CN102773494A - Method for preparing silver-coated copper powder through radiation reduction - Google Patents
Method for preparing silver-coated copper powder through radiation reduction Download PDFInfo
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- CN102773494A CN102773494A CN2011101237063A CN201110123706A CN102773494A CN 102773494 A CN102773494 A CN 102773494A CN 2011101237063 A CN2011101237063 A CN 2011101237063A CN 201110123706 A CN201110123706 A CN 201110123706A CN 102773494 A CN102773494 A CN 102773494A
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Abstract
The invention provides a method for preparing silver-coated copper powder through radiation reduction, comprising the following steps of (1) preparing the copper powder: adding ammonia water into copper sulphate solution, dripping a reducing agent solution into the copper sulphate solution, reacting at 70-80 DEG C, and washing obtained copper powder by using dilute sulphuric acid and deionized water so as to obtain clean copper powder; (2) preparing the silver-coated copper powder through the radiation reduction: adding the clean copper powder into the deionized water which contains a dispersing agent, after adding silver ammonia solution and an active particle catcher and feeding an inert gas, placing the mixture in a radiation source to perform a radiation reduction reaction in a stirring state, wherein the irradiation dose rate is 0.8-6.0 kGy/h, and the absorbed dose is 10-30 kGy; and finally washing a reaction product by using the deionized water to obtain the silver-coated copper powder with a grain size of 0.5 mum-6.5 mum. The plating layer of the silver-coated copper powder prepared by the method is compact without hole corrosion, the conductive performance is good, the process is simple, the production cost is low, and the method is in favour of the development of electronic industry.
Description
Technical field
The present invention relates to utilize nuclear radiation tech to prepare the technical field of metal powder material, that concrete is a kind of preparation method through radiation reduction preparation silver-plated copper powder.
Background technology
The fast development of electronics industry makes it to being that the demand of electric slurry of major function phase is more and more with silver powder.But silver is that slurry not only costs an arm and a leg, and silver ion can produce ELECTROMIGRATION PHENOMENON under wet heat condition and cause coating resistance to raise, and electric conductivity descends; Therefore, in order to reduce cost and to keep the silver powder good electrical conductivity, people are studying with the substitute products of silver-plated copper powder as silver powder.Chinese patent document (publication number CN 1425738) discloses " a kind of stannous chloride that utilizes is the repeatedly silver-plated method of sensitizer " preparation silver-coated copper powder; Needs were repeatedly silver-plated when the method prepared silver-plated copper powder; Reduced silver-plated efficient; And the silver-plated copper powder of the method preparation need pass through high-temperature heat treatment and just can make smooth surface closely knit, increased silver powder bonding possibility when heat treatment.Chinese patent document (publication number CN 1704502A) discloses " a kind of is the method that complexing agent prepares silver-plated copper powder with ammoniacal liquor ", adds chelating agent and Cu in this method
2+Effect stops the absorption of cuprammonium complex ion on the copper powder surface, thereby guarantees the generation of displacement reaction between copper and the silver ion.But this arts demand is with the surface of a large amount of organic reagent cleaning powders, and therefore, its industrial applications has certain degree of difficulty.Chinese patent document (publication number CN 101244459A) discloses a kind of modifying function that utilizes rare earth metal, improves the method for the catalytic activity on copper powder surface; Chinese patent document (publication number CN 1403233A) discloses a kind of copper powder of handling through dispersant, the silver-coating method in the liquor argenti nitratis ophthalmicus of adding organic amine compound complexing, the silver-plated copper powder that can obtain having high electrical conductivity; Chinese patent document (publication number CN 101294281A) discloses silver-plated method in a kind of acid Ag-containing solution of polynary complexing agent complexing, can obtain silver-plated copper powder for low-temperature slurry; It is the method that complexing agent prepares flake silver-plated copper powder with strong basicity salt such as sodium potassium tartrate tetrahydrate, natrium citricum, potassium rhodanide etc. that Chinese patent document (publication number CN 101032750A) discloses a kind of; This complex technical process, and the potassium rhodanide of one of its complexing agent is a toxicant.Relevant introduction also has: " East China University of Science's journal " (2002,28 (4): 402): under the effect of macromolecule dispersant PVP and PVA, prepare the copper silver metal powder of different-shape with the method for copper powder displacement silver nitrate." material protection " (2006,39 (9): 28): adopt chemical reduction method at micron order copper powder electroplate, improved its antioxygenic property, can form continuous silver layer basically.
To sum up, at present the silver-plated copper powder technology of preparing of report is the method that displacement method or displacement method combine with chemical reduction method.Because the generation of displacement reaction causes copper ion to be diffused into the solution through silver coating from the copper powder surface, making in the prepared silver-plated copper powder that silver layer is loose has a hole, easy oxidation under the high temperature, and its combination property has been compared big gap with the fine silver powder.
Summary of the invention
The objective of the invention is to overcome the weak point of prior art, provide a kind of and prepare the method for silver-plated copper powder through radiation reduction, it have silver coating dense non-porous hole, technology simply, advantage that production cost is lower.
For realizing above-mentioned purpose, the technical scheme that the present invention takes is:
A kind ofly prepare the method for silver-plated copper powder, it is characterized in that its processing step comprises through radiation reduction:
(1) preparation of copper powder
At first, in the mixed aqueous solution of sulfur acid copper (10～250 g/L) and dispersant (2-100 g/L), add ammoniacal liquor, the addition of ammoniacal liquor is suitable for system just in time is dissolved as; Then, (50～120 g/L) is added drop-wise in the copper-bath that has added ammoniacal liquor with the reducing agent aqueous solution, under 70～80 ℃ of conditions, reacts 0.5～5 hour; The copper powder of gained is repeatedly cleaned with dilute sulfuric acid and deionized water, obtain clean copper powder;
(2) through radiation reduction preparation silver-plated copper powder
The copper powder that step (1) is obtained joins in the deionized water that contains dispersant; Under stirring, add silver ammino solution and active particle agent for capturing; Feed inert gas and deoxygenation; Place radiation source then, under stirring, carry out the radiation reduction reaction: radiation dose rate is 0.8～6.0 kGy/h, and absorbed dose of radiation is 10～30kGy;
At last, use washed with de-ionized water, obtain the silver-plated copper powder of surface compact, its particle diameter is 0.5 μ m～6.5 μ m.
The described reducing agent of step (1) is a kind of in hydrazine hydrate, formaldehyde, ascorbic acid or the glucose.
The material of step (2) form by weight being: 5～30 parts of copper powders, 0.5～5 part of dispersant, 5～70 parts of silver, 100～500 parts of deionized waters.
The described dispersant of step (2) is a kind of in polyvinylpyrrolidone (PVP), gelatin, the polyvinyl alcohol (PVA).
The described active ion agent for capturing of step (2) is a kind of in isopropyl alcohol, n-butanol or the isoamyl alcohol.
The described radiation source of step (2) be cobalt-60 (
60Co).
The present invention is to utilize the gamma-ray irradiation reduction that radioactive substance produces to form silver coating compared with prior art, though have the generation of replacement ag plating at the initial stage of reaction; But because the inhibition of cuprammonium complex ion, making the radiation reduction silver-plated is main silver-plated mode, therefore; In silver-plated process, do not need the displacement between copper ion and silver ion, so just reduced the hole that stays when copper ion is come in and gone out silver layer; So the silver coating that obtains is comparatively fine and close, good in oxidation resistance; In addition, technology is fairly simple, production cost is lower, and the development of electronics industry is had bigger facilitation.
The specific embodiment
Provide below that the present invention is a kind of prepare the specific embodiment of the method for silver-plated copper powder, introduction through radiation reduction
3Individual embodiment.But be noted that enforcement of the present invention is not limited to following embodiment.
Embodiment 10.5 the preparation of μ m silver-plated copper powder
Prepare silver-plated copper powder by described preparation method, the steps include:
(1) at first, copper sulphate 125g, polyvinylpyrrolidone (PVP) 50g, NaOH 50g are joined in the 1.5L water and dissolve, place 70 ℃ of water-baths; Then, the aqueous solution (240g/L) 0.5L that will contain glucose slowly is added drop-wise in the copper sulfate solution, reacts half an hour under 70 ℃ of conditions, in system, adds the 0.lL hydrazine hydrate then, continues to react half an hour; Reaction finishes the back with dilute sulfuric acid and washed with de-ionized water, obtains clean copper powder;
(2) getting copper powder 20g that step (1) obtains places 100g to contain the deionized water of polyethylene of dispersing agent pyrrolidones (PVP) 10 g/L, dispersed with stirring; Add silver ammino solution (20 g/L) 0.5L, add active particle agent for capturing (account for weight of solvent mark 0.5%), logical nitrogen 5 minutes is put into Co-60 source irradiation then, and radiation dose rate and irradiation absorbed dose of radiation are respectively 1.0 kGy/h and 3 kGy; Reaction is repeatedly cleaned with deionized water after accomplishing, and obtains the silver-plated copper powder of 0.5 μ m, and wherein silver content is 50%.
Embodiment 22.0 the preparation of μ m silver-plated copper powder
Prepare silver-plated copper powder by described preparation method, the steps include:
(1) at first, copper sulphate 125g and polyvinylpyrrolidone (PVP) 20g joined in the 0.5L water dissolve, add 0.15L ammoniacal liquor, place 70 ℃ of water-baths; Then, the aqueous solution (220 g/L) 0.5L that will contain ascorbic acid slowly is added drop-wise in the aqueous solution of copper sulphate, and reaction is 3 hours under 70 ℃ of conditions, and reaction finishes the back with dilute sulfuric acid and washed with de-ionized water, obtains clean copper powder;
(2) getting copper powder 20g part that step (1) obtains places 100g to contain the deionized water of polyethylene of dispersing agent pyrrolidones (PVP) 10 g/L, dispersed with stirring; Add silver ammino solution (20 g/L) 0.4L, add active particle agent for capturing (account for weight of solvent mark 0.5%), logical nitrogen 5 minutes is put into Co-60 source irradiation then, and radiation dose rate and irradiation absorbed dose of radiation are respectively 1.0 kGy/h and 3 kGy; Reaction is repeatedly cleaned with deionized water after accomplishing, and obtains the silver-plated copper powder of 2.0 μ m, and wherein silver content is 40%.
Embodiment 36.5 the preparation of μ m silver-plated copper powder
Prepare silver-plated copper powder by described preparation method, the steps include:
(1) at first, copper sulphate 300g and polyvinylpyrrolidone (PVP) 20g joined in the 1.0L water dissolve, add 0.45L ammoniacal liquor, place 70 ℃ of water-baths; Then, the aqueous solution (300 g/L) 1.0L that will contain ascorbic acid is added dropwise in the aqueous solution of copper sulphate, and reaction is 5 hours under 70 ℃ of conditions, and reaction finishes the back with dilute sulfuric acid and washed with de-ionized water, obtains clean copper powder;
(2) getting copper powder 30g part that step (1) obtains places 100g to contain the deionized water of polyethylene of dispersing agent pyrrolidones (PVP) 20 g/L, dispersed with stirring; Add silver ammino solution (20 g/L) 0.3L, add active particle agent for capturing (account for weight of solvent mark 0.5%), logical nitrogen 5 minutes is put into Co-60 source irradiation then, and radiation dose rate and irradiation absorbed dose of radiation are respectively 1.0 kGy/h and 3 kGy; Reaction is repeatedly cleaned with deionized water after accomplishing, and obtains the silver-plated copper powder of 6.5 μ m, and wherein silver content is 30%.
Claims (6)
1. one kind prepares the method for silver-plated copper powder through radiation reduction, it is characterized in that its processing step comprises:
(1) preparation of copper powder
At first, in the mixed aqueous solution of sulfur acid copper 10～250 g/L and dispersant 2-100 g/L, add ammoniacal liquor, the addition of ammoniacal liquor is suitable for system just in time is dissolved as; Then, the reducing agent aqueous solution 50～120 g/L are added drop-wise in the copper-bath that has added ammoniacal liquor, under 70～80 ℃ of conditions, reacted 0.5～5 hour; The copper powder of gained is repeatedly cleaned with dilute sulfuric acid and deionized water, obtain clean copper powder;
(2) through radiation reduction preparation silver-plated copper powder
The copper powder that step (1) is obtained joins in the deionized water that contains dispersant; Under stirring, add silver ammino solution and active particle agent for capturing; Feed inert gas and deoxygenation; Place radiation source then, under stirring, carry out the radiation reduction reaction: radiation dose rate is 0.8～6.0 kGy/h, and absorbed dose of radiation is 10～30kGy;
At last, use washed with de-ionized water, obtain the silver-plated copper powder of surface compact, its particle diameter is 0.5 μ m～6.5 μ m.
2. according to claim 1ly a kind ofly prepare the method for silver-plated copper powder through radiation reduction, it is characterized in that, the described reducing agent of step (1) is a kind of in hydrazine hydrate, formaldehyde, ascorbic acid or the glucose.
3. according to claim 1ly a kind ofly prepare the method for silver-plated copper powder, it is characterized in that through radiation reduction, the material of step (2) form by weight being: 5～30 parts of copper powders, 0.5～5 part of dispersant, silver-colored 5～70 parts, 100～500 parts of deionized waters.
4. according to claim 1ly a kind ofly prepare the method for silver-plated copper powder through radiation reduction, it is characterized in that, the described dispersant of step (2) is a kind of in polyvinylpyrrolidone, gelatin, the polyvinyl alcohol.
5. according to claim 1ly a kind ofly prepare the method for silver-plated copper powder through radiation reduction, it is characterized in that, the described active ion agent for capturing of step (2) is a kind of in isopropyl alcohol, n-butanol or the isoamyl alcohol.
6. according to claim 1ly a kind ofly prepare the method for silver-plated copper powder, it is characterized in that the described radiation source of step (2) is a cobalt-60 through radiation reduction.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103752842A (en) * | 2013-11-11 | 2014-04-30 | 南京工业大学 | Substitution and chemistry deposition compound preparation method for nano silver coated copper powder |
| CN103894603A (en) * | 2014-04-11 | 2014-07-02 | 上海理凯材料科技有限公司 | Method for preparing tinned copper through chemical reduction |
| CN105127449A (en) * | 2015-10-20 | 2015-12-09 | 陈键 | Method for preparing copper powder with silver-plated surface |
| CN105364082A (en) * | 2014-08-18 | 2016-03-02 | 上海理凯材料科技有限公司 | Method for preparing silver powder through radiation reduction |
| CN113814396A (en) * | 2021-10-18 | 2021-12-21 | 苏州卡睿杰新材料科技有限公司 | Submicron silver-plated copper powder for heterojunction solar cell low-temperature slurry and preparation method thereof |
| CN115319088A (en) * | 2022-08-17 | 2022-11-11 | 中国科学院兰州化学物理研究所 | Preparation method of silver-coated copper crystal grains or copper powder |
| CN115728443A (en) * | 2023-01-10 | 2023-03-03 | 长春黄金研究院有限公司 | Method for measuring cyanide ions in complex water |
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| CN101612670A (en) * | 2009-07-13 | 2009-12-30 | 浙江省技术物理应用研究所 | A kind ofly in the aqueous solution, use 60The Co-gamma-rays prepares the method for nano-silver powder |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103752842A (en) * | 2013-11-11 | 2014-04-30 | 南京工业大学 | Substitution and chemistry deposition compound preparation method for nano silver coated copper powder |
| CN103894603A (en) * | 2014-04-11 | 2014-07-02 | 上海理凯材料科技有限公司 | Method for preparing tinned copper through chemical reduction |
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| CN105364082A (en) * | 2014-08-18 | 2016-03-02 | 上海理凯材料科技有限公司 | Method for preparing silver powder through radiation reduction |
| CN105364082B (en) * | 2014-08-18 | 2018-01-19 | 上海理凯材料科技有限公司 | The method that radiation reduction prepares silver powder |
| CN105127449A (en) * | 2015-10-20 | 2015-12-09 | 陈键 | Method for preparing copper powder with silver-plated surface |
| CN113814396A (en) * | 2021-10-18 | 2021-12-21 | 苏州卡睿杰新材料科技有限公司 | Submicron silver-plated copper powder for heterojunction solar cell low-temperature slurry and preparation method thereof |
| CN115319088A (en) * | 2022-08-17 | 2022-11-11 | 中国科学院兰州化学物理研究所 | Preparation method of silver-coated copper crystal grains or copper powder |
| CN115728443A (en) * | 2023-01-10 | 2023-03-03 | 长春黄金研究院有限公司 | Method for measuring cyanide ions in complex water |
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Application publication date: 20121114 |