CN1206064C - Silver-plated copper powder and its prepn process - Google Patents
Silver-plated copper powder and its prepn process Download PDFInfo
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- CN1206064C CN1206064C CN 02139151 CN02139151A CN1206064C CN 1206064 C CN1206064 C CN 1206064C CN 02139151 CN02139151 CN 02139151 CN 02139151 A CN02139151 A CN 02139151A CN 1206064 C CN1206064 C CN 1206064C
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Abstract
The present invention discloses silver-plated copper powder with high performance and a preparing method thereof. The method comprises the following steps: the pickled copper powder is dispersed in solution containing a dispersant, and organic amine-group compound complex silver nitrate solution with finite concentration is added to the pickled copper powder under certain temperature and a certain stirring condition; after reaction, the copper powder is washed by water, is filtered and separated and is dried in a vacuum mode so as to achieve the silver-plated copper powder. A silver content is from 4.5 to 30% (weight ratio). Compared with the prior art, the silver-plated copper powder has the characteristics of stable electricity conduction and high electric conductivity. Powder volume resistivity can achieve 2*10<-4> omega. Cm. The silver-plated copper powder can be widely used for electric conduction glue, electricity conducting or static conducting paint and various material fields with electricity conducting or static conducting requirements. Silver can be saved by 30 to 70%, and the silver-plated copper powder is novel electricity conducting composite powder.
Description
Technical field
The present invention relates to a kind of preparation method of high performance silver-plated copper powder.This silver-plated copper powder has good anti-oxidant, and anti-migration performance can be widely used in the various conductive resins that the conduction demand is arranged, and electrically conducting coating is in the conductive rubber.Be particularly suitable for the demanding environment of electric conductivity, as the surface-assembled conductive resin.
Background technology
Because the progress of technique of integrated circuit packaging, traditional scolding tin technology can't satisfy the demands, high-performance conducting resin progressively replaces scolding tin and becomes main connection material, widely used now is the conductive resin of silver system, but silver is under the direct-current biasing effect, easily migration taking place and cause short circuit, reduces the safety coefficient of using greatly.For this reason, it is stable that many investigators are devoted to study a kind of conduction, again the conductive resin of anti-migration.The anti-migration performance of copper is much higher than silver, but copper easy oxidation in air forms one deck insulating zone of oxidation.Coat other metal or alloy on the copper surface and become a kind of research direction.Application for a patent for invention [publication number: CN1262043A] discloses and has a kind ofly prepared the method that silver coats copper powder with replacement(metathesis)reaction, and the powder antioxidant property of this method preparation is improved, and is a kind of high-efficient antibacterial agent, but the electroconductibility of not mentioned powder in the literary composition.Document [copper powder chemical silvering and performance thereof] has been introduced a kind of preparation method of composite powder equally, but the gained powder resistivity is higher, and powder resistivity is 3 * 10
-3More than the Ω .cm, fail to reach the surface-assembled required electroconductibility requirement of conductive resin.Document [research of novel conductive glue] adopts copper and silver cyanide generation replacement(metathesis)reaction to prepare composite powder, higher through three made powder electric conductivitys of replacement(metathesis)reaction, can satisfy the conduction requirement of surface-assembled, but prussiate is the deadly poisonous compound that just is being under an embargo and is using with conductive resin.
Summary of the invention
The present invention is exactly at the problems referred to above, and a kind of preparation method of silver-plated copper powder is provided, this method process safety, simple effective, compliance with environmental protection requirements, prepared composite powder electric conductivity height.
Technical scheme provided by the invention is: a kind of silver-plated copper powder, and the surface of copper powder is by silver-plated coating, and it basic composition is: 4.5～30% silver, 70～95.5% copper (weight percent).
The content of above-mentioned silver is 10～20%, and the content of copper is 80～90% (weight percents).
The preparation method of above-mentioned silver-plated copper powder, with the diluted acid pickling of copper powder with 5-10% (weight percent), remove the copper powder oxide on surface, again it is dispersed in the solution that contains dispersion agent, keeps 30-50 ℃ of solution temperature, under stirring condition, add silver nitrate solution with the organic amine compound complexing, reaction is finished after wash, filtering separation, gained powder are in vacuum drying oven, and 40～80 ℃ of oven dry promptly get required silver-plated copper powder.
Above-mentioned dispersion agent is a sodium-acetate, sodium oxalate, disodium ethylene diamine tetraacetate, Padil, Trisodium Citrate, gelatin, gum arabic, the mixture of one or both in methylcellulose gum and the ethyl cellulose, consumption is 1-80%, and the consumption of Silver Nitrate is 5-80%, and above per-cent is weight ratio.
Above-mentioned aminated compounds is one or both the mixture in quadrol, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, polyethylene polyamine, thanomin, the pyridine.
According to the present invention, described dilute acid soln can be sulfuric acid, nitric acid or formic acid.
Process safety of the present invention, simple effective, compliance with environmental protection requirements, prepared composite powder has the electric conductivity height, and (volume specific resistance of powder is less than 2 * 10
-4Ω .cm), be the conductive resin that filler is made with this powder, (weight ratio of conductive filler material and resin is 75: 25 o'clock to the electric conductivity height, volume specific resistance 5 * 10
-4Ω .cm) anti-transfer ability strong (improving nearly a hundred times) than sliver-powder conducting glue, conduction stable (through 100% 1000 hour humid heat test of 60 ℃ of relative humidity, volume specific resistance raises less than 20%).The reaction efficiency height, the displacement efficiency of silver can reach more than 90%, can economize on silver-colored 30%-70%.
Embodiment
Embodiment 1: get the dilution heat of sulfuric acid of copper powder 15 gram addings 5%, stir repeatedly, after removing fully to the oxide compound on copper powder surface, use the distilled water flushing copper powder, flush away sulfuric acid changes copper powder over to and contains in 5% the sodium citrate solution, keeps 50 ℃ of solution temperatures, stir, the 0.15mol/L silver nitrate solution 50ml that adds the quadrol complexing continues to stir 10 minutes, and gained powder water washes repeatedly, filter, 80 ℃ of vacuum-dryings can obtain required silver-plated copper powder.Silver-plated efficient is 90%, and the content of silver is 4.7%.This powder is mixed with E-51 Resins, epoxy and solidifying agent, and wherein powder and high molecular component weight ratio are 75: 25, and made conductive adhesive performance and powder property are listed in table 1.
Embodiment 2: the salpeter solution of getting copper powder 50 gram addings 5%, after the oxide compound that is stirred to the copper powder surface is removed fully, use the distilled water flushing copper powder, the copper powder of washing is changed in 10% the sodium acetate soln, keep 25 ℃ of solution temperatures, stir, the 0.6mol/L silver nitrate solution 100ml that adds diethylenetriamine and the complexing of polyethylene polyamine mixture continues to stir 12 minutes, and the gained powder is through flushing, filter, drying can get required silver-plated copper powder.Silver-plated efficient is 87%, and the content of silver is 10%.With embodiment 1 glue, gained conductive resin and powder property are listed in table 1.
Embodiment 3: the formic acid solution of getting copper powder 30 gram addings 10%, after the oxide compound that is stirred to the copper powder surface is removed fully, use the distilled water flushing copper powder, the copper powder of washing is changed in the methylcellulose gum mixing solutions of 5% sodium oxalate and 5%, keep 40 ℃ of stirrings of solution temperature, add the 0.7mol/L silver nitrate solution 80ml of thanomin complexing, continue to stir 10 minutes, the gained powder washes repeatedly, filters, and drying can obtain silver-plated copper powder.Silver-plated efficient 85%, the content of silver is 26%.With embodiment 1 glue, gained conductive resin and powder property are listed in table 1.
The mixture replacing of one or both in the sodium malate of the dispersion agent in the foregoing description, disodium ethylene diamine tetraacetate, Padil, gelatin, gum arabic, the ethyl cellulose, the mixture replacing of one or both in aminated compounds triethylene tetramine, tetraethylene pentamine, polyethylene polyamine, the pyridine can obtain required silver-plated copper powder equally.
Comparative example 1
Silver Nitrate quadrol complexing directly adds solution in embodiment 1, other components, and reaction conditions is constant, and the gained powder reaches and lists in table 1 with embodiment 1 made conductive adhesive performance.
Comparative example 2
Do not add dispersion agent in embodiment 2, copper powder directly adds in the entry, and other processes are constant, and the gained powder property reaches and lists in table 1 with embodiment 1 made conductive adhesive performance.
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | |
| Powder resistivity (* 10 -4Ω.cm) | 3.1 | ?2.0 | ?2.7 | ?9.8 | ?10.2 |
| Conductive resin resistivity (* 10 -4Ω.cm) | 6.8 | ?5.6 | ?5.0 | ?46.5 | ?55.8 |
| 1000 hours (60 ℃ of RH100%) humid heat tests (* 10 -4Ω.cm) | 8.2 | ?7.1 | ?6.5 | ?60.4 | ?68.4 |
Claims (4)
1. the preparation method of a silver-plated copper powder, it is characterized in that: get copper powder earlier, adopting weight percent is the diluted acid pickling of 5-10%, remove the copper powder oxide on surface, again it is dispersed in the sodium-acetate that contains 1-80wt%, sodium oxalate, disodium ethylene diamine tetraacetate, Padil, Trisodium Citrate, in the solution of the mixture of one or both in methylcellulose gum and the ethyl cellulose, keep 20-60 ℃ of solution temperature, under stirring condition, add silver nitrate solution with the organic amine compound complexing, reaction is finished after wash, filtering separation, gained powder are in vacuum drying oven, and 50～100 ℃ of oven dry promptly get required silver-plated copper powder.
2. method according to claim 1 is characterized in that: the consumption of Silver Nitrate is 5-80wt%.
3. method according to claim 1 and 2 is characterized in that: described aminated compounds is one or both the mixture in quadrol, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, polyethylene polyamine, thanomin, the pyridine.
4. method according to claim 1 and 2 is characterized in that: described dilute acid soln is sulfuric acid, nitric acid or formic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN 02139151 CN1206064C (en) | 2002-10-10 | 2002-10-10 | Silver-plated copper powder and its prepn process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02139151 CN1206064C (en) | 2002-10-10 | 2002-10-10 | Silver-plated copper powder and its prepn process |
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| Publication Number | Publication Date |
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| CN1403233A CN1403233A (en) | 2003-03-19 |
| CN1206064C true CN1206064C (en) | 2005-06-15 |
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| CN 02139151 Expired - Fee Related CN1206064C (en) | 2002-10-10 | 2002-10-10 | Silver-plated copper powder and its prepn process |
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Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101244459B (en) * | 2008-03-25 | 2010-06-16 | 合肥工业大学 | Chemical plating silver copper powder, chemical plating liquid and chemical plating method |
| CN102137728B (en) * | 2008-08-29 | 2013-09-11 | 石原产业株式会社 | Metallic copper dispersion, process for producing the metallic copper dispersion, electrode, wiring pattern, and coating film formed using the metallic copper dispersion, decorative article and antimicrobial article with the coating film formed there |
| CN101887767B (en) * | 2010-06-11 | 2011-08-17 | 山东大学 | Method for preparing conductive paste by taking copper powder with surface coverage silver nanostructures as packing |
| CN102002694B (en) * | 2010-12-14 | 2012-07-04 | 江西理工大学 | Method for preparing uniform silver conducting layer on surface of metal or nonmetal material |
| CN102133636B (en) * | 2011-03-10 | 2012-11-21 | 昆明理工大学 | Method for preparing anti-migration flaky silver coated copper powder |
| CN102328076A (en) * | 2011-06-20 | 2012-01-25 | 宁波广博纳米新材料股份有限公司 | Preparation method of silver coated copper powder for electronic slurry |
| JP5631910B2 (en) * | 2011-10-21 | 2014-11-26 | 三井金属鉱業株式会社 | Silver coated copper powder |
| CN102814496A (en) * | 2012-08-14 | 2012-12-12 | 烟台德邦科技有限公司 | Silver-plated copper powder and preparation method thereof |
| CN103084581B (en) * | 2013-01-08 | 2015-02-04 | 河南大学 | Preparation method for copper nanowire |
| CN103084583B (en) * | 2013-01-17 | 2014-09-10 | 东南大学 | Method for preparing compound of zinc oxides and silver nano |
| CN103252505B (en) * | 2013-05-21 | 2015-12-23 | 昆明理工大学 | A kind of preparation method of silver-plated copper powder |
| JP5920540B1 (en) * | 2015-03-26 | 2016-05-18 | 住友金属鉱山株式会社 | Copper powder and copper paste, conductive paint, conductive sheet using the same |
| CN105149575A (en) * | 2015-10-23 | 2015-12-16 | 乐山新天源太阳能科技有限公司 | Preparation method of silver coated copper powder |
| CN105355541A (en) * | 2015-10-23 | 2016-02-24 | 乐山新天源太阳能科技有限公司 | Solar cell recycling method |
| CN115475937A (en) * | 2021-05-28 | 2022-12-16 | 季华实验室 | Method for rapidly coating silver shell on copper particles |
| CN114226724B (en) * | 2021-12-22 | 2024-01-16 | 合肥工业大学 | Copper@silver core-shell structure particle and related preparation method and application |
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