CN100448570C - Preparation method of nanometer copper-silver bimetallic composite powder - Google Patents
Preparation method of nanometer copper-silver bimetallic composite powder Download PDFInfo
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- CN100448570C CN100448570C CNB200710063444XA CN200710063444A CN100448570C CN 100448570 C CN100448570 C CN 100448570C CN B200710063444X A CNB200710063444X A CN B200710063444XA CN 200710063444 A CN200710063444 A CN 200710063444A CN 100448570 C CN100448570 C CN 100448570C
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Abstract
The invention provides a nano-copper-silver double metal powder preparation method--crystal nucleon growth method. The method prepares nano-copper seed crystal using chemical reduction copper ions, makes the copper and silver generate on nano-copper seed crystal to preparing copper silver double metal powder. The process is: first dissolving a small amount of copper ion salts cupric nitrate into water, preparing cup ammonium solution with ammonia complication, then deacidizing it into sol containing nano-copper seed crystal in the water solution of hydrazine hydrate, then making the silver nitrate and cupric nitrate grow on the nano-copper seed crystal in the deacidized process to forming copper-silver double metal particles, preparing final product after washing and drying. The method solves the shortcomings of big waste of copper and silver and non-uniform product quality in prior art. The particle size of prepared nano-copper-silver double metal powder is less than 100 nm, and it has good dispersion and good oxidation resistance property.
Description
Technical field
The invention belongs to metal dust preparing technical field in the metal material, particularly relate to a kind of preparation method of nanometer copper-silver bimetallic composite powder.
Background technology
Along with development of science and technology, the application of nanosized copper silver metal powder more and more widely.As in the conductive filler field, because copper nanoparticle is very easily oxidized at normal temperatures, lose original physics, chemical characteristic, cause electric conductivity to descend, and copper-silver metal powder not only has the character of copper powder and silver powder concurrently, also avoid the weak shortcoming of copper powder non-oxidizability, can under the prerequisite that does not influence its electric conductivity, reduce the cost of silver powder simultaneously, therefore received great concern.In the conducting resinl field, the nanometer copper-silver bimetallic powder has also been brought into play great advantage, and the security of silver conductive adhesive is lower, and the copper conductive adhesive oxide layer that very easily oxidation formation is insulated in air, therefore, copper-silver bimetallic is one of means that address this problem.In addition, copper-silver metal powder has the antibacterial characteristics of copper powder and silver powder again, has strengthened antibiotic broad spectrum activity, has avoided when the copper powder size shortcoming that its fungicidal effectiveness can't long preservation during less than 500nm.Therefore, the nanometer copper-silver bimetallic powder has a good application prospect.
The method for preparing at present copper-silver metal powder mainly is the chemical replacement reaction method, promptly utilizes the displacement reaction of silver ion and copper simple substance, uses the copper on the silver replacement copper particle surface, thereby obtains the copper-silver bimetallic particle of interspersing property.(East China University of Science's journal, 2002,28 (4): 402-405) utilize chemical reduction method to prepare copper powders may earlier, utilize the chemical replacement reaction method to prepare the copper-silver metal powder of particle diameter more than 7 μ m again such as Wu Xiuhua.(Acta PhySico-Chimica Sinica, 2000,16 (4): 366-369) reported that also with commodity micron copper powder be raw material, utilized this method to prepare copper-silver metal powder, prepared product particle diameter is similarly micron order to Gao Baojiao etc.But this kind method exists very big drawback.On the one hand,, therefore be difficult in the water and disperse, so, cause silver ion inhomogeneous, cause to obtain the uniform copper-silver bimetallic powder of quality with mixing of copper powder because copper nanoparticle has high surface energy.On the other hand, by the silver-plated copper-silver metal powder that can only obtain the type of interspersing once, if the copper-silver metal powder of coated with uniform silver must just can obtain through repeatedly silver-plated, this is great waste to silver, and the copper ion that cements out also has been lost in reactant liquor in vain.In addition, copper nanoparticle is not used to and silver ion generation displacement reaction usually, and is too small and part copper particle displacement back is replaced fully by silver with the particle diameter that prevents copper.Therefore, be generally micron order with the copper powder of silver ion generation displacement reaction, so, prepared copper-silver metal powder also has bigger particle diameter usually.Chinese patent CN1197708 discloses a kind of preparation method of nanosized copper silver metal powder, and promptly copper silver coprecipitation has made the copper-silver bimetallic of particle diameter at 25-60nm.This method is that the copper silver that will contain under the effect of reducing agent in the mixed liquor of copper silver ion restores.Though this method can obtain the nanoscale product, but still there is very big drawback.Because the nucleation rate difference of copper, silver, therefore under the reducing agent effect, tend to be restored separately and can't form alloy, on the XRD spectra of copper-silver bimetallic product, (see the Figure of description of this patent) and can only see the characteristic diffraction peak of silver and can't see the characteristic diffraction peak of copper.
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing the nanosized copper silver bimetallic composite powder.This method has been avoided the waste and the loss of silver and copper, and the nanosized copper silver bimetallic composite powder quality that obtains by this method is even, and particle diameter is less than 100nm, narrow particle size distribution and have good non-oxidizability.
A kind of method for preparing the nanosized copper silver bimetallic composite powder provided by the present invention may further comprise the steps:
1. the preparation of the aqueous solution
(1) preparation of copper ammon solution: with solid Cu (NO
3)
23H
2O is water-soluble, is made into the aqueous solution of concentration in the 0.01-0.1M scope, and ammoniacal liquor is added in this copper nitrate aqueous solution, and beginning solution becomes muddiness is treated to stop to add ammoniacal liquor after solution becomes clearly once more;
(2) preparation of copper nitrate+silver nitrate aqueous solution: respectively with solid Cu (NO
3)
23H
2O and AgNO
3Water-soluble, be made into concentration all copper nitrate in the 0.1-1M scope and silver nitrate aqueous solution, with these two kinds of aqueous solution, the mol ratio of copper silver is 1 in the mixed liquor: 5-5: 1 again;
(3) preparation of hydrazine hydrate aqueous solution: hydrazine hydrate is mixed with water, and dose volume concentration is the hydrazine hydrate aqueous solution of 1-20%;
2. solution reduction produces nanometer copper crystal seed
The copper ammon solution for preparing is mixed with hydrazine hydrate solution, and temperature is controlled at 15-95 ℃, stirs 5-30 minute, obtains nanometer copper colloidal sol russet;
3. copper nitrate+the silver nitrate aqueous solution for preparing is joined in the nanometer copper colloidal sol that contains the reducing agent hydrazine hydrate, stir, insulation finishes until reaction, produces a large amount of black copper silver bimetal powder sediments in the solution;
4. adopt conventional washing and drying means, finally obtain black nano copper-silver bimetallic powder.
The inventive method is to utilize chemical reduction method to prepare nanometer copper crystal seed in solution earlier, copper ion and silver ion is grown and independent nucleation on nanometer copper crystal seed in the process that is reduced, thereby obtain nanometer copper-silver bimetallic composite powder.Because nanometer copper crystal seed is stable dispersion in solution, has so just avoided mixing uneven drawback, thereby obtained the uniform copper-silver bimetallic powder of quality.In addition,, therefore avoided obtaining the defective of copper-silver bimetallic, prevented the loss of copper, made copper and silver all have higher utilization rate by sacrifice copper owing to be to have adopted reduction reaction rather than displacement reaction in the preparation process.
The inventive method is compared with the disclosed method of present technology, has the following advantages:
1. the nucleus growth method that is adopted has greatly improved raw material availability, has prevented the waste and the loss of silver and copper.
2. owing to provide the copper particle of crystal seed in system, evenly to disperse in the technology, therefore avoided owing to mix the inhomogeneous uneven shortcoming of product quality that causes.
3. the particle mean size of prepared copper-silver metal powder is less than 100nm.
4. owing to contain nanometer copper crystal seed and excessive reductant hydrazine hydrate in the system, so copper and silver can directly be grown on crystal seed in precipitation process and avoided independent nucleation and can't form the drawback of alloy.
Description of drawings
Fig. 1 is preparation technology's flow chart of the present invention.
Fig. 2 is the XRD spectra of the nanometer copper-silver bimetallic powder that makes.
Fig. 3 is the transmission electron microscope photo of the nanometer copper-silver bimetallic powder that makes among the embodiment 1.
Fig. 4 is the transmission electron microscope photo of the nanometer copper-silver bimetallic powder that makes among the embodiment 2.
Fig. 5 is the transmission electron microscope photo of the nanometer copper-silver bimetallic powder that makes among the embodiment 3.
Fig. 6 is the nanometer copper-silver bimetallic powder that makes and the thermogravimetric curve figure of pure copper nanoparticle.
The specific embodiment
Take by weighing 0.24g solid Cu (NO
3)
23H
2O is dissolved in the 100ml water, is made into the aqueous solution that concentration is 0.01M.Add certain amount of ammonia water then, beginning solution becomes muddiness is treated to stop to add ammoniacal liquor after solution becomes clearly once more.Take by weighing 8.4g Cu (NO
3)
23H
2O is dissolved in 100ml water, is made into the aqueous solution that concentration is 0.35M, takes by weighing 1.19g AgNO simultaneously
3Be dissolved in 50ml water, be made into the aqueous solution that concentration is 0.14M, again this two solution is mixed, make 150ml Cu (NO
3)
2+ AgNO
3Mixed solution, Cu/Ag mol ratio are 5: 1.Measure the 10ml hydrazine hydrate and mix with 90ml water, its volumetric concentration is 10%.The copper ammon solution for preparing is mixed under brute force stirs with hydrazine hydrate solution, 50 ℃ of insulations of water-bath, solution becomes bronzing rapidly, continues insulation, stirs 10 minutes.With the Cu (NO for preparing
3)
2+ AgNO
3The aqueous solution joins in the bronzing nanometer copper colloidal sol that contains reducing agent, the powerful stirring, and insulation finishes until reaction, produces a large amount of black precipitate in the solution.Product is filtered, and wash with water 5 times, the consumption of each water is 50ml, removes remaining water for 3 times with absolute ethanol washing again, and the consumption of each absolute ethyl alcohol is 50ml.Copper-silver bimetallic placed carried out drying in the vacuum drying chamber 5 hours, its temperature is controlled at 60 ℃, obtains the black copper silver bimetallic composite powder.Through XRD (seeing Fig. 2 (a)), TEM (see figure 3) and TG (seeing Fig. 6 (b)) analyze with copper-silver bimetallic composite powder.
Take by weighing 0.24g solid Cu (NO
3)
23H
2O is dissolved in the 100ml water, is made into the aqueous solution that concentration is 0.01M.Add certain amount of ammonia water then, beginning solution becomes muddiness is treated to stop to add ammoniacal liquor after solution becomes clearly once more.Take by weighing 4.8g Cu (NO
3)
23H
2O is dissolved in 100ml water, is made into the aqueous solution that concentration is 0.2M, takes by weighing 1.7g AgNO simultaneously
3Be dissolved in 50ml water, be made into the aqueous solution that concentration is 0.2M, again this two solution is mixed, make 150ml Cu (NO
3)
2+ AgNO
3Mixed solution, Cu/Ag mol ratio are 2: 1.Measure the 10ml hydrazine hydrate and mix with 90ml water, its volumetric concentration is 10%.Other steps are with embodiment 1.Through XRD (seeing Fig. 2 (b)), TEM (see figure 4) and TG (seeing Fig. 6 (c)) analyze with the copper-silver bimetallic composite powder that makes.
Embodiment 3
Take by weighing 0.24g solid Cu (NO
3)
23H
2O is dissolved in the 100ml water, is made into the aqueous solution that concentration is 0.01M.Add certain amount of ammonia water then and begin the solution becomes muddiness, treat to stop to add ammoniacal liquor after solution becomes clearly once more.Take by weighing 0.96g Cu (NO
3)
23H
2O is dissolved in 25ml water, is made into the aqueous solution that concentration is 0.16M, takes by weighing 4.25g AgNO simultaneously
3Be dissolved in 75ml water, be made into the aqueous solution that concentration is 0.33M, again this two solution is mixed, make 100ml Cu (NO
3)
2+ AgNO
3Mixed solution, Cu/Ag mol ratio are 1: 5.Measure the 10ml hydrazine hydrate and mix with 90ml water, its volumetric concentration is 10%.Other steps are with embodiment 1.Through XRD (seeing Fig. 2 (c)), TEM (see figure 5) and TG (seeing Fig. 6 (d)) analyze with the copper-silver bimetallic composite powder that makes.
As seen from Figure 2, contain the silver and the characteristic peak of copper in the XRD spectra of product simultaneously, prove that what make is copper-silver metal powder.From Fig. 2, can also find out significantly, along with the increase of Cu/Ag mol ratio, the characteristic peak strength-enhanced of copper and the characteristic peak intensity of silver weakens, the content that proves copper silver in the product changes with the variation of Cu/Ag mol ratio.
By Fig. 3 and Fig. 4 as seen, when the Cu/Ag mol ratio was respectively 5: 1 and 2: 1, its pattern of prepared copper-silver metal powder was a chain, and particle minor axis size is between 20-50nm, and particle mean size is 30nm, narrow particle size distribution, and the reunion amount is little.
As seen from Figure 5, when the Cu/Ag mol ratio is 1: 5, the chain particle of its pattern for being formed by connecting by tiny spheric granules, the minor axis size is less than 10nm, because particle diameter is minimum, the reunion amount slightly increases.
As seen from Figure 6, nearly 20% (the seeing Fig. 6 (a)) of the weightening finish of pure copper nanoparticle, the Cu/Ag mol ratio is that the heat weightening finish of 5: 1 copper-silver metal powder is 10% (seeing Fig. 6 (b)), the Cu/Ag mol ratio is that 2: 1 product heat weightening finish is 9% (seeing Fig. 6 (c)), and the Cu/Ag mol ratio to be 1: 5 product heat weightening finish be less than 3% (seeing Fig. 6 (d)), can obviously find out thus, the non-oxidizability of prepared nanometer copper-silver bimetallic powder is compared with pure copper nanoparticle and is improved, and along with the non-oxidizability of the increase product of silver content strengthens gradually.
Claims (6)
1. method for preparing the nanosized copper silver bimetallic composite powder may further comprise the steps:
(1) preparation of the aqueous solution
1. the preparation of copper ammon solution: with solid Cu (NO
3)
23H
2O is water-soluble, is made into the aqueous solution of concentration in the 0.01-0.1M scope, and ammoniacal liquor is added in this copper nitrate aqueous solution, and beginning solution becomes muddiness is treated to stop to add ammoniacal liquor after solution becomes clearly once more;
2. the preparation of copper nitrate+silver nitrate aqueous solution: respectively with solid Cu (NO
3)
23H
2O and AgNO
3Water-soluble, be made into concentration all copper nitrate in the 0.1-1M scope and silver nitrate aqueous solution, with these two kinds of aqueous solution, the mol ratio of copper silver is 1 in the mixed liquor: 5-5: 1 again;
3. the preparation of hydrazine hydrate aqueous solution: hydrazine hydrate is mixed with water, and dose volume concentration is the hydrazine hydrate aqueous solution of 1-20%;
(2) solution reduction produces nanometer copper crystal seed
The copper ammon solution for preparing is mixed with hydrazine hydrate solution, and temperature is controlled at 15-95 ℃, stirs 5-30 minute, obtains nanometer copper colloidal sol russet;
(3) copper nitrate+silver nitrate aqueous solution for preparing is joined in the nanometer copper colloidal sol that contains the reducing agent hydrazine hydrate, stir, insulation finishes until reaction, produces a large amount of black copper silver bimetal powder sediments in the solution;
(4) adopt conventional washing and drying means, finally obtain black nano copper-silver bimetallic powder.
2. according to the method for claim 1, it is characterized in that the concentration range of copper nitrate solution is at 0.01-0.03M when wherein preparing copper ammon solution.
3. according to the method for claim 1, it is characterized in that the concentration of copper nitrate solution is 0.1-0.4M when wherein preparing copper nitrate+silver nitrate aqueous solution.
4. according to the method for claim 1, it is characterized in that the concentration of liquor argenti nitratis ophthalmicus is 0.1-0.4M when wherein preparing copper nitrate+silver nitrate aqueous solution.
5. according to the method for claim 1, it is characterized in that the volumetric concentration of wherein preparing hydrazine hydrate solution is 5-15%.
6. according to the method for claim 1, it is characterized in that the temperature in (2) step is 25-50 ℃, stirs 10-15 minute.
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| CN102554264B (en) * | 2012-02-28 | 2013-11-06 | 东北大学 | Preparation method of palladium-silver alloy powder for conductive paste |
| US9700940B2 (en) | 2012-09-27 | 2017-07-11 | Lockheed Martin Corporation | Metal nanoparticles formed around a nucleus and scalable processes for producing same |
| CN103691965A (en) * | 2013-12-20 | 2014-04-02 | 华南理工大学 | Preparation method for copper/silver heterojunction nano-particles |
| CN104754875B (en) * | 2015-03-08 | 2018-01-23 | 北京化工大学 | The preparation method of copper@silver metal conducting films and its application on a printed circuit board |
| CN106392097A (en) * | 2016-09-29 | 2017-02-15 | 武汉科技大学 | Cu-Ag bimetallic nano material, preparation method and application thereof |
| CN106513706B (en) * | 2016-12-01 | 2018-03-16 | 上海银波生物科技有限公司 | A kind of preparation method for being used for Nano Silver nucleus in ball shape silver powder production technology |
| CL2017003488A1 (en) * | 2017-12-29 | 2018-05-25 | Univ Chile | Bimetallic method for the construction of nanoparticle (nps) of metallic copper, for coating with smaller nanoparticles of the secondary metal. |
| CN111595914B (en) * | 2020-06-24 | 2022-06-07 | 河北工业大学 | Preparation method of titanium oxide nanotube array-based photoelectrochemical detection electrode |
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| CN1197708A (en) * | 1998-03-03 | 1998-11-04 | 浙江大学 | Preparation of nanometer silver-copper alloy powder |
| JP2000248303A (en) * | 1999-03-03 | 2000-09-12 | Dowa Mining Co Ltd | Production of silver-coated copper powder |
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| CN1751828A (en) * | 2005-10-24 | 2006-03-29 | 南京大学 | Method for preparing micron/submicron bimetal nano ball shell |
| JP2006161081A (en) * | 2004-12-03 | 2006-06-22 | Dowa Mining Co Ltd | Silvered copper powder, its manufacturing method, and conductive paste |
-
2007
- 2007-02-01 CN CNB200710063444XA patent/CN100448570C/en not_active Expired - Fee Related
Patent Citations (5)
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| CN1197708A (en) * | 1998-03-03 | 1998-11-04 | 浙江大学 | Preparation of nanometer silver-copper alloy powder |
| JP2000248303A (en) * | 1999-03-03 | 2000-09-12 | Dowa Mining Co Ltd | Production of silver-coated copper powder |
| US20040221685A1 (en) * | 2002-10-30 | 2004-11-11 | In-Bum Jeong | Method for manufacturing nano-scaled copper powder by wet reduction process |
| JP2006161081A (en) * | 2004-12-03 | 2006-06-22 | Dowa Mining Co Ltd | Silvered copper powder, its manufacturing method, and conductive paste |
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