CN102371358A - Aqueous-phase preparation method for re-dispersible nano-copper particles - Google Patents
Aqueous-phase preparation method for re-dispersible nano-copper particles Download PDFInfo
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- CN102371358A CN102371358A CN2011103673279A CN201110367327A CN102371358A CN 102371358 A CN102371358 A CN 102371358A CN 2011103673279 A CN2011103673279 A CN 2011103673279A CN 201110367327 A CN201110367327 A CN 201110367327A CN 102371358 A CN102371358 A CN 102371358A
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Abstract
The invention belongs to the technical field of nanometer materials, in particular to an aqueous-phase preparation method for re-dispersible nano-copper particles. A copper salt and a mixed organic protective agent are dissolved into water or a mixed solution of water and an organic solvent; under the action of ammonia water and a reducing agent, a crimson solution is obtained; the solution is centrifuged to obtain sediments; and the sediments are washed by ultrasound in carbinol to obtain the nano-copper particle. The cleaned nano-copper particle can be dispersed in a solvent under the assistance of a stabilizer with lower boiling point, wherein the diameter of the nano-copper particle is less than 30nm. The preparation method has the advantages of simple technology and low cost as well as no need of heating and environment friendliness due to the adoption of water as the solvent, and is suitable for preparing the nano-copper particle on a large scale.
Description
Technical field
The invention belongs to technical field of nano material, be specifically related to a kind of aqueous phase preparation method of redispersible nanometer copper particle.
Background technology
Nanometer copper surface-active is big, has excellent catalytic performance and bactericidal property; Nanometer copper has the ultra ductility of moulding, and this mechanical property provides advantage for the elastic material of making under the normal temperature; Nanometer copper has high electric conductivity, operational stability and chilling process ability in addition, thereby in fields such as electrically conductive ink, conducting resinls good application prospects is arranged.At present, the method for preparing nanometer copper particle mainly contains chemical reduction method, electrolysis, mechanical milling method, steam condensation method, arc plasma process etc.With respect to gold and Nano silver grain; The nanometer copper activity is higher; Be prone to oxidizedly, thereby the surface protection for preparing in the process at nanometer copper particle is extremely important, but a large amount of stabilizing agents can bring harmful effect to the low-temperature sintering performance and the electric conductivity of nanometer copper particle; Therefore, selection of stabilizers and removing method have significant effects for the preparation and the application of nanometer copper particle.Chinese patent 200610104573.4 discloses a kind of preparation method of stabilized nano copper particle: it uses copper nitrate as presoma; Softex kw and sulfur compound are stabilizing agent, and sodium borohydride is a reducing agent, in the solution of second alcohol and water, has synthesized copper nano-particle; Owing to add sulfur compound; And use chloroform extraction, the preparation process is complicated, and product purity is not high.Chinese patent 200910054883.3 discloses a kind of preparation method of nanometer copper particle; Use mantoquita, stabilizing agent and reducing agent, synthesized copper nano-particle under the condition that in organic solvent, heats, be reflected in the organic solvent and carry out; Need heating; The process relative complex needs to use ethanol and acetone repeatedly to clean, and can cause the oxidation of nanometer copper in the process.
Summary of the invention
The objective of the invention is to overcome the too loaded down with trivial details deficiency of aforementioned nanometer copper particle preparation technology, the short-cut method of the redispersible nanometer copper particle of a kind of preparation of water is provided.
The redispersible nanometer copper particle aqueous phase preparation method that the present invention proposes, concrete steps are following:
(1) mantoquita and organic protective agent are dissolved in the solvent, at room temperature stirred 15-25 minute, add ammoniacal liquor, solution becomes dark blue purple from blue stain, continues to stir 50-60 minute;
(2) feed nitrogen, protection dropwise adds reducing agent then, continues stirring reaction 30-40 minute, obtains dark red solution;
(3) with above-mentioned solution centrifugal, obtain deposition, sediment is supersound washing in methyl alcohol, promptly obtains nanometer copper particle.
Among the present invention, the solvent of use is a water, or the mixture of water and ethanol, EGME etc. the organic solvent that can dissolve each other with water, and amount of solvent is the corresponding 50-100ml of every 0.01mol mantoquita.
Among the present invention, the mantoquita that uses is a kind of in the mantoquitas such as Schweinfurt green, copper lactate, copper nitrate, copper sulphate or several kinds mixture wherein.
Among the present invention; The reducing agent that uses can be organic reducing agents such as hydrazine hydrate, formaldehyde or acetaldehyde, perhaps is inorganic reducing agents such as sodium hypophosphite, and reducing agent itself is easier to water-soluble; More soluble in water or the methyl alcohol of product after it is oxidized, the mol ratio 2:1-4:1 of reducing agent and mantoquita.
Among the present invention, the protective agent that uses is the mixture of two kinds in the organic matters such as polyvinylpyrrolidone, softex kw, nation of department 80 or two or more compositions, can water-soluble and methyl alcohol.The mol ratio of used protective agent and mantoquita is 1:1-10:1.
Among the present invention, the nanometer copper particle that obtains, particle diameter is less than 30nm.
The copper nano-particle that obtains among the present invention is lower than at boiling points such as lactic acid, softex kws in the presence of 250 ℃ the stabilizing agent; Can be dispersed in the lower boiling mixed solvents such as ethanol, methyl alcohol, EGME again; Nanometer shot copper footpath after the dispersion is suitable for the application of multiple occasions such as electrically conductive ink less than 30nm.
The present invention has the following advantages:
1, technology is simple, need not heat, and the reaction time is short;
2, last handling process is easy, only uses washed with methanol just can remove the most of material that adds when synthesizing;
3, water is as solvent, and more environmental protection is fit to the preparation water-soluble conducting ink;
4, the copper nano-particle after the cleaning can be scattered in the solvent that contains stabilizing agent again, and the footpath of the nanometer shot copper after disperseing is fit to the application of multiple occasion less than 30nm.
Description of drawings
Fig. 1 is the transmission electron microscope photo (TEM) of nanometer copper particle.
Fig. 2 is the XRD figure of centrifugal, dry back nanometer copper particle.
The specific embodiment
The invention is further illustrated by the following examples.
Embodiment 1: the 0.01mol Schweinfurt green is dissolved in the 50ml water, adds 5g polyvinylpyrrolidone and 1g softex kw, after the stirring and dissolving; Continue to stir 20 minutes, add ammoniacal liquor then, solution becomes dark blue purple from blue stain; Continue to stir 50-60 minute, feed nitrogen protection, dropwise add the 10ml hydrazine hydrate again; Obtained dark red solution in lasting stirring reaction 30-40 minute afterwards; Solution centrifugal is obtained deposition, and sediment supersound washing 1 time in methyl alcohol promptly obtains nanometer copper particle.
Embodiment 2: the 0.01mol Schweinfurt green is dissolved in the mixed solution of 25ml water and 25ml ethanol, adds 5g polyvinylpyrrolidone and 1g softex kw, after the stirring and dissolving; Continue to stir 20 minutes, add ammoniacal liquor then, solution becomes dark blue purple from blue stain; Continue to stir 50-60 minute, feed nitrogen protection, dropwise add the 10ml hydrazine hydrate again; Obtained dark red solution in lasting stirring reaction 30-40 minute afterwards; Solution centrifugal is obtained deposition, and sediment supersound washing 1 time in methyl alcohol promptly obtains nanometer copper particle.
Embodiment 3: get 0.3g through washed with methanol, dried copper nano-particle, join in the mixed solution of 50ml ethanol and 1ml lactic acid, ultrasonic 2-3 minute, copper nano-particle was dispersed in the solution, and particle diameter is less than 30nm.
Claims (5)
1. the aqueous phase preparation method of a nanometer copper particle is characterized in that concrete steps are following:
(1) mantoquita and organic protective agent are dissolved in the solvent, at room temperature stirred 15-25 minute, add ammoniacal liquor, solution becomes dark blue purple from blue stain, continues to stir 50-60 minute;
(2) feed nitrogen, protection dropwise adds reducing agent then, continues stirring reaction 30-40 minute, obtains dark red solution;
(3) with above-mentioned solution centrifugal, obtain deposition, sediment is supersound washing in methyl alcohol, promptly obtains nanometer copper particle;
Wherein, described solvent is a water, or the mixture of water and the organic solvent that can dissolve each other with water, and amount of solvent is the corresponding 50-100ml of every 0.01mol mantoquita.
2. the preparation method of nanometer copper particle as claimed in claim 1 is characterized in that said mantoquita is a kind of in the mantoquitas such as Schweinfurt green, copper lactate, copper nitrate, copper sulphate, perhaps several kinds mixture wherein.
3. according to claim 1 or claim 2 the preparation method of nanometer copper particle is characterized in that said protective agent is two kinds or the mixture of two or more compositions in polyvinylpyrrolidone, softex kw, the nation of department 80; The mol ratio of protective agent and mantoquita is 1:1-10:1.
4. according to claim 1 or claim 2 the preparation method of nanometer copper particle is characterized in that used reducing agent is hydrazine hydrate, formaldehyde or acetaldehyde, perhaps is sodium hypophosphite, and the mol ratio of reducing agent and mantoquita is 2:1-4:1.
5. according to claim 1 or claim 2 the preparation method of nanometer copper particle; It is characterized in that; With copper nano-particle when lactic acid or softex kw boiling point or decomposition temperature are lower than 250 ℃ stabilizing agent and exist; Be scattered in the lower boiling mixed solvent of ethanol, methyl alcohol or EGME, the nanometer shot copper footpath after the dispersion is used for the electrically conductive ink occasion less than 30nm.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102601383A (en) * | 2012-03-30 | 2012-07-25 | 电子科技大学 | Method for preparing ultrafine copper powder at room temperature |
| CN102898887A (en) * | 2012-10-12 | 2013-01-30 | 复旦大学 | Method for preparing organic copper salt ink and copper conductive film |
| CN103752844A (en) * | 2014-01-08 | 2014-04-30 | 洛阳理工学院 | Preparation method of nano spherical lead powder |
| CN104289727A (en) * | 2014-10-22 | 2015-01-21 | 苏州正业昌智能科技有限公司 | Method for preparing nano-silver by taking modified chitosan as reducing agent |
| CN107020389A (en) * | 2017-04-06 | 2017-08-08 | 江苏大学 | A kind of preparation method of high-dispersion nano copper |
| CN108079991A (en) * | 2017-12-26 | 2018-05-29 | 扬州大学 | A kind of preparation method and applications of the monodispersed loaded nano copper catalyst of standard |
| CN108315771A (en) * | 2018-02-11 | 2018-07-24 | 中国工程物理研究院材料研究所 | A kind of electrochemical preparation method of sub-nanometer size copper particle elctro-catalyst |
| CN110586952A (en) * | 2018-06-22 | 2019-12-20 | 天津理工大学 | Room temperature preparation method of nano metal powder and conductive ink thereof |
| CN112916864A (en) * | 2021-01-21 | 2021-06-08 | 范期奎 | Water-phase copper nanocrystal and preparation method and application thereof |
| CN114210972A (en) * | 2021-11-03 | 2022-03-22 | 中科检测技术服务(重庆)有限公司 | Novel nano copper welding material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102601383A (en) * | 2012-03-30 | 2012-07-25 | 电子科技大学 | Method for preparing ultrafine copper powder at room temperature |
| CN102898887A (en) * | 2012-10-12 | 2013-01-30 | 复旦大学 | Method for preparing organic copper salt ink and copper conductive film |
| CN103752844A (en) * | 2014-01-08 | 2014-04-30 | 洛阳理工学院 | Preparation method of nano spherical lead powder |
| CN104289727A (en) * | 2014-10-22 | 2015-01-21 | 苏州正业昌智能科技有限公司 | Method for preparing nano-silver by taking modified chitosan as reducing agent |
| CN107020389A (en) * | 2017-04-06 | 2017-08-08 | 江苏大学 | A kind of preparation method of high-dispersion nano copper |
| CN108079991A (en) * | 2017-12-26 | 2018-05-29 | 扬州大学 | A kind of preparation method and applications of the monodispersed loaded nano copper catalyst of standard |
| CN108315771A (en) * | 2018-02-11 | 2018-07-24 | 中国工程物理研究院材料研究所 | A kind of electrochemical preparation method of sub-nanometer size copper particle elctro-catalyst |
| CN110586952A (en) * | 2018-06-22 | 2019-12-20 | 天津理工大学 | Room temperature preparation method of nano metal powder and conductive ink thereof |
| CN112916864A (en) * | 2021-01-21 | 2021-06-08 | 范期奎 | Water-phase copper nanocrystal and preparation method and application thereof |
| CN114210972A (en) * | 2021-11-03 | 2022-03-22 | 中科检测技术服务(重庆)有限公司 | Novel nano copper welding material |
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Application publication date: 20120314 |