CN103894603B - The method of zinc-plated copper powder is prepared in electronation - Google Patents
The method of zinc-plated copper powder is prepared in electronation Download PDFInfo
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- CN103894603B CN103894603B CN201410145959.4A CN201410145959A CN103894603B CN 103894603 B CN103894603 B CN 103894603B CN 201410145959 A CN201410145959 A CN 201410145959A CN 103894603 B CN103894603 B CN 103894603B
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Abstract
The invention discloses a kind of method that zinc-plated copper powder is prepared in electronation, it is characterized in that, comprise the steps: to utilize the pink salt that can ionize out very low concentrations tin ion or stannous ion in water, be chemically reduced agent and be reduced into tin simple substance and deposition is coated on Copper Powder Surface, obtain the described zinc-plated copper powder of nucleocapsid structure.The present invention forms tin coating by the method for electronation.Do not add complexing agent thiocarbamide in system, in reaction, do not have the generation of immersion tin.Therefore, in zinc-plated process, there is not the displacement between copper ion and tin ion, the hole stayed when also just decreasing copper ion discrepancy tin layers, so the tin coating obtained is comparatively fine and close.Its application has larger impetus by the development of electronic device and product.
Description
Technical field
The present invention relates to a kind of preparation method of zinc-plated copper powder, particularly a kind of electronation and prepare the method for zinc-plated copper powder.
Background technology
Copper powder, due to the performance of its excellence and cheap price, is widely used in the fields such as electronic information, lubrication, catalysis and powder metallurgy.But it is very easily oxidized in atmosphere, and granularity is thinner, is oxidized more serious.In order to improve the antioxygenic property of copper powder, can at Copper Powder Surface clad metal tin.Under normal temperature, tin is very stable in atmosphere, the oxidation film of Surface Creation one deck densification, stops the continuation oxidation of tin, therefore zinc-plated at Copper Powder Surface, can improve the oxidisability of copper powder to a certain extent.The stability of zinc-plated copper powder, electric conductivity, wearability, corrosion resistance and electromagnetic wave shielding are all fine, have good application prospect.
Document [Chinese Journal of Inorganic Chemistry, 2004,20(9): 1055] under the extraordinary complexant thiocarbamide and polyvinylpyrrolidone existent condition of copper, with the surface clad tin of displacement method at copper nanoparticle, prepared Nanometer Copper-bimetallic ruthenium/tin powder, its non-oxidizability is better than the copper nanoparticle of corresponding size.Product can be used as lube oil additive and antiseptic.Document [electronic component and material, 2008,27(10): 58] is complexing agent with thiocarbamide, and inferior sodium phosphate is reducing agent, has prepared zinc-plated copper powder by replacing the method combined with reducing process.Document [plating and finish, 2006,28(5): 8] adopt sodium hypophosphite to make reducing agent, zinc-plated in flake copper surface chemistry, obtain the zinc-plated copper powder of sheet.Coating quality can be obtained by Controlling Technology parameter good, and there is the sheet tin coated copper powder product of fine electric conductivity and low-apparent-density.Document [plating and finish, 2002,24(5): 20] have studied a kind of novel methane base sulfonic acid chemical tin plating process.With methyl sulfonic acid tin for main salt, thiocarbamide, allylthiourea etc. are promoter, and sodium hypophosphite, hydrazine hydrate etc. are reducing agent, can in Copper base material chemical plating stannum.Document [Wuhan University of Technology's journal, 2010,32(19): 19] using thiocarbamide as current potential adjusting agent, using Loprazolam tin for the acid solution of main salt is as plating solution, adopt immersion plating in Copper base material, prepared tin coating.
In sum, the zinc-plated copper powder technology of preparing of report is displacement method or replaces the method combined with chemical reduction method at present.Due to the generation of displacement reaction, cause copper ion needs to be diffused into solution from Copper Powder Surface through tin coating, to make in prepared zinc-plated copper powder that tin coating is loose hole, compactness is poor.
Summary of the invention
The object of this invention is to provide a kind of method that zinc-plated copper powder is prepared in electronation, to overcome the defect that prior art exists.
Method of the present invention, comprises the steps:
Utilize and can ionize out the pink salt of very low concentrations tin ion or stannous ion in water, be chemically reduced agent and be reduced into tin simple substance and deposition is coated on Copper Powder Surface, obtain the described zinc-plated copper powder of nucleocapsid structure.
Concrete comprises the steps:
(1) pink salt is added in the dispersion of copper powder, then add sodium borohydride and NaOH, at N
2lower 50 DEG C ~ 80 DEG C reactions of condition 5 ~ 48 hours, then collect the elementary body of zinc-plated copper powder from product;
The dispersion of described copper powder is the product of Salzburg vitriol, water, ammoniacal liquor, reducing agent and dispersant;
(2) the elementary body of zinc-plated copper powder step (1) obtained, is placed in high boiling medium, is heated 230 DEG C ~ 260 DEG C under an inert atmosphere, keeps 0.5 ~ 1 hour, from reaction system, then collects described zinc-plated copper powder;
Described high boiling medium is selected from triethanolamine or glycerine etc.;
The dispersion of described copper powder is preparation like this:
By Salzburg vitriol, water, ammoniacal liquor, reducing agent and dispersant, 70-80 DEG C is reacted 1 ~ 3 hour, obtains the dispersion of copper powder;
The weight of water is 2 ~ 20 times of Salzburg vitriol;
The weight of ammoniacal liquor is 1 ~ 4 times of Salzburg vitriol, and ammonia concn is 25 ~ 28%;
The weight of reducing agent is 0.4 ~ 1 times of Salzburg vitriol;
The weight of dispersant is 8% ~ 30% times of Salzburg vitriol;
Described reducing agent be selected from weight concentration be 80% hydrazine hydrate solution, ascorbic acid or weight concentration be the formalin etc. of 37%;
Described dispersant is selected from polyvinylpyrrolidone, gelatin, polyvinyl alcohol or polyethylene glycol etc.;
In zinc-plated copper powder prepared by the present invention, Theil indices is 1%-70%, and be preferably 10%, particle diameter is 0.1 μm-6.5 μm, is preferably 0.5 ~ 2 μm, and tin layers is fine and close, good in oxidation resistance.
The present invention compared with prior art, is form tin coating by the method for electronation.Do not add complexing agent thiocarbamide in system, in reaction, do not have the generation of immersion tin.Therefore, in zinc-plated process, there is not the displacement between copper ion and tin ion, the hole stayed when also just decreasing copper ion discrepancy tin layers, so the tin coating obtained is comparatively fine and close.Its application has larger impetus by the development of electronic device and product.
Detailed description of the invention
Embodiment 1
The preparation of 1 μm of zinc-plated copper powder:
By Salzburg vitriol 125g, concentration be 28% ammoniacal liquor 300g, gelatin 25g join in 0.5L water and dissolve, be placed in 70 DEG C of water-baths.By concentration be 37% formalin 100g join in the aqueous solution of copper sulphate, 70 DEG C reaction 2 hours.
In above-mentioned copper powder system, add stannous hydroxide (47g), NaOH (2g) and sodium borohydride (10g), 80 DEG C are reacted 10 hours.Repeatedly wash down by deionized water after having reacted, obtain the elementary body of zinc-plated copper powder.
Product is put into glycerine and be heated 240 DEG C under an inert atmosphere, be incubated after 1 hour and take out separation, drying, the zinc-plated copper powder described in acquisition; Zinc-plated copper powder size is 1 μm, and the weight content of tin is 10%.
Embodiment 2
The preparation of 0.5 μm of zinc-plated copper powder:
By copper sulphate 125g, concentration be 28% ammoniacal liquor 300g and polyethylene glycol 10g join in 0.5L water and dissolve, be placed in 70 DEG C of water-baths.Join in the aqueous solution of copper sulphate by the hydrazine hydrate aqueous solution 50g of concentration 80%, 70 DEG C are reacted 2 hours;
In above-mentioned system, directly add stannic hydroxide (37g) and sodium borohydride (8g) and 2g NaOH, 70 DEG C are reacted 24 hours, repeatedly wash down by deionized water after having reacted, obtain the elementary body of zinc-plated copper powder, product is put into glycerine and be heated 240 DEG C under an inert atmosphere, be incubated after 1 hour and take out separation, drying, zinc-plated copper powder described in acquisition, particle diameter is 0.5 μm, and wherein the weight content of tin is 10%.
Embodiment 3
The preparation of 2.0 μm of zinc-plated copper powders
Copper sulphate 125g, polyvinyl alcohol 10g are joined in 0.5L water and dissolves, add the ammoniacal liquor that 150g weight concentration is 25%, be placed in 70 DEG C of water-baths.Being dissolved in by ascorbic acid 110g after in 200g water joins in the aqueous solution of copper sulphate, and 70 DEG C are reacted 3 hours;
In above-mentioned system, directly add stannic hydroxide (28g) and sodium borohydride (6g), NaOH 2g, 60 DEG C are reacted 24 hours.Repeatedly wash down by deionized water after having reacted, obtain the elementary body of zinc-plated copper powder, product is put into triethanolamine and be heated 240 DEG C under an inert atmosphere, be incubated after 0.5 hour and take out separation, drying, zinc-plated copper powder described in acquisition, particle diameter is 2.0 μm, and wherein Theil indices is 10%.
Claims (3)
1. the method for zinc-plated copper powder is prepared in electronation, it is characterized in that, comprises the steps:
(1) pink salt is joined in the dispersion of copper powder, then add sodium borohydride and NaOH, at N
2react under condition, from product, then collect the elementary body of zinc-plated copper powder;
(2) the elementary body of zinc-plated copper powder step (1) obtained, is placed in triethanolamine or glycerine, is heated maintenance temperature under an inert atmosphere, from reaction system, then collect described zinc-plated copper powder;
In step (1), the weight of pink salt is 0.05-0.6 times of Salzburg vitriol weight;
The weight of sodium borohydride is 0.1-0.5 times of pink salt weight;
The weight of NaOH is 0.01-0.1 times of pink salt weight;
The dispersion of copper powder is preparation like this:
By Salzburg vitriol, water, ammoniacal liquor, reducing agent and dispersant, 70-80 DEG C is reacted 1 ~ 3 hour, obtains the dispersion of copper powder;
The weight of water is 2 ~ 20 times of Salzburg vitriol;
The weight of ammoniacal liquor is 1 ~ 4 times of Salzburg vitriol, and ammonia concn is 25 ~ 28%;
The weight of reducing agent is 0.4 ~ 1 times of Salzburg vitriol;
The weight of dispersant is 8% ~ 30% times of Salzburg vitriol;
Described reducing agent is selected from ascorbic acid, weight concentration be 80% hydrazine hydrate solution or weight concentration be the formalin of 37%;
Described dispersant is selected from polyvinylpyrrolidone, gelatin, polyvinyl alcohol or polyethylene glycol;
Described pink salt is selected from stannous hydroxide, sodium stannite, stannic hydroxide or sodium stannate.
2. method according to claim 1, is characterized in that, in step (1), is added by pink salt in the dispersion of copper powder, then adds sodium borohydride and NaOH, at N
2lower 50 DEG C ~ 80 ° DEG C reactions of condition 5 ~ 48 hours.
3. method according to claim 1, is characterized in that, in step (2), is heated 230 DEG C ~ 260 DEG C under an inert atmosphere, keeps 0.5 ~ 1 hour.
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| CN104439282A (en) * | 2014-12-15 | 2015-03-25 | 湖南师范大学 | Needle-shaped nanometer Cu-Sn-B alloy and preparation method |
| JP6587099B2 (en) * | 2015-12-15 | 2019-10-09 | 三菱マテリアル株式会社 | Solder powder, method for producing the same, and method for preparing solder paste using the powder |
| CN109261959B (en) * | 2018-11-22 | 2020-02-07 | 昆明理工大学 | Tin-added intermediate layer silver-coated copper powder with high oxidation resistance and high binding force and preparation method thereof |
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| CN102773494A (en) * | 2011-05-13 | 2012-11-14 | 华东理工大学 | Method for preparing silver-coated copper powder through radiation reduction |
| CN103441243A (en) * | 2013-07-04 | 2013-12-11 | 天津大学 | Preparation method and application of hollow tin alloy nanoparticles with a particle size of less than 50 nm |
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| JP3640555B2 (en) * | 1998-11-30 | 2005-04-20 | 株式会社巴川製紙所 | COMPOSITE PARTICLE FOR CONDUCTIVE LAYER USED FOR POWDER COATING AND PROCESS FOR PRODUCING THE SAME |
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| 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 |
| CN103441243A (en) * | 2013-07-04 | 2013-12-11 | 天津大学 | Preparation method and application of hollow tin alloy nanoparticles with a particle size of less than 50 nm |
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| "化学还原法制备超细铜粉的研究进展";杜多林等;《金属矿山》;20070730(第7期);第13-17页 * |
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