CN103817345A - Three-step reduction method preparation process for nanocopper - Google Patents
Three-step reduction method preparation process for nanocopper Download PDFInfo
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- CN103817345A CN103817345A CN201410083209.9A CN201410083209A CN103817345A CN 103817345 A CN103817345 A CN 103817345A CN 201410083209 A CN201410083209 A CN 201410083209A CN 103817345 A CN103817345 A CN 103817345A
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Abstract
The invention relates to a three-step reduction method preparation process for nanocopper. The preparation process comprises the following steps: 1, preparing copper sulfate solution, potassium hydroxide solution, ascorbic acid, formaldehyde solution and potassium borohydride solution; 2, single-step reduction: ascorbic acid solution is dropwise added into the copper sulfate solution while stirring is carried out; 3, two-step reduction: the formaldehyde solution is added; 4, three-step reduction: the potassium hydroxide solution is added, the pH value of the solution is adjusted to 9-13, the potassium borohydride solution is dropwise added and is stirred until sediment is completely generated, and copper powder is obtained by filtration; 5; cleaning and drying the copper powder to obtain 300-800 nm nanocopper. By means of three reduction reagents, and according to the reducibility difference of the reduction reagents, the reduction reagents are added into the dissolvable copper sulfate solution in sequence to prepare the nanocopper, and the nanocopper is thinner in grain size, smaller in distribution range and more uniform.
Description
Technical field
The present invention relates to copper powder preparing technical field, be specifically related to a kind of three stage reduction method preparation technologies of copper nanoparticle.
Background technology
The preparation method of copper powder is of a great variety, has high-energy ball milling method and vapour deposition process in physical method.Ball-milling method is by selecting suitable ball mill and milling material, utilize rotation or the vibrations of ball mill, make hard ball carry out strong shock, fragmentation, grinding to material, copper billet is broken into ultra-fine grain, the advantage technique of ball-milling method is simple, output is high, shortcoming is that the copper powder size distribution making is wide, and impurity is many, purity is not high.Vapour deposition is metallic copper quick cooling method of producing copper powder in the inert gas such as argon gas, helium of utilizing after heat fused.Preparing Copper Powder by Electrolysis is the common methods of a kind of comparative maturity and industrial production copper powder, is generally in copper electrolysis cells, and interval 20min wipes the copper powder that is deposited on negative electrode off, to avoid particle to grow up.The copper powder scraping off, then the copper powder that just can obtain finally obtaining through techniques such as ball milling, sub-sieves.Ultrasonic electrolytic process is improved electrolysis, and it is to utilize ultrasonic vibration and cavitation generation high pressure or jet to make the copper particle of deposition depart from cathode surface, and is suspended in electrolyte with molecule.In addition also have, hydro-thermal method, gamma-radiation irradiation method, polyalcohol method and the microwave polyol method etc. of high temperature, high pressure.In numerous preparation methods of copper powder, the method for preparing copper powder by the mantoquita of reduction solubility is that one of common method of copper powder is prepared in laboratory and industry.And conventional reducing agent has the reducing agents such as glucose, ascorbic acid, hydrogen peroxide, formaldehyde, inferior sodium phosphate, hydrazine hydrate, potassium borohydride.In numerous laboratory experiments, be only mostly by a kind of go back original reagent should be used for preparing copper powder, as: Liao Rong has prepared the copper powder of 40～200nm take formaldehyde as reducing agent; The copper powder of Zhao Bin take hydrazine hydrate as the prepared～500nm that goes back original reagent, the copper powder size of preparing is very wide in range.
Summary of the invention
The object of the invention is the deficiency for solving the problems of the technologies described above, a kind of three stage reduction method preparation technologies of copper nanoparticle are provided, the copper powder particle size range making is 300～800nm, and particle size distribution is little, more even.
The present invention is the deficiency solving the problems of the technologies described above, and the technical scheme adopting is: a kind of three stage reduction method preparation technologies of copper nanoparticle, comprise the following steps:
(1) ascorbic acid, the formalin of 0.1～0.5mol/L and the solution of potassium borohydride of 0.1～2mol/L of the copper-bath that, compound concentration is 0.1～1.0mol/L, the potassium hydroxide solution of 5～10 mol/L, 0.1～0.5mol/L, and the solution preparing is placed in respectively to constant temperature water bath, make the temperature of solution remain on 30～90 ℃, for subsequent use;
(2), a step reduction: in constant temperature water bath, drip ascorbic acid solution while stirring in copper-bath, dropwise rear continuation and stir 1～10min;
(3), two step reduction: in constant temperature water bath, continue to add formalin, continue to stir 1～10min after adding;
(4), three step reduction: in constant temperature water bath, continue to add potassium hydroxide solution, regulator solution pH value is 9～13, then drips solution of potassium borohydride, is stirred to precipitation and generates completely, filters and obtains copper powder;
(5), step (4) filtered to the copper powder obtaining use respectively deionized water and absolute ethanol washing three times, then dry in the drier that is full of inert gas, make the copper nanoparticle of 300～800nm.
Every 50～150ml copper-bath adds 10～50ml ascorbic acid.
Every 50～150ml copper-bath adds 10～60ml formalin.
Every 50～150ml copper-bath adds 10～60ml potassium hydroxide solution.
Every 50～150ml copper-bath adds 100～400ml solution of potassium borohydride.
beneficial effect
The present invention goes back original reagent by three kinds, according to the difference of respectively going back original reagent reproducibility, adds successively in the copper-bath of solubility, carrys out preparing nano copper powder, and the particle diameter that can make copper powder is thinner, distribution is less, more even.
The specific embodiment
Three stage reduction method preparation technologies of copper nanoparticle, comprise the following steps:
(1) ascorbic acid, the formalin of 0.1～0.5mol/L and the solution of potassium borohydride of 0.1～2mol/L of the copper-bath that, compound concentration is 0.1～1.0mol/L, the potassium hydroxide solution of 5～10 mol/L, 0.1～0.5mol/L, and the solution preparing is placed in respectively to constant temperature water bath, make the temperature of solution remain on 30～90 ℃, for subsequent use;
Every 50～150ml copper-bath preparation 10～50ml ascorbic acid, 10～60ml formalin, 10～60ml potassium hydroxide solution and 100～400ml solution of potassium borohydride.
(2), a step reduction: in constant temperature water bath, drip ascorbic acid solution while stirring in copper-bath, dropwise rear continuation and stir 1～10min;
(3), two step reduction: in constant temperature water bath, continue to add formalin, continue to stir 1～10min after adding;
(4), three step reduction: in constant temperature water bath, continue to add potassium hydroxide solution, regulator solution pH value is 9～13, then drips solution of potassium borohydride, is stirred to precipitation and generates completely, filters and obtains copper powder;
(5), step (4) filtered to the copper powder obtaining use respectively deionized water and absolute ethanol washing three times, then dry in the drier that is full of inert gas, make the copper nanoparticle of 300～800nm.
below specific embodiments of the invention:
embodiment 1
Three stage reduction method preparation technologies of copper nanoparticle, comprise the following steps:
(1) potassium hydroxide solution of copper-bath 100ml, 7mol/L that, compound concentration is 0.5mol/L, the formalin 20ml of ascorbic acid 15ml, 0.15mol/L of 0.2mol/L and the solution of potassium borohydride 200ml of 1.0mol/L, and the solution preparing is placed in respectively to constant temperature water bath, make the temperature of solution remain on 70 ℃, for subsequent use;
(2), a step reduction: in constant temperature water bath, drip ascorbic acid solution while stirring in copper-bath, dropwise rear continuation and stir 3min;
(3), two step reduction: in constant temperature water bath, continue to add formalin, continue to stir 5min after adding;
(4), three step reduction: in constant temperature water bath, continue to add potassium hydroxide solution, regulator solution pH value is 11, then drips solution of potassium borohydride, is stirred to precipitation and generates completely, filters and obtains copper powder;
(5), step (4) filtered to the copper powder obtaining use respectively deionized water and absolute ethanol washing three times, then dry in the drier that is full of inert gas, make the copper nanoparticle of 300～800nm.
embodiment 2
Three stage reduction method preparation technologies of copper nanoparticle, comprise the following steps:
(1) potassium hydroxide solution of copper-bath 150ml, 5mol/L that, compound concentration is 0.1mol/L, the formalin 30ml of ascorbic acid 10ml, 0.4mol/L of 0.5mol/L and the solution of potassium borohydride 300ml of 0.5mol/L, and the solution preparing is placed in respectively to constant temperature water bath, make the temperature of solution remain on 60 ℃, for subsequent use;
(2), a step reduction: in constant temperature water bath, drip ascorbic acid solution while stirring in copper-bath, dropwise rear continuation and stir 3min;
(3), two step reduction: in constant temperature water bath, continue to add formalin, continue to stir 5min after adding;
(4), three step reduction: in constant temperature water bath, continue to add potassium hydroxide solution, regulator solution pH value is 10, then drips solution of potassium borohydride, is stirred to precipitation and generates completely, filters and obtains copper powder;
(5), step (4) filtered to the copper powder obtaining use respectively deionized water and absolute ethanol washing three times, then dry in the drier that is full of inert gas, make the copper nanoparticle of 300～800nm.
embodiment 3
Three stage reduction method preparation technologies of copper nanoparticle, comprise the following steps:
(1) potassium hydroxide solution of copper-bath 60ml, 10mol/L that, compound concentration is 0.9mol/L, the formalin 50ml of ascorbic acid 30ml, 0.3mol/L of 0.4mol/L and the solution of potassium borohydride 150ml of 1.5mol/L, and the solution preparing is placed in respectively to constant temperature water bath, make the temperature of solution remain on 90 ℃, for subsequent use;
(2), a step reduction: in constant temperature water bath, drip ascorbic acid solution while stirring in copper-bath, dropwise rear continuation and stir 6min;
(3), two step reduction: in constant temperature water bath, continue to add formalin, continue to stir 8min after adding;
(4), three step reduction: in constant temperature water bath, continue to add potassium hydroxide solution, regulator solution pH value is 13, then drips solution of potassium borohydride, is stirred to precipitation and generates completely, filters and obtains copper powder;
(5), step (4) filtered to the copper powder obtaining use respectively deionized water and absolute ethanol washing three times, then dry in the drier that is full of inert gas, make the copper nanoparticle of 300～800nm.
Claims (5)
1. three stage reduction method preparation technologies of copper nanoparticle, is characterized in that: comprise the following steps:
(1) ascorbic acid, the formalin of 0.1～0.5mol/L and the solution of potassium borohydride of 0.1～2mol/L of the copper-bath that, compound concentration is 0.1～1.0mol/L, the potassium hydroxide solution of 5～10 mol/L, 0.1～0.5mol/L, and the solution preparing is placed in respectively to constant temperature water bath, make the temperature of solution remain on 30～90 ℃, for subsequent use;
(2), a step reduction: in constant temperature water bath, drip ascorbic acid solution while stirring in copper-bath, dropwise rear continuation and stir 1～10min;
(3), two step reduction: in constant temperature water bath, continue to add formalin, continue to stir 1～10min after adding;
(4), three step reduction: in constant temperature water bath, continue to add potassium hydroxide solution, regulator solution pH value is 9～13, then drips solution of potassium borohydride, is stirred to precipitation and generates completely, filters and obtains copper powder;
(5), step (4) filtered to the copper powder obtaining use respectively deionized water and absolute ethanol washing three times, then dry in the drier that is full of inert gas, make the copper nanoparticle of 300～800nm.
2. three stage reduction method preparation technologies of a kind of copper nanoparticle as claimed in claim 1, is characterized in that: every 50～150ml copper-bath adds 10～50ml ascorbic acid.
3. three stage reduction method preparation technologies of a kind of copper nanoparticle as claimed in claim 1, is characterized in that: every 50～150ml copper-bath adds 10～60ml formalin.
4. three stage reduction method preparation technologies of a kind of copper nanoparticle as claimed in claim 1, is characterized in that: every 50～150ml copper-bath adds 10～60ml potassium hydroxide solution.
5. three stage reduction method preparation technologies of a kind of copper nanoparticle as claimed in claim 1, is characterized in that: every 50～150ml copper-bath adds 100～400ml solution of potassium borohydride.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111590088A (en) * | 2020-07-13 | 2020-08-28 | 江西省科学院应用物理研究所 | Preparation method of superfine nano copper powder |
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| US5389122A (en) * | 1993-07-13 | 1995-02-14 | E. I. Du Pont De Nemours And Company | Process for making finely divided, dense packing, spherical shaped silver particles |
| US20060090596A1 (en) * | 2004-10-29 | 2006-05-04 | Goia Dan V | Aqueous-based method for producing ultra-fine metal powders |
| CN101077529A (en) * | 2007-07-05 | 2007-11-28 | 中南大学 | Method for preparing nano copper powder and copper slurry |
| JP2008069457A (en) * | 2007-10-09 | 2008-03-27 | Mitsui Mining & Smelting Co Ltd | Drop-shaped copper powder, method for producing drop-shaped copper powder, and electrically conductive paste |
| US20090148600A1 (en) * | 2007-12-05 | 2009-06-11 | Xerox Corporation | Metal Nanoparticles Stabilized With a Carboxylic Acid-Organoamine Complex |
| CN103170644A (en) * | 2013-03-27 | 2013-06-26 | 宁夏东方钽业股份有限公司 | Technology of preparing superfine copper powder through multistep liquid phase reduction method |
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Patent Citations (6)
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| US5389122A (en) * | 1993-07-13 | 1995-02-14 | E. I. Du Pont De Nemours And Company | Process for making finely divided, dense packing, spherical shaped silver particles |
| US20060090596A1 (en) * | 2004-10-29 | 2006-05-04 | Goia Dan V | Aqueous-based method for producing ultra-fine metal powders |
| CN101077529A (en) * | 2007-07-05 | 2007-11-28 | 中南大学 | Method for preparing nano copper powder and copper slurry |
| JP2008069457A (en) * | 2007-10-09 | 2008-03-27 | Mitsui Mining & Smelting Co Ltd | Drop-shaped copper powder, method for producing drop-shaped copper powder, and electrically conductive paste |
| US20090148600A1 (en) * | 2007-12-05 | 2009-06-11 | Xerox Corporation | Metal Nanoparticles Stabilized With a Carboxylic Acid-Organoamine Complex |
| CN103170644A (en) * | 2013-03-27 | 2013-06-26 | 宁夏东方钽业股份有限公司 | Technology of preparing superfine copper powder through multistep liquid phase reduction method |
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| 黄凌云等: ""我国超细铜粉研究及生产现状"", 《化学通报》, no. 5, 31 May 2008 (2008-05-31), pages 356 - 360 * |
Cited By (1)
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| CN111590088A (en) * | 2020-07-13 | 2020-08-28 | 江西省科学院应用物理研究所 | Preparation method of superfine nano copper powder |
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Effective date of registration: 20170704 Address after: 471200 Temple Bay Village, three Tuen Mun Town, Ruyang County, Henan, Luoyang Patentee after: Luoyang Senda emulsifier Co. Ltd. Address before: 471000 Henan province Luoyang City Ze road hi tech Development Zone Patentee before: Luoyang Institute Of Science And Technology |
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