CN101474678B - Method for preparing antioxidated superfine copper powder - Google Patents
Method for preparing antioxidated superfine copper powder Download PDFInfo
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- CN101474678B CN101474678B CN 200810162684 CN200810162684A CN101474678B CN 101474678 B CN101474678 B CN 101474678B CN 200810162684 CN200810162684 CN 200810162684 CN 200810162684 A CN200810162684 A CN 200810162684A CN 101474678 B CN101474678 B CN 101474678B
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Abstract
A preparation method of anti-oxidation superfine copper powder belongs to the powder technical field. The process flow of the method is as follows: taking soluble divalent cupric salt as a starting material for making cupric salt solution, adding and evenly mixing a dispersant and a trace additive, then adding NaOH solution to the cupric salt solution with the NaOH/Cu<2+> mol ratio being 2 to cause the Cu<2+> to precipitate as Cu(OH)2, adding a hydrazine hydrate as a reducing agent to obtained jelly with the N2H4/Cu mol ratio being 1.5-2.5 and obtaining pure copper powder by two-stage heat preserving reaction: (1) a first stage: preserving at the temperature of 30-50 DEG C, and converting the Cu(OH)2 into Cu2O after reaction; and (2) a second stage: adjusting pH value of the solution withNaOH to 11-13, heating suspending liquid obtained from the first stage to 60-70 DEG C, keeping the temperature until the reaction is finished to obtain the pure copper powder, and then cleaning and drying the copper powder by centrifugal separation. The raw materials used in the method are cheap and available, and the superfine copper powder with the average particle size below 0.5 micron prepared by the method does not need any anti-oxidation treatment, does not discolor after being kept in the air for more than one year, has anti-oxidation temperature of more than 100 DEG C proved by thermogravimetric analysis and is especially suitable for being used as an electronic material.
Description
Technical field
The present invention relates to a kind of technical field, relate in particular to a kind of preparation method of antioxidant ultrafine copper powder about the powder preparation.
Background technology
Superfine cupper powder is as a kind of functional material, has broad application prospects in fields such as powder metallurgy, electric slurry, lubricated, catalysis.Especially when the conductive filler, lower and do not have material " migration " problem of silver powder because of its price, have very big potential value in fields such as electromagnetic shielding, electric slurries.The copper powder that uses as conductive filler not only will have very high purity, and its granularity, shape, the non-oxidizability (weatherability) when normal temperature is preserved waits also is the important evidence of its quality of evaluation.As the copper powder that uses of the conducting resinl that is used for the ceramic capacitor outer electrode, require to have 0.5 μ m following and comparatively uniform grain sizes distribute.On the other hand, copper powder is easily oxidation in air, and the more little this tendency of particle diameter is just serious more, has greatly influenced performance, has limited its range of application.Therefore, prepare superfine cupper powder and become the direction that the scientific worker makes great efforts with high antioxygenic property.
The preparation method of copper powder has a lot, as physical evaporation-condensation method, mechanical crushing method, atomization, electrolysis, liquid phase reduction etc.Physical evaporation-condensation method is by forming the copper particle with the metallic vapour condensation of copper in inert gas filled vacuum chamber, this method can be prepared the sphericity height, antioxygenic property is better and the very tiny copper powder of granularity, but the particle size distribution range of powder is bigger, and used equipment is very expensive, the production cost height causes powder price also higher.Mechanical crushing method be adopt equipment such as high energy ball mill with the blister copper powder through long ball mill grinding, make short grained copper powder.The copper powder size distribution of this method preparation is very inhomogeneous, and it is comparatively serious to reunite, and the cycle is long, and is difficult to avoid the pollution of impurity.Atomization is with inert gas the metallic copper of liquid state to be atomized into the droplet and the method for solidify out into powder rapidly, and the copper powder of this method preparation is spherical in shape, but granularity is usually at micron order.Electrolysis is the industrial method for preparing copper powder commonly used, acquisition be the higher skeleton of purity, granularity is usually at tens microns.Liquid phase reduction is meant by selecting appropriate reductant, the compound reduction of copper is become the method for pure copper powder in solution.The copper powder particle of this method preparation is tiny, and is easy to control its distribution, and raw materials used cheap and easy to get, equipment is simple, is the main method for preparing superfine cupper powder at present.Through years of researches, developed multiple reducing agent system, wherein Chang Yong reducing agent has formaldehyde, ascorbic acid, hydrazine hydrate etc.It is that reducing agent, copper sulphate are the research that the copper source prepares superfine cupper powder that people such as Liu Zhijie, Zhao Bin has carried out with the ascorbic acid, has obtained the powder of granularity 0.5～7 μ m.Afterwards, the technology that hydrazine hydrate is made reducing agent is studied again, prepare and have the superfine cupper powder that different-grain diameter distributes, and tested the aerial stability of powder, show that the following copper powder of 0.5 μ m can be oxidized to cuprous oxide gradually in air, have only when its granularity reaches could existence stable in the air more than the 0.5 μ m.Chinese patent CN101011747A is cuprous with electrolytic oxidation to be initial former grain, hydrazine hydrate is a reducing agent, in the solution that has added as stannous chloride, react, obtain the superfine cupper powder of particle mean size 0.2～1 μ m, and improve the weatherability of gained copper powder by the tin that adds trace.This method reaction is very slow, and every batch of manufacturing cycle is longer, and is initiation material with cuprous oxide, and cost is also higher.It is initiation material that patent CN1872459A has announced with the cupric oxide, carry out the method that solvent thermal reaction prepares copper powder in submicro in autoclave.Owing to need to consume a large amount of ethanol (solvent) in the course of reaction, reaction simultaneously must be carried out under high temperature, high pressure again, need special device, so this method industrial applications difficulty is bigger.
In general, although it is a lot of to adopt liquid phase reduction to prepare the report of superfine cupper powder at present, but these methods or have the difficult control of copper powder granularity, gained copper powder antioxygenic property is poor, the antioxidant ultrafine copper powder in field such as electronic material be can not obtain being applicable to, need do special anti-oxidant treatment, or preparation process special solvent or device needed, cause cost higher, therefore be necessary at new ultra-fine, the anti-oxidant copper powder production method of these problem exploitations.
Summary of the invention
The objective of the invention is to avoid prior art defective and by the technology of improving liquid phase reduction prepare a kind of particle diameter below 0.5 μ m, be evenly distributed and in air, have the superfine cupper powder of good antioxygenic property.
Purpose of the present invention is achieved through the following technical solutions.
A kind of preparation method of antioxidant ultrafine copper powder is characterized in that this method comprises the following steps:
(1), prepare copper salt solution and NaOH solution respectively:
(a) get mantoquita and be equipped with deionized water, make Cu
2+Concentration be 0.02mol/L～0.2mol/L;
(b) get NaOH and be equipped with deionized water, by weight percentage 20～30% preparations;
(2), in above-mentioned copper salt solution, add dispersant and trace mineral supplement and mix abundant dissolving, wherein the adding percentage by weight of dispersant is 0.1g/L～1g/L, the adding percentage by weight of additive is 10mg/L～50mg/L;
(3), press NaOH: Cu
2+=2 mol ratio slowly adds NaOH solution in the above-mentioned copper salt solution, and with the 300r/min vigorous stirring, makes Cu
2+Be precipitated as the Cu (OH) of sky-blue
2Jelly;
(4), in above-mentioned precipitation, N in molar ratio
2H
4: the ratio of Cu=1.5～2.5 slowly adds hydrazine hydrate and makes reducing agent, continues to stir;
(5), divide two stage insulation reaction to obtain pure copper powder then;
(a) suspension of generation all changes into orange red 30 ℃～50 ℃ insulations the phase I, Cu (OH)
2Be converted into Cu
2O, insulation finishes;
(b) second stage with pH to 11～13 of 10～20%NaOH adjusting suspension, is warming up to 60 ℃～70 ℃ earlier, continues insulation reaction, and the bubble in orange red suspension all is converted into colourless i.e. reaction to be finished, and obtains the fine copper powder;
(6), the powder of above-mentioned generation is collected in the centrifugation mode earlier, be neutral with washed with de-ionized water to pH then, clean 2 times with absolute ethyl alcohol again, in air, obtain the superfine cupper powder of particle diameter below 0.5 μ m after dry 6～12 hours below 60 ℃.
Described mantoquita is copper sulphate or copper nitrate.
Described dispersant is neopelex or polyvinylpyrrolidone PVP or polyethylene glycol PEG.
Described additive is 2,2 '-bipyridyl.
Compared with prior art, the present invention is initiation material with the cupric salt, the hydrazine hydrate of disposable adding capacity is made reducing agent, divide two stage insulation reaction to obtain superfine cupper powder, in preparation process, adopt trace 2 first, 2 '-bipyridyl is as additive, the pattern and the size distribution of copper powder have been improved greatly, greatly improved the aerial antioxygenic property of copper powder, below the copper powder average grain diameter 0.5 μ m of acquisition, outward appearance is bright coppery, need not any anti-oxidation processing, can preserve nondiscolouring more than 1 year in air, (TGA) shows by thermogravimetric analysis, and powder is basic non-oxidation below 100 ℃ in air.The used cost of material of the present invention is low, and course of reaction does not need high temperature, condition of high voltage or maintenances such as vacuum, inert atmosphere, so to the no specific (special) requirements of device, greatly reduce the cost of powder preparation, and be suitable for suitability for industrialized production.
Description of drawings
Fig. 1 is preparation technology's flow chart of antioxidant ultrafine copper powder.
Fig. 2 is embodiment 1 a superfine cupper powder SEM shape appearance figure.
Fig. 3 is the XRD figure spectrum of embodiment 1 superfine cupper powder.
Fig. 4 is the thermogravimetric analysis curve map of embodiment 1 superfine cupper powder.
The specific embodiment
Preparation technology's flow process that the present invention prepares the antioxidant ultrafine copper powder is described below in conjunction with concrete technology with embodiment as shown in Figure 1 below:
Embodiment 1
Compound concentration is the copper-bath 100ml of 0.02mol/L respectively, 20% NaOH solution 8ml.At CuSO
4Add neopelex in the solution, fully dissolving makes its concentration reach 0.1g/L.Add 2 then, 2 '-bipyridyl, making its concentration is 10mg/L.Under the vigorous stirring of 300r/min, NaOH solution is slowly added CuSO
4In the solution, make Cu
2+Be precipitated as Cu azury (OH)
2Jelly.The hydrazine hydrate that slowly adds 0.003mol then, reaction is acutely carried out, and generates a large amount of bubbles, and precipitation changes orange suspension into.Insulation reaction in two stages afterwards.Phase I is warming up to 30 ℃ with above-mentioned suspension, continues to stir insulation, becomes orange red until the precipitation color.Carry out the second stage reaction then, elder generation makes it remain on 11～12 with 20% NaOH adjustment suspension pH, is warming up to 65 ℃ of insulations, and it is that second stage finishes that the bubble that generates in orange red suspension becomes colourless.The powder that generates is collected in the mode of centrifugation, with washed with de-ionized water to neutral, and then with absolute ethyl alcohol dehydration 2 times, with powder 50 ℃ of dry 8h down in air.
According to the pattern of embodiment 1 gained powder as shown in Figure 2, as can be seen, the powder crystallization densification, good dispersion is not reunited substantially between particle, and average grain diameter is below 0.5 μ m, and the particle diameter narrow distribution.Fig. 3 is the X diffracting spectrum of placing in this powder air after 6 months, as can be seen, the characteristic peak that wherein has only elemental copper, there is not the oxide of copper to exist, the thermogravimetric analysis result that powder is done under air atmosphere as shown in Figure 4, as can be seen, basic not weightening finish demonstrates good antioxygenic property below 100 ℃.
Embodiment 2
Compound concentration is the copper-bath 100ml of 0.1mol/L respectively, 20% NaOH solution 40ml.At CuSO
4Add neopelex in the solution, fully dissolving makes its concentration reach 0.5g/L.Add 2 then, 2 '-bipyridyl, making its concentration is 30mg/L.Under the vigorous stirring of 300r/min, NaOH solution is slowly added CuSO
4In the solution, make Cu
2+Be precipitated as Cu (OH)
2Jelly.The hydrazine hydrate that slowly adds 0.02mol then, reaction is acutely carried out, and generates a large amount of bubbles, and precipitation changes orange suspension into.Insulation reaction in two stages afterwards.Phase I is warming up to 40 ℃ with above-mentioned suspension, continues to stir insulation, becomes orange red until the precipitation color.Carry out the second stage reaction then, elder generation makes it remain on 12～13 with 20% NaOH adjustment suspension pH, is warming up to 60 ℃ of insulations, and it is that second stage finishes that the bubble that generates in orange red suspension becomes colourless.The powder that generates is collected in the mode of centrifugation, with washed with de-ionized water to neutral, and then with absolute ethyl alcohol dehydration 2 times, with powder 60 ℃ of dry 6h down in air.
Show that through detections such as SEM, thermogravimetric analysis also having the following uniform grain sizes of 0.5 μ m distributes according to embodiment 2 gained powder, antioxygenic property is good in the air.
Embodiment 3
Compound concentration is the copper-bath 100ml of 0.2mol/L respectively, 20% NaOH solution 80ml.At CuSO
4Add PVP in the solution, fully dissolving makes its concentration reach 1.0g/L.Add 2 then, 2 '-bipyridyl, making its concentration is 50mg/L.Under the vigorous stirring of 300r/min, NaOH solution is slowly added CuSO
4In the solution, make Cu
2+Be precipitated as Cu (OH)
2Jelly.The hydrazine hydrate that slowly adds 0.05mol then, reaction is acutely carried out, and generates a large amount of bubbles, and precipitation changes orange suspension into.Insulation reaction in two stages afterwards.Phase I is warming up to 30 ℃ with above-mentioned suspension, continues to stir insulation, becomes orange red until the precipitation color.Carry out the second stage reaction then, elder generation makes it remain on 11～12 with 20% NaOH adjustment suspension pH, is warming up to 70 ℃ of insulations, and it is that second stage finishes that the bubble that generates in orange red suspension becomes colourless.The powder that generates is collected in the mode of centrifugation, with washed with de-ionized water to neutral, and then with absolute ethyl alcohol dehydration 2 times, with powder 45 ℃ of dry 8h down in air.
Show that through detections such as SEM, thermogravimetric analysis also having the following uniform grain sizes of 0.5 μ m distributes according to embodiment 3 gained powder, antioxygenic property is good in the air.
Claims (3)
1. the preparation method of an antioxidant ultrafine copper powder is characterized in that this method comprises the following steps:
(1), prepare copper salt solution and NaOH solution respectively:
(a) get mantoquita and be equipped with deionized water, make Cu
2+Concentration be 0.02mol/L～0.2mol/L;
(b) get NaOH and be equipped with deionized water, by weight percentage 20～30% preparations;
(2), in above-mentioned copper salt solution, add dispersant and trace mineral supplement 2,2 '-bipyridyl also mixes abundant dissolving, wherein the adding percentage by weight of dispersant is 0.1g/L～1g/L, the adding percentage by weight of additive is 10mg/L～50mg/L;
(3), press NaOH: Cu
2+=2 mol ratio slowly adds NaOH solution in the above-mentioned copper salt solution, and with the 300r/min vigorous stirring, makes Cu
2+Be precipitated as the Cu (OH) of sky-blue
2Jelly;
(4), in above-mentioned precipitation, N in molar ratio
2H
4: the ratio of Cu=1.5～2.5 slowly adds hydrazine hydrate and makes reducing agent, continues to stir;
(5), divide two stage insulation reaction to obtain pure copper powder then;
(a) suspension of generation all changes into orange red 30 ℃～50 ℃ insulations the phase I, Cu (OH)
2Be converted into Cu
2O, insulation finishes;
(b) second stage with pH to 11～13 of 10～20%NaOH adjusting suspension, is warming up to 60 ℃～70 ℃ earlier, continues insulation reaction, and the bubble in orange red suspension all is converted into colourless i.e. reaction to be finished, and obtains the fine copper powder;
(6), the powder of above-mentioned generation is collected in the centrifugation mode earlier, be neutral with washed with de-ionized water to pH then, clean 2 times with absolute ethyl alcohol again, in air, obtain the superfine cupper powder of particle diameter below 0.5 μ m after dry 6～12 hours below 60 ℃.
2. the preparation method of a kind of antioxidant ultrafine copper powder according to claim 1 is characterized in that described mantoquita is copper sulphate or copper nitrate.
3. the preparation method of a kind of antioxidant ultrafine copper powder according to claim 1 is characterized in that described dispersant is neopelex or polyvinylpyrrolidone PVP or polyethylene glycol PEG.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9975110B1 (en) | 2016-11-23 | 2018-05-22 | Honda Motor Co., Ltd. | Method for producing metal catalyst nanoparticles |
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| CN103480855A (en) * | 2013-05-28 | 2014-01-01 | 昆明物语科技有限公司 | Preparation method of superfine copper powder for copper paste |
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| CN114749677B (en) * | 2022-04-26 | 2023-04-11 | 苏州星翰新材料科技有限公司 | Preparation method and application of micron copper powder |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9975110B1 (en) | 2016-11-23 | 2018-05-22 | Honda Motor Co., Ltd. | Method for producing metal catalyst nanoparticles |
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