CN1605419A - Method for preparing nanometer copper powder by chemical reduction in water solution - Google Patents
Method for preparing nanometer copper powder by chemical reduction in water solution Download PDFInfo
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- CN1605419A CN1605419A CN 200410009842 CN200410009842A CN1605419A CN 1605419 A CN1605419 A CN 1605419A CN 200410009842 CN200410009842 CN 200410009842 CN 200410009842 A CN200410009842 A CN 200410009842A CN 1605419 A CN1605419 A CN 1605419A
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Abstract
The present invention is chemical reduction process of preparing nanometer copper powder in water solution, and relates to electrochemical process for preparing powdered material. The preparation process adopts the proper combination of main salt, reductant and additives, the main salt is copper sulfate or copper chloride, the reductant is sodium hypophosphorate, sodium borohydride and formaldehyde, and the additives include silver nitrate or palladium chloride, gelatin or SDBS, potassium sodium tartrate or triethanolamine and sodium hydroxide or potassium hydroxide. During the preparation, outer ultrasonic field is applied. The preparation process is simple and high in preparation speed, and has no coagulation of copper powder to ensure the medium powder size smaller than 100 nm for ideal use effect of the nanometer copper powder.
Description
Technical field
The present invention relates to use the electrochemical production powder body material, particularly relate to the preparation of copper powder.
Background technology
Because having many uses of copper powder, the research of its preparation method receives very big concern both domestic and external.Chemical method is the elementary particle by the chemical reaction product matter of material---molecule, atom and ion etc., becomes superfines through nucleating growth and coalescence, and it is a kind of effective way for preparing copper powder.
According to " Materials Science and Engineering journal " 2003, Vol.21, Nol, the method for introducing among the p57-59 for preparing copper powder adopts KBH
4Make reducing agent, prepared the copper powder of grain diameter, but the size of copper powder is very inhomogeneous at 50～500nm, can not guarantee that its median particle diameter is below 100nm, therefore, this powder is not the nano-powder of determining under the meaning, and its result of use also can be different with nano-powder.
Again according to " mechanical engineering material " 1998, Vol.22, No3, the p33-37 reported method adopts CuCl
2Be main salt, KBH
4Be reducing agent, the preparation copper powder, but the particle diameter of its copper powder of preparing is to be inferred by the specific area of copper powder, and the image reunion of copper powder under transmission electron microscope, can't determine its shape and diameter.This shows that method described in the literary composition be can not determine the copper powder of preparation at nanoscale, promptly median particle diameter is less than 100nm.
According to another " East China University of Science's journal " 1997, Vol.23, No3, the p372-376 reported method adopts CuSO
4Be main salt, hydrazine hydrate is that reducing agent is prepared the copper powder that median particle diameter is 591nm.Adopt the glucose prereduction method to prepare the copper powder that median particle diameter is 891nm.Because the copper powder particle particle diameter of these method preparations is big, its effect must be affected.
In a word, chemical reduction method can adopt multi-form raw material and reaction condition to make copper powder.But that the subject matter that exists is prepared copper powder particle size is big, out-of-shape, be easy to reunite etc.Therefore limited the result of use of copper powder.So, seek a suitable chemical reaction, select corresponding reaction mass, make that preparation equipment is simple relatively, reaction condition is gentle.Select effective dispersant, reducing the reunion of copper powder particle, the nucleation of control copper powder and the speed of growth of nucleus, adding appropriate catalyst simultaneously all is to adopt chemical reduction method to prepare the key of superfine cupper powder to increase chemical reaction velocity etc.
Summary of the invention
The present invention is directed to chemical reduction method and prepare the problem that copper nanoparticle exists, proposition is in the aqueous solution, adopt chemical reduction method, main salt, reducing agent, additive are carried out appropriate combination, add physical field simultaneously and prepare copper nanoparticle, make the preparation method not only easy, and when obtaining higher preparation speed, avoid the reunion of copper powder and grow up, less than 100nm, make copper nanoparticle in use bring into play desirable effect with the median particle diameter of the particle of the copper nanoparticle that guarantees preparation.
Implementation process of the present invention is as follows: following main salt, reducing agent, additive A, additive B, addition of C, additive D are made up, and wherein main salt is any in copper sulphate, the copper chloride, and content is 20～50g/L.Reducing agent is a kind of in inferior sodium phosphate, potassium borohydride, the formaldehyde, and content is 10～300g/L.Additive is chosen any one kind of them from A, B, each class of C, D.Additive A is silver nitrate, palladium bichloride, and content is 1～10mg/L; Additive B is gelatin, neopelex, and content is 10～50g/L; Addition of C is sodium potassium tartrate tetrahydrate, triethanolamine, and content is 10～50g/L; Additive D is potassium hydroxide, NaOH, and content is 20～60g/L.Evenly mix reaction mass configuration back, is heated to 60～80 ℃, adds ultrasonic field simultaneously, and its power is 600～800W.After treating that material reaction produces copper powder, the material that will contain copper powder with condenser is cooled to room temperature, separates copper powder and solution with supercentrifuge, and copper powder is dry under protective atmosphere.
The preparation method of copper nanoparticle set forth in the present invention, it is a distinguishing feature that the process that chemical reduction method prepares nano-powder is introduced in the effect of ultrasonic field.Compared with prior art, following characteristics are arranged:
When in the aqueous solution, preparing copper powder, copper atom in the aqueous solution, reduce need overcome certain energy barrier could forming core, grow up, the adding of ultrasonic field is given the forming core of copper atom and grown up provides energy, if there is not the effect of ultrasonic field, the percent reduction of copper is very low in solution system of the present invention, speed is slow, even can not reduce.Simultaneously, the later growth process of copper atom forming core in the ultrasonic field energy control solution reduces and reunites, and makes the particle size of the copper powder of preparing can remain on nanometer scale.
The present invention is in the characteristics of solution condition aspect: add in additive B and the addition of C and can effectively control the reunion of copper nanoparticle and grow up, make and adopt method of the present invention can prepare nano level copper powder.
Because the method that this method adopts electronation to combine with physical field prepares copper powder, therefore can prepare the copper powder of particle median particle diameter less than 100m, proper nano-powder just is for the performance of effectively utilizing copper nanoparticle provides possible.
In addition, owing to nano powder preparation process of the present invention can be carried out under atmosphere, normal temperature, needing no vacuum and high-tension apparatus, thereby the preparation equipment investment is little, technology is simple, preparation cost is low, realizes large-scale industrial production easily.
Moreover because the main applied chemistry course of reaction of nano powder preparation process of the present invention, cheap, the easy acquisition of selected cost of material is so powder preparation efficiency height and preparation cost are low.
Description of drawings
Fig. 1 is copper nanoparticle preparation flow figure
Fig. 2 is the copper nanoparticle transmission electron microscope photo
Fig. 3 is the particle size distribution figure of three kinds of prepared copper nanoparticles of reducing agent
The specific embodiment
Embodiment 1: adopt method of the present invention to prepare copper nanoparticle
Preparation process is as follows:
(a) following material is mixed by prescription.
Copper sulphate 20g/L
Formaldehyde 300g/L
Silver nitrate 5mg/L
Gelatin 25g/L
Sodium potassium tartrate tetrahydrate 15g/L
NaOH 45g/L
(b) material that mixes is heated to 80 ℃.
(c) in reactor, add ultrasonic field 800W and react, generate copper nanoparticle.
(d) material that reacts completely is cooled to room temperature.
(e) copper nanoparticle in the material is separated with solution.
(f) copper nanoparticle is dry under inert gas shielding.
Embodiment 2: adopt method of the present invention to prepare copper nanoparticle
Preparation process is as follows:
(a) following material is mixed by prescription.
Copper chloride 45g/L
Inferior sodium phosphate 20g/L
Palladium bichloride 10mg/L
Neopelex 30g/L
Triethanolamine 25g/L
Potassium hydroxide 30g/L
(b) material that mixes is heated to 75 ℃.
(c) in reactor, add ultrasonic field 700W and react, generate copper nanoparticle.
(d) material that reacts completely is cooled to room temperature.
(e) copper nanoparticle in the material is separated with solution.
(f) copper nanoparticle is dry under inert gas shielding.
Embodiment 3: adopt method of the present invention to prepare copper nanoparticle
Preparation process is as follows:
(a) following material is mixed by prescription.
Copper sulphate 30g/L
Potassium borohydride 25g/L
Silver nitrate 2mg/L
Gelatin 30g/L
Triethanolamine 28g/L
NaOH 37g/L
(b) material that mixes is heated to 70 ℃.
(c) in reactor, add ultrasonic field 750W and react, generate copper nanoparticle.
(d) material that reacts completely is cooled to room temperature.
(e) copper nanoparticle in the material is separated with solution.
(f) copper nanoparticle is dry under inert gas shielding.
Adopt the foregoing description, equipment investment is little, technology is simple, preparation cost is low, and technical process is seen Fig. 1.Adopt the spherical in shape and even particle size of copper nanoparticle that this method obtained, as shown in Figure 2.With the copper powder of three kinds of reducing agents (corresponding three embodiment) preparation, test its grain diameter with laser particle size analyzer, the result shows that the distribution of particles of copper nanoparticle is narrow, its median particle diameter is about 60nm, as shown in Figure 3.This shows, because the present invention has added two kinds of additives of B, C simultaneously in solution, effect they have brought into play two in the preparation process of copper powder aspect, the copper ion reduction rate is under control on the one hand, and the growth process of Hai Yuan copper atom is suppressed on the other hand.The adding of ultrasonic field in addition makes it when energy being provided for the electronation process, has limited generating growing up of copper atom again.The result of solution condition and physical field two aspect comprehensive functions makes whole copper powder reduction process be in the state of high nucleation rate, low growth rate, and the median particle diameter that has guaranteed the copper powder that employing the inventive method prepares is in nanometer scale.
Claims (1)
1, a kind of method that in the aqueous solution, prepares copper nanoparticle with chemical reduction method, with main salt, reducing agent, additive makes up, after treating that material reaction produces copper powder, the material that will contain copper powder with condenser is cooled to room temperature, separate copper powder with supercentrifuge, dry under protective atmosphere again, it is characterized in that, main salt is copper sulphate, in the copper chloride any, content are 20～50g/L, and reducing agent is an inferior sodium phosphate, sodium borohydride, a kind of in the formaldehyde, content is 10～300g/L, additive is from A, B, C, choose any one kind of them in each class of D, additive A is a silver nitrate, palladium bichloride, content are 1～10mg/L; Additive B is gelatin, neopelex, and content is 10～50g/L; Addition of C is sodium potassium tartrate tetrahydrate, triethanolamine, and content is 10～50g/L; Additive D is potassium hydroxide, NaOH, and content is 20～60g/L, and evenly mix reaction mass configuration back, is heated to 60～80 ℃, adds ultrasonic field simultaneously, and its power is 600～800W.
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| CN 200410009842 CN1247354C (en) | 2004-11-23 | 2004-11-23 | Method for preparing nanometer copper powder by chemical reduction in water solution |
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| CN1247354C CN1247354C (en) | 2006-03-29 |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1299864C (en) * | 2005-04-26 | 2007-02-14 | 黄德欢 | Preparation method of nano-bronze powder |
| CN100366368C (en) * | 2006-03-23 | 2008-02-06 | 福州大学 | Non aqueous solution homogeneous phase reduction preparation method of nano-metallic silver |
| CN100402203C (en) * | 2006-04-30 | 2008-07-16 | 扬州大学 | Method for preparing high purified copper powder in submicro |
| CN100427246C (en) * | 2005-11-04 | 2008-10-22 | 清华大学 | Method for synthesizing Nano balls of cuprous oxide, and application of Nano balls of cuprous oxide |
| CN100427247C (en) * | 2006-01-17 | 2008-10-22 | 电子科技大学 | Method for preparing copper powder |
| CN100493781C (en) * | 2007-04-06 | 2009-06-03 | 深圳市危险废物处理站 | Method of producing sheet shaped silver-plated copper powder |
| CN101942679A (en) * | 2010-10-25 | 2011-01-12 | 江苏技术师范学院 | Method for preparing, pre-treating and dispersing superfine copper powder |
| CN101507470B (en) * | 2009-03-16 | 2012-05-30 | 浙江大学 | Preparation method of nano chrome additive |
| CN102764898A (en) * | 2012-08-09 | 2012-11-07 | 深圳市圣龙特电子有限公司 | method for preparing ultrafine copper powder for electronic paste |
| RU2584288C2 (en) * | 2014-07-09 | 2016-05-20 | Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский Томский политехнический университет" | Synthesis of zero-valence transition metal nanoparticles with surface covalently modified with organic functional groups |
| CN108941605A (en) * | 2018-08-02 | 2018-12-07 | 西安雷晶新材料科技有限公司 | A kind of preparation method of superfine cupper powder |
| CN110248750A (en) * | 2017-03-08 | 2019-09-17 | 株式会社Adeka | The manufacturing method of copper powder, resin combination, the method and solidfied material for forming solidfied material |
| CN111618314A (en) * | 2020-05-15 | 2020-09-04 | 哈尔滨工业大学(深圳)(哈尔滨工业大学深圳科技创新研究院) | Preparation method of nano silver-coated copper solder based on sonochemistry |
-
2004
- 2004-11-23 CN CN 200410009842 patent/CN1247354C/en not_active Expired - Fee Related
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1299864C (en) * | 2005-04-26 | 2007-02-14 | 黄德欢 | Preparation method of nano-bronze powder |
| CN100427246C (en) * | 2005-11-04 | 2008-10-22 | 清华大学 | Method for synthesizing Nano balls of cuprous oxide, and application of Nano balls of cuprous oxide |
| CN100427247C (en) * | 2006-01-17 | 2008-10-22 | 电子科技大学 | Method for preparing copper powder |
| CN100366368C (en) * | 2006-03-23 | 2008-02-06 | 福州大学 | Non aqueous solution homogeneous phase reduction preparation method of nano-metallic silver |
| CN100402203C (en) * | 2006-04-30 | 2008-07-16 | 扬州大学 | Method for preparing high purified copper powder in submicro |
| CN100493781C (en) * | 2007-04-06 | 2009-06-03 | 深圳市危险废物处理站 | Method of producing sheet shaped silver-plated copper powder |
| CN101507470B (en) * | 2009-03-16 | 2012-05-30 | 浙江大学 | Preparation method of nano chrome additive |
| CN101942679B (en) * | 2010-10-25 | 2012-10-17 | 江苏技术师范学院 | Method for preparing, pre-treating and dispersing superfine copper powder |
| CN101942679A (en) * | 2010-10-25 | 2011-01-12 | 江苏技术师范学院 | Method for preparing, pre-treating and dispersing superfine copper powder |
| CN102764898A (en) * | 2012-08-09 | 2012-11-07 | 深圳市圣龙特电子有限公司 | method for preparing ultrafine copper powder for electronic paste |
| CN102764898B (en) * | 2012-08-09 | 2014-10-22 | 深圳市圣龙特电子有限公司 | Method for preparing ultrafine copper powder for electronic paste |
| RU2584288C2 (en) * | 2014-07-09 | 2016-05-20 | Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский Томский политехнический университет" | Synthesis of zero-valence transition metal nanoparticles with surface covalently modified with organic functional groups |
| CN110248750A (en) * | 2017-03-08 | 2019-09-17 | 株式会社Adeka | The manufacturing method of copper powder, resin combination, the method and solidfied material for forming solidfied material |
| CN110248750B (en) * | 2017-03-08 | 2021-07-23 | 株式会社Adeka | Method for producing copper powder, resin composition, method for forming cured product, and cured product |
| CN108941605A (en) * | 2018-08-02 | 2018-12-07 | 西安雷晶新材料科技有限公司 | A kind of preparation method of superfine cupper powder |
| CN111618314A (en) * | 2020-05-15 | 2020-09-04 | 哈尔滨工业大学(深圳)(哈尔滨工业大学深圳科技创新研究院) | Preparation method of nano silver-coated copper solder based on sonochemistry |
| CN111618314B (en) * | 2020-05-15 | 2023-01-03 | 哈尔滨工业大学(深圳)(哈尔滨工业大学深圳科技创新研究院) | Preparation method of nano silver-coated copper solder based on sonochemistry |
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| CN1247354C (en) | 2006-03-29 |
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