CN108986950B - A kind of preparation method of phosphate/nano silver composite conductive powder - Google Patents
A kind of preparation method of phosphate/nano silver composite conductive powder Download PDFInfo
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- ethylene glycol
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 239000002131 composite material Substances 0.000 title claims abstract description 71
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 68
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 68
- 239000010452 phosphate Substances 0.000 title claims abstract description 68
- 239000000843 powder Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 105
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 239000007787 solid Substances 0.000 claims abstract description 29
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 25
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 25
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 238000010792 warming Methods 0.000 claims abstract description 14
- 101710134784 Agnoprotein Proteins 0.000 claims abstract description 12
- 238000001291 vacuum drying Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 5
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 43
- 239000007788 liquid Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 17
- ZTFZSHLWORMEHO-UHFFFAOYSA-A pentaaluminum;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O ZTFZSHLWORMEHO-UHFFFAOYSA-A 0.000 claims description 14
- 239000004020 conductor Substances 0.000 claims description 11
- 229910052709 silver Inorganic materials 0.000 claims description 10
- 239000004332 silver Substances 0.000 claims description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 9
- 239000006228 supernatant Substances 0.000 claims description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 9
- 239000011701 zinc Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 6
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 claims description 5
- 229910000165 zinc phosphate Inorganic materials 0.000 claims description 5
- 229940077935 zinc phosphate Drugs 0.000 claims description 5
- IQBJFLXHQFMQRP-UHFFFAOYSA-K calcium;zinc;phosphate Chemical compound [Ca+2].[Zn+2].[O-]P([O-])([O-])=O IQBJFLXHQFMQRP-UHFFFAOYSA-K 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 4
- CXDLXIMRJLZPDZ-UHFFFAOYSA-K potassium;zinc;phosphate Chemical compound [K+].[Zn+2].[O-]P([O-])([O-])=O CXDLXIMRJLZPDZ-UHFFFAOYSA-K 0.000 claims description 4
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 4
- 229910052716 thallium Inorganic materials 0.000 claims description 4
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims description 4
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 claims description 4
- AYGUCHAPOTYFRT-UHFFFAOYSA-H zinc molybdenum(4+) diphosphate Chemical compound [Zn+2].[Mo+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O AYGUCHAPOTYFRT-UHFFFAOYSA-H 0.000 claims description 4
- RTOOMIOWOJBNTK-UHFFFAOYSA-K sodium;zinc;phosphate Chemical compound [Na+].[Zn+2].[O-]P([O-])([O-])=O RTOOMIOWOJBNTK-UHFFFAOYSA-K 0.000 claims description 3
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 2
- 239000008187 granular material Substances 0.000 abstract description 27
- 239000002994 raw material Substances 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 231100000252 nontoxic Toxicity 0.000 abstract description 4
- 230000003000 nontoxic effect Effects 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 25
- 230000008569 process Effects 0.000 description 8
- GVFOJDIFWSDNOY-UHFFFAOYSA-N antimony tin Chemical compound [Sn].[Sb] GVFOJDIFWSDNOY-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 241000209094 Oryza Species 0.000 description 4
- 235000007164 Oryza sativa Nutrition 0.000 description 4
- 235000009566 rice Nutrition 0.000 description 4
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 4
- 238000005253 cladding Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Inorganic materials [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- -1 phosphoric acid Salt Chemical class 0.000 description 2
- 150000003016 phosphoric acids Chemical class 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- IDQBJILTOGBZCR-UHFFFAOYSA-N 1-butoxypropan-1-ol Chemical compound CCCCOC(O)CC IDQBJILTOGBZCR-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- 240000007087 Apium graveolens Species 0.000 description 1
- 235000015849 Apium graveolens Dulce Group Nutrition 0.000 description 1
- 235000010591 Appio Nutrition 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- XUBKPYAWPSXPDZ-UHFFFAOYSA-N [Ba].OS(O)(=O)=O Chemical compound [Ba].OS(O)(=O)=O XUBKPYAWPSXPDZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000037396 body weight Effects 0.000 description 1
- 235000008429 bread Nutrition 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007073 chemical hydrolysis Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 238000004917 polyol method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
- H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Conductive Materials (AREA)
Abstract
The present invention relates to chemistry and chemical materials preparation field, it is desirable to provide a kind of preparation method of phosphate/nano silver composite conductive powder.Include: that ethylene glycol, polyvinylpyrrolidone and phosphate are added into reaction flask, adjusts pH value to 9~11 with NaOH solution while stirring；100~150 DEG C are warming up to, AgNO is added dropwise3Ethylene glycol solvent, stop after the reaction was continued 30~60min, be stored at room temperature 12~for 24 hours, be precipitated to solid, be deposited on bottom of bottle；Solid is washed with deionized, centrifugal treating, after vacuum drying final products.Preparation process of the present invention is simple, and no pyroprocess saves the energy, using advantages of nontoxic raw materials, free from environmental pollution, is conducive to industrial production and popularization and application.Nano-silver conductive is good, partial size is small, surface energy is high, is easy to deposit, is loaded to phosphate surface.The composite granule performance being prepared is stable, resistivity is small, and composite granule also has the function of that antirust, anticorrosion, application range are more extensive.
Description
Technical field
The present invention relates to a kind of phosphate/nano silver composite conductive powder preparation method, for anti-corrosion of metal, conduction,
In antistatic equal fields, belong to chemistry and chemical materials preparation field.
Background technique
Conductive powder body is the critical material of modern high technology, is suitable for production conductive coating, antistatic coating, conductive modeling
Material, conductive rubber, conductive paper, electronic component, electrical equipment shell, printed circuit board etc. are widely used in chemical industry, electronics, electricity
The fields such as device, Aeronautics and Astronautics, printing, packaging, ship.Metallic conduction powder and carbon series conductive powder are that current application amount is maximum
Two class powders, but there is defect poorer than great, corrosion resistance in the former, and the latter has the defects of pollution environment, decorative difference, limit
It is commonly used its has been made.
Composite conductive powder tool is prepared by covering one layer of antimony tin (ATO) conductive material in insulating powder body surface bread
There are the advantages such as at low cost, good combination property, is the emphasis of current research.Such as money Jian Hua (Qian Jianhua, Sun Ke, Liu Lin, Xing Jin
Juan, conductive TiO2The preparation of powder and performance study [J], chemical research and application, 2016,28 (3): 350-354) useization
Coprecipitation is learned, with SnCl4·5H2O, SbCl3Micro-nano TiO is coated Deng for raw material2, optimize through reaction process such as pH value adjustings
And 500 DEG C of calcinings, prepare ATO cladding TiO2Composite granule, minimum specific resistance is up to 12 Ω cm；CN102708947B is public
A kind of preparation method of ultra-fine spherical composite conductive powder based on konilite or cristobalite is opened, this method is by konilite mineral
Or cristobalite raw material passes through addition macromolecule dispersing agent, sizes mixing, wet method super-fine shaping, after reaching certain fineness, in Ultrafine Grinding
A small amount of acid solution adjustment slurry pH is added, using crystallization SnCl4And SbCl3Hydrolysis cladding, filters pressing, UF membrane washing, dry, roasting
Burn etc., obtain superfine spherical composite conductive powder, resistivity < 50 Ω cm, 1~5 μm of average grain diameter；Yao superfine (Yao Chao, Wu Feng
Celery, Linxi is flat, Wang Xin, light-colored conductive mica powder development [J], nonmetallic ore, 2003,26 (4): 15-19) with SnCl4·5H2O,
SbCl3For raw material, ATO is coated on ultrafine mica powder surface using chemical coprecipitation, forms conductive layer, powder minimum specific resistance
15 Ω cm can be reached.
The advantages that antimony tin (ATO) conductive material is although conductive good, but due to being with SnCl4·5H2O or
SbCl3For raw material, through made of the techniques such as chemical hydrolysis cladding, sintering, there are many defects.Such as SnCl4、SbCl3Raw material is rotten
Corrosion is strong, and toxicity is big, and pollution environment is serious；Preparation process needs high temperature sintering, will cause energy waste etc..In consideration of it, exploitation
Target nontoxic, environmental pollution is small, the NEW TYPE OF COMPOSITE conductive powder body of excellent combination property is still vast researcher struggle.
Summary of the invention
The technical problem to be solved by the present invention is to overcome deficiency in the prior art, it is multiple to provide a kind of phosphate/nano silver
Close the preparation method of conductive powder body.
In order to solve the technical problem, solution of the invention is:
A kind of preparation method of phosphate/nano silver composite conductive powder is provided, comprising the following steps:
(1) ethylene glycol, polyvinylpyrrolidone and phosphate are added into reaction flask, with NaOH solution tune while stirring
Reacting liquid pH value is saved to 9~11；
(2) reaction solution is warming up to 100~150 DEG C, AgNO is added dropwise3Ethylene glycol solution, the reaction was continued 30~60min；Stop
After only reacting, it is stored at room temperature 12~for 24 hours, it is precipitated to solid, is deposited on bottom of bottle；
(3) supernatant liquid is outwelled, solid is washed with deionized, centrifugal treating, is repeated 3 times, final obtained solid warp
After vacuum drying, phosphate/nano silver composite conductive powder is obtained；
Wherein, ethylene glycol: polyvinylpyrrolidone: phosphate: AgNO3Weight ratio be 500~2000: 1~2: 50~
200:1；The ethylene glycol includes AgNO3The ethylene glycol used in ethylene glycol solution as solvent.
In the present invention, the phosphate/nano silver composite conductive powder that obtains being prepared is with the phosphorus of partial size d=0.5~5 μm
Hydrochlorate is carrier, and on its surface, deposition has coated silver-colored conductive material, and silver-colored conductive material and carrier quality ratio are 0.1~0.5%；Institute
Stating silver-colored conductive material is silver nano-grain, partial size d=5~100nm.
In the present invention, the phosphate is trbasic zinc phosphate, aluminum phosphate, calcium zinc orthophosphate activated by thallium, zinc aluminophosphate, potassium zinc phosphate, trbasic zinc phosphate
One of sodium, trbasic zinc phosphate molybdenum, tripolyphosphate zinc or aluminium triphosphate are a variety of.
In the present invention, the weight average molecular weight Mw=10000 or 24000 of polyvinylpyrrolidone in step (1).
In the present invention, AgNO in step (2)3The concentration of ethylene glycol solution be 0.1~0.3g/ml, rate of addition be 10~
30 ml/min。
In the present invention, the rate of centrifugal treating is 3000~8000 turns/min in step (3), and temperature when vacuum drying is
50~100 DEG C.
Inventive principle description:
Phosphate is non-toxic, has no stimulation of the skin, and without toxic heavy metal elements such as lead, chromium, thermal stability is good, energy
Wear-resisting, the corrosion resistance for significantly improving coating are the maximum a kind of environmental rust resisting pigments of current dosage.The present invention is with AgNO3
Silver nano-grain is synthesized by polyol process reaction and the protective effect of the interface PVP for silver-colored source, deposition is loaded to phosphate table
Face, then the techniques such as washed, centrifugation, dry, prepare phosphate/nano silver composite conductive powder, which not only has anti-
Function of becoming rusty can be used in the fields such as anti-corrosion of metal, conduction, antistatic also with conducting function.
Compared with prior art, the invention has the advantages that:
(1) phosphate/nano silver composite conductive powder preparation process in the present invention is simple, and no pyroprocess saves energy
Source is conducive to industrial production and popularization and application using advantages of nontoxic raw materials, free from environmental pollution.
(2) nano-silver conductive is good, partial size is small, surface energy is high, is easy to deposit, is loaded to phosphate surface.
(3) the composite granule performance being prepared is stable, resistivity is small, and composite granule also has antirust, anticorrosion function
Can, application range is more extensive.
Specific embodiment
Implementation of the invention is described combined with specific embodiments below.
Phosphate of the present invention/nano silver composite conductive powder preparation method, comprising the following steps:
(1) ethylene glycol, polyvinylpyrrolidone and phosphate are added into reaction flask, with NaOH solution tune while stirring
Reacting liquid pH value is saved to 9~11；
(2) reaction solution is warming up to 100~150 DEG C, AgNO is added dropwise3Ethylene glycol solution, the reaction was continued 30~60min；Stop
After only reacting, it is stored at room temperature 12~for 24 hours, it is precipitated to solid, is deposited on bottom of bottle；
(3) supernatant liquid is outwelled, solid is washed with deionized, centrifugal treating, is repeated 3 times, final obtained solid warp
After vacuum drying, phosphate/nano silver composite conductive powder is obtained；
Wherein, ethylene glycol: polyvinylpyrrolidone: phosphate: AgNO3Weight ratio be 500~2000: 1~2: 50~
200:1；The ethylene glycol includes AgNO3The ethylene glycol used in ethylene glycol solution as solvent.Phosphate is trbasic zinc phosphate, phosphorus
In sour aluminium, calcium zinc orthophosphate activated by thallium, zinc aluminophosphate, potassium zinc phosphate, sodium-zinc-phosphate, trbasic zinc phosphate molybdenum, tripolyphosphate zinc or aluminium triphosphate
It is one or more.The weight average molecular weight Mw=10000 or 24000 of polyvinylpyrrolidone (PVP)； AgNO3Ethylene glycol solution
Concentration be 0.1~0.3g/ml, rate of addition be 10~30ml/min；The rate of centrifugal treating is 3000~8000 turns/min,
Temperature when vacuum drying is 50~100 DEG C.
The phosphate that the present invention prepares/nano silver composite conductive powder is with the phosphate of partial size d=0.5~5 μm
For carrier, on its surface, deposition has coated silver-colored conductive material, and silver-colored conductive material and carrier quality ratio are 0.1~0.5%；The silver
Conductive material is silver nano-grain, partial size d=5~100nm.
Phosphate/nano silver composite conductive powder performance test explanation:
1, the nano silver partial size in phosphate/nano silver composite conductive powder is tested by transmission electron microscope (TEM).
2, nano silver and phosphate weight ratio calculation method are as follows: P=(M1-M0)/M0, wherein P is weight ratio, M1For phosphoric acid
Salt/nano silver composite conductive powder body weight, M0For phosphate weight.
3, the resistivity measurement method of composite conductive powder are as follows: weigh certain mass composite conductive powder and be put into polytetrafluoroethylene (PTFE)
In mold, it is compressed into chip sample under 4MPa pressure, measures resistance value with multimeter, with vernier caliper measurement thickness,
And its resistivity is acquired by following formula:
ρ=RA/H
In formula: ρ is resistivity, unit Ω cm；R is resistance, unit Ω；A is example cross section product, unit cm2；H is
Thickness of sample, unit cm.
The formula of each embodiment, preparation parameter and performance are as follows:
Embodiment 1
A kind of phosphate/nano silver composite conductive powder, preparation method are as follows:
1) ethylene glycol 1.78L (1.98kg), polyvinylpyrrolidone (PVP, Mw=10000) 2g are added into reaction flask
With trbasic zinc phosphate (d=0.5 μm) 200g, reacting liquid pH value is adjusted to 9 with NaOH in whipping process；2) 100 DEG C are warming up to, is added dropwise
AgNO3Solution (EG solvent, concentration 0.1g/ml) 20ml (AgNO3For 2g, ethylene glycol 0.02kg), drop rate 10ml/min,
60min is reacted, after stopping reaction, is stored at room temperature for 24 hours, is precipitated to solid, is deposited on bottom of bottle；3) supernatant liquid is outwelled, solid
It is washed with deionized, is centrifuged (8000 turns/min of rate), be repeated 3 times, the final vacuum dried (drying temperature 100 of solid
DEG C), obtain phosphate/nano silver composite conductive powder, 35 Ω cm of resistivity, wherein nano silver 80~100nm of partial size receives
Meter Yin Yu phosphate weight ratio is 0.22%.
Embodiment 2
A kind of phosphate/nano silver composite conductive powder, preparation method are as follows:
1) ethylene glycol 1.79L (1.99kg), polyvinylpyrrolidone (PVP, Mw=24000) 2g are added into reaction flask
With zinc aluminophosphate (d=5 μm) 200g, reacting liquid pH value is adjusted to 11 with NaOH in whipping process；2) 150 DEG C are warming up to, is added dropwise
AgNO3Solution (EG solvent, concentration 0.1g/ml) 10ml (AgNO3For 1g, ethylene glycol 0.01kg), drop rate 30ml/min,
30min is reacted, after stopping reaction, is stored at room temperature 12h, is precipitated to solid, is deposited on bottom of bottle；3) supernatant liquid is outwelled, solid
It being washed with deionized, is centrifuged (3000 turns/min of rate), be repeated 3 times, final solid is vacuum dried (50 DEG C of drying temperature),
Obtain phosphate/nano silver composite conductive powder, 65 Ω cm of resistivity, wherein nano silver 5~40nm of partial size, nano silver with
Phosphate weight ratio is 0.1%.
Embodiment 3
A kind of phosphate/nano silver composite conductive powder, preparation method are as follows:
1) ethylene glycol 1.785L (1.985kg), polyvinylpyrrolidone (PVP, Mw=24000) are added into reaction flask
4g and aluminium triphosphate (d=1 μm) 200g adjusts reacting liquid pH value to 10 using NaOH in whipping process；2) 120 are warming up to
DEG C, AgNO is added dropwise3Solution (EG solvent, concentration 0.2g/ml) 15ml (AgNO3For 3g, ethylene glycol 0.015kg), drop rate
20ml/min reacts 30min, after stopping reaction, is stored at room temperature 15h, is precipitated to solid, is deposited on bottom of bottle；3) by supernatant liquid
It outwells, solid is washed with deionized, is centrifuged (5000 turns/min of rate), is repeated 3 times, and final solid is vacuum dried (dry
80 DEG C of temperature), obtain phosphate/nano silver composite conductive powder, 12 Ω cm of resistivity, wherein nano silver partial size 40~
60nm, nano silver and phosphate weight ratio are 0.43%.
Embodiment 4
A kind of phosphate/nano silver composite conductive powder, preparation method are as follows:
1) ethylene glycol 1.79L (1.99kg), polyvinylpyrrolidone (PVP, Mw=24000) 4g are added into reaction flask
With zinc aluminophosphate (d=1 μm) 150g, sodium-zinc-phosphate (d=2 μm) 50g, reacting liquid pH value is adjusted using NaOH in whipping process
To 10；2) 110 DEG C are warming up to, AgNO is added dropwise3Solution (EG solvent, concentration 0.3g/ml) 10ml (AgNO3For 3g, ethylene glycol is
0.01kg), drop rate 20ml/min reacts 30min, after stopping reaction, is stored at room temperature 15h, is precipitated to solid, is deposited on bottle
Bottom；3) supernatant liquid is outwelled, solid is washed with deionized, is centrifuged (6000 turns/min of rate), is repeated 3 times, final solid
Vacuum dried (80 DEG C of drying temperature) obtains phosphate/nano silver composite conductive powder, 20 Ω cm of resistivity, wherein receive
Rice silver granuel 50~70nm of diameter, nano silver and phosphate weight ratio are 0.45%.
Embodiment 5
A kind of phosphate/nano silver composite conductive powder, preparation method are as follows:
1) ethylene glycol 1.78L (1.98kg), polyvinylpyrrolidone (PVP, Mw=10000) 4g are added into reaction flask
With calcium zinc orthophosphate activated by thallium (d=3 μm) 50g, potassium zinc phosphate (d=2 μm) 150g, reacting liquid pH value is adjusted using NaOH in whipping process
To 9.5；2) 130 DEG C are warming up to, AgNO is added dropwise3Solution (EG solvent, concentration 0.2g/ml) 20ml (AgNO3For 4g, ethylene glycol is
0.02kg), drop rate 18ml/min reacts 40min, after stopping reaction, is stored at room temperature 20h, is precipitated to solid, is deposited on bottle
Bottom；3) supernatant liquid is outwelled, solid is washed with deionized, is centrifuged (5000 turns/min of rate), is repeated 3 times, final solid
Vacuum dried (90 DEG C of drying temperature), obtains phosphate/nano silver composite conductive powder, and resistivity is 25 Ω cm, wherein
Nano silver 60~80nm of partial size, nano silver and phosphate weight ratio are 0.50%.
Embodiment 6
A kind of phosphate/nano silver composite conductive powder, preparation method are as follows:
1) ethylene glycol 1.782L (1.988kg), polyvinylpyrrolidone (PVP, Mw=24000) are added into reaction flask
4g and tripolyphosphate zinc (d=2 μm) 180g, trbasic zinc phosphate molybdenum (d=4 μm) 20g adjust reaction solution using NaOH in whipping process
PH value is to 10.5；2) 120 DEG C are warming up to, AgNO is added dropwise3Solution (EG solvent, concentration 0.2g/ml) 18ml (AgNO3For 3.6g, second
Glycol is 0.012kg), drop rate 25ml/min reacts 40min, after stopping reaction, is stored at room temperature 12h, it is precipitated to solid,
It is deposited on bottom of bottle；3) supernatant liquid to be outwelled, solid is washed with deionized, is centrifuged (6000 turns/min of rate), it is repeated 3 times,
Final solid is vacuum dried (80 DEG C of drying temperature), obtains phosphate/nano silver composite conductive powder, and resistivity is 20 Ω
Cm, wherein nano silver 40~60nm of partial size, nano silver and phosphate weight ratio are 0.40%.
Comparative example
Following comparative example is tested based on the minimum embodiment 3 of the resistivity in above-mentioned 6 cases.
Comparative example 1
" aluminium triphosphate (d=1 μm) 200g " in embodiment 3 is changed to " aluminium triphosphate (d=6 μm) 200g ",
It is remaining to be same as embodiment 3.Composite granule resistivity is 85 Ω cm, wherein nano silver 40~60nm of partial size, nano silver and phosphate
Weight ratio is 0.43%.
Comparative example 2
" aluminium triphosphate (d=1 μm) 200g " in embodiment 3 is changed to " aluminium triphosphate (d=0.4 μm) 200g ",
Remaining is same as embodiment 3.Composite granule resistivity is 25 Ω cm, wherein nano silver 40~60nm of partial size, nano silver and phosphoric acid
Salt weight ratio is 0.43%.
Comparative example 1~2 illustrates that the partial size of aluminium triphosphate has a larger impact to composite granule resistivity, and partial size is too greatly or too
It is small to be unsuitable for preparation Low-resistivity composite conductive powder.
Comparative example 3
" AgNO will be added dropwise in embodiment 33Solution (EG solvent, concentration 0.2g/ml) 15ml ", which is changed to, " is added dropwise AgNO3It is molten
Liquid (EG solvent, concentration 0.2g/ml) 9ml ", remaining is same as experimental example 3.Composite granule resistivity is 80 Ω cm, wherein is received
Rice silver granuel 40~50nm of diameter, nano silver and phosphate weight ratio are 0.08%.
Comparative example 4
" AgNO will be added dropwise in embodiment 33Solution (EG solvent, concentration 0.2g/ml) 15ml ", which is changed to, " is added dropwise AgNO3It is molten
Liquid (EG solvent, concentration 0.2g/ml) 21ml ", remaining is same as experimental example 3.Composite granule resistivity is 18 Ω cm, wherein is received
Rice silver granuel 60~80nm of diameter, nano silver and phosphate weight ratio are 0.55%.
Comparative example 3~4 illustrates AgNO3Dosage has larger impact to composite conductive powder body resistivity, and dosage is very few, reaction life
At nanometer silver content it is few, composite granule resistivity increase it is obvious, if dosage is excessive, PVP and AgNO3Weight ratio reduces, synthesis
Nano silver partial size is bigger than normal, and composite granule resistivity is caused also slightly to increase.
Comparative example 5
" aluminium triphosphate (d=1 μm) 200g " in embodiment 3 is changed to " aluminium triphosphate (d=1 μm) 700g ",
It is remaining to be same as experimental example 3.Composite granule resistivity is 400 Ω cm, wherein nano silver 40~60nm of partial size, nano silver and phosphoric acid
Salt weight ratio is 0.02%.
Comparative example 6
" aluminium triphosphate (d=1 μm) 200g " in embodiment 3 is changed to " aluminium triphosphate (d=1 μm) 120g ",
It is remaining to be same as experimental example 3.Composite granule resistivity is 12 Ω cm, wherein nano silver 40~60nm of partial size, nano silver and phosphate
Weight ratio is 0.7%.
To know from comparative example 5~6, aluminium triphosphate dosage has larger impact to composite conductive powder body resistivity, and dosage is excessive,
Insulant composition is high in composite granule, and resistivity increases significantly, and dosage is very few, and composite granule change in resistance is little, but can be big
Width increases composite conductive powder cost.
Comparative example 7
It is changed to " reacting liquid pH value is adjusted to 10 using NaOH in whipping process " in embodiment 3 " in whipping process not
Using NaOH ", remaining is same as experimental example 3.Composite granule resistivity is 45 Ω cm, wherein nano silver 30~50nm of partial size receives
Meter Yin Yu phosphate weight ratio is 0.3%.
Comparative example 7 illustrates that NaOH addition is critically important, because reaction solution can enhance reduction of ethylene glycol ability in alkalinity, raising is received
The silver-colored yield of rice, and NaOH is not added, reaction solution is in neutrality, and reduction of ethylene glycol ability is general, and nano silver yield is relatively low, therefore, compound
Powder resistance rate is also increase accordingly.
Comparative example 8
It is changed to " being warming up to 90 DEG C " by " being warming up to 120 DEG C " in embodiment 3, remaining is same as experimental example 3.Composite granule electricity
Resistance rate is 150 Ω cm, wherein nano silver 80~100nm of partial size, nano silver and phosphate weight ratio are 0.2%.
Comparative example 9
It is changed to " being warming up to 160 DEG C " by " being warming up to 120 DEG C " in embodiment 3, remaining is same as experimental example 3.Composite granule
Resistivity is 20 Ω cm, wherein nano silver 5~40nm of partial size, nano silver and phosphate weight ratio are 0.4%.
8 reaction temperature of comparative example is too low, and nano silver low yield, conductive compositions are few, and composite granule resistivity is bigger than normal, comparative example
9, reaction temperature is excessively high, and nano silver partial size is less than normal, also slightly improves composite granule resistivity.
Comparative example 10
" drop rate 20ml/min " in embodiment 3 is changed to " drop rate 8ml/min ", remaining is same as experimental example 3.
Composite granule resistivity is 20 Ω cm, wherein nano silver 40~60nm of partial size, nano silver are with phosphate weight ratio
0.35%.
Comparative example 11
" drop rate 20ml/min " in embodiment 3 is changed to " drop rate 35ml/min ", remaining is same as experimental example
3.Composite granule resistivity is 25 Ω cm, wherein nano silver 40~60nm of partial size, nano silver are with phosphate weight ratio
0.40%.
Comparative example 10~11 illustrates AgNO3Drop rate is too fast or too slow all to increase composite granule resistivity.
Comparative example 12
By in embodiment 3 ", reaction 30min " is changed to " reaction 70min ", remaining is same as experimental example 3.Composite granule resistance
Rate is 25 Ω cm, wherein nano silver 60~80nm of partial size, nano silver and phosphate weight ratio are 0.39%.
Comparative example 13
By in embodiment 3 ", reaction 30min " is changed to " reaction 20min ", remaining is same as experimental example 3.Composite granule resistance
Rate is 85 Ω cm, wherein nano silver 40~50nm of partial size, nano silver and phosphate weight ratio are 0.31%.
From the data of comparative example it can be seen that 12 reaction time of comparative example is too long, nano silver partial size increases, and increases composite guide
Electric powder resistance rate, comparative example 13 shorten the reaction time, and nano silver yield reduces, and composite granule resistance increases more apparent.
The phosphate that the present invention prepares/nano silver composite conductive powder can be used for coating preparation, for example, prepare resist it is quiet
Electric protection coating.
One is typically as described below using example:
The anti-static and anti-corrosive paint is made of A, B two-component；Wherein, component A by following weight percentage raw material
Composition: aqueous epoxy resins 40~60%, phosphate/nano silver composite conductive powder 5~10%, titanium dioxide 5~15%, sulfuric acid
Barium 3~8%, talcum powder 1~5%, dispersing agent 0.2~0.8%, defoaming agent 0.2~0.8%, dipropylene glycol methyl ether 1~3%, third
Glycol butyl ether 1~3%, deionized water 9.4~28.6%；B component is epoxy hardener, and the weight of B component accounts for component A weight
5~8%；
The preparation of coating is the following steps are included: (1) takes each component by the proportion relation, successively into the material cylinder of dispersion machine
Be added deionized water, dipropylene glycol methyl ether, propandiol butyl ether, dispersing agent, defoaming agent, phosphate/nano silver composite conductive powder,
Titanium dioxide, barium sulfate and talcum powder disperse 30~60min at 1000~2000rpm of revolving speed；(2) dispersing speed is reduced extremely
300~800rpm is added aqueous epoxy resins, continues 20~40min of stirring, obtain component A；(3) when in use, by described heavy
Amount ratio will seek B component and be added in component A, obtain anti-static and anti-corrosive paint after mixing evenly.
The above list is only a few specific embodiments of the present invention for finally, it should also be noted that.Obviously, this hair
Bright to be not limited to above embodiments, acceptable there are many deformations.Those skilled in the art can be from present disclosure
All deformations for directly exporting or associating, are considered as protection scope of the present invention.
Claims (5)
1. a kind of phosphate/nano silver composite conductive powder preparation method, which comprises the following steps:
(1) ethylene glycol, polyvinylpyrrolidone and phosphate are added into reaction flask, stirring while is adjusted anti-with NaOH solution
Answer liquid pH value to 9 ~ 11；
(2) reaction solution is warming up to 100 ~ 150 DEG C, AgNO is added dropwise3Ethylene glycol solution, the reaction was continued 30 ~ 60 min；Stop anti-
Ying Hou is stored at room temperature 12 ~ 24 h, is precipitated to solid, is deposited on bottom of bottle；
(3) supernatant liquid is outwelled, solid is washed with deionized, centrifugal treating, is repeated 3 times, final obtained solid is through vacuum
After drying, phosphate/nano silver composite conductive powder is obtained；
Wherein, ethylene glycol: polyvinylpyrrolidone: phosphate: AgNO3Weight ratio be 500 ~ 2000: 1 ~ 2: 50 ~ 200: 1；Institute
Stating ethylene glycol includes AgNO3The ethylene glycol used in ethylene glycol solution as solvent；What is be prepared obtains phosphate/nano silver
Composite conductive powder is using the phosphate of partial size d=0.5 ~ 5 μm as carrier, and on its surface, deposition has coated silver-colored conductive material,
Silver-colored conductive material and carrier quality ratio are 0.1 ~ 0.5%；The silver conductive material is silver nano-grain, partial size d=5 ~ 100 nm.
2. the method according to claim 1, wherein the phosphate be trbasic zinc phosphate, aluminum phosphate, calcium zinc orthophosphate activated by thallium,
At least one of zinc aluminophosphate, potassium zinc phosphate, sodium-zinc-phosphate, trbasic zinc phosphate molybdenum, tripolyphosphate zinc or aluminium triphosphate.
3. the method according to claim 1, wherein in step (1) polyvinylpyrrolidone weight average molecular weight
Mw=10000 or 24000.
4. the method according to claim 1, wherein AgNO in step (2)3The concentration of ethylene glycol solution be 0.1 ~
0.3g/ml, rate of addition are 10 ~ 30 ml/min.
5. the method according to claim 1, wherein the rate of centrifugal treating is 3000 ~ 8000 in step (3)
Turn/min, temperature when vacuum drying is 50 ~ 100 DEG C.
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