprising," "including," "having," or other like terms in this specification is intended to cover a non-exclusive inclusion, such that a process, method, or article of manufacture that comprises a list of elements does not include additional elements but may include other elements not expressly listed or inherent to such process, method, or article of manufacture.
As in the understanding of "review guidelines," the expressions "greater than", "less than", "exceeding" and the like are understood to exclude this number in the present application; the expressions "above", "below", "within" and the like are understood to include this number. Furthermore, in the description of embodiments of the present application, the meaning of "a plurality of" is two or more (including two), and similarly, the expression "a plurality of" is also to be understood as such, for example, "a plurality of" and the like, unless specifically defined otherwise.
In the present application, the cullet suitable for the preparation method may include tempered or unreinforced glass, and the cullet further includes soda lime glass, alkali-free glass, alkali aluminosilicate glass, alkali-containing borosilicate glass, and alkali aluminoborosilicate glass. Glass ceramic or single crystal mechanism materials may also be included.
In the present application, unless otherwise indicated, the glass composition is expressed as the amount by weight of a specific component contained therein, in terms of oxide. Any component having more than one oxidation state may be present in the glass composition in any oxidation state. However, unless otherwise indicated, the concentration of such components is expressed as the oxide in which such components are in their lowest oxidation state.
The reasons for numerical limitation of the contents of the components of the cullet of the examples will be explained below.
SiO 2 As a main glass forming body, which is one of essential components, mainly constitutes a glass network main structure which imparts excellent chemical stability, mechanical properties and forming properties to glass, and thus the cullet component contains SiO 2 5-15wt％。
Al 2 O 3 Is one of the components of glass and belongs to the network intermediate composition. In the glass component with high alkali concentration, alkali ions are used for preparing the glass component with high alkali concentration 3+ The ions undergo charge balance to oxidize a plurality ofAluminum tends to be glass aluminum oxide tetrahedra, constituting the glass network host structure, thereby improving glass stability and mechanical properties. Al (Al) 2 O 3 The volume of the aluminum oxide tetrahedron formed in the glass is larger than that of the silicon oxide tetrahedron in the glass, the volume of the glass is expanded, thereby reducing the density of the glass, providing an exchange channel for the glass in the ion exchange process, and therefore, the broken glass component contains Al 2 O 3 5-15wt％。
Na 2 O is one of the components of the glass, and Na with high concentration in the glass 2 O, so that the glass contains enough Na + And K in potassium nitrate molten salt + The ions exchange, thereby creating high compressive stresses on the glass surface. In addition, na 2 O can provide a large amount of free oxygen source, has a destructive effect on the silica network structure of the glass, greatly reduces the viscosity of the glass, and is helpful for melting and clarifying the glass 2 Too high an O concentration will deteriorate the mechanical and chemical stability properties of the glass, especially in silicate glasses with high alumina concentration and phosphorus content, na 2 O is easier to exchange with hydrogen ions in water and dissolve into water, so that the change of chemical properties of the glass surface is accelerated, and Na is therefore 2 The content of O is controlled to be 5-15wt%.
B 2 O 3 Is a network forming body oxide in glass, B 2 O 3 Is a base glass forming agent. In these glasses, B 3+ The ions coordinate with oxygen in triangles or tetrahedra and are bound in random configuration angles. The viscosity of the high-temperature glass can be obviously reduced; high concentration B 2 O 3 The volatilization of oxides in the high-temperature melting process is unfavorable for the stabilization of glass components, and B 2 O 3 Can lower the glass strain point temperature and tends to be on the glass surface, and the glass surface resistance can be deteriorated, thus B 2 O 3 The content is controlled to be 1-10wt%.
P 2 O 5 Is a component of a glass forming body, which is formed by [ PO ] 4 ]Tetrahedral phase is interconnected into a network, but P 2 O 5 The formed network structure is in a layered structure, and the layers are connected by Van der Waals force, so that the glass network structure is looseIn the state, network gaps become large, so that the mutual diffusion of Na ions in glass and K ions in molten salt is facilitated, and the ion exchange plays an important role in rapidly obtaining a higher compressive stress layer in the glass strengthening process. But P in glass 2 O 5 Has the advantages of low viscosity, poor chemical stability and large thermal expansion coefficient, thus having low concentration P 2 O 5 Can provide good chemical stability of glass and high concentration of P 2 O 5 The glass degree deteriorates the chemical stability of the glass and P 2 O 5 The raw material source cost of (2) is relatively high. Through research, P in glass carrier is found 2 O 5 Has close correlation with the precipitation amount of antibacterial metal ions, thus P 2 O 5 The content of (2) is controlled at P 2 O 5 50-70wt％。
CaO mainly plays a role in stabilizing the glass, and CaO and Na are added into the glass components 2 O will break the lattice structure and adjust the reactivity of the glass by optimizing CaO and Na 2 The proportion of O content can release the metal ions with antibacterial effect more easily. For glass compositions which do not contain alkali metals, caO and P can be adjusted 2 O 5 The content ratio of (2) to obtain excellent antibacterial properties, whereby the CaO content of the cullet component is controlled to 5 to 10% by weight.
Optimizing CaO and Na in glass components by purposeful adjustment 2 O and P 2 O 5 According to the content proportion relation of the metal ions, the antibacterial metal ions are implanted into the glass carrier by combining the preparation method of the process to obtain a final inorganic antibacterial agent product, the inorganic antibacterial agent can obtain uniform metal ion loading with high concentration in related application scenes, and the strong sterilization and bacteriostasis effects are still kept after the durability test.
Examples
In order to further clearly illustrate and describe the technical solutions of the present application, the following non-limiting examples are provided. Embodiments of the present application take numerous efforts to ensure accuracy with respect to numbers but some errors and deviations should be accounted for.
The component content of the cullet raw materials of each example was measured by XRF, as shown in table 1.
Table 1 example base cullet component content table
Example 1
According to the base glass prepared by the glass components in table 1, the base glass is crushed, the crushed glass particles are screened by a filter screen, the size of the crushed glass is controlled to be 100 microns, the crushed glass after screening is cleaned and dried, the cleaned and dried crushed glass, an antibacterial agent and a solvent are mixed, the relation ratio of the crushed glass size/(the antibacterial agent+the solvent) is 2, wherein the crushed glass content is 50wt%, the silver nitrate powder content is 5wt%, and the potassium nitrate content is 45wt% to form a uniform antibacterial mixture. Heating the antibacterial mixture at 410 deg.C for 20min; and cleaning and drying the crushed glass after the heating treatment. Grinding the dried broken glass, wherein the size of the particles of the antibacterial agent after grinding is 20 mu m, and thus the composite inorganic antibacterial agent can be obtained.
Examples 4 and 7
According to the base glass prepared by the glass components in table 1, the base glass is crushed, the crushed glass particles are screened by a filter screen, the size of the crushed glass is controlled to be 150 microns, the crushed glass after screening is cleaned and dried, the cleaned and dried crushed glass, an antibacterial agent and a solvent are mixed, the relation ratio of the crushed glass size/(the antibacterial agent+the solvent) is 2.7, wherein the crushed glass content is 45wt%, the silver nitrate powder content is 8wt%, and the potassium nitrate content is 47wt% to form a uniform antibacterial mixture. Heating the antibacterial mixture to 430 ℃; heating time is 10min. And cleaning and drying the crushed glass after the heating treatment. Grinding the dried broken glass, wherein the size of the particles of the antibacterial agent after grinding is 30 mu m, and thus the composite inorganic antibacterial agent can be obtained.
Examples 10 and 13
According to the base glass prepared by the glass components in table 1, the base glass is crushed, the crushed glass particles are screened by a filter screen, the size of the crushed glass is controlled to be 100 microns, the crushed glass after screening is cleaned and dried, the cleaned and dried crushed glass, an antibacterial agent and a solvent are mixed, the relation ratio of the crushed glass size/(the antibacterial agent+the solvent) is 2.8, wherein the crushed glass content is 65wt%, the silver nitrate powder content is 5wt%, and the potassium nitrate content is 30wt% to form a uniform antibacterial mixture. Heating the antibacterial mixture to 370 ℃; heating time is 30min. And cleaning and drying the crushed glass after the heating treatment. Grinding the dried broken glass, wherein the size of the particles of the antibacterial agent after grinding is 15 mu m, and thus the composite inorganic antibacterial agent can be obtained.
Examples 11 and 14
According to the base glass prepared by the glass components in table 1, the base glass is crushed, the crushed glass particles are screened by a filter screen, the size of the crushed glass is controlled to be 200 microns, the crushed glass after screening is cleaned and dried, the cleaned and dried crushed glass, an antibacterial agent and a solvent are mixed, the relation ratio of the crushed glass size/(the antibacterial agent+the solvent) is 3.3, wherein the crushed glass content is 40wt%, the silver nitrate powder content is 10wt%, and the potassium nitrate content is 50wt% to form a uniform antibacterial mixture. Heating the antibacterial mixture to 370 ℃; heating time is 20min. And cleaning and drying the crushed glass after the heating treatment. Grinding the dried broken glass, wherein the size of the particles of the antibacterial agent after grinding is 50 mu m, and thus the composite inorganic antibacterial agent can be obtained.
Example 2
According to the base glass prepared by the glass components in table 1, the base glass is crushed, the crushed glass particles are screened by a filter screen, the size of the crushed glass is controlled to be 100 microns, the crushed glass after screening is cleaned and dried, the cleaned and dried crushed glass, an antibacterial agent and a solvent are mixed, the relation ratio of the crushed glass size/(the antibacterial agent+the solvent) is 2.5, wherein the crushed glass content is 60wt%, the silver nitrate powder content is 5wt%, the potassium nitrate content is 33wt% and the lithium nitrate content is 2wt% to form a uniform antibacterial mixture. Heating the antibacterial mixture to 390 ℃; heating time is 10min. And cleaning and drying the crushed glass after the heating treatment. Grinding the dried broken glass, wherein the size of the particles of the antibacterial agent after grinding is 15 mu m, and thus the composite inorganic antibacterial agent can be obtained.
Examples 5 and 8
According to the base glass prepared by the glass components in table 1, the base glass is crushed, the crushed glass particles are screened by a filter screen, the size of the crushed glass is controlled to be 150 microns, the crushed glass after screening is cleaned and dried, the cleaned and dried crushed glass, an antibacterial agent and a solvent are mixed, the relation ratio of the crushed glass size/(the antibacterial agent+the solvent) is 3, wherein the crushed glass content is 50wt%, the silver nitrate powder content is 5wt%, the potassium nitrate content is 42wt% and the lithium nitrate content is 3wt% to form a uniform antibacterial mixture. Heating the antibacterial mixture to 390 ℃; heating time is 20min. And cleaning and drying the crushed glass after the heating treatment. Grinding the dried broken glass, wherein the size of the particles of the antibacterial agent after grinding is 10 mu m, and thus the composite inorganic antibacterial agent can be obtained.
Examples 3 and 6
According to the base glass prepared by the glass components in the table 1, crushing the base glass, sieving the crushed glass particles by a filter screen, screening to control the size of the crushed glass, controlling the size of the screened crushed glass particles to be 100 microns, cleaning and drying the screened crushed glass, mixing the cleaned and dried crushed glass, an antibacterial agent and a soluble agent, wherein the relation ratio of the size of the crushed glass/(the antibacterial agent+the soluble agent) is 1.6; wherein the broken glass content is 40wt%, the copper sulfate powder content is 40wt%, the potassium sulfate content is 15wt%, and the sodium sulfate content is 5wt% to form a uniform antibacterial mixture. Heating the antibacterial mixture for 40min; the heating temperature was 430 ℃. And cleaning and drying the crushed glass after the heating treatment. Grinding the dried broken glass, wherein the size of the particles of the antibacterial agent after grinding is 15 mu m, and thus the composite inorganic antibacterial agent can be obtained.
Examples 9 and 12
According to the base glass prepared by the glass components in table 1, the base glass is crushed, the crushed glass particles are screened by a filter screen, the size of the crushed glass is controlled to be 100 microns, the crushed glass after screening is cleaned and dried, the cleaned and dried crushed glass, an antibacterial agent and a solvent are mixed, the relation ratio of the crushed glass size/(the antibacterial agent+the solvent) is 1.8, wherein the crushed glass content is 45wt%, the copper sulfate powder content is 35wt%, the potassium sulfate content is 15wt% and the sodium sulfate content is 5wt% to form a uniform antibacterial mixture. Heating the antibacterial mixture to 450 ℃; heating time is 60min. And cleaning and drying the crushed glass after the heating treatment. Grinding the dried broken glass, wherein the size of the particles of the antibacterial agent after grinding is 30 mu m, and thus the composite inorganic antibacterial agent can be obtained.
Example 15
According to the base glass prepared by the glass components in table 1, the base glass is crushed, the crushed glass particles are screened by a filter screen, the size of the crushed glass is controlled to be 200 microns, the crushed glass after screening is cleaned and dried, the cleaned and dried crushed glass, an antibacterial agent and a solvent are mixed, the relation ratio of the crushed glass size/(the antibacterial agent+the solvent) is 3.3, wherein the crushed glass content is 40wt%, the copper sulfate powder content is 35wt%, the potassium sulfate content is 20wt% and the sodium sulfate content is 5wt% to form a uniform antibacterial mixture. Heating the antibacterial mixture to 450 ℃; heating time is 30min. And cleaning and drying the crushed glass after the heating treatment. Grinding the dried broken glass, wherein the size of the particles of the antibacterial agent after grinding is 40 mu m, and thus the composite inorganic antibacterial agent can be obtained.
Table 2 comparative example base cullet component content table
Comparative example 1
According to the base glass prepared by the glass components in table 2, the base glass is crushed, the crushed glass particles are screened by a filter screen, the size of the crushed glass is controlled to be 200 microns, the crushed glass after screening is cleaned and dried, the cleaned and dried crushed glass, an antibacterial agent and a solvent are mixed, the relation ratio of the size of the crushed glass/(the antibacterial agent+the solvent) is 4, wherein the crushed glass content is 50wt%, the silver nitrate powder content is 5wt%, and the potassium nitrate content is 45wt% to form a uniform antibacterial mixture. Heating the antibacterial mixture to 410 ℃; heating time is 20min. And cleaning and drying the crushed glass after the heating treatment. Grinding the dried broken glass, wherein the size of the particles of the antibacterial agent after grinding is 20 mu m, and thus the composite inorganic antibacterial agent can be obtained.
Comparative example 2
According to the base glass prepared by the glass components in table 2, the base glass is crushed, the crushed glass particles are screened by a filter screen, the size of the crushed glass is controlled to be 150 microns, the crushed glass after screening is cleaned and dried, the cleaned and dried crushed glass, an antibacterial agent and a solvent are mixed, the relation ratio of the crushed glass size/(the antibacterial agent+the solvent) is 3.7, wherein the crushed glass content is 60wt%, the silver nitrate powder content is 5wt%, the potassium nitrate content is 33wt% and the lithium nitrate content is 2wt% to form a uniform antibacterial mixture. Heating the antibacterial mixture to 390 ℃; heating time is 10min. And cleaning and drying the crushed glass after the heating treatment. Grinding the dried broken glass, wherein the size of the particles of the antibacterial agent after grinding is 15 mu m, and thus the composite inorganic antibacterial agent can be obtained.
Comparative example 3
According to the base glass prepared by the glass components in table 2, the base glass is crushed, the crushed glass particles are screened by a filter screen, the size of the crushed glass is controlled to be 100 microns, the crushed glass after screening is cleaned and dried, the cleaned and dried crushed glass, an antibacterial agent and a solvent are mixed, the relation ratio of the crushed glass size/(the antibacterial agent+the solvent) is 1.4, wherein the crushed glass content is 30wt%, the copper sulfate powder content is 40wt%, the potassium sulfate content is 25wt% and the sodium sulfate content is 5wt% to form a uniform antibacterial mixture. Heating the antibacterial mixture to 430 ℃; heating time is 30min. And cleaning and drying the crushed glass after the heating treatment. Grinding the dried broken glass, wherein the size of the particles of the antibacterial agent after grinding is 15 mu m, and thus the composite inorganic antibacterial agent can be obtained.
The durability test process comprises the steps of adding an antibacterial agent into a paint base paint, stirring, uniformly spraying the paint on a sample wafer after stirring, air-drying the sample, repeatedly testing the sample for 3 cycles according to the test method under the conditions that the temperature of an aging test box is 40 ℃ and the humidity (93+/-3)% RH, adopting a xenon arc lamp, a filter is Dayl right, the wavelength range is 300-800 nm, the radiation energy is fixed to 575W/m < 2 >, the 24h is 1 cycle, the irradiation is carried out for 8h, and the lamp is stopped for 16h, and then the antibacterial property of the sample is detected.
The antibacterial performance detection of the application is carried out by detecting the sample wafer passing through the durability test according to the GB/T21866-2008 antibacterial coating (paint film) antibacterial property detection method and antibacterial effect method, and the antibacterial rate of at least staphylococcus aureus, escherichia coli and pseudomonas aeruginosa can be more than or equal to 99.9 percent by detecting the antibacterial agent of the application, as shown in table 3.
Table 3 antibacterial property test on antibacterial agent samples
And (3) detecting the antibacterial effective bacteriostasis range of the antibacterial agent sample, taking out 100 mu L of bacterial suspension, uniformly coating the bacterial suspension in a culture dish, respectively placing 0.05g of antibacterial agent powder of example 1, example 2, example 3 and comparative example 1, comparative example 2 and comparative example 3 in the culture dish after the bacterial suspension is solidified, placing the culture dish in a constant temperature incubator at 37 ℃ for culturing for 18-24 hours, and taking out to observe the antibacterial effective distance. As shown in Table 4 and figures 1-3, the inorganic antibacterial agent of the application has the effective antibacterial range of 11-26mm, has better antibacterial effect, can reduce the use amount of the antibacterial agent and reduce the cost.
Table 4 effective antibacterial range detection for antimicrobial samples
Antibacterial tests of the antibacterial agent samples of examples 1 to 3 according to the present application were conducted on representative gram-negative E.coli and gram-positive Staphylococcus aureus, respectively, and the minimum inhibitory concentrations (MIC values) of the antibacterial agent samples on two representative strains were tested according to the "sterilizing technical Specification" 2002 edition.
Table 5 minimum inhibitory concentration of antimicrobial samples
As shown in Table 5, the antimicrobial samples of examples 1-3 of the present application tested the minimum inhibitory concentration (MIC value) of 450ppm or less, which is significantly lower than the minimum inhibitory concentration value of the comparative example, for the inhibition tests of representative gram-negative E.coli, gram-positive Staphylococcus aureus, respectively.
Embodiments of the application of the inorganic antibacterial agents described herein may comprise cosmetic products, oral care products, personal care products, laundry care products or household care products. Various embodiments of the inorganic antimicrobial agent may also be included in touch-sensitive display screens or covers for hand electronics, non-touch-sensitive components of electronics, surfaces of household appliances, surfaces of medical devices, surfaces of biological or pharmaceutical packaging containers or automotive components, and in some cases, the inorganic antimicrobial agent may be included in coatings, coated fabrics for packaging, orthodontic devices for sports equipment, traumatism care, antimicrobial sprays, and biomedical devices. Inorganic antibacterial agents can also be used for water purification, wastewater treatment and for air purification.
While specific embodiments of the application have been described above, it will be appreciated by those skilled in the art that the specific embodiments described are illustrative only and not intended to limit the scope of the application, and that equivalent modifications and variations of the application in light of the spirit of the application will be covered by the claims of the present application.
Claims (20)
1. An inorganic antimicrobial agent characterized in that: the inorganic antibacterial agent is in a powder shape, the average particle diameter of the inorganic antibacterial agent is 10-50 mu m, broken glass is used as a carrier, the broken glass, the antibacterial agent and a solvent are mixed, metal ions in the antibacterial agent are implanted into the glass carrier through a low-temperature alkali metal ion exchange method, and the content of the antibacterial metal ions is 3-8.5wt% through XRF detection; the glass component of the support comprises SiO 2 、Al 2 O 3 、B 2 O 3 、P 2 O 5 、CaO、Na 2 O; wherein 80wt% is more than or equal to P 2 O 5 +CaO is more than or equal to 60wt%; and 0.9 is more than or equal to CaO/Na 2 O is more than or equal to 0.7, and the broken glass component is P 2 O 5 50-70wt%、Na 2 O 5-15wt%、B 2 O 3 1-10wt%、CaO 5-10wt%、Al 2 O 3 5-15wt%、SiO 2 5-15wt% of the total mass ratio is 100%, wherein the solvent is at least one of powdery potassium nitrate, sodium nitrate and lithium nitrate; the ratio of the cullet size/(the antibacterial agent + the solvent) is 1-3.5.
2. The inorganic antibacterial agent according to claim 1, characterized in that: the effective antibacterial range of the inorganic antibacterial agent is 10-26mm.
3. The inorganic antibacterial agent according to claim 1, characterized in that: the antimicrobial metal ion comprises at least one of silver, copper, or zinc.
4. The inorganic antibacterial agent according to claim 1, characterized in that: the minimum antibacterial concentration of the inorganic antibacterial agent is less than or equal to 500ppm.
5. The inorganic antibacterial agent according to claim 1, characterized in that: the antibacterial rate of the inorganic antibacterial agent after passing the durability test is more than or equal to 99.9%.
6. A process for the preparation of an inorganic antibacterial agent as claimed in any one of claims 1 to 5, characterized in that: the method comprises the following steps:
step one: sieving the broken glass particles by a filter screen;
step two: cleaning and drying the screened broken glass;
step three: mixing the crushed glass, the antibacterial agent and the solvent which are cleaned and dried in the second step to form a uniform antibacterial mixture;
step four: performing low-temperature alkali metal ion exchange treatment on the antibacterial mixture, wherein the treatment heating temperature is 350-450 ℃; heating for 10min-60min;
step five: cleaning and drying the crushed glass after the treatment in the step four;
step six: grinding the crushed glass cleaned and dried in the step five to obtain the inorganic antibacterial agent.
7. The method of manufacturing according to claim 6, wherein: in the first step, the size of the screened cullet particles is controlled to be 100-200 microns, and the cullet particles are in regular geometric shapes or irregular shapes.
8. The method of manufacturing according to claim 7, wherein: the content of the broken glass is 40-70 wt%.
9. The method of manufacturing according to claim 8, wherein: the content of the broken glass is 50-60 wt%.
10. The method of manufacturing according to claim 6, wherein: the antibacterial agent in the third step is at least one of a silver compound, a copper compound or a zinc compound.
11. The method of manufacturing according to claim 10, wherein: the silver compound is silver nitrate powder, and the content is 4-10 wt%.
12. The method of manufacturing according to claim 11, wherein: the content of the silver nitrate powder is 5-8 wt%.
13. The method of manufacturing according to claim 10, wherein: the copper compound is copper sulfate powder, and the content is 35-45 wt%.
14. The method of manufacturing according to claim 6, wherein: in the third step, the content of the soluble solvent is 30-55 wt percent.
15. The method of manufacturing according to claim 14, wherein: the content of the solvent is 40-55 wt%.
16. The method of manufacturing according to claim 6, wherein: in the third step, the content of the soluble solvent is 20-30 wt percent.
17. The method of manufacturing according to claim 6, wherein: and step six, grinding the cleaned and dried broken glass, wherein the size of the inorganic antibacterial agent particles after grinding is 10-48 mu m.
18. The method of manufacturing according to claim 6, wherein: the broken glass particles in the first step are obtained by crushing basic broken glass, wherein the basic broken glass comprises strengthened or unreinforced glass.
19. The method of manufacturing according to claim 6, wherein: the broken glass particles in the first step are obtained by crushing basic broken glass, wherein the basic broken glass comprises one of soda lime glass, alkali aluminosilicate glass, alkali-containing borosilicate glass and alkali aluminoborosilicate glass.
20. The method of manufacturing according to claim 6, wherein: the broken glass particles in the first step are obtained by crushing basic broken glass, wherein the basic broken glass comprises glass ceramic or monocrystalline mechanism materials.
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| US20120115981A1 (en) * | 2009-07-10 | 2012-05-10 | Universita' Degli Studi Di Torino | Composite bone cements with a pmma matrix, containing bioactive antibacterial glasses or glassceramics |
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| US20150239777A1 (en) * | 2014-02-26 | 2015-08-27 | Corning Incorporated | High strength antimicrobial glass |
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| CN114195404A (en) * | 2021-11-08 | 2022-03-18 | 醴陵旗滨电子玻璃有限公司 | A kind of preparation method of antibacterial glass |
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