CN100544861C - The preparation method of superfine cupper powder - Google Patents
The preparation method of superfine cupper powder Download PDFInfo
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Abstract
The present invention relates to the preparation method of submicron metal, relate in particular to the preparation method of nano level superfine copper powder.The preparation method of superfine cupper powder provided by the invention comprises: earlier the cupric compound soln using is carried out the reduction reaction first time with 1～2 times the reductant solution that cupric compound is reduced to the required theoretical consumption of monovalence copper compound, make the solution that contains the monovalence copper compound, the soln using that again this is contained the monovalence copper compound carries out the reduction reaction second time with 1～2 times the reductant solution that the monovalence copper compound is reduced to the required theoretical consumption of elemental copper, makes superfine cupper powder.Preparation method according to superfine cupper powder of the present invention, can increase the reaction speed that copper ion is reduced to elemental copper, control the nucleation of copper powder and the speed of growth of nucleus better, thereby obtain stabilized uniform nano level superfine copper powder thinner, narrow diameter distribution.
Description
Technical field
The present invention relates to the preparation method of submicron metal, relate in particular to the preparation method of nano level superfine copper powder.
Background technology
(specific insulation of silver is 1.59 * 10 to superfine cupper powder owing to have the same good electric conductivity with silver
-6Ω cm, the specific insulation of copper are 1.72 * 10
-6Ω cm) and low price (silver price 1/20), can replace noble metals such as super fine silver powder, bronze, be widely used in electricity fields such as electrically-conducting paint, conducting resinl, electrode material, and can be used for fields such as aerospace flight technology, microelectronics, chemistry, biology, medical science.
The preparation method of superfine cupper powder is a lot.Specifically can be divided into physics method and chemical method two big classes.The physics method comprises ball-milling method, gas evaporation method, plasma method etc.; Chemical method comprises electrolysis, microemulsion method, sol-gel process, liquid phase chemical reduction method etc.Liquid phase reduction is low owing to its preparation cost, to less demanding, the reaction of equipment easily advantage such as control be widely adopted.
At present, about adopting liquid phase reduction to prepare the method for superfine cupper powder, its basic technology is as follows: prepare soluble copper salts such as certain density copper sulphate, copper nitrate, copper chloride, add an amount of complexing agent and dispersion stabilizer therein after, select appropriate reductant, make required copper powder.
For example, CN1605419A proposes disclosed the preparation in the method for copper nanoparticle with chemical reduction method in the aqueous solution, in mantoquita, add A, B, four kinds of complexing agents of C, D or dispersant, a kind of reducing agent that utilization is selected from inferior sodium phosphate, sodium borohydride, the formaldehyde carries out reduction reaction, makes copper powder.This method is by selecting additives such as suitable complexing agent and dispersion stabilizer; and ultrasonic field; control copper powder particle aggregation and grow up; make the particle size of the copper powder of preparing to remain on nanoscale; and under inert gas shielding dry copper powder, solve problem of oxidation to the copper powder for preparing.
In addition, CN1082468A discloses a kind of superfine cupper powder and preparation method thereof, described method adopts the reaction system of alcohols solvent, and adopt the mode of two sections intensifications to reduce, but the employed reaction temperature of this method higher (being generally more than 150 ℃), reaction system is band press operation (0.1～1.0MPa), and be the non-aqueous reaction system, thereby preparation cost is higher.
Adopting liquid phase reduction to prepare in the process of superfine cupper powder, the uniform copper powder particle in order to obtain thin, key is the nucleation of control copper powder and the speed of growth of nucleus.If the course difference of growing up from the nucleation to the nucleus can distribute to the particle diameter of copper powder particle and cause considerable influence.The oxide of copper is mainly with CuO and Cu
2The form of O exists.In copper powder production, bivalent cupric ion may need the intermediate state process of experience univalent copper ion to the generation of elemental copper, also may directly generate elemental copper from bivalent cupric ion certainly, and because Cu+Cu
2+→ 2Cu
+The existence of side reaction becomes the otherness of this reaction mechanism mechanism of reaction and can not ignore, thereby the otherness of this reaction mechanism mechanism of reaction also be can not ignore the influence that final copper particle particle diameter distributes.
Therefore, wish to develop and to solve the distribute preparation method of stable and uniform nano level superfine copper powder of problems such as wide and copper oxidation of in the copper powder production process particle aggregation, particle diameter better.
Summary of the invention
Thereby the speed of growth that the purpose of this invention is to provide a kind of nucleation that can control copper powder better and nucleus obtains the preparation method of the stabilized uniform nano level superfine copper powder of thinner and narrow diameter distribution.
The preparation method of superfine cupper powder provided by the invention comprises: earlier the cupric compound soln using is carried out the reduction reaction first time with 1～2 times the reductant solution that cupric compound is reduced to the required theoretical consumption of monovalence copper compound, make the solution that contains the monovalence copper compound, the soln using that again this is contained the monovalence copper compound carries out the reduction reaction second time with 1～2 times the reductant solution that the monovalence copper compound is reduced to the required theoretical consumption of elemental copper, makes superfine cupper powder.
According to superfine cupper powder preparation method of the present invention, owing to make monovalence copper compound solution earlier, this monovalence copper compound solution is reduced make superfine cupper powder then, so can increase the reaction speed that copper ion is reduced to elemental copper, can control the nucleation of copper powder and the speed of growth of nucleus better, thereby obtain stabilized uniform nano level superfine copper powder thinner, narrow diameter distribution.
The specific embodiment
Describe the preparation method of superfine cupper powder of the present invention below in detail.
At first, cupric compound soln using reductant solution is carried out the reduction reaction first time, make the solution that contains the monovalence copper compound.
Wherein, above-mentioned cupric compound can be water-soluble inorganic acid salt or acylate, and for example copper sulphate, copper nitrate, copper chloride and/or copper formate etc. are preferably copper sulphate.The concentration of above-mentioned cupric compound solution can be 0.01～0.5mol/L, is preferably 0.05～0.3mol/L.
The employed reducing agent of the above-mentioned reduction reaction first time can be selected from one or more in formaldehyde, inferior sodium phosphate, ascorbic acid, sodium borohydride, potassium borohydride, hydrazine hydrate, hydrazine, the sodium sulfite, is preferably sodium sulfite.The used reductant solution concentration of the above-mentioned reduction reaction first time can be 0.01～0.5mol/L, is preferably 0.05～0.3mol/L.The use amount of above-mentioned reducing agent is according to the kind decision of the amount of copper ion and reducing agent, is generally cupric compound is reduced to 1～2 times of the required theoretical consumption of monovalence copper compound, is preferably 1.1～1.3 times.
Preferably, also contain complexing agent in the above-mentioned cupric compound solution.Above-mentioned complexing agent is selected from succinimide, maleimide and dimethyl hydantoin, is preferably dimethyl hydantoin.The content of above-mentioned complexing agent is by the decision of the amount of bivalent cupric ion, is generally 1～5 times of molal quantity of bivalent cupric ion, is preferably 3～4 times.Owing to contain complexing agent in the cupric compound solution, make reduction reaction speed even, and the univalent copper ion of generation is combined with complexing agent and stable existence in solution.
Described first time reduction reaction condition preferably, reaction temperature is 30～80 ℃, the reaction time is 10～20 minutes; More preferably reaction temperature is 60～80 ℃, and the reaction time is 12～18 minutes.
Then, the above-mentioned solution that contains the monovalence copper compound is carried out heated constant temperature to be handled, carrying out under the churned mechanically situation with given pace, the required reductant solution of reduction reaction is for the second time added in the above-mentioned solution that contains the monovalence copper compound, carry out the reduction reaction second time, make superfine cupper powder.
Described second time reduction reaction condition preferably, reaction temperature is 30～80 ℃, the reaction time is 10～20 minutes; More preferably reaction temperature is 60～80 ℃, and the reaction time is 12～18 minutes.
The employed reducing agent of the above-mentioned reduction reaction second time can be identical or different with the employed reducing agent of the above-mentioned reduction reaction first time, and can be for being selected from formaldehyde, inferior sodium phosphate, ascorbic acid, sodium borohydride, potassium borohydride, hydrazine hydrate, hydrazine, the sodium sulfite one or more.The used reductant solution concentration of this reduction reaction second time can be 0.01～0.5mol/L, is preferably 0.05～0.3mol/L.The use amount of the used reducing agent of the above-mentioned reduction reaction second time is according to the kind decision of the amount of copper ion and reducing agent, is generally the monovalence copper compound is reduced to 1～2 times of the required theoretical consumption of elemental copper, is preferably 1.1～1.3 times.
In addition, before carrying out above-mentioned second time of reduction reaction, preferably in the above-mentioned solution that contains the monovalence copper compound, add dispersion stabilizer, fully stir, make it to form uniform and stable system.The addition of above-mentioned dispersion stabilizer can be preferably 1～3% for 0.1～5% of copper ion weight in the solution (in the gross weight of the copper raw material that adds).
Above-mentioned dispersion stabilizer is selected from polyvinylpyrrolidone (PVP), polyacrylamide (PAA), polyvinyl alcohol (PVA) and gelatin.Wherein the molecular weight of above-mentioned polyvinylpyrrolidone is preferably 40,000～100,000 scopes, the molecular weight of above-mentioned polyacrylamide is preferably 3,000,000～5,000,000 scopes, the molecular weight of above-mentioned polyvinyl alcohol is preferably 20,000～50,000 scopes, and the molecular weight of gelatin is preferably 100,000～150,000.
Above-mentioned second time, reduction reaction can be carried out under nitrogen or inert gas shielding, perhaps above-mentioned first time reduction reaction and for the second time reduction reaction all can under nitrogen or inert gas shielding, carry out.
In addition, the preparation method of superfine cupper powder of the present invention also comprises: after carrying out above-mentioned second time of reduction reaction, gained solution is carried out centrifugation, then with separating obtained superfine cupper powder respectively with alcohols solvents such as deionized water and ethanol wash and centrifugation after, vacuum drying.Above-mentioned washing, separation are preferably carried out under nitrogen or inert gas shielding.Above-mentioned vacuum drying temperature can be 60～100 ℃, is preferably 70～80 ℃, and can be preferably 1～2 hour drying time for 30 minutes～4 hours.
Preferably, described first time reduction reaction and for the second time reduction reaction under condition of stirring, carry out.
In the present invention, described solution is generally the aqueous solution.
Embodiment
Enumerate specific embodiment below and further describe the present invention, but the present invention is not limited to these embodiment, change without departing from the spirit and scope of the present invention and distortion still belong to protection domain of the present invention.
Embodiment 1
Under agitation, 0.05mol copper chloride, 0.2mol dimethyl hydantoin, 0.03mol sodium sulfite and water (water is added to 1 liter of solution total amount) are fully mixed, under 50 ℃, carry out the reduction reaction 15 minutes first time, make 1 liter the solution that contains the monovalence copper compound.
With the molecular weight of 0.02mol potassium borohydride, 0.2mol potassium hydroxide and 0.2g is polyvinylpyrrolidone (PVP) the Chemical Reagent Co., Ltd., Sinopharm Group system of 50,000～100,000 scopes) being dissolved in the water is mixed with the reductant solution of 200ml; this reductant solution is joined in the above-mentioned solution that contains the monovalence copper compound, carrying out the reduction reaction 20 minutes second time under 50 ℃, under nitrogen protection atmosphere.Centrifugation goes out the copper powder that is generated.
Afterwards, under nitrogen protection, the copper powder that generates is washed with deionized water and absolute ethyl alcohol respectively, after the centrifugation, copper powder 80 ℃ of following vacuum drying 1 hour, is made superfine cupper powder.Ultimate yield is 90%, and purity is 99%, and average grain diameter is 20 nanometers, d10=10nm, d50=18nm, d90=27nm.(wherein, d10 is meant that particle diameter accounts for 10% less than the particle of 10nm, and to be particle diameter account for 50% less than the particle of 18nm to the implication of d50, and to be particle diameter account for 90% less than the particle of 27nm to the implication of d90, and what the three embodied is the distribution situation of particle diameter.)
Embodiment 2
Under agitation, 0.3mol copper sulphate, 1.0mol maleimide, 60 milliliters 36% (volume fraction) formaldehyde and water (water is added to 1 liter of solution total amount) are fully mixed, under 60 ℃, carry out the reduction reaction 10 minutes first time, make 1 liter the solution that contains the monovalence copper compound.
With the molecular weight of 60 milliliters 36% (volume fraction) formaldehyde and 1.0g is polyacrylamide (PAA) the Chemical Reagent Co., Ltd., Sinopharm Group system of 3,000,000～5,000,000 scopes) being dissolved in the water is mixed with the reductant solution of 200ml; this reductant solution is joined in the above-mentioned solution that contains the monovalence copper compound, carrying out the reduction reaction 20 minutes second time under 60 ℃, under argon shield.Centrifugation goes out the copper powder that is generated.
Afterwards, under argon shield, the copper powder that generates is washed with deionized water and absolute ethyl alcohol respectively, after the centrifugation, copper powder at 70 ℃ of following vacuum drying 2h, is made superfine cupper powder.Ultimate yield is 90%, purity is 99%, average grain diameter is 15 nanometers, d10=8nm, d50=13nm, d90=23nm are (wherein, d10 is meant that particle diameter accounts for 10% less than the particle of 8nm, to be particle diameter account for 50% less than the particle of 13nm to the implication of d50, and to be particle diameter account for 90% less than the particle of 23nm to the implication of d90, and what the three embodied is the distribution situation of particle diameter.)。
Embodiment 3
Under agitation, 0.1mol copper formate, 0.4mol maleimide, 0.08mol sodium sulfite and water (water is added to 1 liter of solution total amount) are fully mixed, under 50 ℃, carry out the reduction reaction 15 minutes first time, make 1 liter of monovalence copper compound solution.
The gelatin (Chemical Reagent Co., Ltd., Sinopharm Group's system) of 0.03mol potassium borohydride, 0.3mol potassium hydroxide and 1.2g is dissolved in the water is mixed with the reductant solution of 200ml; this reductant solution is joined in the above-mentioned solution that contains the monovalence copper compound, carrying out the reduction reaction 10 minutes second time under 50 ℃, under nitrogen protection atmosphere.Centrifugation goes out the copper powder that is generated.
Afterwards, under nitrogen protection, the copper powder that generates is washed with deionized water and anhydrous isopropyl alcohol respectively, after the centrifugation, copper powder 90 ℃ of following vacuum drying 40 minutes, is made superfine cupper powder.Ultimate yield is 90%, and purity is 99%, and average grain diameter is 10 nanometers, d10=5nm, d50=8nm, d90=13nm.(wherein, d10 is meant that particle diameter accounts for 10% less than the particle of 5nm, and to be particle diameter account for 50% less than the particle of 8nm to the implication of d50, and to be particle diameter account for 90% less than the particle of 13nm to the implication of d90, and what the three embodied is the distribution situation of particle diameter.)
Embodiment 4
Under agitation, 0.04mol copper nitrate, 0.2mol dimethyl hydantoin, 0.05mol ascorbic acid and water (water is added to 1 liter of solution total amount) are fully mixed, under 60 ℃, carry out the reduction reaction 10 minutes first time, make 1 liter the solution that contains the monovalence copper compound.
With the molecular weight of 0.02mol potassium borohydride, 0.2mol potassium hydroxide and 0.2g is the preferred corporate system of polyvinylpyrrolidone (PVP) traditional Chinese medicines group's chemical reagent of 40,000～60,000 scopes) being dissolved in the water is mixed with the reductant solution of 200ml, this reductant solution is joined in the above-mentioned solution that contains the monovalence copper compound, under 60 ℃, carry out the reduction reaction 10 minutes second time.Centrifugation goes out the copper powder that is generated.
Afterwards, the copper powder that generates is washed with deionized water and absolute ethyl alcohol respectively, after the centrifugation, copper powder 80 ℃ of following vacuum drying 1 hour, is made superfine cupper powder.Ultimate yield is 90%, and purity is 99%, and average grain diameter is 16 nanometers, d10=8nm, d50=12nm, d90=21nm.(wherein, d10 is meant that particle diameter accounts for 10% less than the particle of 8nm, and to be particle diameter account for 50% less than the particle of 12nm to the implication of d50, and to be particle diameter account for 90% less than the particle of 21nm to the implication of d90, and what the three embodied is the distribution situation of particle diameter.)
Comparative Examples 1
Under agitation, with 0.3mol copper sulphate and 1.0mol maleimide and water (water is added to 1 liter of solution total amount) mixing, prepare 1 liter of copper sulphate mixed solution.With the molecular weight of 120 milliliters 36% (volume fraction) formaldehyde and 1.0g is that being dissolved in the water is mixed with the reductant solution of 200ml for the polyacrylamide (PAA) (the preferred corporate system of traditional Chinese medicines group chemical reagent) of 3,000,000～5,000,000 scopes; this reductant solution is joined in the above-mentioned copper sulphate mixed solution, carrying out reduction reaction 30 minutes under 60 ℃, under argon shield atmosphere.
Afterwards, under argon shield, wash with deionized water and absolute ethyl alcohol respectively, after the centrifugation, copper powder at 70 ℃ of following vacuum drying 2h, is made superfine cupper powder generating copper powder.Ultimate yield is 80%, purity is 90%, average grain diameter is 28 nanometers, d10=11nm, d50=25nm, d90=38nm are (wherein, d10 is meant that particle diameter accounts for 10% less than the particle of 11nm, to be particle diameter account for 50% less than the particle of 25nm to the implication of d50, and to be particle diameter account for 90% less than the particle of 38nm to the implication of d90, and what the three embodied is the distribution situation of particle diameter.)。
From the experimental result of embodiment 1 to 4 and Comparative Examples 1 as can be seen, adopt two step reduction method of the present invention, after promptly earlier the cupric compound reduction being made the monovalence copper compound, again this monovalence copper compound solution is reduced, compare with a stage reduction method, can make stabilized uniform nano level superfine copper powder more fine grain, narrow diameter distribution.
Claims (11)
1, a kind of preparation method of superfine cupper powder, it is characterized in that, this method comprises: earlier the cupric compound soln using is carried out the reduction reaction first time with 1～2 times the reductant solution that cupric compound is reduced to the required theoretical consumption of monovalence copper compound, make the solution that contains the monovalence copper compound, the soln using that again this is contained the monovalence copper compound carries out the reduction reaction second time with 1～2 times the reductant solution that the monovalence copper compound is reduced to the required theoretical consumption of elemental copper, makes superfine cupper powder; Described cupric compound is water miscible inorganic acid salt or acylate; Also contain complexing agent in the described cupric compound solution, described complexing agent is selected from succinimide, maleimide and dimethyl hydantoin.
2, the preparation method of superfine cupper powder as claimed in claim 1 is characterized in that, described cupric compound is copper sulphate, copper nitrate, copper chloride and/or copper formate, and the concentration of described cupric compound solution is 0.01～0.5mol/L.
3, the preparation method of superfine cupper powder as claimed in claim 1, it is characterized in that, the employed reducing agent of the described reduction reaction first time is to be selected from formaldehyde, inferior sodium phosphate, ascorbic acid, sodium borohydride, potassium borohydride, hydrazine hydrate, hydrazine, the sodium sulfite one or more, and the concentration of the used reductant solution of the described reduction reaction first time is 0.01～0.5mol/L.
4, the preparation method of superfine cupper powder as claimed in claim 1 is characterized in that, described first time, the condition of reduction reaction was, reaction temperature is 30～80 ℃, and the reaction time is 10～20 minutes; Described second time, the condition of reduction reaction was, reaction temperature is 30～80 ℃, and the reaction time is 10～20 minutes.
5, the preparation method of superfine cupper powder as claimed in claim 1, it is characterized in that, described employed reducing agent of the reduction reaction second time and the employed reducing agent of the described reduction reaction first time are identical or different, and for being selected from formaldehyde, inferior sodium phosphate, ascorbic acid, sodium borohydride, potassium borohydride, hydrazine hydrate, hydrazine, the sodium sulfite one or more, the concentration of the used reductant solution of the described reduction reaction second time is 0.01～0.5mol/L.
6, the preparation method of superfine cupper powder as claimed in claim 1 is characterized in that, the content of described complexing agent is 1～5 times of molal quantity of bivalent cupric ion.
7, the preparation method of superfine cupper powder as claimed in claim 1, it is characterized in that, before carrying out described second time of reduction reaction, in the described solution that contains the monovalence copper compound, add dispersion stabilizer, the addition of described dispersion stabilizer be in the solution copper ion weight 0.1～5%.
8, the preparation method of superfine cupper powder as claimed in claim 7 is characterized in that, described dispersion stabilizer is selected from polyvinylpyrrolidone, polyacrylamide, polyvinyl alcohol and gelatin.
9, the preparation method of superfine cupper powder as claimed in claim 1, it is characterized in that, described preparation method also comprises: after carrying out described second time of reduction reaction, gained solution is carried out centrifugation, after then separating obtained superfine cupper powder being washed also centrifugation with deionized water and alcohols solvent respectively, vacuum drying.
10, as the preparation method of any described superfine cupper powder in the claim 1 to 9; it is characterized in that; described second time, reduction reaction was carried out under nitrogen or inert gas shielding, perhaps described first time reduction reaction and for the second time reduction reaction all under nitrogen or inert gas shielding, carry out.
11, the preparation method of superfine cupper powder as claimed in claim 9 is characterized in that, described washing and being separated under the inert gas shielding is carried out.
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| TWI450778B (en) * | 2010-01-11 | 2014-09-01 | Oriental Happy Entpr Co Ltd | A method of industry-scale for producing sub-micro and nano copper powder |
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|---|---|---|---|---|
| TWI450778B (en) * | 2010-01-11 | 2014-09-01 | Oriental Happy Entpr Co Ltd | A method of industry-scale for producing sub-micro and nano copper powder |
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