CN103817345B - A kind of three stage reduction method preparation technologies of copper nanoparticle - Google Patents
A kind of three stage reduction method preparation technologies of copper nanoparticle Download PDFInfo
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- CN103817345B CN103817345B CN201410083209.9A CN201410083209A CN103817345B CN 103817345 B CN103817345 B CN 103817345B CN 201410083209 A CN201410083209 A CN 201410083209A CN 103817345 B CN103817345 B CN 103817345B
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Abstract
The present invention relates to a kind of three stage reduction method preparation technologies of copper nanoparticle, comprise the following steps: (1), preparation copper-bath, potassium hydroxide solution, ascorbic acid, formalin and solution of potassium borohydride; (2), a step reduction: drip ascorbic acid solution while stirring in copper-bath; (3), two step reduction: add formalin; (4), three step reduction: add potassium hydroxide solution, regulate solution ph to be 9 ~ 13, then drip solution of potassium borohydride, be stirred to precipitation and generate completely, filter and obtain copper powder; (5), copper powder washing drying is obtained afterwards the copper nanoparticle of 300 ~ 800nm.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, can make that the particle diameter of copper powder is thinner, distribution is less evenly.
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, hard ball is made to 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 obtained copper powder size distributes wide, and impurity is many, purity is not high.Vapour deposition is that the metallic copper after utilizing heat fused cools the method producing copper powder fast in the inert gas such as argon gas, helium.Preparing Copper Powder by Electrolysis is a kind of comparative maturity and the common methods of industrial production copper powder, is generally that the copper powder being deposited on negative electrode is wiped off by interval 20min in copper electrolysis cells, to avoid particle growth.The copper powder scraped off, then through copper powder that the technique such as ball milling, sub-sieve just can finally be obtained.Ultrasonic electrolytic process is the electrolysis improved, and it utilizes ultrasonic vibration and cavitation generation high pressure or jet to make the copper particle of deposition depart from cathode surface, and be suspended in electrolyte with molecule.In addition, the hydro-thermal method of high temperature, high pressure, gamma-radiation irradiation method, polyol process and microwave polyol method etc. are also had.In numerous preparation methods of copper powder, the method being prepared copper powder by the mantoquita of reduction solubility is one of laboratory and industry common method preparing copper powder.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 prepare copper powder, as: Liao Rong is that the copper powder of 40 ~ 200nm prepared by reducing agent with formaldehyde; Zhao Bin goes back original reagent and prepares ~ the copper powder of 500nm, and the copper powder size prepared 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, provide a kind of three stage reduction method preparation technologies of copper nanoparticle, obtained copper powder particle size scope is 300 ~ 800nm, and particle size distribution is little, more evenly.
The present invention is the deficiency solved the problems of the technologies described above, and the technical scheme adopted is: a kind of three stage reduction method preparation technologies of copper nanoparticle, comprise the following steps:
(1), compound concentration is the solution of potassium borohydride of the copper-bath of 0.1 ~ 1.0mol/L, the potassium hydroxide solution of 5 ~ 10mol/L, the ascorbic acid of 0.1 ~ 0.5mol/L, the formalin of 0.1 ~ 0.5mol/L and 0.1 ~ 2mol/L, and the solution prepared is placed in constant temperature water bath respectively, the temperature of solution is made to remain on 30 ~ 90 DEG C, for subsequent use;
(2), a step reduction: in constant temperature water bath, drip ascorbic acid solution while stirring in copper-bath, dropwise rear continuation stirring 1 ~ 10min;
(3), two step reduction: in constant temperature water bath, continue to add formalin, continue stirring 1 ~ 10min after adding;
(4), three step reduction: in constant temperature water bath, continue to add potassium hydroxide solution, regulate solution ph to be 9 ~ 13, then drip solution of potassium borohydride, be stirred to precipitation and generate completely, filter and obtain copper powder;
(5), by step (4) filter the copper powder obtained and use deionized water and absolute ethanol washing three times respectively, then dry in the drier being full of inert gas, the copper nanoparticle of obtained 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, can make that the particle diameter of copper powder is thinner, distribution is less evenly.
Detailed description of the invention
Three stage reduction method preparation technologies of copper nanoparticle, comprise the following steps:
(1), compound concentration is the solution of potassium borohydride of the copper-bath of 0.1 ~ 1.0mol/L, the potassium hydroxide solution of 5 ~ 10mol/L, the ascorbic acid of 0.1 ~ 0.5mol/L, the formalin of 0.1 ~ 0.5mol/L and 0.1 ~ 2mol/L, and the solution prepared is placed in constant temperature water bath respectively, the temperature of solution is made to remain on 30 ~ 90 DEG C, 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 stirring 1 ~ 10min;
(3), two step reduction: in constant temperature water bath, continue to add formalin, continue stirring 1 ~ 10min after adding;
(4), three step reduction: in constant temperature water bath, continue to add potassium hydroxide solution, regulate solution ph to be 9 ~ 13, then drip solution of potassium borohydride, be stirred to precipitation and generate completely, filter and obtain copper powder;
(5), by step (4) filter the copper powder obtained and use deionized water and absolute ethanol washing three times respectively, then dry in the drier being full of inert gas, the copper nanoparticle of obtained 300 ~ 800nm.
below specific embodiments of the invention:
embodiment 1
Three stage reduction method preparation technologies of copper nanoparticle, comprise the following steps:
(1), compound concentration is the potassium hydroxide solution of copper-bath 100ml, 7mol/L of 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 prepared is placed in constant temperature water bath respectively, the temperature of solution is made to remain on 70 DEG C, 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 after adding to stir 5min;
(4), three step reduction: in constant temperature water bath, continue to add potassium hydroxide solution, regulate solution ph to be 11, then drip solution of potassium borohydride, be stirred to precipitation and generate completely, filter and obtain copper powder;
(5), by step (4) filter the copper powder obtained and use deionized water and absolute ethanol washing three times respectively, then dry in the drier being full of inert gas, the copper nanoparticle of obtained 300 ~ 800nm.
embodiment 2
Three stage reduction method preparation technologies of copper nanoparticle, comprise the following steps:
(1), compound concentration is the potassium hydroxide solution of copper-bath 150ml, 5mol/L of 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 prepared is placed in constant temperature water bath respectively, the temperature of solution is made to remain on 60 DEG C, 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 after adding to stir 5min;
(4), three step reduction: in constant temperature water bath, continue to add potassium hydroxide solution, regulate solution ph to be 10, then drip solution of potassium borohydride, be stirred to precipitation and generate completely, filter and obtain copper powder;
(5), by step (4) filter the copper powder obtained and use deionized water and absolute ethanol washing three times respectively, then dry in the drier being full of inert gas, the copper nanoparticle of obtained 300 ~ 800nm.
embodiment 3
Three stage reduction method preparation technologies of copper nanoparticle, comprise the following steps:
(1), compound concentration is the potassium hydroxide solution of copper-bath 60ml, 10mol/L of 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 prepared is placed in constant temperature water bath respectively, the temperature of solution is made to remain on 90 DEG C, 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 after adding to stir 8min;
(4), three step reduction: in constant temperature water bath, continue to add potassium hydroxide solution, regulate solution ph to be 13, then drip solution of potassium borohydride, be stirred to precipitation and generate completely, filter and obtain copper powder;
(5), by step (4) filter the copper powder obtained and use deionized water and absolute ethanol washing three times respectively, then dry in the drier being full of inert gas, the copper nanoparticle of obtained 300 ~ 800nm.
Claims (5)
1. three stage reduction method preparation technologies of copper nanoparticle, is characterized in that: comprise the following steps:
(1), compound concentration is the solution of potassium borohydride of the copper-bath of 0.1 ~ 1.0mol/L, the potassium hydroxide solution of 5 ~ 10mol/L, the ascorbic acid of 0.1 ~ 0.5mol/L, the formalin of 0.1 ~ 0.5mol/L and 0.1 ~ 2mol/L, and the solution prepared is placed in constant temperature water bath respectively, the temperature of solution is made to remain on 30 ~ 90 DEG C, for subsequent use;
(2), a step reduction: in constant temperature water bath, drip ascorbic acid solution while stirring in copper-bath, dropwise rear continuation stirring 1 ~ 10min;
(3), two step reduction: in constant temperature water bath, continue to add formalin, continue stirring 1 ~ 10min after adding;
(4), three step reduction: in constant temperature water bath, continue to add potassium hydroxide solution, regulate solution ph to be 9 ~ 13, then drip solution of potassium borohydride, be stirred to precipitation and generate completely, filter and obtain copper powder;
(5), by step (4) filter the copper powder obtained and use deionized water and absolute ethanol washing three times respectively, then dry in the drier being full of inert gas, the copper nanoparticle of obtained 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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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101077529A (en) * | 2007-07-05 | 2007-11-28 | 中南大学 | Method for preparing nano copper powder and copper slurry |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| US8470066B2 (en) * | 2004-10-29 | 2013-06-25 | Clarkson University | Aqueous-based method for producing ultra-fine metal powders |
| JP4756652B2 (en) * | 2007-10-09 | 2011-08-24 | 三井金属鉱業株式会社 | Drop-shaped copper powder, method for producing drop-shaped copper powder and conductive paste |
| US20090148600A1 (en) * | 2007-12-05 | 2009-06-11 | Xerox Corporation | Metal Nanoparticles Stabilized With a Carboxylic Acid-Organoamine Complex |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101077529A (en) * | 2007-07-05 | 2007-11-28 | 中南大学 | Method for preparing nano copper powder and copper slurry |
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| "我国超细铜粉研究及生产现状";黄凌云等;《化学通报》;20080531(第5期);356-360 * |
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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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