CN101618462A - Method for manufacturing metal nanometer particle - Google Patents
Method for manufacturing metal nanometer particle Download PDFInfo
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- CN101618462A CN101618462A CN200910139847A CN200910139847A CN101618462A CN 101618462 A CN101618462 A CN 101618462A CN 200910139847 A CN200910139847 A CN 200910139847A CN 200910139847 A CN200910139847 A CN 200910139847A CN 101618462 A CN101618462 A CN 101618462A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2301/00—Metallic composition of the powder or its coating
- B22F2301/10—Copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2304/00—Physical aspects of the powder
- B22F2304/05—Submicron size particles
- B22F2304/054—Particle size between 1 and 100 nm
Abstract
A method for manufacturing metal nanometer replaces two stages (firstly producing cuprous oxide, then producing copper particles by a reducing agent) of a metal particle producing process by one stage, such that it is capable of simplifying the working process obviously, obtaining metal copper particles easily by a short-time reaction at a low temperature (15-60 DEG C), omitting a complicated rinshing process of removing metal salts by secondary rinshing, and particle size dispersion is uniform and there is non requirement of a hierarchical process, thus the method is suitable for lot production. The method includes a first stage of dissolving metal precursor in a dissolvent containing a glycols dissolvent; a second stage of adding organic amine to the prepared solution, stirring until the color of the solution does not change; and a third stage of slowly adding more than one compounds selected from hydrazine derivatives, sodium hypophosphate, hydroxyl amine and sodium borohydride to the solution containing the organic amine of the second stage, so as to deoxidize and precipitate the metal(s).
Description
Technical field
The present invention relates to the manufacture method of metal nanoparticle, be particularly related to a kind of like this manufacture method of metal nanoparticle, this method is with the metallic particles generative process in existing 2 stages (after at first generating cuprous oxide, generate the copper particle by reducing agent again) be reduced to for 1 stage, thus can significantly simplify working process; Can under low temperature (15～60 ℃), the reaction by the short time easily obtain metallic copper particle; Do not need to remove the washing step of the complexity of slaine through secondary water washing; Therefore even particle size distribution and do not require the classification operation is suitable for producing in batches.
Background technology
Recently, because the tendency of the miniaturization of electronic unit and the multiple substrate of employing, require day by day to form the fine wiring of film shape,, need homodisperse fine metallic particles in solvent in order to be applied to so multiple mode of printing by multiple mode of printing.
Especially, flexible printed wiring board (FPCB:flexible printed circuit board) for printed circuit on resin molding, a series of operation through complicated lithography (Lithography), i.e. coating, drying, exposure, etching and removal etc., itself is damaged flexible substrate, therefore press for can be on resin molding the direct metal ink of the dispersed nano particle of protracting circuit.
In addition, under the situation of the nano particle below the 80nm, sintering temperature and thermal conductivity factor can carry out sintering with the sintering temperature (more than 500 ℃) well below general metallic particles owing to the surface characteristic change of particle is risen greatly, the variation thereby the kind of the substrate that can use becomes.
In the past, kept uniform dispergated nano particle like this, studied several different methods such as mechanical milling method, coprecipitation, spray-on process, sol-gel process, electrolysis and microemulsion method in order to make.But under the situation of coprecipitation, the size of particle and the elimination of distribution are impossible, and electrolysis and sol-gel process have manufacturing funds height, produce the problem of difficulty in batches.Therefore in addition, though microemulsion method is controlled size, shape and the distribution of particle easily, there is the situation of practicability difficulty in manufacturing process's complexity.
Recently, the someone attempts making the multiple metallic particles that comprises copper by the wet type reducing process, and the reducing process that has proposed known use hydrazine especially is as the means that are suitable for making the above particle of 0.5 μ m.
In addition; in following patent documentation 1; proposed by the copper method for making granules of forming with the next stage: under the condition of the more than one compound that has the group of forming from amino acid and salt, ammonia, ammonium salt, organic amine and dimethylglyoxime; in copper salt solution, add alkali hydroxide; add reduced sugar and make the cuprous oxide solids precipitation, then use hydrazine to make the reduction of cuprous oxide particle.
But the particle of the copper that the manufacture method that proposes with described Japan Patent obtains is 90～650nm, and particle size is bigger, and bad dispersibility and easy precipitation can not be implemented in the lower sintering temperature that needs when FPCB makes.Particularly, under the situation of using organic amine, have to add the more carbohydrate reducing agent of volume in order to generate cuprous oxide, therefore through complicated course of reaction, under the situation of carbohydrate reducing agent, thereby the size that vigorous reaction is difficult to control particle takes place in having the solution of high basicity.
[patent documentation 1] Japanese publication communique 1990-294414 number
Summary of the invention
Thus, the object of the present invention is to provide a kind of manufacture method of metal nanoparticle, this method is reduced to the metallic particles generative process (after at first generating cuprous oxide, generating the copper particle by reducing agent again) in existing 2 stages 1 stage, thereby can significantly simplify working process; Can under low temperature (15～60 ℃), the reaction by the short time easily obtain metallic copper particle; Do not need to remove the washing step of the complexity of slaine through secondary water washing; Therefore even particle size distribution and do not require the classification operation is suitable for producing in batches.
In order to reach described purpose, the invention provides a kind of manufacture method of metal nanoparticle, it is characterized in that described manufacture method comprises: the 1st stage, dissolution of metals precursor in containing the solvent of glycolic solvents; In the 2nd stage, in the solution that in described the 1st stage, produces, add organic amine, till the color that is stirred to solution does not change; And the 3rd stage, in the interpolation in described the 2nd stage slowly add more than one the compound of from the group that hydrazine derivate, sodium hypohosphate, azanol and sodium borohydride are formed, selecting in the solution of organic amine, thereby metallic reducing is separated out.
Preferably, in described the 1st stage or the 2nd stage, also comprise dispersion stabilizer or polar solvent.In addition, preferably, described metal nanoparticle is a copper nano particles, and granularity is 20～90nm.
The manufacture method of metal nanoparticle of the present invention is reduced to the metallic particles generative process (after at first generating cuprous oxide, generating the copper particle by reducing agent again) in existing 2 stages 1 stage, thereby can significantly simplify working process; Can under low temperature (15～60 ℃), the reaction by the short time easily obtain metallic copper particle; Do not need to remove the washing step of the complexity of slaine through secondary water washing; Therefore even particle size distribution and do not require the classification operation is suitable for producing in batches.
Description of drawings
Fig. 1 observes the result that the granularity of the nano metal powder that produces by one embodiment of the present of invention obtains by SEM.
Fig. 2 is surface analysis (EDS) result of the nano metal powder that produces by one embodiment of the present of invention.
The specific embodiment
The manufacture method of metal nanoparticle of the present invention comprises: the 1st stage, dissolution of metals precursor in containing the solvent of glycolic solvents; In the 2nd stage, in the solution that in described the 1st stage, produces, add organic amine, till the color that is stirred to solution does not change; And the 3rd stage, in the interpolation in described the 2nd stage slowly add more than one the compound of from the group that hydrazine derivate, sodium hypohosphate, azanol and sodium borohydride are formed, selecting in the solution of organic amine, thereby metallic reducing is separated out.Preferably, in described the 1st stage or the 2nd stage, also comprise generation size of intervening particle and dispersion stabilizer or the polar solvent that disperses.
Different with existing wet type reducing process, the present invention is that the easy state that reduces is with after being suitable for batch process making metal precursor, thereby drop into reducing agent and can obtain nano particle easily, operation is uncomplicated, and can induce the generation of uniform nuclear, can make undersized nano particle thus with 20～90nm.
In the present invention, as the metal precursor that is used to form metallic particles, certainly use the metal precursor that can be dissolved in glycolic solvents, preferably mantoquita or silver salt as concrete example, can use from AgNO
3, Ag
2O, AgO, CH
2COOAg, AgCl, Ag
2SO
4, Cu (NO
3)
2, CuSO
4, Cu
2O, CuCl
2, CuO, CuCO
3The slaine of more than one in the group of forming is not limited thereto.
In the present invention, described glycolic solvents is can the dissolution of metals precursor and dispersant and stably keep the solvent of solution shape simultaneously, can use more than one the solvent of from the group that ethylene glycol, diethylene glycol (DEG), triethylene glycol, propane diols, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol methyl ether, DGDE, butyl carbitol, dipropylene glycol methyl ether and glycerine are formed, selecting, preferably, use boiling point at the solvent below 200 ℃.
In the present invention, solvent can only be made up of described glycolic solvents, also can comprise polar solvent or water.
In addition, described polar solvent of the present invention is brought into play following effect: under the situation of ion reducing metal precursor, the oxygen multiple bond of polar solvent, nitrogen, sulphur etc. produce physics, chemisorbed with particle, help in the potentiality that improve the particle growth, to suppress particle and grow up, thereby can keep the nano particle state.As such polar solvent; can use from 2-Pyrrolidone (2-Pyrrolidone); acetyl-pyrrolidine ketone; ethyl pyrrolidone; methyl pyrrolidone; vinyl pyrrolidone; the cyclohexyl pyrrolidones; dimethyl pyrrolidone; dodecyl pyrrolidone; dimethyl sulfoxide (DMSO); sulfolane; methyl sulfolane; dimethylsulfolane; formamide; NMF; dimethyl formamide; acetamide; the polar solvent of more than one that select in the group that methylacetamide and dimethylacetylamide are formed; preferably, use pyrrolidones or acid amides kind.
Containing under the situation of polar solvent, in the present invention, it is better that described solvent comprises the polar solvent of the glycolic solvents of 80～99.9 weight portions and 0.1～20 weight portion, containing under the situation of water, it is better that described solvent comprises the water of the glycolic solvents of 80～99.9 weight portions and 0.1～20 weight portion, contain at the same time under the situation of polar solvent and water, it is better that described solvent comprises the water of the polar solvent of glycolic solvents, 0.1～20 weight portion of 60～99.9 weight portions and 0.1～20 weight portion.At this moment, can further reduce the particle size of the metal dust that produces and make particle become even.
In the nucleation initial stage, identical with polar solvent, have the particle of the above size of critical value in generation after, dispersion stabilizer is in the phenomenon of condensing of growth that suppresses particle and particle agglutination, stable particle grown up to play an important role.Also promptly along with reaction is carried out, the concentration of metal precursor diminishes, thereby the distribution of particle broadens, be the generation that suppresses particle, not equal to be the carrying out that dispersion stabilizer suppresses the growth reaction of particle, the distribution of particle is diminished.
In the present invention, described dispersion stabilizer is preferably selected more than one from the group of PVP (PVP) and copolymer and dicarboxylic acids and derivative composition thereof.Under the situation of described PVP, the advantageous applications molecular weight is 40, PVP below 000, under the situation of PVP copolymer, more suitable is the copolymer of PVP and carboxylic acid or carboxylic acid anhydrides.As the object lesson that can form this copolymer, be maleic acid (Maleic acid), maleic anhydride (Maleic anhydride) and acrylic acid etc., object lesson as copolymer, can enumerate poly-(vinyl pyrrolidone-co-maleic acid), poly-(vinyl pyrrolidone-co-maleic anhydride), poly-(vinyl pyrrolidone-co-acrylic acid), poly-(vinyl pyrrolidone-co-alkyl acrylate) etc., be not limited to this.
In addition, it is 100～10 that described dicarboxylic acids and derivative thereof preferably use molecular weight, 000 monomer or oligomer, object lesson as such dispersion stabilizer, suitable is the derivative of butanedioic acid and the derivative of phthalic acid, more specifically, has dimethyl succinate salt, dimethyl succinate, diethyl succinate, butanedioic acid hydrogen ethyl ester, butanedioic acid hydrogen methacryloxy ethyl ester (2-Methaacryloyoxy ethyl hydrogen succinate), butanedioic acid dimethyl allene acyloxy ethyl ester (Methaacryoloxy ethyl succinate), poly-ethyl succinate, repefral, dibutyl phthalate, diallyl phthalate, polydiallyl phthalate, the M-phthalic acid methyl esters, phthalic acid methacryloxy ethyl ester and dimethyl allene acyloxy phthalic acid ester etc. are not limited to this.
Preferably, in solvent, drop into described metal precursor after, be stirred well to dissolving fully after, it is better to drop into dispersion stabilizer.
In addition, in the present invention, described organic amine can use alkylamine, dialkylamine, trialkylamine, alcoxyl amine, alkyl alkoxy amine, alkanolamine, the dioxane hydramine, three alkanolamines, the alkyl alkanolamine, alkyl dioxane hydramine, diamines, straight chain amine such as triamine, and piperazines, cyclic amine such as imidazoles etc., as example more specifically, has ethamine, diethylamine, dimethylamine, triethylamine, trimethylamine, butylamine, dibutylamine, tri-butylamine, oleyl amine, two oleyl amines, ethoxy propylamine, ethoxy ethanol amine, monoethanolamine, diethanol amine, triethanolamine, methylethanolamine, carbinol methine amine, ehtylethanolamine, dimethylethanolamine, methyl diethanolamine, ethylenediamine, diethylenetriamines, amino ethoxy ethamine, two (3-aminopropyl) amine, the 2-[(3-aminopropyl) amino] ethanol, piperazine, methyl piperazine, the hydroxyethyl piperazine, aminoethylpiperazine, imidazoles, methylimidazoles etc. are not limited to this.
For described organic amine, in the pre-treatment that is used for making nano particle,, generate the copper particle not having to drop under the state of organic amine under the situation of reducing agent, big but the size of particle becomes, size distribution broadens, and almost loses purposes as nano particle.
Preferably, in described the 2nd stage, in being dissolved with the solution of slaine, drop into organic amine, be stirred to basicity and become till 10～12, and keep stirring till the color of solution no longer changes.
The reducing agent performance of adding in the 3rd stage of the present invention makes the effect of metallic reducing, can use more than one of hydrazine, azanol, sodium pyrophosphate, sodium borohydride, D-sorbite, pyrocatechol, catechol, use the equivalent identical better with the metal precursor that in described solution, dissolves.
In addition, under the situation of the organic amine that has used alkyl amine, is preferred with temperature maintenance at 15～30 ℃, surpassing under 30 ℃ the situation, particle is grown up and is difficult to the particle of the nano-scale that obtains expecting, under less than 15 ℃ situation, has the problem that reaction takes a long time and size distribution broadens.In addition, under the situation of the organic amine of alkanol amine, is preferred with temperature maintenance at 30～60 ℃, surpassing under 60 ℃ the situation, particle is grown up and is difficult to the particle of the nano-scale that obtains expecting, under less than 30 ℃ situation, reacts not thorough, unreacted reactant remains in a large number, has the problem that reaction takes a long time and size distribution broadens.Described alkylamine is compared reactive good with the alkanol amine, therefore can react at low temperatures, and under the situation of alkanolamine, reactive relatively low with slaine can react under relatively-high temperature.
In described method, the nano particle of having finished reaction cool off with distilled water or acetone etc. after reaction is finished immediately rapidly, and separates with byproduct of reaction etc. by centrifugation, implement 2～3 times this method, the various accessory substances that flush away adheres to metal etc.
The described nano particle that cleans up can be put into the solvent that contains dispersion stabilizer, and (glycolic solvents and polar solvent are respectively with 80～99: preserve the mixed mixed solvent of 1～20 weight ratio), after this, can adopt the separation method of ultrasonic wave dispersion or 3 edge runners (3roll mill) etc. further to disperse.At this moment, in manufacture method of the present invention, the metal nanoparticle that produces can have the size distribution of average 20～90nm, preferably can have the size distribution of 20～60nm.
Below, illustrate in greater detail the present invention with reference to following embodiment.These embodiment are used for the illustration embodiments of the invention, and scope of the present invention can not limit by following embodiment certainly.
[experimental example 1]
Is 20 at 10ml ultra-pure water and 90ml ethylene glycol and 5ml as the 2-Pyrrolidone and the 4g molecular weight of polar solvent, in the solvent mixture that PVP more than 000 (PVP) is formed, by forcing the CuSO as metal precursor of 0.1 mole of stirring and dissolving
4After, add 0.2 mole triethylamine, implement to force to stir, till the mixed solution of green becomes gelatinous green matter., with 10 fen clock time slowly drop into 0.1 mole hydrazine, implement to force to stir, till solution becomes reddish black or peony thereafter.The reaction temperature of this moment maintains 25 ℃.
Reclaim the reddish black powder by centrifugation, repeat to clean several times and reclaim with acetone and water, finally being mixed into nano metal powder content is 30 weight % in the mixed solution (90: 10 weight ratios) of propane diols list ethylether and N-methyl pyrrolidone, preserves then.
The result who observes the granularity of described nano metal powder by SEM is to have confirmed to have the size distribution of 50～80nm.
[experimental example 2]
At 10ml ultra-pure water and 90ml diethylene glycol (DEG) and 5ml is in the solvent mixture formed of the PVP more than 20,000, by forcing the CuSO as metal precursor of 0.1 mole of stirring and dissolving as the N-methyl pyrrolidone of polar solvent and 4g molecular weight
4After, add 0.1 mole triethanolamine, implement to force to stir, till the mixed solution of green becomes gelatinous green matter.Thereafter, solution temperature is warming up to 50 ℃ after, waiting temperature is stable, slowly drops into 0.1 mole azanol with 10 fens clock times, implements to force stirring, till the solution becomes laking.Reclaim the peony powder by centrifugation, repeat to clean several times and reclaim with acetone and water, finally being mixed into nano metal powder content is 30 weight % in the mixed solution (90: 10 weight ratios) of propane diols list ethylether and N-methyl pyrrolidone, preserves then.
The result who observes the granularity of described nano metal powder by SEM is, confirmed that the uniform grain sizes that has 40～80nm as shown in Figure 1 distributes, the result of surface analysis (EDS) is to have confirmed that the major part of nano particle is Cu and the oxide that does not form the CuO form as shown in Figure 2.
[experimental example 3]
At 10ml ultra-pure water and 90ml ethylene glycol and 5ml is in the solvent mixture formed of the PVP more than 20,000, by forcing the CuSO as metal precursor of 0.1 mole of stirring and dissolving as the N-NMF of polar solvent and 4g molecular weight
4After, add 0.1 mole diethylamine, implement to force to stir, till the mixed solution of green becomes gelatinous green matter.Thereafter, slowly dropping into 0.1 mole hydrazine with 10 fens clock times is 30% ultra-pure water solution, implements to force to stir, till the solution becomes laking.Reclaim the peony powder by centrifugation, repeat to clean several times and reclaim with acetone and water, finally being mixed into nano metal powder content is 30 weight % in the mixed solution (90: 10 weight ratios) of propane diols list ethylether and N-methyl pyrrolidone, preserves then.
The result who observes the granularity of described nano metal powder by SEM is to have confirmed to have the size distribution of 50～90nm.
[experimental example 4]
At 10ml ultra-pure water and 90ml ethylene glycol and 5ml is in the solvent mixture formed of the PVP more than 20,000, by forcing the CuSO as metal precursor of 0.1 mole of stirring and dissolving as the 2-Pyrrolidone of polar solvent and 4g molecular weight
4After, add 0.2 mole methyl piperazine, implement to force to stir, till the mixed solution of green becomes gelatinous green matter., with 10 fen clock time slowly drop into 0.1 mole hydrazine, implement to force to stir, till solution becomes reddish black or peony thereafter.The reaction temperature of this moment maintains 25 ℃.
Reclaim the reddish black powder by centrifugation, repeat to clean several times and reclaim with acetone and water, finally being mixed into nano metal powder content is 30 weight % in the mixed solution (90: 10 weight ratios) of propane diols list ethylether and N-methyl pyrrolidone, preserves then.
The result who observes the granularity of described nano metal powder by SEM is to have confirmed to have the size distribution of 60～90nm.
[experimental example 5]
In the solvent mixture that 10ml ultra-pure water and 90ml diethylene glycol (DEG) and 5ml form as the N-methyl pyrrolidone and the 4g butanedioic acid methacryloxy ethyl ester of polar solvent, by forcing the AgNO as metal precursor of 0.1 mole of stirring and dissolving
3After, add 0.1 mole MEA and implement and force to stir till even mixing.Thereafter, solution temperature is warming up to 50 ℃ after, waiting temperature is stable, slowly dropping into D-sorbite with 10 fens clock times is 50% ultra-pure water solution, implements to force stirring, till solution becomes Dark grey.Reclaim the peony powder by centrifugation, repeat to clean several times and reclaim with acetone and water, finally being mixed into nano metal powder content is 30 weight % in the mixed solution (90: 10 weight ratios) of propane diols list ethylether and N-methyl pyrrolidone, preserves then.
The result who observes the granularity of described nano metal powder by SEM is to have confirmed to have the size distribution of 30～50nm.
Claims (15)
1. the manufacture method of a metal nanoparticle is characterized in that, described manufacture method comprises: the 1st stage, dissolution of metals precursor in containing the solvent of glycolic solvents; In the 2nd stage, in the solution that in described the 1st stage, produces, add organic amine, till the color that is stirred to solution does not change; And the 3rd stage, in the interpolation in described the 2nd stage slowly add more than one the compound of from the group that hydrazine derivate, sodium hypohosphate, azanol and sodium borohydride are formed, selecting in the solution of organic amine, thereby metallic reducing is separated out.
2. the manufacture method of metal nanoparticle according to claim 1 is characterized in that, described solvent contains the glycolic solvents of 80～99.9 weight portions and the polar solvent of 0.1～20 weight portion.
3. the manufacture method of metal nanoparticle according to claim 2 is characterized in that, described solvent contains the glycolic solvents of 80～99.9 weight portions and the water of 0.1～20 weight portion.
4. the manufacture method of metal nanoparticle according to claim 2 is characterized in that, the total solvent in the described solution contains the glycolic solvents of 60～99.8 weight portions, the polar solvent of 0.1～20 weight portion and the water of 0.1～20 weight portion.
5. the manufacture method of metal nanoparticle according to claim 1, it is characterized in that described glycolic solvents is selected more than one from the group that ethylene glycol, diethylene glycol (DEG), triethylene glycol, propane diols, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol methyl ether, DGDE, butyl carbitol, dipropylene glycol methyl ether and glycerine are formed.
6. the manufacture method of metal nanoparticle according to claim 2; it is characterized in that described polar solvent is selected more than one from the group that 2-Pyrrolidone, acetyl-pyrrolidine ketone, ethyl pyrrolidone, methyl pyrrolidone, vinyl pyrrolidone, cyclohexyl pyrrolidones, dimethyl pyrrolidone, dodecyl pyrrolidone, dimethyl sulfoxide (DMSO), sulfolane, methyl sulfolane, dimethylsulfolane, formamide, NMF, dimethyl formamide, acetamide, methylacetamide and dimethylacetylamide are formed.
7. the manufacture method of metal nanoparticle according to claim 1 is characterized in that, also adds dispersion stabilizer in described the 1st stage or the 2nd stage.
8. the manufacture method of metal nanoparticle according to claim 7, it is characterized in that described dispersion stabilizer is from poly-(vinyl pyrrolidone-co-maleic acid), poly-(vinyl pyrrolidone-co-maleic anhydride), poly-(vinyl pyrrolidone-co-acrylic acid), poly-(vinyl pyrrolidone-co-alkyl acrylate), dimethyl succinate salt, dimethyl succinate, diethyl succinate, butanedioic acid hydrogen ethyl ester, butanedioic acid hydrogen methacryloxy ethyl ester, butanedioic acid dimethyl allene acyloxy ethyl ester, poly-ethyl succinate, repefral, dibutyl phthalate, diallyl phthalate, polydiallyl phthalate, the M-phthalic acid methyl esters, select more than one in the group that phthalic acid methacryloxy ethyl ester and dimethyl allene acyloxy phthalic acid ester are formed.
9. the manufacture method of metal nanoparticle according to claim 1 is characterized in that, adds described organic amine and becomes till 10～12 up to the basicity of solution.
10. the manufacture method of metal nanoparticle according to claim 1, it is characterized in that described organic amine is from ethamine, diethylamine, dimethylamine, triethylamine, trimethylamine, butylamine, dibutylamine, tri-butylamine, oleyl amine, two oleyl amines, ethoxy propylamine, ethoxy ethanol amine, monoethanolamine, diethanol amine, triethanolamine, methylethanolamine, carbinol methine amine, ehtylethanolamine, dimethylethanolamine, methyl diethanolamine, ethylenediamine, diethylenetriamines, amino ethoxy ethamine, two (3-aminopropyl) amine, the 2-[(3-aminopropyl) amino] ethanol, piperazine, methyl piperazine, the hydroxyethyl piperazine, aminoethylpiperazine, imidazoles, select more than one in the methylimidazole.
11. the manufacture method of metal nanoparticle according to claim 1 is characterized in that, described organic amine is an alkylamine, and described 3 stages carry out under 15～30 ℃.
12. the manufacture method of metal nanoparticle according to claim 1 is characterized in that, described organic amine is an alkanolamine, and described 3 stages carry out under 30～60 ℃.
13. the manufacture method of metal nanoparticle according to claim 1 is characterized in that, described metal precursor is the mantoquita or the silver salt that can dissolve in glycolic solvents.
14. the manufacture method of metal nanoparticle according to claim 1 is characterized in that, described metal nanoparticle is a copper nano particles.
15. the manufacture method of metal nanoparticle according to claim 1 is characterized in that, the granularity of described metal nanoparticle is 20～90nm.
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| TWI586462B (en) * | 2010-05-06 | 2017-06-11 | 東進世美肯有限公司 | Method for preparing copper nanoparticle which is capable of being calcined under atmospheric pressure and the copper nanoparticle prepared from the same |
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| CN111992734A (en) * | 2020-08-21 | 2020-11-27 | 山东建邦胶体材料有限公司 | Preparation method of nano-silver with controllable particle size |
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| WO2011139102A2 (en) * | 2010-05-06 | 2011-11-10 | 주식회사 동진쎄미켐 | Method for producing copper nanoparticles capable of being fired at atmospheric pressure |
| WO2014069866A1 (en) * | 2012-10-31 | 2014-05-08 | 주식회사 동진쎄미켐 | Copper paste composition for printed electronics |
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| TWI586462B (en) * | 2010-05-06 | 2017-06-11 | 東進世美肯有限公司 | Method for preparing copper nanoparticle which is capable of being calcined under atmospheric pressure and the copper nanoparticle prepared from the same |
| CN102389949A (en) * | 2011-03-11 | 2012-03-28 | 中国科学院福建物质结构研究所 | Method for preparing sea urchin-shaped nanometer copper particles |
| CN102389949B (en) * | 2011-03-11 | 2015-09-16 | 中国科学院福建物质结构研究所 | A kind of preparation method of sea urchin-shaped nanometer copper particles |
| CN104684669A (en) * | 2012-10-01 | 2015-06-03 | 同和电子科技有限公司 | Method for producing fine silver particles |
| CN106170835A (en) * | 2012-10-31 | 2016-11-30 | 东进世美肯株式会社 | Printed electronic copper paste composition |
| CN106170835B (en) * | 2012-10-31 | 2018-12-04 | 东进世美肯株式会社 | Printed electronic copper paste composition |
| CN103722181A (en) * | 2014-01-21 | 2014-04-16 | 江苏欧耐尔新型材料有限公司 | Method for preparing nano silver powder by using dispersing agent through liquid-phase reduction method |
| CN103722181B (en) * | 2014-01-21 | 2016-01-20 | 江苏欧耐尔新型材料有限公司 | Liquid phase reduction uses dispersant to prepare the method for nano-silver powder |
| CN103990810A (en) * | 2014-05-30 | 2014-08-20 | 洛阳理工学院 | Technology for preparing nanometer indium powder |
| CN104128616A (en) * | 2014-08-12 | 2014-11-05 | 苏州思美特表面材料科技有限公司 | Method for preparing metal powder |
| CN104148668A (en) * | 2014-08-22 | 2014-11-19 | 宁波蓝威环保科技有限公司 | Preparation method of liquid phase nanometer silver colloid |
| CN106670496A (en) * | 2015-11-10 | 2017-05-17 | 南京理工大学 | Preparation method of copper nanowires or copper nanoparticles |
| CN110653380A (en) * | 2019-10-31 | 2020-01-07 | 合肥工业大学 | Method for rapidly preparing gold nanoparticles in alcohol phase at normal temperature |
| CN111774583A (en) * | 2020-07-30 | 2020-10-16 | 金川集团股份有限公司 | Preparation method of superfine silver powder with high tap mass and high specific surface |
| CN111992734A (en) * | 2020-08-21 | 2020-11-27 | 山东建邦胶体材料有限公司 | Preparation method of nano-silver with controllable particle size |
| CN111992734B (en) * | 2020-08-21 | 2022-02-22 | 山东建邦胶体材料有限公司 | Preparation method of nano-silver with controllable particle size |
| CN112024906A (en) * | 2020-08-26 | 2020-12-04 | 山东建邦胶体材料有限公司 | Surface treatment liquid in silver powder preparation process and adding mode |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101618462B (en) | 2014-09-10 |
| KR20100004376A (en) | 2010-01-13 |
| KR101482532B1 (en) | 2015-01-16 |
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