CN106424751A - Preparation method of nano copper powder - Google Patents
Preparation method of nano copper powder Download PDFInfo
- Publication number
- CN106424751A CN106424751A CN201611015074.8A CN201611015074A CN106424751A CN 106424751 A CN106424751 A CN 106424751A CN 201611015074 A CN201611015074 A CN 201611015074A CN 106424751 A CN106424751 A CN 106424751A
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- powder
- copper
- copper nanoparticle
- calcium
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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
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
- B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
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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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
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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
Abstract
The invention discloses a preparation method of nano copper powder. Copper oxide and calcium oxide powder are made into calcium cuprate powder by mechanical mixing and calcination technologies, then the calcium cuprate powder is reduced in a hydrogen atmosphere, then cleaning with a dilute hydrochloric acid solution is carried out, and the nano copper powder is obtained. The preparation method is simple in technology, the used raw materials are low-cost and are easy to obtain, no special equipment is required in a mixing stage, a calcination stage or a reduction stage, and rapid continuous mass production can be realized. The prepared nano copper powder is uniform in particle size, good in dispersity and low in oxygen content, and the mean particle size of primary particles is around 20 nanometers.
Description
Technical field
The present invention relates to prepared by Metallic Functional Materials, a kind of preparation method of copper nanoparticle is specifically provided, belongs to metal
Field of powder preparation.
Background technology
Copper nanoparticle has that particle size is little, specific surface area big, Active sites number is many, resistivity is low, quantum chi
The various features such as very little effect and macro quanta tunnel effect, in the system of the material such as electric slurry, ceramic material and chemical catalyst
It is with a wide range of applications in standby.With the increasingly depleted of Precious Metals Resources and the continuous decline of electronic devices and components price, use
The low price such as copper metal replaces the noble metals such as silver to become a main trend of electronic devices and components development as conductive and Heat Conduction Material,
Wherein the preparation that the noble metal powders such as super fine silver powder are used for electric slurry is replaced to have with copper nanoparticle and its composite
Certain probability.
At present, the preparation method of copper powder is a lot, can be classified as solid phase method, vapor phase method and liquid phase method three major types.Solid phase
The Typical Representative of method is uniformly to mix sodium and copper chloride, prepares, using solid-state displacement reaction, the copper that minimum particle size is 20 nm
Powder, but exist copper powder particle size uneven and oxidizable the shortcomings of.Vapor phase method be using discharge-induced explosion, DC arc plasma, electricity
Copper is evaporated by beamlet etc., condensed prepares the copper powder that minimum particle size is 20 nm.Vapor phase method can prepare even-grained receiving
Rice copper powder, but have that yield is extremely low, cost intensive and copper powder oxidizable the shortcomings of.Liquid phase method is the Cu in reducing solution2+With system
For the method for going out copper powder, electroreduction and reducing agent can be had to reduce two kinds according to method of reducing difference.Although liquid phase method is recognized
For being the most potential method of the excellent copper nanoparticle of processability, but fail always to make a breakthrough and apply, its key issue
It is, either electroreduction or reducing agent reduction, the pH of the copper powder performance that liquid phase method is prepared and solution in preparation process
Value is closely related.When solution alkaline, Cu2+And Cu+Inherently generate corresponding hydroxide to precipitate, thus the copper for preparing
Cu must be contained in powder2O；When solution is in acidity, because of H in solution+The spy that there is suppression copper powder forming core and promote copper powder to grow up
Property, thus be difficult to prepare even-grained copper nanoparticle.
As can be seen here, the preparation method of although copper powder is a lot, but does not still have a kind of method of practicality can be used to so far
The copper nanoparticle of prepared sizes all uniform low oxygen contents, develops new preparation method to obtain the copper nanoparticle of more dominance energy,
With positive realistic meaning and good application prospect.
Content of the invention
Present invention aims to existing technology of preparing and technologic deficiency, provide a kind of calcium cuprate hydrogen reduction system
The method of standby copper nanoparticle.For solving the above problems, the present invention prepares calcium cuprate powder using mechanical mixture and calcining technology, so
Afterwards calcium cuprate powder is reduced in a hydrogen atmosphere, then clean through dilute hydrochloric acid solution, obtain copper nanoparticle.
The present invention is achieved by the following technical solutions.
A kind of preparation method of copper nanoparticle of the present invention, comprises the steps.
（1）Batch mixing：By cupric oxide powder and lime powder according to 1:2～1:4 mol ratio carries out ball milling mixing, obtains
Mixed uniformly copper oxide+calcium oxide precursor powder.
（2）Calcining：Precursor powder is placed in atmosphere furnace, in 900～1300 DEG C of 3 ~ 5h of temperature lower calcination, calcination atmosphere
For oxygen, argon or air atmosphere, calcium cuprate intermediate powder is obtained.
（3）Reduction：By step（2）The calcium cuprate intermediate powder of gained is heated under 0.5～2 L/min of hydrogen gas stream
300～450 DEG C, 90～240 min are reduced, obtains the mixture of copper nanoparticle and calcium oxide.
（4）Cleaning：Reduzate is cleaned with concentration repeatedly for 10% ~ 20% dilute hydrochloric acid solution containing surface modifier, so
Use washes of absolute alcohol afterwards, residual ion and excess surface modifying agent is removed, copper nanoparticle is obtained, wherein surface modifier is poly-
Vinylpyrrolidone（PVP）, Polyethylene Glycol（PEG）Or the one or two kinds of in gelatin.
（5）Dry：Wet-milling is put in vacuum drying oven and is dried, obtain copper nanoparticle.
The technique effect of the present invention.
（1）Copper nanoparticle homogeneous grain diameter, favorable dispersibility prepared by the calcium cuprate Process of Hydrogen Reduction of present invention offer, puts down
All particle diameter is for the primary particle particle diameter distribution of 20 nm, 90 % in the range of 15～25nm.
（2）In reduzate cleaning process, calcium oxide synchronously can be applied from copper powder particle sur-face peeling transient surface modifying agent
Copper nanoparticle surface is distributed in, realizes the dispersion of copper nanoparticle and anti-oxidation while carry out, prepared copper nanoparticle good dispersion,
Oxygen content is low.
（3）Process is simple, with low cost：Raw material copper oxide and calcium oxide are common industrial raw material, batch mixing, calcining and reduction
Stage all no especial equipment requirements, being capable of quickly serialization large-scale production.
Description of the drawings
Fig. 1 is the X-ray diffraction spectrogram of copper nanoparticle prepared by embodiment 1.
Fig. 2 is the transmission electron microscope photo of copper nanoparticle prepared by embodiment 1.
Specific embodiment
The present invention will be described further by following examples, but protection scope of the present invention not limited to this.
Embodiment 1.
Copper nanoparticle is prepared, should be carried out according to the following steps：According to 1:2 mol ratio, precise 1.00kg cupric oxide powder
End（CuO）With 1.41kg lime powder（CaO）, in planetary ball mill for dry grinding 4h, after uniform mixing, it is placed in tubular type atmosphere
In stove, under oxygen atmosphere, 950 DEG C of calcining 3h, obtain calcium cuprate（Ca2CuO3）Powder；By calcium cuprate powder in 1.5 L/min
Hydrogen gas stream in be heated to 350 DEG C of 120 min of reduction, then with containing polyvinylpyrrolidone（PVP）Dilute hydrochloric acid solution
（10%）Cleaning reduzate four times, then with washes of absolute alcohol reduzate three times, product is dried to obtain copper nanoparticle.
Embodiment 2.
Copper nanoparticle is prepared, should be carried out according to the following steps：According to 1:2.5 mol ratio, precise 1.00kg copper oxide
Powder（CuO）With 1.76 kg lime powders（CaO）, in planetary ball mill for dry grinding 4h, after uniform mixing, it is placed in tubular type gas
In atmosphere stove, under air atmosphere, 950 DEG C of calcining 3h, obtain calcium cuprate（Ca2CuO3）Powder；By calcium cuprate powder in 1.5 L/
400 DEG C of 120 min of reduction are heated in the hydrogen gas stream of min, then with containing polyvinylpyrrolidone（PVP）Dilute hydrochloric acid molten
Liquid（10%）Cleaning reduzate four times, then with washes of absolute alcohol reduzate three times, product is dried to obtain copper nanoparticle.
Embodiment 3.
Copper nanoparticle is prepared, should be carried out according to the following steps：According to 1:2.5 mol ratio, precise 1.00kg copper oxide
Powder（CuO）With 1.76kg lime powder（CaO）, in planetary ball mill for dry grinding 4h, after uniform mixing, it is placed in tubular type gas
In atmosphere stove, 1050 DEG C of calcining 3h, obtain calcium cuprate under an argon atmosphere（Ca2CuO3）Powder；By calcium cuprate powder in 2 L/min
Hydrogen gas stream in be heated to 450 DEG C of 90 min of reduction, then with containing Polyethylene Glycol（PEG）Dilute hydrochloric acid solution（20%）Clearly
Wash reduzate four times, then with washes of absolute alcohol reduzate three times, product is dried to obtain copper nanoparticle.
Embodiment 4.
Copper nanoparticle is prepared, should be carried out according to the following steps：According to 1:4 mol ratio, 1.00 kg cupric oxide powder of precise
End（CuO）With 2.82kg lime powder（CaO）, in planetary ball mill for dry grinding 7h, after uniform mixing, it is placed in tubular type atmosphere
In stove, under air atmosphere, 950 DEG C of calcining 3h, obtain calcium cuprate（Ca2CuO3）Powder；By calcium cuprate powder in 1.5 L/min
Hydrogen gas stream in be heated to 380 DEG C of 120 min of reduction, then with containing polyvinylpyrrolidone（PVP）Dilute hydrochloric acid solution
（20%）Cleaning reduzate four times, then with washes of absolute alcohol reduzate three times, product is dried to obtain copper nanoparticle.Institute
The X-ray diffraction spectrogram of copper nanoparticle and transmission electron microscope photo respectively as shown in Figures 1 and 2, product particle size is homogeneous,
Favorable dispersibility, mean diameter is the primary particle particle diameter distribution of 20 nm, 90 % in the range of 15～25nm.
Claims (1)
1. a kind of preparation method of copper nanoparticle, is characterized in that comprising the steps：
（1）Batch mixing：By cupric oxide powder and lime powder according to 1:2～1:4 mol ratio carries out ball milling mixing, obtains uniform
The copper oxide of mixing+calcium oxide precursor powder；
（2）Calcining：Precursor powder is placed in atmosphere furnace, in 900～1300 DEG C of 3 ~ 5h of temperature lower calcination, calcination atmosphere is oxygen
Gas, argon or air atmosphere, obtain calcium cuprate intermediate powder；
（3）Reduction：By step（2）The calcium cuprate intermediate powder of gained is heated to 300 under 0.5～2 L/min of hydrogen gas stream
～450 DEG C, 90～240 min are reduced, obtains the mixture of copper nanoparticle and calcium oxide；
（4）Cleaning：Reduzate, Ran Houyong are cleaned with concentration repeatedly for 10% ~ 20% dilute hydrochloric acid solution containing surface modifier
Washes of absolute alcohol, removes residual ion and excess surface modifying agent, obtains copper nanoparticle；Wherein surface modifier is polyethylene
One or two kinds of in ketopyrrolidine, Polyethylene Glycol or gelatin；
（5）Dry：Wet-milling is put in vacuum drying oven and is dried, obtain copper nanoparticle.
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| CN201611015074.8A CN106424751A (en) | 2016-11-18 | 2016-11-18 | Preparation method of nano copper powder |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107199347A (en) * | 2017-04-07 | 2017-09-26 | 南昌大学 | A kind of preparation method of superfine spherical iron powder |
| CN109047792A (en) * | 2018-10-29 | 2018-12-21 | 合肥工业大学 | A method of quickly preparing copper nanoparticle |
| CN113479925A (en) * | 2021-08-10 | 2021-10-08 | 福州大学 | Preparation method and application of calcium cuprate nanosheet with ultrafast relaxation time |
| CN116441556A (en) * | 2023-06-15 | 2023-07-18 | 华北电力大学 | Hydrogen-assisted wet-heat synthesis method of ultra-pure copper powder and ultra-pure copper powder material |
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| US4778517A (en) * | 1987-05-27 | 1988-10-18 | Gte Products Corporation | Hydrometallurgical process for producing finely divided copper and copper alloy powders |
| JPH04325608A (en) * | 1991-04-25 | 1992-11-16 | Mitsubishi Gas Chem Co Inc | Production of copper powder |
| JPH10183206A (en) * | 1996-12-25 | 1998-07-14 | Sumitomo Metal Mining Co Ltd | Production of spheroidal copper powder |
| CN103752841A (en) * | 2014-01-24 | 2014-04-30 | 合肥工业大学 | Preparing method for nano-copper powder |
| CN103785856A (en) * | 2014-02-26 | 2014-05-14 | 北京科技大学 | Composite material in which carbon spheres are loaded with copper nanoparticles and preparation method thereof |
| CN106077694A (en) * | 2016-08-08 | 2016-11-09 | 南昌大学 | A kind of preparation method of spherical cobalt powder |
-
2016
- 2016-11-18 CN CN201611015074.8A patent/CN106424751A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4778517A (en) * | 1987-05-27 | 1988-10-18 | Gte Products Corporation | Hydrometallurgical process for producing finely divided copper and copper alloy powders |
| JPH04325608A (en) * | 1991-04-25 | 1992-11-16 | Mitsubishi Gas Chem Co Inc | Production of copper powder |
| JPH10183206A (en) * | 1996-12-25 | 1998-07-14 | Sumitomo Metal Mining Co Ltd | Production of spheroidal copper powder |
| CN103752841A (en) * | 2014-01-24 | 2014-04-30 | 合肥工业大学 | Preparing method for nano-copper powder |
| CN103785856A (en) * | 2014-02-26 | 2014-05-14 | 北京科技大学 | Composite material in which carbon spheres are loaded with copper nanoparticles and preparation method thereof |
| CN106077694A (en) * | 2016-08-08 | 2016-11-09 | 南昌大学 | A kind of preparation method of spherical cobalt powder |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107199347A (en) * | 2017-04-07 | 2017-09-26 | 南昌大学 | A kind of preparation method of superfine spherical iron powder |
| CN109047792A (en) * | 2018-10-29 | 2018-12-21 | 合肥工业大学 | A method of quickly preparing copper nanoparticle |
| CN113479925A (en) * | 2021-08-10 | 2021-10-08 | 福州大学 | Preparation method and application of calcium cuprate nanosheet with ultrafast relaxation time |
| CN113479925B (en) * | 2021-08-10 | 2022-07-08 | 福州大学 | Preparation method and application of calcium cuprate nanosheet |
| CN116441556A (en) * | 2023-06-15 | 2023-07-18 | 华北电力大学 | Hydrogen-assisted wet-heat synthesis method of ultra-pure copper powder and ultra-pure copper powder material |
| CN116441556B (en) * | 2023-06-15 | 2023-08-22 | 华北电力大学 | Hydrogen-assisted wet-heat synthesis method of ultra-pure copper powder and ultra-pure copper powder material |
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