CN104858447A - Preparation method and equipment for high-conductivity nano silver for PCB - Google Patents
Preparation method and equipment for high-conductivity nano silver for PCB Download PDFInfo
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- CN104858447A CN104858447A CN201510197484.8A CN201510197484A CN104858447A CN 104858447 A CN104858447 A CN 104858447A CN 201510197484 A CN201510197484 A CN 201510197484A CN 104858447 A CN104858447 A CN 104858447A
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- silver
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- salt compound
- dissolution kettle
- reducing agent
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 165
- 238000002360 preparation method Methods 0.000 title claims abstract description 48
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 79
- 238000004090 dissolution Methods 0.000 claims abstract description 75
- 238000000034 method Methods 0.000 claims abstract description 69
- -1 silver salt compound Chemical class 0.000 claims abstract description 66
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000005260 corrosion Methods 0.000 claims abstract description 27
- 229910052709 silver Inorganic materials 0.000 claims abstract description 20
- 239000004332 silver Substances 0.000 claims abstract description 20
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 19
- RECVMTHOQWMYFX-UHFFFAOYSA-N oxygen(1+) dihydride Chemical group [OH2+] RECVMTHOQWMYFX-UHFFFAOYSA-N 0.000 claims abstract description 14
- RBWNDBNSJFCLBZ-UHFFFAOYSA-N 7-methyl-5,6,7,8-tetrahydro-3h-[1]benzothiolo[2,3-d]pyrimidine-4-thione Chemical compound N1=CNC(=S)C2=C1SC1=C2CCC(C)C1 RBWNDBNSJFCLBZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000843 powder Substances 0.000 claims description 83
- 239000000243 solution Substances 0.000 claims description 75
- 239000006185 dispersion Substances 0.000 claims description 61
- 230000008569 process Effects 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Natural products CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000008367 deionised water Substances 0.000 claims description 23
- 229910021641 deionized water Inorganic materials 0.000 claims description 23
- 239000011550 stock solution Substances 0.000 claims description 18
- 230000003647 oxidation Effects 0.000 claims description 16
- 238000007254 oxidation reaction Methods 0.000 claims description 16
- 239000002671 adjuvant Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 238000012986 modification Methods 0.000 claims description 14
- 230000004048 modification Effects 0.000 claims description 14
- 238000011084 recovery Methods 0.000 claims description 14
- 238000005119 centrifugation Methods 0.000 claims description 13
- 239000010808 liquid waste Substances 0.000 claims description 13
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical group FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 12
- 239000002270 dispersing agent Substances 0.000 claims description 12
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 12
- 239000003607 modifier Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 10
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 9
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 9
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 9
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 9
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000005642 Oleic acid Substances 0.000 claims description 9
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 9
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 9
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 9
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 239000012279 sodium borohydride Substances 0.000 claims description 7
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 5
- 229920000084 Gum arabic Polymers 0.000 claims description 5
- 241000978776 Senegalia senegal Species 0.000 claims description 5
- 239000000205 acacia gum Substances 0.000 claims description 5
- 235000010489 acacia gum Nutrition 0.000 claims description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 5
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 5
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 238000000703 high-speed centrifugation Methods 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229910001380 potassium hypophosphite Inorganic materials 0.000 claims description 2
- CRGPNLUFHHUKCM-UHFFFAOYSA-M potassium phosphinate Chemical compound [K+].[O-]P=O CRGPNLUFHHUKCM-UHFFFAOYSA-M 0.000 claims description 2
- 239000007788 liquid Substances 0.000 abstract description 19
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 4
- 230000009467 reduction Effects 0.000 abstract description 3
- 239000007791 liquid phase Substances 0.000 abstract description 2
- 238000003860 storage Methods 0.000 abstract 2
- 238000007605 air drying Methods 0.000 abstract 1
- 238000005342 ion exchange Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 19
- 239000002699 waste material Substances 0.000 description 19
- 238000005516 engineering process Methods 0.000 description 15
- 239000002245 particle Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 7
- 238000005245 sintering Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- 239000002912 waste gas Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 229910001447 ferric ion Inorganic materials 0.000 description 4
- XRRQZKOZJFDXON-UHFFFAOYSA-N nitric acid;silver Chemical compound [Ag].O[N+]([O-])=O XRRQZKOZJFDXON-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000036632 reaction speed Effects 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000001384 succinic acid Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 238000011953 bioanalysis Methods 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- KKKDGYXNGYJJRX-UHFFFAOYSA-M silver nitrite Chemical compound [Ag+].[O-]N=O KKKDGYXNGYJJRX-UHFFFAOYSA-M 0.000 description 2
- 229940083025 silver preparation Drugs 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 101710134784 Agnoprotein Proteins 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000000914 phenoxymethylpenicillanyl group Chemical group CC1(S[C@H]2N([C@H]1C(=O)*)C([C@H]2NC(COC2=CC=CC=C2)=O)=O)C 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229940100890 silver compound Drugs 0.000 description 1
- 150000003379 silver compounds Chemical class 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
Abstract
The invention discloses a preparation method and equipment for high-conductivity nano silver for a PCB. With adoption of the preparation method, high-conductivity nano silver is prepared through adopting silver nitrate or silver perchlorate as a silver source and adopting the liquid phase reduction method. The prepared nano silver is excellent in conductivity, has an electrical resistivity of 2* 10<-3> omega. cm-6.5* 10<-3> omega. cm, and can be used for the PCB. The equipment comprises a dissolution kettle I, a dissolution kettle II, a silver salt compound purifying column, a reducing agent purifying column, a silver salt compound dissolution kettle, a reducing agent dissolution kettle, a silver salt compound liquid storage tank, a reducing agent liquid storage tank, a temperature control anti-corrosion reaction still, a high-efficient feeding device, a centrifugal separator, a silver recycling device, a temperature control forced air drying box, a tail gas collection treatment device, an effluent treatment device and a water ion exchange device. The preparation method is simple and fewer in working procedures; the equipment is simple in structure, requires less for large-scale production equipment, and facilitates industrialization.
Description
Technical field
The invention belongs to nano material synthesis technical field, be specifically related to a kind of preparation method and equipment of high connductivity Nano Silver.
Background technology
Printed electronics manufactures a new technology of electronic device based on traditional printing methods, can be widely used in large area, the various electronics of flexibility and low cost or photovoltaic.In " 13 " science and technology development forecasting that in August, 2014, the Ministry of Science and Technology promulgated, printed electronic material and technique lists one of prediction field first in.China in 2002 replaces the U.S. becomes the large wiring board producing country in third place in the world, China's production in 2003 and export amount all reach 6,000,000,000 U.S. dollars, 2007-2011 annual growth reaches 9.6%, be greater than 2.5% of the world, 2012 annual value of production reach 22,000,000,000 U.S. dollars, within 2013, China improves further in technology, management etc., and estimate that 2015 annual value of production reach 27,900,000,000 U.S. dollars, growth rate is stabilized in 5% thereafter.Existing 3000 many enterprises in the whole nation carry out printed substrate (PCB) and make, and larger enterprise focuses mostly in coastal area, and Shenzhen is more, and the enterprise of maximum-norm is Shenzhen Shennan Circuits Co., Ltd., and its profit reaches 2,600,000,000 yuan.Traditional etch process, equipment investment is high, production process reaches 26 steps, and discharging of waste liquid is large, and acidic etching waste liquid discharge capacity is about 2,560,000 tons/year, serious to environment, production cost is high, and occupation area of equipment is large, and production efficiency is low, and the printed substrate obtained only plays support and the effect being connected electronic devices and components, i.e. conducting wire plate in the electronic device.Electric PC board is that modern enterprise adopts advanced printing technology of preparing, its base material contains electronic component (as multi-layer sheet embedded set resistance, electric capacity, and embedding IC device etc.) and connection line, can directly form functional electronic circuit, microminiaturization for electronic equipment is implemented to become possibility, at present, domestic and international electric PC board research and development key technology, that advanced printed electronics and nano material production technology combine and produce, but because key technology can not be grasped by existing enterprise, therefore printed electronics fails to find broad application.
At present, the method preparing nano-silver powder has a lot, generally speaking can be divided into Physical, as methods such as comminuting method, mechanical ball milling, vacuum evaporation condensations; Bioanalysis, as methods such as microorganism, plant tissue reduction; Chemical method, if any methods such as liquid phase chemical reduction, phonochemistry method, microemulsions; The Physical cycle is long, and equipment requirement is high, and investment is large; Bioanalysis is high to conditional request; The solution phase chemical reduction cycle is short, and cost is low, and industrialization is comparatively easy.
At present, the patent about the preparation method of nano-silver powder has a lot, but existing patent just simply relates to preparation method, does not relate to complete technological process, equipment and the process to waste liquid, waste gas.The application relates to the preparation method of nano-silver powder, technological process, equipment and the process to waste liquid, waste gas.Existing have with the closely-related patent of the preparation method of nano-silver powder: the people such as Yue Hongqin disclose " preparation method of nano-silver powder " (201110095156.9), this patent take silver nitrite as precursor power nano-silver powder, silver nitrate, PVA, natrium nitrosum etc. are initiation material, prepare silver nitrite presoma, again high-purity nano silver powder is prepared in its thermal decomposition at 180 DEG C ~ 250 DEG C, silver in the waste water simultaneously produced preparation process reclaims, and achieves recycling of silver.These inventive method raw material are easy to get, the conversion ratio of silver is high, preparation technology is comparatively simple, small investment, and production cost is lower, and silver powder purity is high; Nano-silver powder prepared by the method can be widely used in the fields such as health care, electronics industry, effective catalyst; The people such as Gao Lingfan disclose " preparation method of nano-silver powder " (200810230927.9), and the method is: AgNO
3, polyvinyl alcohol, emulsifying agent mixing, to add after qs glycerin reaction 30 minutes, add deionized water, use vavuum pump filtering and washing, then dewater, finally carry out the nano-silver powder that drying can obtain 50 ~ 100nm.
Li Zhongchun discloses " preparation method of flaky nanometer silver powder " (201210500911.1), a preparation method for flaky nanometer silver powder, it is obtained by reacting at the temperature of 0 ~ 100 DEG C by the silver salt solution and ferrous salt solution containing surfactant (polyvinylpyrrolidone, lauryl sodium sulfate etc.).The flaky nanometer silver powder pattern adopting the method to obtain is single, and purity is high.The advantages such as the reaction time is short, efficiency is high, reaction condition is gentle, Processes and apparatus is simple, production cost is low, easy and simple to handle, green non-pollution, are applicable to industrialization large-scale production; Liu Fusheng discloses " a kind of preparation method of modified Nano silver powder " (201410058076.X), the method with mercaptan, silane coupler, cationic surfactant, corrosion inhibiter and organic solvent containing sulfydryl for raw material, surface modification is carried out to nano-silver powder, prepare modified Nano silver powder, solve nano-silver powder easily reunite, with the problem of other materials compound tense intermiscibility difference.It is simple that this preparation method has production technology, and equipment investment is little, and energy consumption is low, non-environmental-pollution, and modified Nano silver powder applied range, is conducive to applying, has broad application prospects; " a kind of preparation method of spherical nano-silver powder " (200810046690.9), Shi Xiaoliang etc. disclose a kind of preparation method of spherical nano-silver powder.The preparation process of this spherical nano-silver powder is 1) spray pyrolysis, 2) preparation of spherical nano-silver powder, this preparation method is simple, easy to control, pollution-free, cost is low, be suitable for industrial-scale production, prepared spherical nano-silver powder is Nano grade, and powder diameter is evenly distributed, pattern rule, yield are high; " a kind of nano-silver powder and manufacture method and application " thereof thereof (200910241459.X), Chen Qiao etc. disclose a kind of nano-silver powder for DC electrode slurry and low temperature bonding nanometer silver paste and manufacture method thereof, this nano-silver powder adopt chemical reduction method, adopt hydrazine hydrate, glycerine or triethanolamine reduce at 90 ~ 92 DEG C silver compound processing technology preparation; Adopt the nano-silver powder produced in this way and be applied to the DC electrode slurry carrying out sintering at the temperature of 800 DEG C; Be applied to the nanometer silver paste of the chips such as SiC or GaN that to bond at 260 DEG C ~ 270 DEG C, electrode have that solderability is good, electric conductivity is high, electric performance stablity and large, the reliable advantages of higher of adhesion strength; Liu Fusheng discloses " a kind of method of preparing nano silver powder in viscous medium " (201110278418.5), the method with surfactant, thickener, silver salt, reducing agent etc. for raw material, viscous medium is obtained with the preparation of surfactant, thickener, complexing agent, defoamer, antioxidant and deionized water, add silver salt to stir, reduce its viscosity, obtain nano-silver powder through press filtration, washing and vacuum drying; The method has that raw material is easy to get, production technology is brief, production efficiency is high, production cost is low, energy consumption is low, powder is not easily reunited, powder dispersity is good, be suitable for large-scale production, solves the problem of the oxidizable and easy reunion that the existing chemical preparation process of nano-silver powder exists.
The materials such as silver powder, to environment, even cause human body poisoning, therefore particularly important to the process of waste liquid.The traditional method for governing pollution of chemistry has chemical precipitation method, flocculent precipitation, electrolysis etc., it is the solid matter utilizing silver ion and some chemical reagent generation chemical reaction to generate indissoluble that chemical precipitation method disposes waste liquid, and is then separated a kind of method removing silver ion, in practical operation, the normal sodium chloride that adopts removes silver ion, satisfactory for result, applied widely, cost is low, but excessive sodium chloride can make process waste water increase, as having again gas to release when being worth reduction, the environmental protection of liquid waste processing silver needs strictly to control addition, flocculent precipitation adds ferrous sulfate after certain pretreatment, caustic soda, flocculation and precipitation is utilized to form the alumen ustum of larger particles, silver ion is removed after separation, this technique needs a large amount of chemical reagent, add treatment cost of waste liquor, lime can be utilized to save the consumption of caustic soda, but the sludge quantity produced is comparatively large and be difficult to utilize, easy generation secondary pollution, need process further, electrolysis can silver ion in Recycling of waste liquid, substantially the recycling of silver can be realized, but a large amount of chlorine can be produced in electrolytic process, cause etching the loss of liquid chlorine and contaminated environment, utilize solution to absorb chlorine and can avoid environmental pollution.The method is simple to operate, technical feasibility, but produces a large amount of ammonia, adverse condition, and still there is secondary pollution problem after liquid waste processing.A large amount of mud, waste liquid, waste residue not only contaminated environment but also cause the wasting of resources is produced in administering method process traditionally, products obtained therefrom purity is low simultaneously, recycle value and economic worth are not high, are difficult to solve the problem of environmental pollution that brings of waste liquid and can not realize treating both principal and secondary aspect of disease.
A kind of Nano Silver preparation method for PCB high connductivity and equipment, involved production technology is simple, production cost is low, equipment investment is few, process easily controls, productive rate is high, prepared Nano Silver purity is high, very high economic worth can be obtained, avoid waste liquid to enter environment simultaneously, reach economy, society and the unification of environmental benefit.
Summary of the invention
The object of the invention is to provide a kind of preparation method for PCB high connductivity Nano Silver, the method adopts solution phase chemical reduction the nano-silver powder of production to be incorporated the electronic circuit printing technology of existing advanced person, embody excellent electric conductivity agent non-oxidizability, solve micro-silver powder slurry Problems existing: (1) consumption is large, and cost is high; (2) sintering temperature is high, and base material range of choice is narrow; (3) serigraphy pitch is wider.
The concrete operations of said method are as follows:
(1) silver salt compound and reducing agent are dissolved in deionized water respectively, then add the ammoniacal liquor complex silver ion of silver salt compound quality 0.1 ~ 2% respectively, reach and control reaction speed effect, cupric and ferric ions precipitation removing can be made simultaneously;
(2) dispersant is added respectively in silver salt compound solution after cleaning and reductant solution, under normal pressure, 15 DEG C ~ 50 DEG C conditions, stir obtained oxidation solution dispersion and reducing solution dispersion, wherein the addition of dispersant is 0.5 ~ 10% of silver salt compound quality;
(3) in reducing solution dispersion, add adjuvant, under normal pressure, 15 DEG C ~ 50 DEG C conditions, process reducing solution dispersion, wherein the addition of adjuvant is 1 ~ 6% of silver salt compound quality;
(4) regulate oxidation solution dispersion pH to be after 1 ~ 7, pour into wherein by the reducing solution dispersion after process, under normal pressure, 10 DEG C ~ 80 DEG C conditions, react 30 ~ 45min obtain nano silver colloid, the mol ratio of silver salt compound and reducing agent is 1:0.5 ~ 4;
(5) regulate that nano-silver colloid temperature is 15 DEG C ~ 60 DEG C, pH is 1 ~ 5, enrichment nano silver colloid, the nano silver colloid of enrichment is separated through high speed centrifugation and after deionized water and ethanol cyclic washing, obtains the nano-silver powder that wets;
(6) modifier is mixed with the organic matter such as oleic acid, aliphatic acid and absolute ethyl alcohol, modifier is poured directly into wet nano-silver powder and carries out surface modification, the consumption of oleic acid or aliphatic acid is 1% ~ 3% of wet nano-silver powder quality, and namely modified centrifugation, 40 DEG C ~ 100 DEG C drying 4 ~ 8h obtain Nano Silver product.
Described dispersant is polyvinylpyrrolidone, gum arabic, succinic acid, polyacrylic acid or polyethylene glycol.
Described silver salt compound is silver nitrate or silver perchlorate.
Described reducing agent is that hypophosphites is as sodium hypophosphite and potassium hypophosphite, sodium borohydride or hydrazine hydrate.
Described adjuvant is carboxymethyl cellulose.
Another object of the present invention is to provide a kind of equipment completing the above-mentioned preparation method for PCB high connductivity Nano Silver, and it comprises dissolution kettle I 1, dissolution kettle II 2, silver salt compound purifying column 3, reducing agent purifying column 4, silver salt compound dissolution kettle 5, reducing agent dissolution kettle 6, silver salt Compound Stock solution groove 7, reducing agent reservoir 8, temperature control is anti-corrosion reactor 9, efficient charging device 10, centrifugal separator 11, silver recovery unit 12, temperature control air dry oven 13, exhaust collection treating apparatus 14, liquid waste treating apparatus 15, water ion switching equipment 16, dissolution kettle I 1 is connected with silver salt compound purifying column 3 by pump, silver salt compound purifying column 3 is connected with silver salt compound dissolution kettle 5 by pump, silver salt compound dissolution kettle 5 is connected with silver salt Compound Stock solution groove 7 by pump, silver salt Compound Stock solution groove 7 is communicated with by the anti-corrosion reactor 9 of pump and temperature control, dissolution kettle II 2 is connected with reducing agent purifying column 4 by pump, reducing agent purifying column 4 is connected with reducing agent dissolution kettle 6 by pump, reducing agent dissolution kettle 6 is communicated with reducing agent reservoir 8 by pump, reducing agent reservoir 8 is communicated with by the anti-corrosion reactor 9 of efficient charging device 10 and temperature control, temperature control is anti-corrosion, and reactor 9 is connected with centrifugal separator 11, centrifugal separator 11 1 tunnel is connected with temperature control air dry oven 13, temperature control air dry oven 13 is connected with dissolution kettle I 1 by silver recovery unit 12, another road of centrifugal separator 11 successively with exhaust collection treating apparatus 14, liquid waste treating apparatus 15, water ion switching equipment 16 connects, water ion switching equipment 16 respectively with dissolution kettle I 1, dissolution kettle II 2 connects.
When this device uses, (1) takes silver salt compound and deionized water adds containing in the dissolution kettle I 1 stirred, and temperature control is stirred and made silver salt compound solution at ambient pressure; Taking reducing agent and deionized water adds containing in the dissolution kettle II 2 stirred, and reductant solution is prepared in temperature control stirring at ambient pressure; (2) with pump I 17 silver salt compound solution squeezed in silver salt compound purifying column 3 and carry out purified treatment; With pump II 18 reductant solution squeezed in reducing agent purifying column 4 and carry out purified treatment; (3) respectively the silver salt compound solution processed and reductant solution are squeezed into silver salt compound dissolution kettle 5, reducing agent dissolution kettle 6 with pump III 19, pump IV 20; (4) taking dispersant adds in silver salt compound dissolution kettle 5, reducing agent dissolution kettle 6 respectively, stirs obtained oxidation solution dispersion and reducing solution dispersion under normal pressure, 15 DEG C ~ 50 DEG C conditions; (5) taking adjuvant joins in reducing agent dissolution kettle 6, under normal pressure, 15 DEG C ~ 50 DEG C conditions, process reducing solution dispersion further; (6) with pump V 21, pump VI 22, oxidation solution dispersion and the reducing solution dispersion processed are driven into silver salt Compound Stock solution groove 7, reducing agent reservoir 8 respectively; (7) with pump VII 23, the oxidation solution dispersion in silver salt Compound Stock solution groove 7 is squeezed in the anti-corrosion reactor 9 of temperature control, under normal pressure temperature control, regulate pH to be 1 ~ 7, to stir; Reducing solution dispersion in reducing solution reservoir 8 is added by efficient charging device 10 and carries out reaction in the anti-corrosion reactor 9 of temperature control and prepare nano silver colloid; After having reacted, adjustment nano silver colloid is 15 DEG C ~ 60 DEG C, pH is 1 ~ 5, makes nano-silver powder ageing enrichment, the nano silver colloid of enrichment is carried out centrifugation through centrifugal separator 11 and after deionized water and ethanol cyclic washing, obtains wet nano-silver powder; (8) wet nano-silver powder is carried out surface modification in the anti-corrosion reactor 9 of temperature control; Dry by putting into temperature control air dry oven 13 after the nano-silver powder centrifugation of modification; (9)
The nano-silver powder of preparation is detected, is Nano Silver finished product if qualified, it is packed, if defective, Nano Silver is dropped in silver recovery unit 12 and prepare silver nitrate, the silver nitrate of preparation is turned back to dissolution kettle I 1 and be used for again preparing nano-silver powder;
(10) waste liquid produced in nano-silver powder preparation process and waste gas are processed through exhaust collection treating apparatus 14, liquid waste treating apparatus 15; (11) processed by water ion switching equipment 16 by waste liquid after process, the water of acquisition recycles.
The particle diameter of the nano-silver powder that the present invention prepares is 10nm ~ 100nm, and conductance is 2 × 10
-3Ω cm ~ 6.5 × 10
-3Ω cm.
Due to developing rapidly of electronics industry, printed electronics is more and more higher to the particle diameter of silver powder, the Property requirements such as pattern and tap density, and electric slurry prepared by micron order silver powder can not meet the demand of printed electronics.Nano-silver powder prepares slurry as main functionality, and the advantage that it substitutes traditional micro-silver powder has: (1) particle diameter is little, sintering temperature is low; (2) the base material range of choice of electric PC board is wide, and not only can be used for metal base and also can be used for non-metallic substrate, reduce the resistant to elevated temperatures requirement of base material, cost is low simultaneously; (3) print that the product that obtains is finer and smoother, consumption is few, cost reduces by 5%; (4) operational sequence is simple, from 26 traditional step operations, reduces to above-mentioned operation; (5) large-scale production equipment requirement is reduced, be easy to realize industrialization.
The present invention has following characteristics: (1) technique is simple, equipment requirement is low; (2) dispersant dosage is less, easily cleans, cost-saving; (3) waste liquid circulation utilizes, pollution-free, cost-saving; (4) the nano-silver powder particle diameter prepared is little, sintering temperature is low solves the problem that micro-silver powder particle diameter is large, sintering temperature is high; (5) apply nano-silver powder prepared by the present invention, consumption is few, finer and smoother in the printed circuit boards, solves micro-silver powder serigraphy pitch wide, the problem that cost is high; (6) nano-silver powder prepared of the present invention, in slurry preparation process, sintering temperature is low, solves micro-silver powder sintering temperature in slurry application high, the problem that base material range of choice is narrow.Adopt the Nano Silver purity prepared of the present invention high, good conductivity, can obtain very high economic worth, avoids waste liquid to enter environment simultaneously, reaches the unification of economy, society and environmental benefit.
Accompanying drawing explanation
fig. 1 is the schematic flow sheet of the inventive method;
Fig. 2 is the structural representation of apparatus of the present invention;
In figure: 1-dissolution kettle I; 2-dissolution kettle II; 3-silver salt compound purifying column; 4-reducing agent purifying column; 5-silver salt compound dissolution kettle; 6-reducing agent dissolution kettle; 7-silver salt Compound Stock solution groove; 8-reducing agent reservoir; 9-temperature control is anti-corrosion reactor; The efficient charging device of 10-; 11-centrifugal separator; 12-silver recovery unit; 13-temperature control air dry oven; 14-exhaust collection treating apparatus; 15-liquid waste treating apparatus; 16-water ion switching equipment; 17-pump I; 18-pump II; 19-pump III; 20-pump IV; 21-pump V; 22-pump VI; 23-pump VII.
Detailed description of the invention
Below by drawings and Examples, the present invention is described in further detail, but scope is not limited to described content.
Embodiment 1: this is used for the preparation method of PCB high connductivity Nano Silver, and concrete steps are as follows:
(1) 170g industrial nitric acid silver and 176g sodium hypophosphite are dissolved in the deionized water of 1L respectively, add ammoniacal liquor (0.1% of silver nitrate quality) complex silver ion, reach and control reaction speed effect, cupric and ferric ions precipitation removing can be made simultaneously;
(2) add 4.25g dispersant succinic acid respectively in liquor argenti nitratis ophthalmicus after cleaning and sodium hypophosphite solution, under normal pressure, 20 DEG C of parts, stir obtained silver nitrate dispersion and sodium hypophosphite dispersion;
(3) in sodium hypophosphite dispersion, add adjuvant carboxymethyl cellulose, under normal pressure, 20 DEG C of conditions, process sodium hypophosphite dispersion, wherein the addition of adjuvant is 3% of silver nitrate quality;
(4) regulate silver nitrate dispersion pH to be after 3, the sodium hypophosphite dispersion after process is poured into wherein, under normal pressure, 20 DEG C of conditions, reacts 35min obtain nano silver colloid;
(5) regulate that nano-silver colloid temperature is 20 DEG C, pH is 3, enrichment nano silver colloid, the nano silver colloid of enrichment is separated through high speed centrifugation and after deionized water and ethanol cyclic washing, obtains the nano-silver powder that wets;
(6) oleic acid and absolute ethyl alcohol are mixed with modifier, modifier is poured in wet nano-silver powder and carries out surface modification, the consumption of oleic acid is 1% of wet nano-silver powder quality, modified centrifugation, be drying to obtain Nano Silver product, nano-silver powder is spherical, good dispersion, particle diameter is 40nm, conductance is 4 × 10
-3Ω cm(Fig. 1).
Realize the equipment of said method, as shown in Figure 2, it comprises dissolution kettle I 1, dissolution kettle II 2, silver salt compound purifying column 3, reducing agent purifying column 4, silver salt compound dissolution kettle 5, reducing agent dissolution kettle 6, silver salt Compound Stock solution groove 7, reducing agent reservoir 8, temperature control is anti-corrosion reactor 9, efficient charging device 10, centrifugal separator 11, silver recovery unit 12, temperature control air dry oven 13, exhaust collection treating apparatus 14, liquid waste treating apparatus 15, water ion switching equipment 16, dissolution kettle I 1 is connected with silver salt compound purifying column 3 by pump I 17, silver salt compound purifying column 3 is connected with silver salt compound dissolution kettle 5 by pump III 19, silver salt compound dissolution kettle 5 is connected with silver salt Compound Stock solution groove 7 by pump V 21, silver salt Compound Stock solution groove 7 is communicated with by the anti-corrosion reactor 9 of pump VII 23 and temperature control, dissolution kettle II 2 is connected with reducing agent purifying column 4 by pump II 18, reducing agent purifying column 4 is connected with reducing agent dissolution kettle 6 by pump IV 20, reducing agent dissolution kettle 6 is communicated with reducing agent reservoir 8 by pump VI 22, reducing agent reservoir 8 is communicated with by the anti-corrosion reactor 9 of efficient charging device 10 and temperature control, temperature control is anti-corrosion, and reactor 9 is connected with centrifugal separator 11, centrifugal separator 11 1 tunnel is connected with temperature control air dry oven 13, temperature control air dry oven 13 is connected with dissolution kettle I 1 by silver recovery unit 12, another road of centrifugal separator 11 successively with exhaust collection treating apparatus 14, liquid waste treating apparatus 15, water ion switching equipment 16 connects, water ion switching equipment 16 respectively with dissolution kettle I 1, dissolution kettle II 2 connects.
When this device uses, 170g industrial nitric acid silver, 1L deionized water are added in dissolution kettle I 1 and be mixed with liquor argenti nitratis ophthalmicus, 176g sodium hypophosphite, 1L deionized water are added in dissolution kettle II 2 and is mixed with reductant solution; Liquor argenti nitratis ophthalmicus and reductant solution squeezed into silver salt compound purifying column 3 with pump I 17, pump II 18 respectively and go back in reducing agent purifying column 4, adding ammoniacal liquor purification and impurity removal, affecting for avoiding foreign ion; Respectively the liquor argenti nitratis ophthalmicus processed and reductant solution are driven in silver salt compound dissolution kettle 5, reducing agent dissolution kettle 6 with pump III 19, pump IV 20; Dispersant succinic acid is added respectively in silver salt compound dissolution kettle 5, reducing agent dissolution kettle 6, under normal pressure, 20 DEG C of conditions, stir obtained oxidation solution dispersion and reducing solution dispersion; Taking adjuvant joins in reducing agent dissolution kettle 6, under normal pressure, 20 DEG C of conditions, process reducing solution dispersion further; With pump V 21, pump VI 22, oxidation solution dispersion and the reducing solution dispersion processed are driven into silver salt Compound Stock solution groove 7, reducing agent reservoir 8 respectively; With pump VII 23, the oxidation solution dispersion in silver salt Compound Stock solution groove 7 is squeezed in the anti-corrosion reactor 9 of temperature control, normal pressure, 20 DEG C, pH stirs under being 3 conditions; Reducing solution dispersion in reducing solution reservoir 8 is added by efficient charging device 10 and carries out reaction 35min in the anti-corrosion reactor 9 of temperature control and prepare nano silver colloid; After having reacted, regulate that nano silver colloid is 20 DEG C, pH is 3, make nano-silver powder ageing enrichment, the nano silver colloid of enrichment is carried out centrifugation through centrifugal separator 11 and obtain the nano-silver powder that wets after deionized water and ethanol cyclic washing 3 times; Wet nano-silver powder is carried out surface modification in the anti-corrosion reactor 9 of temperature control; Dry 6h at putting into temperature control air dry oven 13 70 DEG C after the nano-silver powder centrifugation of modification can be obtained nano-silver powder; After testing, to qualified nano-silver powder packaging, underproofly utilize silver recovery unit 12 to carry out recovery to prepare silver nitrate, the silver nitrate of preparation is turned back to dissolution kettle I 1 and be used for again preparing nano-silver powder; The waste gas produced in preparation process and waste water utilization exhaust collection treating apparatus 14, liquid waste treating apparatus 15 are processed; Waste liquid after process processes Posterior circle through water ion switch 16 and utilizes.
Embodiment 2: this is used for the preparation method of PCB high connductivity Nano Silver, and concrete steps are as follows:
(1) 100kg industrial nitric acid silver and 22.3kg sodium borohydride are dissolved in the deionized water of 58.2L and 22.3L respectively, add ammoniacal liquor (1% of silver nitrate quality) complex silver ion, reach and control reaction speed effect, cupric and ferric ions precipitation removing can be made simultaneously;
(2) add 1kg dispersant gum arabic in liquor argenti nitratis ophthalmicus after cleaning, in sodium borohydride solution, add 1kg gum arabic, under normal pressure, 30 DEG C of conditions, stir obtained silver nitrate dispersion and sodium borohydride dispersion;
(3) in sodium borohydride dispersion, add 1kg adjuvant carboxymethyl cellulose, under normal pressure, 30 DEG C of conditions, process sodium hypophosphite dispersion;
(4) regulate silver nitrate dispersion pH to be after 2, the sodium hypophosphite dispersion after process is poured into wherein, under normal pressure, 30 DEG C of conditions, reacts 45min obtain nano silver colloid;
(5) regulate that nano-silver colloid temperature is 30 DEG C, pH is 2, enrichment nano silver colloid, the nano silver colloid of enrichment is separated through high speed centrifugation and after deionized water and ethanol cyclic washing, obtains the nano-silver powder that wets;
(6) oleic acid and absolute ethyl alcohol are mixed with modifier, modifier is poured in wet nano-silver powder and carries out surface modification, the consumption of oleic acid is 2% of wet nano-silver powder quality, modified centrifugation, be drying to obtain Nano Silver product, nano-silver powder is spherical, good dispersion, particle diameter is 20nm, 2 × 10
-3Ω cm.
100kg industrial nitric acid silver, 58.2L deionized water, with embodiment 1, are mixed with liquor argenti nitratis ophthalmicus, 22.3kg sodium borohydride (NaBH by the equipment realizing said method in dissolution kettle I 1
4), 22.3L deionized water is mixed with reductant solution in dissolution kettle II 2; Liquor argenti nitratis ophthalmicus and reductant solution squeezed into silver salt compound purifying column 3 with pump I 17, pump II 18 respectively and go back in reducing agent purifying column 4, adding ammoniacal liquor purification and impurity removal, affecting for avoiding foreign ion; Respectively the liquor argenti nitratis ophthalmicus processed and reductant solution are driven in silver salt compound dissolution kettle 5, reducing agent dissolution kettle 6 with pump III 19, pump IV 20; Take 1kg gum arabic and add reductant solution, take 1kg succinic acid and add liquor argenti nitratis ophthalmicus, under normal pressure, 30 DEG C of conditions, stir obtained oxidation solution dispersion and reducing solution dispersion; Taking adjuvant joins in reducing agent dissolution kettle 6, under normal pressure, 30 DEG C of conditions, process reducing solution dispersion further; With pump V 21, pump VI 22, oxidation solution dispersion and the reducing solution dispersion processed are driven into silver salt Compound Stock solution groove 7, reducing agent reservoir 8 respectively; Squeeze in the anti-corrosion reactor 9 of temperature control with pump VII 23 by the oxidation solution dispersion in silver salt Compound Stock solution groove 7, at normal pressure 30, lower adjustment pH is 2, stirs; Reducing solution dispersion in reducing solution reservoir 8 is added by efficient charging device 10 and carries out reaction 45min in the anti-corrosion reactor 9 of temperature control and prepare nano silver colloid; After having reacted, regulate that nano silver colloid is 30 DEG C, pH 2 makes nano-silver powder ageing enrichment, the nano silver colloid of enrichment is carried out centrifugation through centrifugal separator 11 and obtain the nano-silver powder that wets after deionized water and ethanol cyclic washing 3 times; Wet nano-silver powder is carried out surface modification with oleic acid in the anti-corrosion reactor 9 of temperature control; Dry 6h at putting into temperature control air dry oven 13 80 DEG C after the nano-silver powder centrifugation of modification can be obtained nano-silver powder; After testing, to qualified nano-silver powder packaging, underproofly utilize silver recovery unit 12 to carry out recovery to prepare silver nitrate, the silver nitrate of preparation is turned back to dissolution kettle I 1 and be used for again preparing nano-silver powder; The waste gas produced in preparation process and waste water utilization exhaust collection treating apparatus 14, liquid waste treating apparatus 15 are processed; Waste liquid after process processes Posterior circle through water ion switch 16 and utilizes.
embodiment 3:this is used for the preparation method of PCB high connductivity Nano Silver, and concrete steps are as follows:
(1) 250kg industry silver perchlorate and 60.2L hydrazine hydrate (mass percent concentration is 50%) are dissolved in the deionized water of 603L and 60.2L respectively, add ammoniacal liquor (2% of silver perchlorate quality) complex silver ion, reach and control reaction speed effect, cupric and ferric ions precipitation removing can be made simultaneously;
(2) add 1.25kg dispersant polyethylene glycol in silver perchlorate solution after cleaning, in hydrazine hydrate solution, add 1.25kg polyethylene glycol, under normal pressure, 40 DEG C of conditions, stir obtained silver perchlorate dispersion and hydrazine hydrate dispersion;
(3) in hydrazine hydrate dispersion, add adjuvant carboxymethyl cellulose, under normal pressure, 40 DEG C of conditions, process hydrazine hydrate dispersion, wherein the addition of adjuvant is 4% of silver perchlorate quality
(4) regulate silver perchlorate dispersion pH to be after 3, the sodium hypophosphite dispersion after process is poured into wherein, under normal pressure, 70 DEG C of conditions, reacts 30min obtain nano silver colloid;
(5) regulate that nano-silver colloid temperature is 40 DEG C, pH is 3, enrichment nano silver colloid, the nano silver colloid of enrichment is separated through high speed centrifugation and after deionized water and ethanol cyclic washing, obtains the nano-silver powder that wets;
(6) aliphatic acid and absolute ethyl alcohol are mixed with modifier, modifier is poured in wet nano-silver powder and carries out surface modification, the consumption of aliphatic acid is 3% of wet nano-silver powder quality, modified centrifugation, be drying to obtain Nano Silver product, nano-silver powder is spherical, good dispersion, particle diameter is 25nm, conductance is 3. × 10
-3Ω cm.
The equipment realizing said method is with embodiment 1, and 250kg industry silver perchlorate and 603L ionized water are mixed with liquor argenti nitratis ophthalmicus in dissolution kettle I 1, and 60.2L hydrazine hydrate, 60.2L deionized water are mixed with reductant solution in dissolution kettle II 2; With pump I 17, pump II 18, silver perchlorate solution and reductant solution are squeezed in silver salt compound purifying column 3 and reducing agent purifying column 4 respectively, adding ammoniacal liquor purification and impurity removal, affecting for avoiding foreign ion; Respectively the silver perchlorate solution processed and reductant solution are driven in silver salt compound dissolution kettle 5, reducing agent dissolution kettle 6 with pump III 19, pump IV 20; Take polyethylene glycol and add reductant solution, take polyethylene glycol and add silver perchlorate solution, under normal pressure, 40 DEG C of conditions, stir obtained oxidation solution dispersion and reducing solution dispersion; Taking adjuvant joins in reducing agent dissolution kettle 6, under normal pressure, 40 DEG C of conditions, process reducing solution dispersion further; With pump V 21, pump VI 22, oxidation solution dispersion and the reducing solution dispersion processed are driven into silver salt Compound Stock solution groove 7, reducing agent reservoir 8 respectively; With pump VII 23, the oxidation solution dispersion in silver salt Compound Stock solution groove 7 is squeezed in the anti-corrosion reactor 9 of temperature control, at normal pressure 40 DEG C, regulate pH to be 3, to stir; Reducing solution dispersion in reducing solution reservoir 8 is added by efficient charging device 10 and carries out reaction 30min in the anti-corrosion reactor 9 of temperature control and prepare nano silver colloid; After having reacted, regulate that nano silver colloid is 40 DEG C, pH is 3, make nano-silver powder ageing enrichment, the nano silver colloid of enrichment is carried out centrifugation through centrifugal separator 11 and obtain the nano-silver powder that wets after deionized water and ethanol cyclic washing 3 times; Wet nano-silver powder is prepared modifier with aliphatic acid and ethanol in the anti-corrosion reactor 9 of temperature control and carries out surface modification, aliphatic acid quality is 2% of wet nano-silver powder quality; Dry 6h at putting into temperature control air dry oven 13 100 DEG C after the nano-silver powder centrifugation of modification can be obtained nano-silver powder; After testing, to qualified nano-silver powder packaging, underproofly utilize silver recovery unit 12 to carry out recovery to prepare silver nitrate, the silver nitrate of preparation is turned back to dissolution kettle I 1 and be used for again preparing nano-silver powder; The waste gas produced in preparation process and waste water utilization exhaust collection treating apparatus 14, liquid waste treating apparatus 15 are processed; Waste liquid after process processes Posterior circle through water ion switch 16 and utilizes.
Claims (6)
1., for a preparation method for PCB high connductivity Nano Silver, it is characterized in that concrete steps are as follows:
(1) silver salt compound and reducing agent are dissolved in deionized water respectively, then add the ammoniacal liquor complex silver ion of silver salt compound quality 0.1 ~ 2% respectively;
(2) dispersant is added respectively in silver salt compound solution after cleaning and reductant solution, under normal pressure, 15 DEG C ~ 50 DEG C conditions, stir obtained oxidation solution dispersion and reducing solution dispersion, wherein the addition of dispersant is 0.5 ~ 10% of silver salt compound quality;
(3) in reducing solution dispersion, add adjuvant, under normal pressure, 15 DEG C ~ 50 DEG C conditions, process reducing solution dispersion, wherein the addition of adjuvant is 1 ~ 6% of silver salt compound quality;
(4) regulate oxidation solution dispersion pH to be after 1 ~ 7, pour into wherein by the reducing solution dispersion after process, under normal pressure, 10 DEG C ~ 80 DEG C conditions, react 30 ~ 45min obtain nano silver colloid, the mol ratio of silver salt compound and reducing agent is 1:0.5 ~ 4;
(5) regulate that nano-silver colloid temperature is 15 DEG C ~ 60 DEG C, pH is 1 ~ 5, enrichment nano silver colloid, the nano silver colloid of enrichment is separated through high speed centrifugation and after deionized water and ethanol cyclic washing, obtains the nano-silver powder that wets;
(6) oleic acid or aliphatic acid and absolute ethyl alcohol are mixed with modifier, modifier is poured in wet nano-silver powder and carries out surface modification, the consumption of oleic acid or aliphatic acid is 1% ~ 3% of wet nano-silver powder quality, modified centrifugation, is drying to obtain Nano Silver product.
2. the preparation method for PCB high connductivity Nano Silver according to claim 1, is characterized in that: dispersant is polyvinylpyrrolidone, gum arabic, succinic acid, polyacrylic acid or polyethylene glycol.
3. the preparation method for PCB high connductivity Nano Silver according to claim 1 and 2, is characterized in that: silver salt compound is silver nitrate or silver perchlorate.
4. the preparation method for PCB high connductivity Nano Silver according to claim 3, is characterized in that: reducing agent is sodium hypophosphite, potassium hypophosphite, sodium borohydride or hydrazine hydrate.
5. the preparation method for PCB high connductivity Nano Silver according to claim 4, is characterized in that: adjuvant is carboxymethyl cellulose.
6. complete the equipment of the preparation method for PCB high connductivity Nano Silver described in any one of claim 1-5, it is characterized in that: comprise dissolution kettle I (1), dissolution kettle II (2), silver salt compound purifying column (3), reducing agent purifying column (4), silver salt compound dissolution kettle (5), reducing agent dissolution kettle (6), silver salt Compound Stock solution groove (7), reducing agent reservoir (8), temperature control is anti-corrosion reactor (9), efficient charging device (10), centrifugal separator (11), silver recovery unit (12), temperature control air dry oven (13), exhaust collection treating apparatus (14), liquid waste treating apparatus (15), water ion switching equipment (16), dissolution kettle I (1) is connected with silver salt compound purifying column (3) by pump, silver salt compound purifying column (3) is connected with silver salt compound dissolution kettle (5) by pump, silver salt compound dissolution kettle (5) is connected with silver salt Compound Stock solution groove (7) by pump, silver salt Compound Stock solution groove (7) is communicated with by the anti-corrosion reactor of pump and temperature control (9), dissolution kettle II (2) is connected with reducing agent purifying column (4) by pump, reducing agent purifying column (4) is connected with reducing agent dissolution kettle (6) by pump, reducing agent dissolution kettle (6) is communicated with reducing agent reservoir (8) by pump, reducing agent reservoir (8) is communicated with the anti-corrosion reactor of temperature control (9) by efficient charging device (10), temperature control is anti-corrosion, and reactor (9) is connected with centrifugal separator (11), centrifugal separator (11) one tunnel is connected with temperature control air dry oven (13), temperature control air dry oven (13) is connected with dissolution kettle I (1) by silver recovery unit (12), centrifugal separator (11) another road successively with exhaust collection treating apparatus (14), liquid waste treating apparatus (15), water ion switching equipment (16) connects, water ion switching equipment (16) respectively with dissolution kettle I (1), dissolution kettle II (2) connects.
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| CN105562712A (en) * | 2016-01-30 | 2016-05-11 | 北京印刷学院青岛研究院有限公司 | Method for concentrating nano-silver particles in water |
| CN106513705A (en) * | 2016-12-01 | 2017-03-22 | 上海银波生物科技有限公司 | Method and device for preparing spherical silver powder by fractional step method |
| CN108311713A (en) * | 2018-05-16 | 2018-07-24 | 清远市宝晶新材料有限公司 | A kind of Automatic Control manufactures the method and its equipment of silver powder |
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| CN111360281A (en) * | 2020-05-11 | 2020-07-03 | 河南金渠银通金属材料有限公司 | Excellent conductive silver powder and preparation method thereof |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1266761A (en) * | 2000-03-23 | 2000-09-20 | 南京大学 | Process for preparing nm-class silver powder |
| CN101554664A (en) * | 2009-05-20 | 2009-10-14 | 广东风华高新科技股份有限公司 | Method for preparing nano-scale silver powder |
| CN101972855A (en) * | 2010-11-11 | 2011-02-16 | 肇庆市羚光电子化学品材料科技有限公司 | Method for preparing silver micro-powder for high-temperature sintering silver pastes |
| JP2012193454A (en) * | 2012-05-25 | 2012-10-11 | Dowa Holdings Co Ltd | Silver powder, and method of producing the same |
| CN204639140U (en) * | 2015-04-24 | 2015-09-16 | 昆明理工大学 | A kind of equipment preparing PCB high connductivity Nano Silver |
-
2015
- 2015-04-24 CN CN201510197484.8A patent/CN104858447B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1266761A (en) * | 2000-03-23 | 2000-09-20 | 南京大学 | Process for preparing nm-class silver powder |
| CN101554664A (en) * | 2009-05-20 | 2009-10-14 | 广东风华高新科技股份有限公司 | Method for preparing nano-scale silver powder |
| CN101972855A (en) * | 2010-11-11 | 2011-02-16 | 肇庆市羚光电子化学品材料科技有限公司 | Method for preparing silver micro-powder for high-temperature sintering silver pastes |
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