CN111887258A - Composite metal calcium phosphate antibacterial agent, preparation method thereof and inorganic artificial stone thereof - Google Patents
Composite metal calcium phosphate antibacterial agent, preparation method thereof and inorganic artificial stone thereof Download PDFInfo
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- CN111887258A CN111887258A CN202010809260.9A CN202010809260A CN111887258A CN 111887258 A CN111887258 A CN 111887258A CN 202010809260 A CN202010809260 A CN 202010809260A CN 111887258 A CN111887258 A CN 111887258A
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- Prior art keywords
- calcium phosphate
- antibacterial
- composite metal
- silver
- nano calcium
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- 239000001506 calcium phosphate Substances 0.000 title claims abstract description 170
- 229910000389 calcium phosphate Inorganic materials 0.000 title claims abstract description 170
- 235000011010 calcium phosphates Nutrition 0.000 title claims abstract description 170
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 title claims abstract description 170
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 97
- 239000002184 metal Substances 0.000 title claims abstract description 96
- 239000002131 composite material Substances 0.000 title claims abstract description 91
- 239000003242 anti bacterial agent Substances 0.000 title claims abstract description 88
- 239000002969 artificial stone Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 173
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 122
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 61
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 50
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000000084 colloidal system Substances 0.000 claims abstract description 42
- 229910052709 silver Inorganic materials 0.000 claims abstract description 40
- 239000002994 raw material Substances 0.000 claims abstract description 35
- 150000003378 silver Chemical group 0.000 claims abstract description 12
- 239000012190 activator Substances 0.000 claims abstract description 5
- 239000004599 antimicrobial Substances 0.000 claims abstract description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 132
- 239000011787 zinc oxide Substances 0.000 claims description 65
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 56
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims description 44
- 239000000243 solution Substances 0.000 claims description 44
- 239000007788 liquid Substances 0.000 claims description 39
- 238000003756 stirring Methods 0.000 claims description 33
- 239000004332 silver Substances 0.000 claims description 28
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 28
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 26
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 24
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 22
- 229910001923 silver oxide Inorganic materials 0.000 claims description 22
- 238000006722 reduction reaction Methods 0.000 claims description 20
- 229910001431 copper ion Inorganic materials 0.000 claims description 19
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 13
- 239000000725 suspension Substances 0.000 claims description 13
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 12
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 11
- 239000001110 calcium chloride Substances 0.000 claims description 11
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 11
- 230000009467 reduction Effects 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- UKHWJBVVWVYFEY-UHFFFAOYSA-M silver;hydroxide Chemical compound [OH-].[Ag+] UKHWJBVVWVYFEY-UHFFFAOYSA-M 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 238000005245 sintering Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 5
- 239000012716 precipitator Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- FFQJCVTUFKZOTA-UHFFFAOYSA-N [N+](=O)(O)[O-].[Zn].[Cu].[Ag] Chemical compound [N+](=O)(O)[O-].[Zn].[Cu].[Ag] FFQJCVTUFKZOTA-UHFFFAOYSA-N 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 4
- 239000003381 stabilizer Substances 0.000 claims description 4
- 230000003247 decreasing effect Effects 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 14
- 239000000126 substance Substances 0.000 abstract description 12
- 239000000919 ceramic Substances 0.000 abstract description 5
- 230000036541 health Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 36
- 241000222122 Candida albicans Species 0.000 description 16
- 229940095731 candida albicans Drugs 0.000 description 16
- 230000000694 effects Effects 0.000 description 16
- -1 Silver ions Chemical class 0.000 description 14
- 238000001514 detection method Methods 0.000 description 14
- 229910021645 metal ion Inorganic materials 0.000 description 14
- 239000002245 particle Substances 0.000 description 14
- 241000191967 Staphylococcus aureus Species 0.000 description 13
- 241000588724 Escherichia coli Species 0.000 description 12
- 239000000463 material Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 6
- 239000005751 Copper oxide Substances 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 229910000431 copper oxide Inorganic materials 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 4
- 210000000988 bone and bone Anatomy 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- DQBMWCJATVWEAH-UHFFFAOYSA-J P(=O)(OO)([O-])[O-].[Zr+4].OOP(=O)([O-])[O-] Chemical compound P(=O)(OO)([O-])[O-].[Zr+4].OOP(=O)([O-])[O-] DQBMWCJATVWEAH-UHFFFAOYSA-J 0.000 description 2
- 108091007643 Phosphate carriers Proteins 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 238000013268 sustained release Methods 0.000 description 2
- 239000012730 sustained-release form Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000305071 Enterobacterales Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- NEIHULKJZQTQKJ-UHFFFAOYSA-N [Cu].[Ag] Chemical compound [Cu].[Ag] NEIHULKJZQTQKJ-UHFFFAOYSA-N 0.000 description 1
- NZWXMOTXTNDNLK-UHFFFAOYSA-N [Cu].[Zn].[Ag] Chemical compound [Cu].[Zn].[Ag] NZWXMOTXTNDNLK-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000010438 granite Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000004579 marble Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical group [O-2].[Zn+2] RNWHGQJWIACOKP-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
- 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
- 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
- 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
- A01N25/22—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 ingredients stabilising the active ingredients
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/60—Agents for protection against chemical, physical or biological attack
- C04B2103/67—Biocides
- C04B2103/69—Fungicides
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Plant Pathology (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Toxicology (AREA)
- Inorganic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses a composite metal calcium phosphate antibacterial agent, a preparation method thereof and an inorganic artificial stone thereof. The composite metal calcium phosphate antibacterial agent comprises nano calcium phosphate, silver atoms and copper atoms; the nano calcium phosphate is prepared by taking modified nano calcium carbonate as a raw material; silver atom and copper atom colloids are adsorbed on the surface of the nano calcium phosphate; the silver atom acts as an activator and the copper atom acts as an antimicrobial agent to be activated. The composite metal calcium phosphate antibacterial agent contains various antibacterial substances, has a good broad-spectrum antibacterial effect, and is not easy to run off. The composite metal calcium phosphate antibacterial agent prepared by taking the nano calcium carbonate as the raw material has the advantages of very superior cost advantage, suitability for large-scale industrial manufacture and more environmental protection and health. The prepared inorganic artificial stone has good antibacterial effect and meets the standard requirement of JC/T897-2014 antibacterial ceramic product antibacterial performance.
Description
Technical Field
The invention relates to the technical field of antibacterial agents and artificial stones, in particular to a composite metal calcium phosphate antibacterial agent, a preparation method thereof and an inorganic artificial stone thereof.
Background
Silver ions carried by the antibacterial agent in the prior art can be quickly lost when meeting liquid with stronger acidity and alkalinity, and the slow release performance of the antibacterial agent is poor.
Silver ions are an antibacterial agent with excellent bactericidal properties, most of the raw materials are silver nitrate, and the purchase cost is high. And the silver nitrate belongs to strong oxidants, corrosive products and environmental pollutants, so that the use amount of the silver nitrate is reduced, and the method is more environment-friendly.
Calcium phosphate is a main component of biological bones, has biocompatibility, and is introduced into artificial bone materials by the medical field. It is a material carrier meeting the human health standard because it has no harm to human body. The nano calcium phosphate has a porous structure, large specific surface area, strong adsorption capacity, good chemical stability and high temperature resistance, can be used as a carrier to adsorb various antibacterial metal ions, has good binding force between calcium phosphate carrier molecules and the antibacterial metal ions, and has certain dissolution property, so that the antibacterial metal ions have good bactericidal antibacterial sustained-release effect.
Therefore, it is required to develop an antibacterial agent having excellent acid and alkali resistance, which can replace the raw materials of the antibacterial substance carriers in the prior art to reduce the cost, and the prepared antibacterial agent has excellent antibacterial effect and is not easy to run off, so as to meet the requirement of cost optimization of large-scale industrial production.
Disclosure of Invention
The invention provides a composite metal calcium phosphate antibacterial agent, a preparation method thereof and an inorganic artificial stone thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a composite metal calcium phosphate antibacterial agent comprises nanometer calcium phosphate, silver atoms and copper atoms; the nano calcium phosphate is prepared by taking modified nano calcium carbonate as a raw material; silver atom and copper atom colloids are adsorbed on the surface of the nano calcium phosphate; the silver atom acts as an activator and the copper atom acts as an antimicrobial agent to be activated.
Preferably, the corrosion inhibitor further comprises zinc oxide, wherein the zinc oxide is a stabilizer, the zinc oxide is a colloid adsorbed on nano calcium phosphate, and the zinc oxide is used for delaying silver oxide from being alkalized in an alkaline environment, so that the situation that silver oxide is converted into silver hydroxide firstly and separated out, and copper atoms cannot be converted into copper ions is avoided.
Preferably, the molar contents of copper atoms, zinc oxide and silver atoms adsorbed to the nano calcium phosphate are all reduced in sequence.
Preferably, the molar content ratio of copper atoms, zinc oxide and silver atoms adsorbed to the nano calcium phosphate is 4:2: 1.
Further, the invention also provides a preparation method of the composite metal calcium phosphate antibacterial agent, which comprises the following specific steps:
s1) preparing an aqueous solution containing nano calcium carbonate, heating, stirring and heating to a specified temperature, and keeping the constant temperature to prepare a nano calcium carbonate suspension;
s2) adding the surface active agent titanate into the stirred absolute ethyl alcohol until the surface active agent titanate is completely dissolved to prepare titanate solution;
s3), dripping the titanate solution into the nano calcium carbonate suspension while stirring, and continuously stirring for 1 hour to obtain a modified nano calcium carbonate solution;
s4), adding phosphoric acid into the modified nano calcium carbonate solution while stirring, and continuously stirring for 30 minutes to obtain a nano calcium phosphate solution;
s5) adding silver nitrate, copper nitrate and zinc oxide into the nano calcium phosphate solution, stirring and mixing uniformly, continuing stirring for 30 minutes, and gradually dripping a silver precipitator calcium chloride aqueous solution to prepare a composite metal colloid calcium phosphate solution;
s6) filtering the composite metal colloid calcium phosphate solution, cleaning, putting into a reduction sintering furnace, heating and roasting;
s7) adding carbon monoxide into a constant-temperature reduction sintering furnace, and carrying out reduction reaction to obtain composite metal colloid calcium phosphate baking powder;
s8) grinding and sieving the composite metal colloid calcium phosphate baking powder to obtain the composite metal calcium phosphate antibacterial agent.
Further, in the step S1, the molar ratio of the nano calcium carbonate to the water is 1:5, and the constant temperature is 85 ℃; in the step S2, the stirring speed is 150r/min, and the molar ratio of the absolute ethyl alcohol to the titanate is 2: 0.1; in the step S3, the molar ratio of the titanate to the nano calcium carbonate is 0.1: 1; in the step S4, the molar ratio of the phosphoric acid to the nano calcium carbonate is 2: 3.
Further, in the step S5, the silver copper zinc nitric acid solution contains copper nitrate, zinc oxide, silver nitrate and nano calcium phosphate in a mixing molar ratio of 2.5:1:0.5: 16; the molar ratio of the calcium chloride to the silver nitrate solution is 1: 2.
Further, in the step S6, the roasting temperature is 1100-1180 ℃, and the roasting time is 2-3 hours; in the step S7, the pressure of adding the carbon monoxide is 0.1-0.15MPa, and the time of the reduction reaction is 0.8-1 hour; in the step S8, the mesh size of the sieved mesh is 300 mesh.
The invention also provides an inorganic artificial stone, which comprises the raw materials of the antibacterial bonding liquid, wherein the raw materials of the antibacterial bonding liquid comprise the composite metal calcium phosphate antibacterial agent, the antibacterial bonding liquid is used for bonding the solid raw materials of the inorganic artificial stone, and the antibacterial bonding liquid is uniformly distributed in the inorganic artificial stone.
Further, the composite metal calcium phosphate antibacterial agent accounts for 1-3% of the total mass of the inorganic artificial stone; the raw material components of the antibacterial bonding liquid also comprise water, and the antibacterial bonding liquid is a pre-prepared mixed liquid added before the inorganic artificial stone.
The invention has the beneficial effects that:
the composite metal calcium phosphate antibacterial agent is nano silver-loaded calcium phosphate loaded with silver, copper metal colloid and zinc oxide, and has the characteristics of good heat resistance, high-efficiency broad-spectrum antibacterial property, excellent slow release property and the like. The nano calcium carbonate, the zinc oxide and the copper nitrate are wide in raw material source and low in purchase cost, so that the composite metal calcium phosphate antibacterial agent has better cost advantage and more optimized slow release performance compared with the silver ion-loaded antibacterial agent in the prior art.
Compared with the antibacterial agent in the prior art, the composite metal calcium phosphate antibacterial agent has the advantages that antibacterial substances are not easy to lose, the broad-spectrum sterilization effect is good, the cost advantage is superior, and the cost optimization requirement of large-scale industrial production can be met.
The invention provides a preparation method of the composite metal calcium phosphate antibacterial agent, and the prepared inorganic antibacterial agent containing the double-carrier structure and multiple antibacterial substances is convenient to store and use.
The invention also provides an inorganic artificial stone using the composite metal calcium phosphate antibacterial agent, and the prepared inorganic artificial stone has excellent antibacterial performance and antibacterial durability.
Detailed Description
The technical solution of the present invention is further described below in specific embodiments.
A composite metal calcium phosphate antibacterial agent comprises nanometer calcium phosphate, silver atoms and copper atoms; the nano calcium phosphate is prepared by taking modified nano calcium carbonate as a raw material; silver atom and copper atom colloids are adsorbed on the surface of the nano calcium phosphate; the silver atom acts as an activator and the copper atom acts as an antimicrobial agent to be activated.
The nanometer calcium phosphate can release active silver atoms and copper atoms, and metal atom colloid is less prone to being damped and lost than metal ion colloid, so that the slow release effective period of the antibacterial substance can be prolonged.
When silver atoms are in a humid environment containing oxygen, such as contact with water, acid or alkaline solution, the silver atoms are oxidized into silver ions; silver ion/silver electricity in the presence of silver atoms, silver ions and copper atomsThe electrode potential is 0.80 volt, the electrode potential of copper ion/copper is 0.34 volt, and due to the potential difference of the electrode potential, silver ions in the metal colloid can oxidize copper atoms in the colloid into colloidal copper ions, while silver ions are reduced into silver atoms, whose chemical reaction formula is 2Ag++Cu＝2Ag+Cu++Potential difference E thereof0＝ψ(Ag+/Ag-ψCu++0.80-0.34-0.46V, and converting the copper atom in colloid into Cu with antibacterial and bactericidal activity++Ions.
When in oxygen-containing humid environment, silver atoms are oxidized into silver ions, copper atoms in the silver ion oxidized colloid are colloid copper ions and are copper ions with antibacterial activity, and the antibacterial activity of the composite metal calcium phosphate antibacterial agent is activated. The dried composite metal calcium phosphate antibacterial agent has good stability, and antibacterial active substances are not easy to run off.
Calcium phosphate is a main component of biological bones, has biocompatibility, and is introduced into artificial bone materials by the medical field. It is a material carrier meeting the human health standard because it has no harm to human body. The nano calcium phosphate has a porous structure, large specific surface area, strong adsorption capacity, good chemical stability and high temperature resistance, can be used as a carrier to adsorb various antibacterial metal ions, has good binding force between calcium phosphate carrier molecules and the antibacterial metal ions, and has certain dissolution property, so that the antibacterial metal ions have good bactericidal antibacterial sustained-release effect.
The nano calcium phosphate has high temperature resistance and stability, a precursor containing an antibacterial substance can be prepared by a method of wrapping and coprecipitating a phosphoric acid solution, a nano calcium carbonate microemulsion suspension and an antibacterial metal ion salt solution, then the precursor is baked at high temperature to decompose the precursor, and metal ions are oxidized into metal oxides, so that the antibacterial metal ions are stably kept in crystal lattices of calcium phosphate microcrystal particles, the calcium phosphate has weak solubility in the presence of a water-containing solution, and the separated antibacterial metal ions can complete the antibacterial function and have good slow release characteristics.
The composite metal calcium phosphate antibacterial agent contains various antibacterial substances, has a good broad-spectrum antibacterial effect, and is not easy to run off. The nano calcium phosphate prepared by using the nano calcium carbonate as the raw material has the advantages of excellent cost advantage, suitability for large-scale industrial manufacture and environmental protection and health.
Preferably, the corrosion inhibitor further comprises zinc oxide, wherein the zinc oxide is a stabilizer, the zinc oxide is a colloid adsorbed on nano calcium phosphate, and the zinc oxide is used for delaying silver oxide from being alkalized in an alkaline environment, so that the situation that silver oxide is converted into silver hydroxide firstly and separated out, and copper atoms cannot be converted into copper ions is avoided.
The zinc oxide is an antibacterial agent with a good antibacterial effect, has photosensitive bactericidal performance, is wide in raw material source and low in purchase cost, and has superior cost advantage compared with silver nitrate powder because silver nitrate is a raw material of silver atoms.
The silver oxide colloid is adsorbed on the composite metal calcium phosphate antibacterial agent, so that the composite metal calcium phosphate antibacterial agent has better stability and is not easy to lose, contains various active antibacterial substances, has wider product application range and more comprehensive antibacterial effect, and has better finished product advantages while improving the slow release performance.
The zinc oxide adsorbed on the composite metal calcium phosphate antibacterial agent is used for protecting silver oxide from being alkalized in an alkaline environment and preventing the silver oxide from being separated out by being converted into silver hydroxide, so that the conversion rate of copper atoms into copper ions is reduced, and the antibacterial performance of the composite metal calcium phosphate antibacterial agent is reduced. Only after the zinc oxide is consumed by the reaction, the silver oxide is alkalized and converted into silver hydroxide to be separated out.
Therefore, the antibacterial organic artificial stone with the composite metal colloid has the performance of avoiding silver precipitation and discoloration, and the product can have better color or transparent effect.
The zinc oxide has good activity, can improve the adverse effect of precipitation under the alkaline environment of silver ions, and has the following chemical reaction mechanism.
Silver ions react with basic groups in alkaline environment to generate silver hydroxide precipitate
Ag++OH-AgOH ↓ (white)
Unstable decomposition of silver hydroxide precipitate to silver oxide precipitate
2AgOH＝Ag2O ↓ (dark brown) + H2O
When zinc oxide and silver oxide coexist, the chemical reaction activity of the zinc oxide under the alkaline environment is higher than that of the silver oxide, and the zinc oxide firstly reacts with basic groups to delay and prevent the precipitation of the silver oxide.
ZnO++2OH-＝Zn(OH)2↓ (white)
The zinc oxide is used as a stabilizer of silver ions, so that the stability of the antibacterial performance of the composite metal calcium phosphate antibacterial agent can be improved, and the alkaline application range of the composite metal calcium phosphate antibacterial agent can be widened by increasing the using amount and the proportion of the zinc oxide.
Preferably, the molar contents of copper atoms, zinc oxide and silver atoms adsorbed to the nano calcium phosphate are all reduced in sequence.
The composite metal calcium phosphate antibacterial agent contains silver atoms in an oxygen-containing humid environment, and can effectively convert copper atoms into copper ions. Under the condition of keeping the effect of converting copper ions of silver atoms, the use amount of silver nitrate in the raw materials is reduced, and the use amounts of copper nitrate and zinc oxide are increased, so that the cost advantage of the composite metal calcium phosphate antibacterial agent can be effectively improved, and the composite metal calcium phosphate antibacterial agent is more environment-friendly.
Preferably, the molar content ratio of copper atoms, zinc oxide and silver atoms adsorbed to the nano calcium phosphate is 4:2: 1.
The molar content ratio of the copper atoms, the zinc oxide and the silver atoms adsorbed by the silver-loaded calcium phosphate is 4:2:1, so that the cost performance is better, the composite metal calcium phosphate antibacterial agent has a good antibacterial effect, and a better cost advantage can be obtained.
The molar content ratio of the zinc oxide to the silver atoms is 2:1, the probability that the silver oxide is alkalized first can be reduced, the conversion rate of converting the copper atoms adsorbed by the silver-loaded calcium phosphate into copper ions can be improved, and the stability of the antibacterial performance of the composite metal calcium phosphate antibacterial agent can be ensured.
Further, the invention also provides a preparation method of the composite metal calcium phosphate antibacterial agent, which comprises the following specific steps:
s1) preparing an aqueous solution containing nano calcium carbonate, heating, stirring and heating to a specified temperature, and keeping the constant temperature to prepare a nano calcium carbonate suspension;
s2) adding the surface active agent titanate into the stirred absolute ethyl alcohol until the surface active agent titanate is completely dissolved to prepare titanate solution;
s3), dripping the titanate solution into the nano calcium carbonate suspension while stirring, and continuously stirring for 1 hour to obtain a modified nano calcium carbonate solution;
s4), adding phosphoric acid into the modified nano calcium carbonate solution while stirring, and continuously stirring for 30 minutes to obtain a nano calcium phosphate solution;
s5) adding silver nitrate, copper nitrate and zinc oxide into the nano calcium phosphate solution, stirring and mixing uniformly, continuing stirring for 30 minutes, and gradually dripping a silver precipitator calcium chloride aqueous solution to prepare a composite metal colloid calcium phosphate solution;
s6) filtering the composite metal colloid calcium phosphate solution, cleaning, putting into a reduction sintering furnace, heating and roasting;
s7) adding carbon monoxide into a constant-temperature reduction sintering furnace, and carrying out reduction reaction to obtain composite metal colloid calcium phosphate baking powder;
s8) grinding and sieving the composite metal colloid calcium phosphate baking powder to obtain the composite metal calcium phosphate antibacterial agent.
The steps S1, S2 and S3 are used for modifying the nano calcium carbonate micro powder. The nanometer calcium carbonate has a particle size of 15-40nm and a specific surface area of more than 200m2The surface energy is high, the polarity is strong, and the agglomeration is easy to occur. The surface of the nano calcium carbonate has hydrophilic and oleophobic properties, and naturally settles under the influence of gravity in an aqueous solution, and can not be naturally suspended in water to form a suspension. Modified nano calcium carbonate with non-polar hydrophobic film on its surface and water between the particles of nano calcium carbonateThe fixed repulsion can keep a certain distance between the nano calcium carbonate particles in water, avoid the agglomeration phenomenon of the generated nano calcium carbonate particles, and prevent the nano calcium carbonate particles from floating and sinking in the water to form nano calcium carbonate suspension.
After the surface of the nano calcium carbonate particles is activated by adopting the titanate surfactant, the surface of the nano calcium carbonate particles can realize non-polar transformation, the activation index is gradually increased, when a monolayer coating state is formed, the hydrophobic group faces outwards, the optimal modified dispersion effect can be obtained, the nano calcium carbonate particles have hydrophobicity, and the dispersed nano calcium carbonate suspension aqueous solution is obtained.
The nano calcium carbonate is converted into nano calcium phosphate by adding phosphoric acid in step S4.
Adding silver nitrate, copper nitrate and zinc oxide into a nano calcium phosphate aqueous solution, adsorbing for 30 minutes, then dripping a silver precipitator calcium chloride aqueous solution into the aqueous solution to enable silver nitrate to be changed into silver chloride precipitate to be adsorbed on the surface of the nano calcium phosphate, forming a filtered coprecipitate with the nano calcium phosphate, and drying at a high temperature to form the nano calcium phosphate adsorbed with the silver oxide, the zinc oxide and the copper oxide.
The nano calcium phosphate has high temperature resistance stability, and after the nano calcium phosphate is adsorbed by the antibacterial metal ion salt solution at normal temperature, the adsorbed antibacterial metal ions are oxidized into metal oxides by high-temperature roasting, so that the binding force of the antibacterial metal oxides in the nano calcium phosphate is enhanced, the metal ions are further reduced into metal atoms, the dissociated antibacterial metal atoms are controlled, the antibacterial metal elements in the carrier are ensured to generate a good slow release effect, and the nano calcium phosphate has a long-term antibacterial effect.
Ag adsorbed to nano calcium phosphate+、Cu++And Zn++Ionic, Ag after high temperature roasting+、Cu++And Zn++The ions are converted into silver oxide, copper oxide and zinc oxide, and then the silver oxide and the copper oxide are reduced into silver atom colloid and copper atom colloid by carbon monoxide at a high temperature of more than 1000 ℃, and the zinc oxide can not be used for carbon monoxide to be coatedThe reduction is still adsorbed on the surface of nano calcium phosphate in a colloid form, and the colloid of silver and copper atoms and the colloid of zinc oxide are adsorbed on the surface of nano calcium phosphate to form the nano calcium phosphate with antibacterial activity.
Common zinc oxide powder is dissolved into Zn++The ions are oxidized again to oxidize the zinc, and the formed colloid is adsorbed on the zinc oxide on the surface of the silver-loaded calcium phosphate, so that the silver-loaded calcium phosphate has broad-spectrum antibacterial performance and has good antibacterial effect on candida albicans.
The zinc oxide adopts zinc oxide powder, the copper oxide adopts copper nitrate powder, the raw material source is wide, and the purchase cost is low.
Therefore, the composite metal calcium phosphate antibacterial agent is nano calcium phosphate loaded with silver atom, copper atom colloid and zinc oxide colloid, and has the characteristics of good heat resistance, high-efficiency broad-spectrum antibacterial property, excellent slow release property, ultraviolet ray reinforced sterilization and the like. Compared with the silver-loaded zirconium hydroxy phosphate antibacterial agent, the composite metal calcium phosphate antibacterial agent has better cost advantage.
Further, in the step S1, the molar ratio of the nano calcium carbonate to the water is 1:5, and the constant temperature is 85 ℃; in the step S2, the stirring speed is 150r/min, and the molar ratio of the absolute ethyl alcohol to the titanate is 2: 0.1; in the step S3, the molar ratio of the titanate to the nano calcium carbonate is 0.1: 1; in the step S4, the molar ratio of the phosphoric acid to the nano calcium carbonate is 2: 3.
In the step S1, the molar ratio of the nano calcium carbonate to the water is 1:5, and the constant temperature is 85 ℃; in the step S2, the stirring speed is 150r/min, the molar ratio of the absolute ethyl alcohol to the titanate is 2:0.1, the modification effect of the nano calcium carbonate can be improved, and the dispersibility of the nano calcium carbonate and the stability of the suspension thereof can be improved. The molar ratio of the phosphoric acid to the nano calcium carbonate in the step S4 is 2:3, and the equivalent concentration of the phosphoric acid is equal to that of the nano calcium carbonate, so that the nano calcium carbonate can be effectively converted into the nano calcium phosphate.
Further, in the step S5, the silver copper zinc nitric acid solution contains copper nitrate, zinc oxide, silver nitrate and nano calcium phosphate in a mixing molar ratio of 2.5:1:0.5: 16; the molar ratio of the calcium chloride to the silver nitrate solution is 1: 2.
The molar ratio of copper nitrate to zinc oxide to silver nitrate to nano calcium phosphate is 2.5:1:0.5:16, the total content of the silver-copper-zinc ion antibacterial active substance is high, and the adsorption efficiency of zirconium hydroxy phosphate can be improved.
The molar ratio of the calcium chloride to the silver nitrate solution is 1:2, and the equivalent concentration of chloride ions contained in the calcium chloride is the same as that of silver ions contained in the silver-copper-zinc-nitric acid solution, so that the effective rate of precipitation and adsorption of the silver ions can be ensured.
Further, in the step S6, the roasting temperature is 1100-1180 ℃, and the roasting time is 2-3 hours; in the step S7, the pressure of adding the carbon monoxide is 0.1-0.15MPa, and the time of the reduction reaction is 0.8-1 hour; in the step S8, the mesh size of the sieved mesh is 300 mesh.
The roasting temperature is 1100-1180 ℃, is higher than 900 ℃ and is maintained for 2-3 hours, so that the adsorption strength of silver atoms adsorbed on the nano calcium phosphate can be improved, the loss of the silver atoms is reduced, and the stability of the composite metal calcium phosphate antibacterial agent is improved.
The pressure of the added carbon monoxide is lower than 0.1MPa, so that the reduction efficiency of the silver oxide and the copper oxide is reduced, and resources are wasted when the pressure is higher than 0.15 MPa. The reducing gas can also adopt hydrogen, and carbon monoxide is more convenient and lower in cost than hydrogen, so that the method has better economic benefit.
The smaller the particle size of the nano calcium phosphate is, the larger the surface area ratio of the nano calcium phosphate is, the higher the activity of the loaded silver-copper colloid is, the particle size of the conventional nano calcium phosphate is less than 40 nanometers, and the bonded composite metal calcium phosphate antibacterial agent with overlarge particle size can be removed by filtering with a 300-mesh filter screen, so that the bad appearance of particles with uneven distribution is avoided when the antibacterial agent is used.
The dried composite metal calcium phosphate antibacterial agent has good antibacterial effect and is convenient to store and use.
The invention further provides an inorganic artificial stone, which comprises the raw materials of an antibacterial bonding liquid, wherein the raw materials of the antibacterial bonding liquid comprise the composite metal calcium phosphate antibacterial agent, the antibacterial bonding liquid is used for bonding the solid raw materials of the inorganic artificial stone, and the antibacterial bonding liquid is uniformly distributed in the inorganic artificial stone.
The antibacterial bonding liquid is used for bonding solid raw materials of the inorganic artificial stone and is uniformly distributed in the inorganic artificial stone. The composite metal calcium phosphate antibacterial agent included in the antibacterial bonding liquid is uniformly distributed in the inorganic artificial stone and bonded in the inorganic artificial stone, so that the antibacterial effect of the inorganic artificial stone is more stable and uniform.
The solid raw materials of the inorganic artificial stone comprise quartz stone, marble, granite, feldspar, super quartz stone and colorant.
Further, the composite metal calcium phosphate antibacterial agent accounts for 1-3% of the total mass of the inorganic artificial stone; the raw material components of the antibacterial bonding liquid also comprise water, and the antibacterial bonding liquid is a pre-prepared mixed liquid added before the inorganic artificial stone.
The inorganic artificial stone containing 1-3% of the composite metal calcium phosphate antibacterial agent can meet the requirements of JC/T897-2014 'antibacterial ceramic product antibacterial performance' standard through detection on antibacterial performance and antibacterial durability. The content of the composite metal calcium phosphate antibacterial agent contained in the inorganic artificial stone is lower than 1%, and the antibacterial performance index does not reach the standard; the content of the composite metal calcium phosphate antibacterial agent contained in the inorganic artificial stone is higher than 3%, the antibacterial performance is excessive, and resources are wasted.
Because the main raw materials of the inorganic artificial stone in the prior art are mostly cement-series materials, the alkalinity is higher, the raw materials contain water the antibacterial bonding liquid is prepared, then the prefabricated material of the inorganic artificial stone is added, the alkaline damage of the cement-series materials in the inorganic artificial stone can be avoided, the silver ions contained in the antibacterial bonding liquid are prevented from being changed into silver hydroxide, the conversion rate of copper atoms to copper ions is reduced, and the antibacterial performance of the inorganic artificial stone prepared by the composite metal calcium phosphate antibacterial agent is influenced.
Examples and comparative examples
Inorganic artificial stones of examples and comparative examples were prepared as follows, and the silver nitrate, copper nitrate and zinc oxide were commercially available chemically pure powders; the nano calcium carbonate adopts commercially available nano sodium carbonate micro powder, the particle size is 15-40nm, and the specific surface area is more than 200m 2/g.
The method comprises the following specific steps:
1. a composite metal calcium phosphate antibacterial agent comprises nanometer calcium phosphate, silver atoms and copper atoms; the nano calcium phosphate is prepared by taking modified nano calcium carbonate as a raw material; silver atom and copper atom colloids are adsorbed on the surface of the nano calcium phosphate; the silver atom acts as an activator and the copper atom acts as an antimicrobial agent to be activated.
The zinc oxide is used for delaying silver oxide from being alkalized in an alkaline environment, and the silver oxide is prevented from being converted into silver hydroxide firstly and separated out, so that copper atoms cannot be converted into copper ions.
The molar contents of copper atoms, zinc oxide and silver atoms adsorbed to the nano silver-loaded calcium phosphate are sequentially reduced.
The molar content ratio of the copper atoms, the zinc oxide atoms and the silver atoms is 4:2: 1.
2. The preparation method of the composite metal calcium phosphate antibacterial agent comprises the following specific steps:
s1) preparing an aqueous solution containing nano calcium carbonate, heating, stirring and heating to a specified temperature, and keeping the constant temperature to prepare a nano calcium carbonate suspension;
s2) adding the surface active agent titanate into the stirred absolute ethyl alcohol until the surface active agent titanate is completely dissolved to prepare titanate solution;
s3), dripping the titanate solution into the nano calcium carbonate suspension while stirring, and continuously stirring for 1 hour to obtain a modified nano calcium carbonate solution;
s4), adding phosphoric acid into the modified nano calcium carbonate solution while stirring, and continuously stirring for 30 minutes to obtain a nano calcium phosphate solution;
s5) adding silver nitrate, copper nitrate and zinc oxide into the nano calcium phosphate solution, stirring and mixing uniformly, continuing stirring for 30 minutes, and gradually dripping into a silver precipitator calcium chloride aqueous solution to obtain a composite metal colloidal calcium phosphate solution;
s6) filtering the composite metal colloid calcium phosphate solution, cleaning, putting into a reduction sintering furnace, heating and roasting;
s7) adding carbon monoxide into a constant-temperature reduction sintering furnace, and carrying out reduction reaction to obtain composite metal colloid calcium phosphate baking powder;
s8) grinding and sieving the composite metal colloid calcium phosphate baking powder to obtain the composite metal calcium phosphate antibacterial agent.
In the step S1, the molar ratio of the nano calcium carbonate to the water is 1:5, and the constant temperature is 85 ℃; in the step S2, the stirring speed is 150r/min, and the molar ratio of the absolute ethyl alcohol to the titanate is 2: 0.1; in the step S3, the molar ratio of the titanate to the nano calcium carbonate is 0.1: 1; in the step S4, the molar ratio of the phosphoric acid to the nano calcium carbonate is 2: 3;
in the step S5, the mixing molar ratio of the copper nitrate, the zinc oxide, the silver nitrate and the nano calcium phosphate is 2.5:1:0.5:16, and the molar ratio of the calcium chloride to the silver nitrate solution is 1: 2;
in the step S6, the roasting temperature is 1100-1180 ℃, and the roasting time is 2-3 hours; in the step S7, the pressure of adding the carbon monoxide is 0.1-0.15MPa, and the time of the reduction reaction is 0.8-1 hour; in the step S8, the mesh size of the sieved mesh is 300 mesh.
4. The raw materials of the inorganic artificial stone comprise antibacterial bonding liquid, the antibacterial bonding liquid contains the composite metal calcium phosphate antibacterial agent, the raw material components of the antibacterial bonding liquid also comprise water, the antibacterial bonding liquid is prefabricated mixed liquid, and the composite metal calcium phosphate antibacterial agent accounts for 1-3% of the total mass of the inorganic artificial stone.
5. The contents and ratios of the specific raw material components and the parameters in each example are shown in Table 1, and the contents and ratios of the specific raw material components and the parameters in each ratio are shown in Table 2.
6. The inorganic artificial stone prepared in each example and comparative example was sampled with reference to JC/T897-2014 "antibacterial property of antibacterial ceramic article" standard, and the antibacterial properties and antibacterial durability of escherichia coli, staphylococcus aureus and candida albicans were tested, and the test results of examples and base materials are shown in table 1, and the test results of comparative example are shown in table 1.
TABLE 1 data and test results for the examples and substrates
TABLE 2 comparative data and test results
The following is an analysis explanation based on the above cases and test results of the respective examples and comparative examples:
1. according to the standard requirement of JC/T897-2014 antibacterial ceramic product antibacterial performance, the antibacterial rate (%) of the antibacterial performance is more than or equal to 90 percent and the antibacterial rate (%) of the antibacterial durability is more than or equal to 85 percent, and the detection results of the antibacterial rates of the antibacterial performance and the antibacterial rate of the antibacterial durability of escherichia coli, staphylococcus aureus and candida albicans of the base material are unqualified.
2. Analysis of the test results of examples 1 to 5:
(1) the antibacterial performance and antibacterial durability of the escherichia coli, staphylococcus aureus and candida albicans of examples 1-3 were all the percent (%) pass, and the numerical values of the antibacterial rates were increased in order, which shows that the antibacterial effect is enhanced with the increase of the active copper ions.
(2) Examples 1 and 2 differ from example 3 in that: the molar ratio of copper nitrate is less than 2.5, the molar ratio is respectively 2.0 and 2.3, the detection results of the antibacterial performance antibacterial rate (%) and the antibacterial durability antibacterial rate (%) of the enterobacteria, the staphylococcus aureus and the candida albicans in the examples 1 and 2 are both qualified, the qualified standards are met, and the comparison with the detection results of the examples 1 and 2 shows that the effect of the example 3 is the best;
(3) example 4 differs from example 3 in that: the zinc oxide is not added in the embodiment 4, and the detection results of the antibacterial performance and antibacterial durability antibacterial rate of escherichia coli and staphylococcus aureus in the embodiment 4 are both very excellent and higher than 95%; but the detection results of the antibacterial performance and antibacterial durability of the candida albicans in the example 4 are not qualified; the zinc oxide has a relatively outstanding antibacterial effect on candida albicans, and the copper ions have a general antibacterial effect on candida albicans;
(4) example 5 differs from example 4 in that: in example 5, the silver nitrate with the content increased by 0.5 mol ratio is not added, and the detection results of the antibacterial performance and antibacterial durability of the candida albicans of example 5 are qualified, which indicates that the increased content of 0.5 mol of the silver nitrate has a prominent antibacterial effect on the candida albicans; comparing with the examples 1-5, the zinc oxide with the concentration ratio of 1 mol ratio can replace silver ions to have more outstanding antibacterial effect on candida albicans;
(5) the components and the detection results of examples 1 to 5 were comprehensively analyzed to find that: the raw material components of the antibacterial binding liquid also comprise water, and the antibacterial binding liquid is a pre-prepared mixed liquid; the composite metal calcium phosphate antibacterial agent is effective, and the antibacterial binding liquid and the prepared inorganic artificial stone have good antibacterial effect and good durability. The composite metal calcium phosphate antibacterial agent accounts for 1-3% of the total mass of the inorganic artificial stone; the molar mixing ratio of the copper nitrate, the zinc oxide, the silver nitrate and the nano calcium phosphate is 2.5:1:0.5: 16; the inorganic artificial stone prepared from the composite metal calcium phosphate antibacterial agent has good antibacterial effect; the molar content ratio of copper atoms, zinc oxide and silver atoms adsorbed by the nano calcium phosphate is 4:2:1, so that the cost performance is better.
3. Comparative example 1 was analyzed, comparing to example 1, the difference of comparative example 1 is: the time of the reduction reaction of comparative example 1 is 0.5 hour, and the lower limit of less than 0.8 hour decreases the reduction rate of silver oxide, thus decreasing the conversion rate of copper ions of the antibacterial function, resulting in that the results of the tests of antibacterial performance antibacterial rate and antibacterial durability antibacterial rate (%) of escherichia coli, staphylococcus aureus of comparative example 1 are not good.
4. Comparative example 2 was analyzed, and compared to example 1, the difference of comparative example 2 was: the molar ratio of the copper nitrate added in the comparative example 2 is 1.5, and the molar content ratio of the copper atoms, the zinc oxide and the silver atoms adsorbed by the nano calcium phosphate is 4:2:1, so that the content of copper ions with the antibacterial function is reduced, and the detection results of the antibacterial performance antibacterial rate and the antibacterial durability antibacterial rate (%) of escherichia coli and staphylococcus aureus in the comparative example 2 are unqualified.
5. Comparative example 3 was analyzed, and compared to example 1, the difference of comparative example 3 was: the molar ratio of the silver nitrate added in the comparative example 3 is 1, the molar content ratio of copper atoms, zinc oxide and silver atoms higher than that of the nano calcium phosphate is 4:2:1, and the detection results of the antibacterial rate and antibacterial durability antibacterial rate (%) of escherichia coli, staphylococcus aureus and candida albicans in the comparative example 3 reach the highest limit, so that resources are wasted due to excessive quality.
6. Comparative example 4 was analyzed, comparing to example 1, the difference of comparative example 4 is: the molar ratio of the silver nitrate added in the comparative example 4 is 0.3, the molar content ratio of the copper atoms, the zinc oxide and the silver atoms which are adsorbed by the nano calcium phosphate is 4:2:1, so that the copper ions are not completely converted, and the detection results of the antibacterial rate of the antibacterial performance and the antibacterial rate (%) of the antibacterial durability of escherichia coli and staphylococcus aureus in the comparative example 4 are not qualified; therefore, the molar content ratio of the copper atoms, the zinc oxide and the silver atoms adsorbed by the nano calcium phosphate is set to be 4:2:1, which is more suitable.
7. Comparative example 5 was analyzed, and compared to example 1, the difference of comparative example 5 was: the antibacterial bonding liquid of comparative example 5 is not a pre-prepared mixed liquid, and the zinc oxide is not added, silver atoms adsorbed by the nano calcium phosphate are alkalized in an alkaline environment, the effect of copper oxide atoms as copper ions is lost, and the detection results of antibacterial performance antibacterial rate and antibacterial durability antibacterial rate (%) of escherichia coli, staphylococcus aureus and candida albicans of the prepared inorganic artificial stone are not qualified.
8. Comparative example 6 was analyzed, comparing with example 1 and comparative example 5, the difference of comparative example 6 is: although the antibacterial bonding liquid of comparative example 5 is not a pre-prepared mixed liquid, the detection results of the antibacterial performance and antibacterial durability (%) of escherichia coli, staphylococcus aureus and candida albicans of the prepared inorganic artificial stone are all not qualified by adding the zinc oxide, but the antibacterial performance and antibacterial durability (%) of the escherichia coli, staphylococcus aureus and candida albicans of the detection results are better improved than those of comparative example 5, which shows that the zinc oxide has a specific and obvious delaying effect on basification of silver atoms in an alkaline environment and has a good stability effect on the composite metal calcium phosphate antibacterial agent.
9. Comparative examples 7 and 8 were analyzed, and in contrast to example 1, comparative examples 7 and 8 differ by: the content ratios of the added antibacterial active carbon antibacterial agents are different, wherein 0.7 percent of the comparative example 7 is less than 1 percent, and 3.5 percent of the comparative example 8 is more than 3 percent; the results of the tests of the antibacterial performance and antibacterial durability (%) of comparative example 7 were all unqualified; the results of the tests of antibacterial property and antibacterial durability (%) of comparative example 8 were all acceptable, but the improvement in comparison with example 3 was limited, and the results of the tests of antibacterial property and antibacterial durability (%) of example 3 were excellent, so that it was appropriate to set the composite metal calcium phosphate antibacterial agent to 1-3% by mass of the total mass of the inorganic artificial stone.
In conclusion, the inorganic artificial stone prepared by using the composite metal calcium phosphate antibacterial agent has excellent antibacterial effects on escherichia coli, staphylococcus aureus and candida albicans.
The inorganic artificial stone containing 1-3% of the composite metal calcium phosphate antibacterial agent has antibacterial performance and antibacterial durability which can meet the requirements of JC/T897-2014 Standard of antibacterial performance of antibacterial ceramic products.
The composite metal calcium phosphate antibacterial agent disclosed by the invention contains various antibacterial substances, has a good broad-spectrum antibacterial effect, is not easy to run off, has a superior cost advantage, and is suitable for the requirement of large-scale industrial manufacturing.
The invention provides a preparation method of the composite metal calcium phosphate antibacterial agent, and the prepared composite metal calcium phosphate antibacterial agent contains inorganic antibacterial agents of various antibacterial substances, and is convenient to store and use.
The inorganic artificial stone using the composite metal calcium phosphate antibacterial agent has excellent antibacterial performance and antibacterial durability.
The technical principle of the present invention is described above in connection with specific embodiments. The description is made for the purpose of illustrating the principles of the invention and should not be construed in any way as limiting the scope of the invention. Based on the explanations herein, those skilled in the art will be able to conceive of other embodiments of the present invention without inventive effort, which would fall within the scope of the present invention.
Claims (10)
1. The composite metal calcium phosphate antibacterial agent is characterized by comprising nano calcium phosphate, silver atoms and copper atoms; the nano calcium phosphate is prepared by taking modified nano calcium carbonate as a raw material; silver atom and copper atom colloids are adsorbed on the surface of the nano calcium phosphate; the silver atom acts as an activator and the copper atom acts as an antimicrobial agent to be activated.
2. The composite metal calcium phosphate antibacterial agent according to claim 1, further comprising zinc oxide, wherein the zinc oxide is a stabilizer, the zinc oxide is a colloid adsorbed on nano calcium phosphate, and the zinc oxide is used for delaying silver oxide alkalization in an alkaline environment and avoiding silver oxide from being converted into silver hydroxide first to be separated out, so that copper atoms cannot be converted into copper ions.
3. The composite metal calcium phosphate antibacterial agent according to claim 2, wherein the molar contents of copper atoms, zinc oxide and silver atoms adsorbed to the nano calcium phosphate are all decreased in this order.
4. The composite metal calcium phosphate antibacterial agent according to claim 2, wherein the molar content ratio of copper atoms, zinc oxide and silver atoms adsorbed to the nano calcium phosphate is 4:2: 1.
5. The method for preparing a composite metal calcium phosphate antibacterial agent according to any one of claims 1 to 4, comprising the following specific steps:
s1) preparing an aqueous solution containing nano calcium carbonate, heating, stirring and heating to a specified temperature, and keeping the constant temperature to prepare a nano calcium carbonate suspension;
s2) adding the surface active agent titanate into the stirred absolute ethyl alcohol until the surface active agent titanate is completely dissolved to prepare titanate solution;
s3), dripping the titanate solution into the nano calcium carbonate suspension while stirring, and continuously stirring for 1 hour to obtain a modified nano calcium carbonate solution;
s4), adding phosphoric acid into the modified nano calcium carbonate solution while stirring, and continuously stirring for 30 minutes to obtain a nano calcium phosphate solution;
s5) adding silver nitrate, copper nitrate and zinc oxide into the nano calcium phosphate solution, stirring and mixing uniformly, continuing stirring for 30 minutes, and gradually dripping a silver precipitator calcium chloride aqueous solution to prepare a composite metal colloid calcium phosphate solution;
s6) filtering the composite metal colloid calcium phosphate solution, cleaning, putting into a reduction sintering furnace, heating and roasting;
s7) adding carbon monoxide into a constant-temperature reduction sintering furnace, and carrying out reduction reaction to obtain composite metal colloid calcium phosphate baking powder;
s8) grinding and sieving the composite metal colloid calcium phosphate baking powder to obtain the composite metal calcium phosphate antibacterial agent.
6. The method for preparing a composite metal calcium phosphate antibacterial agent according to claim 5, wherein in the step S1, the molar ratio of the nano calcium carbonate to the water is 1:5, and the constant temperature is 85 ℃; in the step S2, the stirring speed is 150r/min, and the molar ratio of the absolute ethyl alcohol to the titanate is 2: 0.1; in the step S3, the molar ratio of the titanate to the nano calcium carbonate is 0.1: 1; in the step S4, the molar ratio of the phosphoric acid to the nano calcium carbonate is 2: 3.
7. The method for preparing a composite metal calcium phosphate antibacterial agent according to claim 5, wherein in step S5, the silver copper zinc nitric acid solution contains copper nitrate, zinc oxide, silver nitrate and nano calcium phosphate in a mixed molar ratio of 2.5:1:0.5: 16; the molar ratio of the calcium chloride to the silver nitrate solution is 1: 2.
8. The method for preparing a composite metal calcium phosphate antibacterial agent according to claim 5, wherein in the step S6, the roasting temperature is 1100-1180 ℃, and the roasting time is 2-3 hours; in the step S7, the pressure of adding the carbon monoxide is 0.1-0.15MPa, and the time of the reduction reaction is 0.8-1 hour; in the step S8, the mesh size of the sieved mesh is 300 mesh.
9. An inorganic artificial stone, wherein a raw material comprises an antibacterial bonding liquid, a raw material component of the antibacterial bonding liquid comprises the composite metal calcium phosphate antibacterial agent according to any one of claims 1 to 4, the antibacterial bonding liquid is used for bonding solid raw materials of the inorganic artificial stone, and the antibacterial bonding liquid is uniformly distributed in the inorganic artificial stone.
10. The inorganic artificial stone according to claim 9, wherein the composite metal calcium phosphate antibacterial agent is 1-3% by mass of the total mass of the inorganic artificial stone; the raw material components of the antibacterial bonding liquid also comprise water, and the antibacterial bonding liquid is a pre-prepared mixed liquid added before the inorganic artificial stone.
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| CN114557365A (en) * | 2022-02-25 | 2022-05-31 | 肇庆市盛浩新材料科技有限公司 | Composite nano zinc oxide, nano slurry and preparation method and application thereof |
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