CN1817522A - Polyhedral crystalline copper powder and production thereof - Google Patents
Polyhedral crystalline copper powder and production thereof Download PDFInfo
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- CN1817522A CN1817522A CN 200510120662 CN200510120662A CN1817522A CN 1817522 A CN1817522 A CN 1817522A CN 200510120662 CN200510120662 CN 200510120662 CN 200510120662 A CN200510120662 A CN 200510120662A CN 1817522 A CN1817522 A CN 1817522A
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Abstract
A polygonal crystalline copper powder with high dispersity and diameter uniformity (1-5 microns) is prepared through preparing the solution of Cu salt and the solution of reducer, adding disperser and ammonia water to both solutions, mixing, reacting, separating, washing and drying.
Description
Technical field:
The present invention relates to a kind of materials of electronic components, the preparation method of micron copper powder particularly, specifically be meet the requirement of copper base electrocondution slurry have crystal copper powder rule crystallization profile, that favorable dispersibility, particle size distribution are narrow and preparation method thereof.
Technical background:
Copper base electrocondution slurry extensively is used in ceramic electron element and for example forms outer electrode on chip capacitor, the chip resistor, and be used in the pottery and plastic substrate on form printed circuit.As the copper powder of slurry main component, characteristic properties such as its grain shape, particle size distribution, non-oxidizability play a crucial role to the electric conductivity of stock quality and electrode.Compare with spheric granules, owing to have big crystal surface, polyhedron-shaped crystalline copper particle has higher oxidation resistance, on the other hand, owing to be more prone to face-face contact between particle, contact-making surface is bigger compared with spheric granules, can guarantee that particle has higher filling rate, thereby guarantees the low-resistivity of slurry.High-quality copper base electrocondution slurry often needs to have the polyhedron-shaped copper powder of big crystal surface as conducting filler.
The method for preparing copper powder has multiple, wherein current comparatively advanced be liquid phase reduction.Liquid phase reduction can be regulated and control size, Size Distribution and the shape of powder flexibly by changing preparation condition, in grain shape control remarkable advantages is arranged especially.Liquid phase reduction prepares copper powder, and reducing agent commonly used comprises hydrazine and derivative thereof, NaBH
4, hypophosphite and ascorbic acid etc.
Because NaBH
4Strong reducing power, have to the ball shaped copper particles of nano-scale usually.Adopt hypophosphite to prepare copper powder, resulting copper powder is of a size of nanometer or sub-micron, is shaped as sphere.
Hydrazine and derivative thereof are a kind of reducing agents the most frequently used in the actual production.It is cheap and easy to get, but its reducing power is very strong, makes the micron-size spherical particles that nucleation and growth control difficulty in the course of reaction, products therefrom mostly are nanoscale or the spherical granule of submicron order or are reunited and formed by granule.By strictness control process conditions, can prepare polyhedron-shaped crystalline particle.For example U.S. Pat 6875252B2 proposition is a raw material with copper sulphate, prepares cuprous oxide under nitrogen protection, adopts hydrazine hydrate reduction cuprous oxide to prepare metallic copper particle then.Have regular polyhedron shape and the uniform copper powder of size though this method can be prepared, manufacturing cycle is long, complex process, and the condition tolerance is poor.The patent application of application number CN200310112029.0, disclosing with cuprous oxide is that precursor, hydrazine hydrate are that reducing agent, long chain cation surfactant are dispersant, has prepared the method with good polyhedron-shaped copper powder in glycol system.But this method has been used comparatively expensive dispersant and solvent, has increased the preparation cost of copper powder.In addition, adopting hydrazine is that another big shortcoming of reducing agent is hydrazine toxicity is very big, does not meet environmental requirement.
Ascorbic acid is a kind of reducing agent of moderate strength, and this makes more or less freely to the control of course of reaction.And, itself with and oxidation product all be nontoxic.Adopt ascorbic acid to prepare copper powder some researchs and report are arranged.For example, in clear 63-186803 of Japan Patent and the clear 63-186804 reported method, adopt the aqueous solution of L-ascorbic acid to reduce copper sulphate and ammoniacal copper complex ion solution respectively, obtaining average grain diameter is the copper powder of 0.8～1.8 μ m, narrow particle size distribution; The flat 5-271721 of patent is a reacting precursor with ammoniacal copper complex ion solution, and the aqueous solution short time of L-ascorbic acid pours into and obtains the copper powder that average grain diameter is the homogeneous of 1～2 μ m; The flat 9-165606 of patent is reducing agent reduction cuprammonium solion with the solid ascorbic acid, prepares size at 2～20 copper powders μ m, narrow diameter distribution.But in the said method, adopt aqueous ascorbic acid only to be applicable to the copper powder of preparation 1～2 μ m, and do not have open technical scheme the shape control of copper powder own.
Summary of the invention:
The objective of the invention is to overcome the shortcoming of above-mentioned prior art, propose a kind of easy, environmental friendliness, based on liquid reactive polyhedron copper powder production method;
That another purpose of the present invention is to provide is narrow at 1～5 mu m range, particle size distribution by the average grain diameter of method for preparing, favorable dispersibility, have the copper powder rule crystallization profile, that reflecting feel is good.
Purpose of the present invention is achieved through the following technical solutions:
A kind of liquid phase preparation process of polyhedral crystalline copper powder: when preparing copper salt solution and reductant solution respectively, dispersant or ammoniacal liquor (ammoniacal liquor substitute) are joined in described copper salt solution or the reductant solution, again two kinds of solution are mixed, keep the temperature conditions reaction 15 minutes～1.0 hours of room temperature-80 ℃, the gained product is made polyhedral crystalline copper powder through separation, washing and drying; Described mantoquita comprises copper chloride, stannous chloride, copper bromide, cuprous bromide, and the concentration of copper salt solution is 0.1～1.0mol/L (calculating by mixing the back volume); Described dispersant is gum arabic or gelatin, and the addition of dispersant is 10～40% of a mantoquita weight; The addition of ammoniacal liquor or its substitute is that ammonia/copper ratio is 1.4～2.0: 1 (mol ratio); Described reductant solution is the aqueous solution of ascorbic acid-NaOH, ascorbic acid-ammoniacal liquor or sodium ascorbate-NaOH, the mol ratio of its ascorbic acid or sodium ascorbate and start material is 1.0～1.2: 1, and the consumption of NaOH or ammoniacal liquor is 1.0～1.5 of ascorbic acid or a sodium ascorbate molal quantity.
Also comprise buffer in the described reductant solution, buffer is acetic acid or sodium acetate, and acetate ion concentration is 0.25～1.0mol/L (calculating by mixing the back volume).Adopt acetic acid acid, sodium acetate as buffer, can make the pH value of solution value keep a constant relatively scope.The dimensional homogeneity that adds the resulting copper powder of buffer afterreaction is than not adding good under the buffer situation.
The concentration of ammoniacal liquor is preferably 25～28%.Described separation, washing and drying means are to react the gains centrifugation, and with washing with ethanol again behind the deionized water cyclic washing, vacuum drying under 60 ℃ of conditions at last.
By the polyhedral crystalline copper powder of method for preparing, have polyhedron-shapedly, average grain diameter is 1～5 μ m, does not reunite between the polyhedron particle.
In said method, the concentration of mantoquita is 0.1～1.0mol/L.Under the same conditions, mantoquita concentration is big more, and then the average-size of the metallic particles of reaction generation is big more.In this concentration range, can prepare the copper powder that average grain diameter is 1～5 μ m.
In said method, ammoniacal liquor and mantoquita molar ratio are 1.4～2.0: 1.If the ammoniacal liquor that adds is excessive, particularly when ammonia/copper ratio greater than 2 (mol ratios), particle size sharply reduces, the copper powder shape is by the polyhedron-shaped class sphere that becomes of big crystal face, copper powder darker in color, gloss difference, easily oxidation.
In said method, if reducing agent/mantoquita (mol ratio) less than 1, then the copper ion reduction is incomplete, and the yield of copper powder is low; If the reducing agent consumption is excessive, then increase the preparation cost of copper powder.
In above-mentioned course of reaction, reaction temperature is controlled at room temperature～80 ℃.With the increase of temperature, reaction speed is accelerated.Reaction time of the present invention is in 15min～1h.Owing to added ammoniacal liquor in the system, too high temperature will make and the volatilization aggravation of ammoniacal liquor be unfavorable for the control of ammoniacal liquor/mantoquita concentration ratio.
The inventive method can prepare average grain diameter can be in 1～5 mu m range flexibly modulation, narrow diameter distribution, favorable dispersibility have a polyhedron-shaped crystal copper powder of particle diameter.Preparation process is simple, easy operating and repetition, and reaction time is short, the inexpensive easy acquisition of reaction raw materials, raw material and product are nontoxic to environment.
Description of drawings
Fig. 1 ESEM (SEM) photo of the copper powder of the inventive method (embodiment 1) preparation
Fig. 2 ESEM (SEM) photo of the copper powder of the inventive method (embodiment 2) preparation
Specific implementation method
The invention will be further described below in conjunction with drawings and Examples, but the scope of protection of present invention is not limited to the scope that embodiment represents.
Embodiment 1:
Ascorbic acid 9.60g, NaOH 2.75g, sodium acetate 12.50g and gum arabic 1.0g are dissolved in the 50ml deionized water, behind the stirring 30min solution are increased to 60 ℃ under the room temperature, add the ammoniacal liquor 10ml of 25-28% then.Copper dichloride dihydrate 8.50g is dissolved in the 30ml deionized water, solution temperature is increased to 60 ℃ equally.Copper chloride solution is added in the mixed solution that contains ascorbic acid that stirs fast reaction 30min.With the copper powder precipitation and centrifugal separation that generates, and spend deionised water three times, ethanol is washed secondary, last 60 ℃ of vacuum drying.Dried copper powder presents bright-coloured pink, and metallic luster is strong.
As shown in Figure 1, with the pattern of the prepared copper powder of scanning electron microscopic observation, find that copper powder is polyhedron-shaped, crystal edge is obvious on the individual particle, and crystal face is big and smooth smooth; Good dispersion between particle does not have and reunites; Particle size distribution range is 2.0～4.0 μ m, and wherein most of particle size concentrates on 2.5～3.5 μ m, and average grain diameter is 3.0 μ m.
Embodiment 2:
With the consumption of dispersant gum arabic change 1.5g into, sodium hydroxide concentration changes 3.0g into, all the other conditions are with embodiment 1.The prepared copper powder that goes out is polyhedron-shaped, and crystal plane is obvious on the individual particle; Good dispersion between particle does not have and reunites; Particle size distribution range is 1.4～3.0 μ m, and wherein most of particle size concentrates on 2.1～2.6 μ m, and average grain diameter is 2.3 μ m.
Embodiment 3:
Ascorbic acid 19.2g, NaOH 5.5g, sodium acetate 12.50g and gum arabic 2.5g are dissolved in the 50ml deionized water, behind the stirring 30min solution are increased to 40 ℃ under the room temperature, add the ammoniacal liquor 20ml of 25-28% then.Copper dichloride dihydrate 17.0g is dissolved in the 30ml deionized water, solution temperature is increased to 40 ℃ equally.Copper chloride solution is added in the ascorbic acid solution that stirs fast reaction 30min.Prepared copper powder is a polyhedral shape, and particle size distribution range is 3.5～5.0 μ m
Embodiment 4:
Copper dichloride dihydrate 8.5g and gum arabic 1.0g are dissolved in the 30ml deionized water, be warming up to 50 ℃ after at room temperature stirring 20min, add 25～28% ammoniacal liquor 9.0ml (addition of ammoniacal liquor is that copper/ammonia ratio is 1.4: 1 (mol)), obtain a blue solution A.Ascorbic acid 9.6g, NaOH 3.0g, sodium acetate 6.2g at room temperature are dissolved in the 50ml deionized water, get solution B.B solution is added in the A solution fast, in 50 ℃ of stirring reaction 30min.Prepared copper powder is a polyhedral shape; Good dispersion between particle does not have and reunites; Particle size distribution range is 1.4～4.4 μ m, and average grain diameter is 3.5 μ m.
Embodiment 5:
Ascorbic acid 4.8g, NaOH 1.5g, sodium acetate 3.2g and gum arabic 1.0g (addition of dispersant gum arabic be stannous chloride quality 40%) are dissolved in the 80ml deionized water, after stirring 30min under the room temperature solution is increased to 60 ℃, adds the ammoniacal liquor 5.0ml of 25-28% then.Stannous chloride solid 2.5g is added in the above-mentioned solution, at 60 ℃ of stirring reaction 60min.The copper powder of gained is polyhedron-shaped, and particle size distribution range is 1.0～2.5 μ m.
Embodiment 6:
Ascorbic acid 9.6g, NaOH 2.2g (addition of NaOH be ascorbic acid molal quantity 1.0), gelatin 1.0g are dissolved in the 50ml deionized water, and heating makes system be warming up to 65 ℃, adds 25～28% ammoniacal liquor 5ml, obtains solution A.Copper dichloride dihydrate 8.50g is dissolved in the 30ml deionized water, gets solution B.The B drips of solution is added among the A stirring reaction.Drip the mixed liquor of 4ml ammoniacal liquor and 7ml deionized water behind the 30min again, continue stirring reaction 30min.At last, with the copper powder centrifugation that generates, with deionized water and ethanol washing several, vacuum drying again.Prepared copper powder is polyhedron-shaped, does not have between particle and reunites, and particle diameter is distributed as 3.2～5.0 μ m, average grain diameter 4.3 μ m.
Embodiment 7:
Dispersant gelatin 1.0g is added in the 50ml deionized water, make it to dissolve fully, add ascorbic acid 9.6g, acetate 7.0ml then, NaOH 8.0g and 25～28% ammoniacal liquor 12ml in 50 ℃ of stirrings.Copper bromide 11.0g is dissolved in the 30ml deionized water.The copper bromide aqueous solution is added in the ascorbic acid solution reaction 1.0hr.Prepared copper powder is shaped as polyhedron, and particle diameter is distributed as 1.0～3.0 μ m.
Embodiment 8
Dispersant gelatin 1.0g is added in the 50ml deionized water, make it to dissolve fully in 50 ℃ of stirrings, add ascorbic acid 9.6g, acetate 7.0ml then, NaOH 8.0g and carbonic hydroammonium 7.9g (addition of carbonic hydroammonium is 2.0 times of copper bromide molal quantity).Copper bromide 11.0g is dissolved in the 30ml deionized water.The copper bromide aqueous solution is added in the ascorbic acid solution reaction 1.0hr.Prepared copper powder is shaped as polyhedron, and particle diameter is distributed as 1.0～3.0 μ m.
Claims (6)
1, a kind of liquid phase preparation process of polyhedral crystalline copper powder, it is characterized in that, when preparing copper salt solution and reductant solution respectively, join dispersant and ammoniacal liquor (ammoniacal liquor substitute) in described copper salt solution or the reductant solution together or respectively, again two kinds of solution of gained are mixed, keep the temperature conditions reaction 15 minutes～1.0 hours of room temperature-80 ℃, the gained product is made polyhedral crystalline copper powder through separation, washing and drying; Described mantoquita comprises copper chloride, stannous chloride, copper bromide, cuprous bromide, and the concentration of copper salt solution is 0.1～1.0mol/L (calculating by mixing the back volume); Described dispersant is gum arabic or gelatin, and the addition of dispersant is 10～40% of a mantoquita weight; The addition of ammoniacal liquor or its substitute is that ammonia/copper ratio is 1.4～2.0: 1 (mol ratio); Described reductant solution is the aqueous solution of ascorbic acid-NaOH, ascorbic acid-ammoniacal liquor or sodium ascorbate-NaOH, the mol ratio of its ascorbic acid or sodium ascorbate and start material is 1.0～1.2: 1, and the consumption of NaOH or ammoniacal liquor is 1.0～1.5 of ascorbic acid or a sodium ascorbate molal quantity.
2, according to the liquid phase preparation process of the described polyhedral crystalline copper powder of claim 1, it is characterized in that, also comprise buffer in the described reductant solution, buffer is acetic acid or sodium acetate, and acetate ion concentration is 0.25～1.0mol/L (calculating by mixing the back volume).
3, according to the liquid phase preparation process of the thin copper powder of the described polyhedron of claim 1, the concentration that it is characterized in that described ammoniacal liquor is 25～28%.
4, according to the liquid phase preparation process of the thin copper powder of the described polyhedron of claim 1, it is characterized in that, described separation, washing and drying means are to react the gains centrifugation, and with washing with ethanol again behind the deionized water cyclic washing, vacuum drying under 60 ℃ of conditions at last.
5, the polyhedral crystalline copper powder for preparing by each described method of claim 1～4.
6, polyhedral crystalline copper powder according to claim 5 is characterized in that, described polyhedral crystalline copper powder has polyhedron-shaped, and average grain diameter is 1～5 μ m, does not reunite between the polyhedron particle.
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| CN102601380A (en) * | 2011-12-21 | 2012-07-25 | 中国科学院过程工程研究所 | Cubic copper powder and method for preparing same |
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| CN102389949A (en) * | 2011-03-11 | 2012-03-28 | 中国科学院福建物质结构研究所 | Method for preparing sea urchin-shaped nanometer copper particles |
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| CN102601380A (en) * | 2011-12-21 | 2012-07-25 | 中国科学院过程工程研究所 | Cubic copper powder and method for preparing same |
| CN102601380B (en) * | 2011-12-21 | 2015-05-20 | 中国科学院过程工程研究所 | Cubic copper powder and method for preparing same |
| CN102672198A (en) * | 2012-06-01 | 2012-09-19 | 河南师范大学 | Method for preparing single copper with porous micro/nano hierarchical structure |
| CN106513696B (en) * | 2015-09-09 | 2019-08-02 | 广州千顺工业材料有限公司 | Micro-nano copper powder and preparation method thereof |
| CN106513696A (en) * | 2015-09-09 | 2017-03-22 | 广州千顺工业材料有限公司 | Micro-nano copper powder and preparation method thereof |
| CN106981324A (en) * | 2017-04-26 | 2017-07-25 | 上海安缔诺科技有限公司 | A kind of copper electrocondution slurry and its production and use |
| CN106981324B (en) * | 2017-04-26 | 2019-01-29 | 上海安缔诺科技有限公司 | A kind of copper electrocondution slurry and its preparation method and application |
| CN107008896A (en) * | 2017-06-16 | 2017-08-04 | 福州大学 | A kind of copper particle with multi-angular structure and preparation method thereof |
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| CN114927258A (en) * | 2022-06-08 | 2022-08-19 | 嘉兴学院 | Environment-friendly antioxidant conductive copper paste and preparation method and application thereof |
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