CN100400708C - A method for preparing silver plated copper powder - Google Patents
A method for preparing silver plated copper powder Download PDFInfo
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- CN100400708C CN100400708C CNB2004100370560A CN200410037056A CN100400708C CN 100400708 C CN100400708 C CN 100400708C CN B2004100370560 A CNB2004100370560 A CN B2004100370560A CN 200410037056 A CN200410037056 A CN 200410037056A CN 100400708 C CN100400708 C CN 100400708C
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- copper powder
- silver
- series
- extraction agent
- plated copper
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Abstract
The present invention relates to a method for preparing silver-plated copper powder. The method comprises the following steps: a chelation extracting agent is used when the silver-plated copper powder is prepared by using silver ammonia solution; the chelation extracting agent and generated Cu<2+> form a chelation compound which enters an organic phase so as to prevent Cu (NH3) 4 <2 +> from being adsorbed onto the surface of the copper powder, which obstructs displacement reaction from continuously proceed. The silver-plated copper powder with normal temperature oxidation resistance can be prepared in one time. The silver-plated copper powder prepared by the present invention has the advantages of smooth surface, even surface silver distribution, good oxidation resistance and conductivity and can be widely applied to preparing conducting paint and conducting glue.
Description
Technical field
The present invention relates to a kind of preparation method of silver-plated copper powder.
Background technology
Along with developing rapidly and communication equipment and various commercialization, domestic electronic appliances universal day by day of electronic industry, electromagnet radiation is on the rise.For improving the performance and the competitive power of electronic product, improve human living environment, take interference protection measure imperative to it.Adopting electromagnetic-shielding conductive coating to carry out shielding electromagnetic wave is a kind of effective and economic method, conductive filler material is as the important component part of electrically conducting coating, its performance, pattern and size-grade distribution all directly affect the conductivity of electromagnetic-shielding conductive coating, thereby influence its shield effectiveness.
Silver is that conductive filler material is the conductive filler material of developing the earliest, it has good electroconductibility and scale resistance, but under the effect of volts DS, the transport phenomena of Yi Fashengyin and cause short circuit, this has become electronic product march toward miniaturization, highly integrated a great problem.Copper powder low price (only be silver-colored price 1/20), anti-migration performance is much higher than silver, and (volume specific resistance is close with silver: ρ to have good electroconductibility
V (Cu)=1.72 * 10
-6Ω cm, ρ
V (Ag)=1.59 * 10
-6Thereby be used widely Ω cm).But copper powder is easily oxidized in preparation and application process, and the conductivity of composite conducting material is weakened.Form silver-plated copper powder at the copper powder electroplate, can improve the resistance of oxidation of copper powder, can keep the premium properties of copper powder again, thereby silver-plated copper powder has vast potential for future development.
Document " with the research of silver ammino solution to micron order copper powder silver plating reaction mechanism " (" Chinese Journal of Inorganic Chemistry ", 2000 16 phases) is pointed out when preparing silver-plated copper powder with silver ammino solution, copper displacement Ag
+The Cu that generates
2+With NH
3Generate [Cu (NH
3)
4]
2+, it is adsorbed in copper powder surface obstruction replacement(metathesis)reaction and proceeds, and therefore, can only obtain interspersing the coating of structure through a silver plating reaction, and surperficial silver content is low, does not possess the normal temperature oxidation-resistance, and causes the waste of a large amount of silver.
Summary of the invention
The present invention is directed to above problem, a kind of preparation method of silver-plated copper powder is provided.The silver-plated copper powder that makes has good oxidation-resistance and electroconductibility, can be widely used in the various conducing composite materials, as: electrically conducting coating, conductive resin, conductive plastics.Especially be adapted to the demanding environment of electric conductivity, as electromagnetic-shielding conductive coating, surface-assembled conductive resin.
The present invention is achieved in that a certain amount of chelating extractant (chelating extractant that has needs to dilute with thinner) is mixed with certain density silver ammino solution, be heated to 40～90 ℃ of temperature of reaction, and constant temperature, to make copper powder under agitation condition by oneself joins in the mixing solutions, reaction 10～40min, the powder that makes is used washing with acetone with acetone or elder generation again with kerosene, under heating condition, wash with dilute sulphuric acid and alcoholic acid mixing solutions, wash with water again, the gained powder is 40～80 ℃ of oven dry in vacuum drying oven, promptly get required silver-plated copper powder.
Chelating extractant of the present invention is methyl ethyl diketone, trifluoroacetylacetone, benzoyl acetone, 1-phenyl-3-methyl-4-Benzoylpyrazols ketone, α-two phenylethyl alcohol oxime, dithizone, cupral, tri-n-octyl amine, and the LIX of (following title is trade(brand)name) General and Mills company series Cu
2+Extraction agent (comprising LIX63, LIX64, LIX64N, LIX65N, LIX70, LIX71, LIX73, LIX860, LIX622, LIX6022, LIX864, LIX865, LIX84, LIX984), the SME series Cu of Shell company
2+Extraction agent (comprise SME529, SME530), the P of Zeneca company series Cu
2+Extraction agent (comprising P50, P17, P5100, P5200, P5300, PT5050) and M series Cu
2+Extraction agent (comprising M5615, M5397, M5640), the Kelex series Cu of Sherex company
2+Extraction agent (comprising Kelex100, Kelex120), the BK series Cu of Beijing Luo Ke industrial and trading company
2+Extraction agent (comprising BK991, BK992, BK993), the RE series Cu of Shanghai Lai Yashi company limited
2+A kind of in the extraction agent (comprising RE608, RE609).The chelating extractant here and the Cu of generation
2+The formation chelate complex also enters in the organic phase, prevents [Cu (NH
3)
4]
2+Be adsorbed in the copper powder surface and hinder proceeding of replacement(metathesis)reaction, can disposablely make silver-plated copper powder with normal temperature resistance of oxidation.
Thinner of the present invention is CHCl
3, CCl
4, a kind of in the kerosene, primary isoamyl alcohol, its consumption is 1～5 times (volume multiple) of chelating extractant.
The used AgNO of the present invention
3Consumption is 2～25% of a copper powder weight, AgNO
3Concentration is 0.01～0.4mol/L.
The used silver ammino solution of the present invention prepares by the following method: prepare certain density AgNO
3Solution, stir slow dropping ammonia down, be clear solution fully to the lucky dissolving of precipitation that generates earlier.
The preparation technology of the used self-control copper powder of the present invention: in 0.1～2.0mol/L copper-bath, add NH
3H2O, NH
3The H2O consumption is 0.5～1.5 times of cupric ion amount of substance, stirs, and be 1.2 times xitix of cupric ion amount of substance at 60～95 ℃ of consumptions that add 0.5～2mol/L down, stirring reaction 0.5～1 hour is again through separating washing, 80 ℃ of dryings of vacuum make copper powder.
The present invention has positive effect compared with the prior art, adopts preparation method of the present invention can disposablely make the silver-plated copper powder with normal temperature oxidation-resistance, and saves AgNO
3Consumption, the silver-plated copper powder smooth surface, the surface silver coating that make are evenly distributed.The contact resistance value of the silver-plated copper powder that makes with the present invention is 0.3 Ω (the universal meter internal resistance value is 0.3 Ω), and after placing 6 months, contact resistance value still is 0.3 Ω.
Embodiment
Embodiment 1: the 0.316gAgNO that contains for preparing 0.025mol/L in a container
3Solution, stir slow dropping ammonia down, be clear solution fully to the lucky dissolving of precipitation that generates earlier.In another container, press V
(RE608)V
(kerosene)=1: 2.5 ratio is diluted RE608.The RE608 of 40mL dilution is mixed with silver ammino solution, be heated to 80 ℃, stirring is down that the self-control copper powder of 3 μ m adds in the mixed solution reaction 20min with the 2g average particle size.The powder that makes is washed three times with kerosene, and washing with acetone one time washs one time under the condition of heating with dilute sulphuric acid and alcoholic acid mixing solutions again, washes twice at last with water, and 80 ℃ of oven dry promptly get required silver-plated copper powder in vacuum drying oven.This silver-plated copper powder smooth surface, surface silver coating are evenly distributed, and its contact resistance value is 0.3 Ω (the universal meter internal resistance value is 0.3 Ω), and after placing 6 months, contact resistance value still is 0.3 Ω.
Embodiment 2: the 0.316gAgNO that contains for preparing 0.025mol/L in a container
3Solution, stir slow dropping ammonia down, be clear solution fully to the lucky dissolving of precipitation that generates earlier.In another container, press α-two phenylethyl alcohol oxime and CHCl
3Volume ratio is that 1: 1 ratio is diluted two phenylethyl alcohol oximes.Two phenylethyl alcohol oximes of 20mL dilution are mixed with silver ammino solution, be heated to 40 ℃, stirring is down that the self-control copper powder of 3 μ m adds in the mixed solution reaction 15min with the 3g average particle size.Powder washing with acetone twice with making washs one time under the condition of heating with dilute sulphuric acid and alcoholic acid mixing solutions again, washes twice at last with water, and 80 ℃ of oven dry promptly get required silver-plated copper powder in vacuum drying oven.The contact resistance value of this silver-plated copper powder is with embodiment 1.
Claims (5)
1. the preparation method of a silver-plated copper powder is characterized in that: a certain amount of chelating extractant is mixed with certain density silver ammino solution, and the chelating extractant that has needs dilute with thinner; Mixed solution is heated to 40～90 ℃ of temperature of reaction, and constant temperature, to make copper powder under agitation condition by oneself joins in the mixing solutions, reaction 10～40min, the powder that makes is used washing with acetone with acetone or elder generation again with kerosene, under heating condition,, wash with water again with dilute sulphuric acid and the washing of alcoholic acid mixing solutions, the gained powder is 40～80 ℃ of oven dry in vacuum drying oven, promptly get required silver-plated copper powder;
The preparation technology of above-mentioned self-control copper powder is: add NH in 0.1～2.0mol/L copper-bath
3H2O, NH
3The H2O consumption is 0.5～1.5 times of cupric ion amount of substance, stirs, and be 1.2 times xitix of cupric ion amount of substance at 60～95 ℃ of consumptions that add 0.5～2mol/L down, stirring reaction 0.5～1 hour is again through separating washing, 80 ℃ of dryings of vacuum make the self-control copper powder.
2. as right 1 described preparation method, it is characterized in that described chelating extractant is the LIX series Cu of methyl ethyl diketone, trifluoroacetylacetone, benzoyl acetone, 1-phenyl-3-methyl-4-Benzoylpyrazols ketone, α-two phenylethyl alcohol oxime, dithizone, cupral, tri-n-octyl amine and General and Mills company
2+Extraction agent: LIX63, LIX64, LIX64N, LIX65N, LIX70, LIX71, LIX73, LIX860, LIX622, LIX6022, LIX864, LIX865, LIX84, LIX984, the SME series Cu of Shell company
2+Extraction agent: SME529, SME530, the P series Cu of Zeneca company
2+Extraction agent: P50, P17, P5100, P5200, P5300, PT5050 and M series Cu
2+Extraction agent: M5615, M5397, M5640, the Kelex series Cu of Sherex company
2+Extraction agent: Kelex100, Kelex120, the BK series Cu of Beijing Luo Ke industrial and trading company
2+Extraction agent: BK991, BK992, BK993, the RE series Cu of Shanghai dishes Ya Shi company limited
2+A kind of among extraction agent: RE608, the RE609.
3. as right 1 described preparation method, it is characterized in that described thinner is CHCl
3, CCl
4, a kind of in the kerosene, primary isoamyl alcohol, its consumption: the volume multiple is 1～5 times of chelating extractant.
4. as right 1 described preparation method, it is characterized in that used AgNO
3Consumption is 2～25% of a copper powder weight, AgNO
3Concentration is 0.01～0.4mol/L.
5. as right 1 described preparation method, it is characterized in that used silver ammino solution prepares by the following method: prepare certain density AgNO
3Solution, stir slow dropping ammonia down, be clear solution fully to the lucky dissolving of precipitation that generates earlier.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100370560A CN100400708C (en) | 2004-05-25 | 2004-05-25 | A method for preparing silver plated copper powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100370560A CN100400708C (en) | 2004-05-25 | 2004-05-25 | A method for preparing silver plated copper powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1704502A CN1704502A (en) | 2005-12-07 |
| CN100400708C true CN100400708C (en) | 2008-07-09 |
Family
ID=35576508
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100370560A Expired - Fee Related CN100400708C (en) | 2004-05-25 | 2004-05-25 | A method for preparing silver plated copper powder |
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|---|---|
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102773494A (en) * | 2011-05-13 | 2012-11-14 | 华东理工大学 | Method for preparing silver-coated copper powder through radiation reduction |
| 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 |
| CN102492376B (en) * | 2011-11-28 | 2013-05-08 | 兰州石化职业技术学院 | Method for preparing perchlorovinyl conductive adhesive dried quickly at room temperature |
| CN103710686B (en) * | 2013-12-31 | 2016-02-03 | 苏州大学 | A kind of method preparing surface-reinforced infrared spectrum SERS substrate |
| CN110369712B (en) * | 2019-08-29 | 2021-08-20 | 嘉兴学院 | Preparation method of silver-coated copper powder |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5178909A (en) * | 1990-07-24 | 1993-01-12 | Mitsui Kinzoku Kogyo Kabushiki Kaisha | Production of silver-coated copper-based powders |
| CN1130553A (en) * | 1995-03-08 | 1996-09-11 | 上海市合成树脂研究所 | Process for preparing copper powder for electromagnetic shield conducting paint |
-
2004
- 2004-05-25 CN CNB2004100370560A patent/CN100400708C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5178909A (en) * | 1990-07-24 | 1993-01-12 | Mitsui Kinzoku Kogyo Kabushiki Kaisha | Production of silver-coated copper-based powders |
| CN1130553A (en) * | 1995-03-08 | 1996-09-11 | 上海市合成树脂研究所 | Process for preparing copper powder for electromagnetic shield conducting paint |
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|---|---|
| CN1704502A (en) | 2005-12-07 |
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