CN104057098A - Preparation method for micro-nano-structure porous copper powder - Google Patents
Preparation method for micro-nano-structure porous copper powder Download PDFInfo
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- CN104057098A CN104057098A CN201410253457.3A CN201410253457A CN104057098A CN 104057098 A CN104057098 A CN 104057098A CN 201410253457 A CN201410253457 A CN 201410253457A CN 104057098 A CN104057098 A CN 104057098A
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Abstract
The invention discloses a preparation method for micro-nano-structure porous copper powder. Firstly, a sodium hydroxide solution and a Cu<2+> ion solution are mixed, and a certain amount of ethylene glycol is dropped into the mixture to obtain a precursor solution containing Cu<2+>; secondly, the precursor solution is moved into a reaction kettle, sealed and subjected to hydrothermal reaction for hours at a certain temperature; finally, sediments obtained after the reaction are washed, settled and dried in vacuum to obtain the micro-nano-structure porous copper powder. The preparation method has the advantages of simple process, safety, reliability, innocuity, zero pollution and lower cost; the micro-nano-structure porous copper powder is high in purity, varied in shape, variable in particle size and pore diameter and large in specific surface area and can meet the requirements on copper powder in a plurality of fields.
Description
Technical field
The invention belongs to the preparing technical field of nano material, relate to a kind of preparation method of micro nano structure porous copper powder.
Background technology
Owing to having higher surface-active and good conduction, heat conductivility, porous copper powder is widely used in the fields such as powder metallurgy, catalyst, electrically-conducting paint, non-enzymatic glucose sensor, surface enhanced Raman scattering substrate and electromagnetic shielding material.
Although tradition is prepared the method (as: gas phase steam method, gamma-rays method, plasma method and electrolysis etc.) of copper powder, all there are many advantages separately, have corresponding deficiency simultaneously, be especially difficult to prepare the porous copper powder of micro nano structure.The de-alloyage of chemistry or electrochemistry is often applied to preparing porous metals.Publication number is the preparation method of the disclosed a kind of nanometer porous copper powder of Chinese patent application of CN102363217A, first adopt ball-milling method to obtain Al-Cu alloy powder, then the alloy powder obtaining is taken off to alloy treatment and obtains nanometer porous copper powder in alkaline solution.The method technique is simple, and the aperture that obtains Porous Cu is less.Publication number is a kind of disclosed method of being prepared porous copper powder by electro-deposition Cu-Al-Mg-Li alloy of the Chinese patent application of CN102912384A, first by electrochemical deposition, prepare the thick product of Cu-Al-Mg-Li alloy, through ball milling, obtain its alloy powder again, finally by acid elution, obtain Porous Cu powder.The method has the features such as technique is simple, energy consumption is low, pollution-free, production cost is low.Although realizing, de-alloyage prepares on a large scale the relatively controlled porous copper powder in particle diameter, aperture, and technique is also fairly simple, but the method alloy used often adopts high-temperature melting method, it has, and energy consumption is high, equipment investment large, pollute the shortcomings such as large, product is oxidizable, and de-alloy process needs corrosion to fall other elements in alloy, this has just caused the significant wastage of resource, increases cost, and the Porous Cu obtaining in addition often contains other impurity elements.Publication number is the preparation method that the Chinese patent application of CN101332514A discloses a kind of porous copper powder, adopt coordination precipitation-thermal decomposition method, first at normal temperatures and pressures synthesize copper powder presoma sediment, then under non-oxidizing atmosphere, thermal decomposition presoma obtains porous copper powder.Although the method is safe and reliable, nontoxic pollution-free, be difficult to obtain the controlled porous copper powder of particle diameter, aperture and pattern.
Therefore, explore the novel preparation method who prepares porous copper powder, to reducing energy consumption, energy-saving and emission-reduction, raising rate of return on investment and enhancing productivity, there is important practical significance.
Summary of the invention
For defect of the prior art, the object of the present invention is to provide a kind of preparation method of micro nano structure porous copper powder.The method process is simple, safe and reliable, nontoxic pollution-free, and cost is lower; By changing concentration, reaction temperature and the time of each composition in presoma, just can obtain the porous copper powder in different grain size, aperture, be convenient to the different porous copper powders that require of preparation of industrialization; High, the granularity of porous copper powder purity of preparation and aperture is controlled, specific area is large, can meet the demand of many fields to copper powder.The Porous Cu that the method obtains is that the nano copper particle self assembly that obtains of reduction forms in reaction, is different from the growth mechanism that the oxide micro-nano rice structure direct-reduction by copper of current report forms.The parameters such as concentration of reaction temperature, time and reactant can be used to regulate pattern, size and the aperture of micro nano structure copper particle.
Object of the present invention is achieved through the following technical solutions:
The preparation method who the present invention relates to a kind of micro nano structure porous copper powder, comprises following steps:
(1) preparation is containing Cu
2+precursor liquid: by sodium hydroxide solution and Cu
2+solion mixes, and obtains nattier blue emulsion after stirring; Then drip ethylene glycol and constantly stir, obtaining the solution of royal blue; Drip deionized water or deionized water and ethanol constant volume;
(2) will be containing Cu
2+precursor liquid packs in autoclave, after sealing, at 120 ℃～250 ℃, reacts 4～24h;
(3) sediment that obtains of reaction washs, obtains micro nano structure porous copper powder after sedimentation and vacuum drying.
Preferably, described containing Cu
2+in precursor liquid, the content of NaOH is 0.1～5.0mol/L, Cu
2+content be 0.05～0.5mol/L, the percent by volume of ethylene glycol is 5%～50%, the percent by volume of ethanol is 0%～50%.The concentration of reactant plays a key effect in preparing micro nano structure porous copper powder.The amount of NaOH during lower than 0.1mol/L, can contain the oxide of copper in product; During higher than 5.0mol/L, be difficult to obtain micro nano structure porous copper powder.Cu
2+amount lower than 0.05mol/L or higher than 0.5mol/L, all can not form porous copper powder.The percent by volume of ethylene glycol lower than 5% time, contains the oxide of copper in product; Higher than 50% time, the copper powder obtaining does not have porous.The percent by volume of ethanol higher than 50% time, is difficult to form porous copper powder.
Preferably, the percent by volume of described ethanol is 0%～10%.This concentration range is conducive to form the uniform micro nano structure porous copper powder of particle diameter and aperture.
Preferably, the percent by volume of described ethylene glycol is 5%～25%.This concentration range is conducive to form micro nano structure porous copper powder, and can realize the adjusting of aperture and particle diameter.
Preferably, in step (2), described reaction temperature is 140 ℃～200 ℃.Porous copper powder particle diameter and aperture uniformity that this temperature range obtains are better.
Preferably, in step (2), the described reaction time is 8～12h.This time range guarantees not contain in porous copper powder the oxide of copper on the one hand, and the uniformity in Porous Cu aperture is better on the other hand, and can realize the adjusting in aperture.
Preferably, described containing Cu
2+cu in precursor liquid
2+be selected from one or more in cupric sulfate pentahydrate, copper chloride dihydrate, nitrate trihydrate copper, a water acetic acid copper, copper sulphate, copper chloride, copper nitrate, Schweinfurt green.
Preferably, described Cu
2+be selected from one or more in cupric sulfate pentahydrate, a water acetic acid copper, copper sulphate, Schweinfurt green.
Compared with prior art, the present invention has following beneficial effect:
1, simple, the nontoxic pollution-free of preparation process of the present invention and cost are lower, can meet the demand of large-scale production.
2, the present invention produces the porous copper powder obtaining, and does not contain the oxide impurity of copper, and crystallinity is better; Particle diameter is 0.5～5 μ m, and aperture is 0～500nm, and controlled range is very large.
3, the present invention can obtain the micro nano structure porous copper powder of different-grain diameter, aperture and pattern by adjusting each constituent concentration of precursor liquid, reaction temperature and time etc., makes it meet multi-purpose demand.
Accompanying drawing explanation
By reading the detailed description of non-limiting example being done with reference to the following drawings, it is more obvious that other features, objects and advantages of the present invention will become:
Fig. 1 is preparation technology's flow chart of micro nano structure porous copper powder in the present invention;
Fig. 2 is the XRD figure of micro nano structure porous copper powder in the present invention;
Fig. 3 is the SEM figure of micro nano structure porous copper powder in the present invention; Wherein, a), for the SEM figure of the micro nano structure porous copper powder for embodiment 1, (b) be the SEM figure of the micro nano structure porous copper powder of embodiment 10.
The specific embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.Following examples will contribute to those skilled in the art further to understand the present invention, but not limit in any form the present invention.It should be pointed out that to those skilled in the art, without departing from the inventive concept of the premise, can also make some distortion and improvement.These all belong to protection scope of the present invention.
embodiment 1
Preparation technology's flow chart of the micro nano structure porous copper powder that the present embodiment relates to as shown in Figure 1, specifically comprises the following steps:
(1) preparation contains Cu precursor liquid: first, 0.8g mono-water acetic acid copper is joined in a certain amount of deionized water; Secondly, the aqueous solution that contains 1.6g NaOH is joined to above-mentioned Cu
2+in solion, obtain light blue emulsion; Again, in above-mentioned solution, add 5mL ethylene glycol; Finally, adding a certain amount of deionized water to make cumulative volume is 40mL.In whole process, need continuous stirring, last stir about 1h.
(2) above-mentioned precursor liquid is packed in autoclave and sealing, then reactor is put into and be set as in advance the stove of 140 ℃, after reaction 12h, take out reactor, make it naturally cooling.
(3) open reactor, by the sediment cyclic washing obtaining, sedimentation for several times, after 70 ℃ of vacuum drying, obtain micro nano structure porous copper powder.
As shown in Figure 2, as shown in Figure 2, all peaks are the peak of corresponding copper all, and the impurity phase that does not contain the oxide of copper in porous copper powder is described for the XRD figure of the micro nano structure porous copper powder that the present embodiment obtains, and sharp-pointed XRD diffraction maximum also shows that the crystallinity of copper powder is better; Fig. 3 (a) is the SEM figure of this micro nano structure porous copper powder, as shown in Figure 3, is porous copper ball, its average grain diameter approximately 3.4 μ m, the about 150nm of average pore size.
embodiment 2
Preparation technology's flow chart of the micro nano structure porous copper powder that the present embodiment relates to as shown in Figure 1, specifically comprises the following steps:
(1) preparation contains Cu precursor liquid: first, 0.5g cupric sulfate pentahydrate is joined in a certain amount of deionized water; Secondly, the aqueous solution that contains 8g NaOH is joined to above-mentioned Cu
2+in solion, obtain light blue emulsion; Again, in above-mentioned solution, add 2mL ethylene glycol; Finally, adding the ethanol of 5mL and a certain amount of deionized water to make cumulative volume is 40mL.In whole process, need continuous stirring, last stir about 30min.
(2) above-mentioned precursor liquid is packed in autoclave and sealing, then reactor is put into and be set as in advance the stove of 250 ℃, after reaction 24h, take out reactor, make it naturally cooling.
(3) open reactor, by the sediment cyclic washing obtaining, sedimentation for several times, after 70 ℃ of vacuum drying, obtain micro nano structure porous copper powder.
The micro nano structure porous copper powder that the present embodiment obtains is branch shape, and the oxide and the crystallinity that do not contain copper are better; Its particle diameter approximately 1.0 μ m, the about 80nm in aperture, length is 3～5 μ m.
embodiment 3
Preparation technology's flow chart of the micro nano structure porous copper powder that the present embodiment relates to as shown in Figure 1, specifically comprises the following steps:
(1) preparation contains Cu precursor liquid: first, 1.6g mono-water acetic acid copper is joined in a certain amount of deionized water; Secondly, the aqueous solution that contains 0.16g NaOH is joined to above-mentioned Cu
2+in solion, obtain light blue emulsion; Again, in above-mentioned solution, add 15mL ethylene glycol; Finally, adding a certain amount of deionized water to make cumulative volume is 40mL.In whole process, need continuous stirring, last stir about 1h.
(2) above-mentioned precursor liquid is packed in autoclave and sealing, then reactor is put into and be set as in advance the stove of 200 ℃, after reaction 16h, take out reactor, make it naturally cooling.
(3) open reactor, by the sediment cyclic washing obtaining, sedimentation for several times, after 70 ℃ of vacuum drying, obtain micro nano structure porous copper powder.
The micro nano structure porous copper powder that the present embodiment obtains is spherical, and the oxide and the crystallinity that do not contain copper are better, its particle diameter approximately 2.0 μ m, the about 30nm in aperture.
embodiment 4
Preparation technology's flow chart of the micro nano structure porous copper powder that the present embodiment relates to as shown in Figure 1, specifically comprises the following steps:
(1) preparation contains Cu precursor liquid: first, 0.8g mono-water acetic acid copper is joined in a certain amount of deionized water; Secondly, the aqueous solution that contains 1.6g NaOH is joined to above-mentioned Cu
2+in solion, obtain light blue emulsion; Again, in above-mentioned solution, add 5mL ethylene glycol; Finally, adding a certain amount of deionized water to make cumulative volume is 40mL.In whole process, need continuous stirring, last stir about 1h.
(2) above-mentioned precursor liquid is packed in autoclave and sealing, then reactor is put into and be set as in advance the stove of 200 ℃, after reaction 12h, take out reactor, make it naturally cooling.
(3) open reactor, by the sediment cyclic washing obtaining, sedimentation for several times, after 70 ℃ of vacuum drying, obtain micro nano structure porous copper powder.
The micro nano structure porous copper powder that the present embodiment obtains is spherical, and the oxide and the crystallinity that do not contain copper are better, its particle diameter approximately 3.2 μ m, the about 100nm in aperture.
embodiment 5
In the preparation of micro nano structure porous copper powder, the amount of institute's hydro-oxidation sodium is a 0.4g, and reaction temperature is 180 ℃, and other conditions are with embodiment 4.
The micro nano structure porous copper powder that the present embodiment obtains is spherical, and the oxide and the crystallinity that do not contain copper are better, its particle diameter approximately 4.0 μ m, the about 350nm in aperture.
embodiment 6
The amount that adds a water acetic acid copper in the preparation of micro nano structure porous copper powder is a 2.4g, and the reaction time is 18h, and other conditions are with embodiment 4.
The micro nano structure porous copper powder that the present embodiment obtains is spherical, and the oxide and the crystallinity that do not contain copper are better, its particle diameter approximately 4.2 μ m, the about 300nm in aperture.
embodiment 7
In the preparation of micro nano structure porous copper powder, the reaction time is a 6h, and other conditions are with embodiment 4.
The micro nano structure porous copper powder that the present embodiment obtains is branch shape, and the oxide and the crystallinity that do not contain copper are better, its particle diameter approximately 2.0 μ m, and the about 90nm in aperture, length is 3～5 μ m.
embodiment 8
The amount that adds a water acetic acid copper in the preparation of micro nano structure porous copper powder is a 4g, and other conditions are with embodiment 4.
The micro nano structure porous copper powder that the present embodiment obtains is spherical, and the oxide and the crystallinity that do not contain copper are better, its particle diameter approximately 4.4 μ m, the about 200nm in aperture.
embodiment 9
The amount that adds ethylene glycol and ethanol in the preparation of micro nano structure porous copper powder is respectively 20mL and a 10mL, and other conditions are with embodiment 1.
The micro nano structure porous copper powder that the present embodiment obtains is spherical, and the oxide and the crystallinity that do not contain copper are better, its particle diameter approximately 3.2 μ m, the about 80nm in aperture.
embodiment 10
The amount that adds ethanol in the preparation of micro nano structure porous copper powder is respectively a 20mL, and reaction temperature is 120 ℃, and other conditions are with embodiment 1.
It is better that the micro nano structure porous copper powder that the present embodiment obtains does not contain oxide and the crystallinity of copper; Its SEM figure, as shown in Fig. 3 (b), is branch shape, its average grain diameter approximately 1.5 μ m, and the about 100nm of average pore size, length is 5～10 μ m.
embodiment 11
The amount that adds ethanol in the preparation of micro nano structure porous copper powder is respectively a 4mL, and reaction temperature is 160 ℃, and other conditions are with embodiment 1.
The micro nano structure porous copper powder that the present embodiment obtains is spherical, and the oxide and the crystallinity that do not contain copper are better, its particle diameter approximately 3.4 μ m, the about 200nm in aperture.
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under Spirit Essence of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (8)
1. a preparation method for micro nano structure porous copper powder, is characterized in that, comprises following steps:
(1) preparation is containing Cu
2+precursor liquid: by sodium hydroxide solution and Cu
2+solion mixes, and obtains nattier blue emulsion after stirring; Then drip ethylene glycol and constantly stir, obtaining the solution of royal blue; Drip deionized water or deionized water and ethanol constant volume;
(2) will be containing Cu
2+precursor liquid packs in autoclave, after sealing, at 120 ℃～250 ℃, reacts 4～24h;
(3) sediment that obtains of reaction washs, obtains micro nano structure porous copper powder after sedimentation and vacuum drying.
2. preparation method according to claim 1, is characterized in that, described containing Cu
2+in precursor liquid, the content of NaOH is 0.1～5.0mol/L, Cu
2+content be 0.05～0.5mol/L, the percent by volume of ethylene glycol is 5%～50%, the percent by volume of ethanol is 0%～50%.
3. preparation method according to claim 2, is characterized in that, the percent by volume of described ethanol is 0%～10%.
4. preparation method according to claim 3, is characterized in that, the percent by volume of described ethylene glycol is 5%～25%.
5. preparation method according to claim 1, is characterized in that, in step (2), described reaction temperature is 140 ℃～200 ℃.
6. preparation method according to claim 1, is characterized in that, in step (2), the described reaction time is 8～12h.
7. preparation method according to claim 1, is characterized in that, described containing Cu
2+cu in precursor liquid
2+be selected from one or more in cupric sulfate pentahydrate, copper chloride dihydrate, nitrate trihydrate copper, a water acetic acid copper, copper sulphate, copper chloride, copper nitrate, Schweinfurt green.
8. preparation method according to claim 7, is characterized in that, described Cu
2+be selected from one or more in cupric sulfate pentahydrate, a water acetic acid copper, copper sulphate, Schweinfurt green.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104475750A (en) * | 2014-12-02 | 2015-04-01 | 广西大学 | Preparation method of superfine copper powder |
| CN107745133A (en) * | 2017-10-07 | 2018-03-02 | 江西省科学院能源研究所 | A kind of inexpensive environment-friendly preparation method thereof of Nanometer Copper |
| CN112021334A (en) * | 2020-09-10 | 2020-12-04 | 中国有色桂林矿产地质研究院有限公司 | Porous copper powder carrier-loaded silver-based antibacterial material and preparation method thereof |
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| CN101332514A (en) * | 2008-07-30 | 2008-12-31 | 中南大学 | Preparation method of porous copper powder |
| CN101590528A (en) * | 2009-06-19 | 2009-12-02 | 山东大学 | A kind of preparation method of nano porous copper |
| CN101596598A (en) * | 2009-07-01 | 2009-12-09 | 济南大学 | A kind of preparation method of whole continuous nano-porous copper |
| CN102240813A (en) * | 2010-05-10 | 2011-11-16 | 中国科学院过程工程研究所 | Preparing method for cubic crystallized copper micro powder |
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2014
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20060042415A1 (en) * | 2004-08-30 | 2006-03-02 | Jeng-Gong Duh | Method for making nano-scale lead-free solder |
| CN101332514A (en) * | 2008-07-30 | 2008-12-31 | 中南大学 | Preparation method of porous copper powder |
| CN101590528A (en) * | 2009-06-19 | 2009-12-02 | 山东大学 | A kind of preparation method of nano porous copper |
| CN101596598A (en) * | 2009-07-01 | 2009-12-09 | 济南大学 | A kind of preparation method of whole continuous nano-porous copper |
| CN102240813A (en) * | 2010-05-10 | 2011-11-16 | 中国科学院过程工程研究所 | Preparing method for cubic crystallized copper micro powder |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104475750A (en) * | 2014-12-02 | 2015-04-01 | 广西大学 | Preparation method of superfine copper powder |
| CN107745133A (en) * | 2017-10-07 | 2018-03-02 | 江西省科学院能源研究所 | A kind of inexpensive environment-friendly preparation method thereof of Nanometer Copper |
| CN112021334A (en) * | 2020-09-10 | 2020-12-04 | 中国有色桂林矿产地质研究院有限公司 | Porous copper powder carrier-loaded silver-based antibacterial material and preparation method thereof |
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Application publication date: 20140924 |