CN101664803B - Preparation method of coated copper-silver metal powder - Google Patents
Preparation method of coated copper-silver metal powder Download PDFInfo
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- CN101664803B CN101664803B CN2009101028107A CN200910102810A CN101664803B CN 101664803 B CN101664803 B CN 101664803B CN 2009101028107 A CN2009101028107 A CN 2009101028107A CN 200910102810 A CN200910102810 A CN 200910102810A CN 101664803 B CN101664803 B CN 101664803B
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Abstract
The invention discloses a preparation method of coated copper-silver metal powder which contains the pretreatment of copper powder, the preparation of silver solution and the preparation of copper-silver metal powder, wherein the preparation method of copper-silver metal powder comprises the following steps: dropwise adding dilute nitric acid in the sol of copper powder to adjusting the pH value to 3.0-5.0, adding ionic masking agent with the dosage of 1-30g/L, fully stirring, injecting inert protective gas such as nitrogen, argon or the like to remove the air in a reactor for protection, then slowly dropping silver nitrate solution in the sol of copper powder while stirring to fully react for 30min, then dropping dilute ammonia water to adjusting the pH value to 7.0-11.0, continuously reacting for 30min, washing the reaction solution with deionized water, 5% of dilute sulphuric acid and ethanol solution for several times after the reaction and drying the obtained copper-silver metal powder at 60-80 DEG C to obtain the finished product. The product obtained by the method of the invention has excellent high temperature oxidation resistance and conductivity and narrow particle size distribution.
Description
Technical field
The present invention relates to the material technology field, relate in particular to a kind of preparation method of copper-silver metal powder.
Background technology
All the time, silver powder is with its electric conductivity, and premium properties such as non-oxidizability are widely used in every field, is that other numerous metal dusts of performance or range of application are all incomparable.With respect to silver powder, the electric conductivity of copper powder is also very good, but because the cause of copper powder surface overactivity, the oxidation rate of copper powder under low-down temperature is just very high, after the very fast oxidation that is inversely proportional to copper powder size, good electric conductivity is all gone, and copper powder is directly used and had reached an impasse.How to guarantee the oxidation resistance of copper powder under the prerequisite that guarantees copper powder excellent conductive capability and production cost, all be the goal in research of author in the scientific research all the time, in recent years, is the main direction of its research to the copper powder surface modification.Reporting more is to adopt chemical replacement method, chemical reduction method, fusion and gasification method etc. to carry out surface silver coating.But in the chemical replacement method, because the existence of ammonium ion in the reaction system, competitive Adsorption has taken place on the copper powder surface in the cuprammonium ion that generates in the course of reaction, has influenced silver-colored surface and has coated, the copper-silver metal powder for preparing mostly coats for interspersing type, and the production application prospect is had a greatly reduced quality; And chemical reduction method has been owing to introduced the cause of high strong reductant, and it is not enough that the silver for preparing coats the copper powder heat endurance, easily wears out with aging generation of reducing agent; The production technology of fusion and gasification method is too complicated, and the working condition harshness is unfavorable for industrial production.
Chinese patent publication number CN1704502A, " a kind of preparation method of silver-plated copper powder " disclosed, it has selected the extraction complexing agent of copper ion for use, but because organic complexing agent is subjected to the influence of pH value bigger, they are active different under different pH value conditions, and this patent is not considered the activity problems of ion extractuin complexing agent under the different pH condition.
Chinese patent publication number CN101294281A (200810058362.0), the serviceability temperature that discloses the copper silver powder that " a kind of preparation method of silver-plated copper powder for low-temperature slurry " this patent prepares is no more than 200 ℃, the silver-plated copper powder that its low temperature limitation makes this method produce can not be applicable to the application that higher temperature requires, and easily oxidation takes place and lose its excellent conductive capability under hot conditions.
Summary of the invention
The objective of the invention is to overcome above-mentioned shortcoming and a kind of preparation method with coated copper-silver metal powder of excellent high temperature oxidation resistance and electric conductivity, powder size narrowly distributing is provided.
The preparation method of coated copper-silver metal powder of the present invention may further comprise the steps:
(1) pre-treatment of copper powder: handle according to a conventional method;
(2) preparation of silver-colored solution:
Take by weighing solid nitric acid silver and be dissolved in the aqueous solution that is configured to 0.05-0.5mol/L in the deionized water;
(3) copper-silver metal powder preparation:
Copper powder colloidal sol drips rare nitric acid at normal temperatures and regulates pH value to 3.0-5.0, add the ion screening agent, consumption is in the 1-30g/L scope, stir, air is protected in inert protective gas such as feeding nitrogen or the argon gas eliminating reactors, slowly drip liquor argenti nitratis ophthalmicus then while stirring to copper powder colloidal sol, fully react and drip weak aqua ammonia behind the 30min again and regulate pH value, continue reaction 30min to 7.0-11.0; After finishing, reaction extracts reaction solution with the deionized water washing, 5% dilute sulfuric acid pickling, and ethanolic solution alcohol washes down for several times, and the copper-silver bimetallic powder is dried under 60-80 ℃ of condition and is got product;
Wherein: ion screening agent kind is an ethylenediamine, tren, TEPA, hydrochloric acid carboxylic amine, hydrazine hydrate, Phen, nitrilotriacetic acid, hydroxyethylethylene diamine tri-acetic acid, Succimer, maleopimaric acid, trichloroacetic acid, natrium citricum, potassium citrate, amion acetic acid, picolinic acid, two hydrogen phenylglycines, cysteine, disodium ethylene diamine tetraacetate, DMPS, dimercaprol dimercaptopropanol, isopropyl alcohol, one or more mixtures in amylene or the ethyl acetate.
The present invention compared with prior art, has significantly effective effect, as can be known from the above technical solutions, the selection of ion screening agent, obtain through testing repeatedly, the ion screening agent that adds can generate the macroion complex compound more stable than ammoniacal copper complex ion with the bivalent cupric ion that generates in the course of reaction, in preparation process, considered simultaneously of the influence of pH value to the ion screening agent, by regulating the pH value, the ion screening agent can be brought into play it and shelter activity in its best pH value scope, close ion with respect to silver-colored ammino, new ionic complex in the absorption on copper powder surface has still less increased the contact area of copper powder and silver ion solution, more helps silver at the copper surface deposition, make formation cladded type structure become possibility, thereby improve the antioxygenic property of copper-silver metal powder.The present invention is applied widely, both has been that the low product of silver content also has excellent high temperature oxidation resistance and electric conductivity, the powder size narrowly distributing.
The specific embodiment
Embodiment 1
The micron order copper powder that takes by weighing 3.0g is with 5% dilute sulfuric acid clean surface oxide, and it is clean with deionized water, stannous chloride activated in water solution 3min with 30g/L, use the palladium chloride aqueous solution sensitization 1min of 5g/L then, clean adding 100ml deionized water, add by PEG: PVP=2: 1 dispersant that mixes also makes abundant dispersion with the mulser high-speed stirred; Add rare nitric acid under the normal temperature and regulate pH value to 3.5, add and press ethylenediamine: tren: maleopimaric acid: potassium citrate=1: 1: 1: the 1 ion screening agent 1.0g that mixes, stir; Air is protected in the mist eliminating reactors such as feeding nitrogen argon gas; Take by weighing silver nitrate 1.03g and be mixed with solution, slowly drop to while stirring in the copper powder colloidal sol, fully drip weak aqua ammonia after the reaction again and regulate pH value to 11.0, pickling behind the abundant once more stirring reaction, the washing, alcohol is washed, in drying box, dry under 60 ℃ copper-silver metal powder.The copper content of this copper-silver metal powder is 80%; silver content is 20%; the resistance that powder records with digital micro-OHM meter under the room temperature after compressing tablet is handled is 0.1 Ω, and it still is 0.1 Ω that powder records resistance after through unprotect roasting 50min under 600 ℃ of conditions, and this resistance value is the digital micro-OHM meter internal resistance.
Embodiment 2
The micron order copper powder that takes by weighing 3.0g is with 5% dilute sulfuric acid clean surface oxide, and it is clean with deionized water, stannous chloride activated in water solution 4min with 40g/L, use the palladium chloride aqueous solution sensitization 1.5min of 8g/L then, clean adding 100ml deionized water, add by PEG: PVP=2: 1 dispersant that mixes also makes abundant dispersion with the mulser high-speed stirred; Add rare nitric acid under the normal temperature and regulate pH value to 4.0, add and press isopropyl alcohol: ethyl acetate: amion acetic acid: natrium citricum=1: 1: 1: the 1 ion screening agent that mixes, stir; Air is protected in the feeding nitrogen eliminating reactor; Take by weighing silver nitrate 2.26g and be mixed with solution, slowly drop to while stirring in the copper powder colloidal sol, fully drip weak aqua ammonia after the reaction again and regulate pH value to 9.0, pickling behind the abundant once more stirring reaction, the washing, alcohol is washed, in drying box, dry under 70 ℃ copper-silver metal powder.The copper content of this copper-silver metal powder is 60%; silver content is 40%; the resistance that powder records with digital micro-OHM meter under the room temperature after compressing tablet is handled is 0.1 Ω, and it still is 0.1 Ω that powder records resistance after through unprotect roasting 50min under 600 ℃ of conditions, and this resistance value is the digital micro-OHM meter internal resistance.
Embodiment 3
The micron order copper powder that takes by weighing 3.0g is with 5% dilute sulfuric acid clean surface oxide, and it is clean with deionized water, stannous chloride activated in water solution 5min with 50g/L, use the palladium chloride aqueous solution sensitization 2min of 10g/L then, clean adding 100ml deionized water, add by PEG: PVP=2: 1 dispersant that mixes also makes abundant dispersion with the mulser high-speed stirred; Add rare nitric acid under the normal temperature and regulate pH value to 5.0, add and press dimercaprol dimercaptopropanol: disodium ethylene diamine tetraacetate: the ion screening agent 1.0g of hydrazine hydrate=mixing in 1: 1: 1, stir; Air is protected in the mist eliminating reactors such as feeding nitrogen argon gas; Take by weighing silver nitrate 2.96g and be mixed with solution, slowly drop to while stirring in the copper powder colloidal sol, fully drip weak aqua ammonia after the reaction again and regulate pH value to 10.0, abundant once more stirring reaction after washing, pickling, washing, alcohol is washed, in drying box, dry under 80 ℃ copper-silver metal powder.The copper content of this copper-silver metal powder is 50%; silver content is 50%; the resistance that powder records with digital micro-OHM meter under the room temperature after compressing tablet is handled is 0.1 Ω, and it still is 0.1 Ω that powder records resistance after through unprotect roasting 50min under 600 ℃ of conditions, and this resistance value is the digital micro-OHM meter internal resistance.
Embodiment 4
The ion screening agent is an ethylenediamine: tren: picolinic acid: amylene=1: 1: 1: 1, and all the other are with embodiment 3.The resistance that this copper-silver bimetallic powder records with digital micro-OHM meter under the room temperature after compressing tablet is handled is 0.1 Ω, and it still is 0.1 Ω that powder records resistance after through unprotect roasting 50min under 600 ℃ of conditions, and this resistance value is the digital micro-OHM meter internal resistance.
Embodiment 5
The ion screening agent is a TEPA: Succimer: two hydrogen phenylglycines: potassium citrate=1: 1: 1: 1, and all the other are with embodiment 3.The resistance that this copper-silver bimetallic powder records with digital micro-OHM meter under the room temperature after compressing tablet is handled is 0.1 Ω, and it still is 0.1 Ω that powder records resistance after through unprotect roasting 50min under 600 ℃ of conditions, and this resistance value is the digital micro-OHM meter internal resistance.
Embodiment 6
The ion screening agent is a trichloroacetic acid: Phen: DMPS=1: 1: 1, all the other are with embodiment 3.The resistance that this copper-silver bimetallic powder records with digital micro-OHM meter under the room temperature after compressing tablet is handled is 0.1 Ω, and it still is 0.1 Ω that powder records resistance after through unprotect roasting 50min under 600 ℃ of conditions, and this resistance value is the digital micro-OHM meter internal resistance.
The above, it only is preferred embodiment of the present invention, be not that the present invention is done any pro forma restriction, any technical solution of the present invention content that do not break away from,, all still belong in the scope of technical solution of the present invention any simple modification, equivalent variations and modification that above embodiment did according to technical spirit of the present invention.
Claims (1)
1. the preparation method of a coated copper-silver metal powder, comprise the pre-treatment of copper powder, the preparation of silver solution, the copper-silver metal powder preparation, it is characterized in that: the copper-silver metal powder preparation is copper powder colloidal sol to be dripped rare nitric acid at normal temperatures regulate pH value to 3.0-5.0, add the ion screening agent, consumption is in the 1-30g/L scope, stir, air is protected in feeding nitrogen or the argon gas eliminating reactor, slowly drip liquor argenti nitratis ophthalmicus then while stirring to copper powder colloidal sol, fully drip weak aqua ammonia behind the reaction 30min again and regulate pH value, continue reaction 30min to 7.0-11.0; After finishing, reaction extracts reaction solution with the deionized water washing, 5% dilute sulfuric acid pickling, and ethanolic solution alcohol washes down for several times, and the copper-silver bimetallic powder is dried under 60-80 ℃ of condition and is got product;
Wherein: ion screening agent kind is an ethylenediamine: tren: maleopimaric acid: potassium citrate=1: 1: 1: the 1 ion screening agent that mixes, isopropyl alcohol: ethyl acetate: amion acetic acid: natrium citricum=1: 1: 1: the 1 ion screening agent that mixes, dimercaprol dimercaptopropanol: disodium ethylene diamine tetraacetate: the ion screening agent of hydrazine hydrate=mixing in 1: 1: 1, ethylenediamine: tren: picolinic acid: amylene=1: 1: 1: the 1 ion screening agent that mixes, TEPA: Succimer: two hydrogen phenylglycines: potassium citrate=1: 1: 1: 1 ion screening agent or the trichloroacetic acid that mixes: Phen: the ion screening agent of DMPS=mixing in 1: 1: 1;
Wherein being formulated as of silver-colored solution takes by weighing solid nitric acid silver and is dissolved in the aqueous solution that is configured to 0.05-0.5mol/L in the deionized water.
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102528072B (en) * | 2012-01-20 | 2013-06-19 | 河南科技大学 | Method for preparing leaf-shaped nanometer silver-copper alloy |
| CN102773475B (en) * | 2012-07-31 | 2014-06-11 | 东南大学 | Copper oxide silver composite powder for conductive paste and preparation method thereof |
| CN103578650A (en) * | 2012-08-10 | 2014-02-12 | 贵州省冶金化工研究所 | Method for preparing core-shell type conductive hollow glass beads |
| CN105436499A (en) * | 2015-12-18 | 2016-03-30 | 贵州省冶金化工研究所 | Preparation method of silver-coated copper double-metal powder |
| CN106583712B (en) * | 2016-11-28 | 2018-08-28 | 清华大学 | A kind of preparation method of wicker copper nano particle |
| CN110369712B (en) * | 2019-08-29 | 2021-08-20 | 嘉兴学院 | Preparation method of silver-coated copper powder |
| CN114073955B (en) * | 2020-08-17 | 2023-09-05 | 中国科学院理化技术研究所 | Floating magnetic microsphere catalyst with heterogeneous composite spherical shell structure and preparation method and application thereof |
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