CN105458295A - Multi-hole micrometer copper ball and preparation method thereof - Google Patents
Multi-hole micrometer copper ball and preparation method thereof Download PDFInfo
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- CN105458295A CN105458295A CN201610071062.0A CN201610071062A CN105458295A CN 105458295 A CN105458295 A CN 105458295A CN 201610071062 A CN201610071062 A CN 201610071062A CN 105458295 A CN105458295 A CN 105458295A
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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
Abstract
The invention provides a multi-hole micrometer copper ball and a preparation method thereof. The preparation method includes the following steps of adding a copper source, an organic acid complexing agent and an organic amine complexing agent in solvent, adding reducing agent hydrazine hydrate to react after the mixture is evenly stirred, conducting centrifugation, taking sediment, and conducting washing and vacuum drying to obtain the multi-hole micrometer copper ball. A multi-hole copper material is prepared through wet method chemical reduction, raw materials low in price serve as reactant, the reaction conditions are environmentally friendly and gentle, the technological process is simple and easy to operate, and the generated multi-hole micrometer copper ball is good in dispersity, high in single dispersity and capable of being produced on a large scale and applied to the fields of efficient catalysis and antibiosis.
Description
Technical field
The present invention relates to the technical field belonging to nano metal material, particularly a kind of multi-pore micron copper ball and preparation method thereof.
Background technology
Porous micro-nano metal is the material of aperture size in micro-nano magnitude, compare traditional porous metals, its aperture size is less, and specific area is higher, thus there is special physical and chemical performance, be all widely used in catalysis, separation, sensor, vibration reduction and cushioning, surface Raman enhancement etc.
At present, the preparation method of porous micro-nano metal material mainly contains template, sedimentation, powder metallurgic method, de-alloyage etc.Template utilizes colloid crystal as template, is filled in the hole of mould material by the raw material of porous material, then by certain physics or chemical method removing mould material, thus obtain the reverse duplicate of masterplate, i.e. porous material.Template is one of common method of poromerics, and wherein the selection of template is the most important, decides the Structure and Properties of porous material, but the equal relative complex of the technique of this method.De-alloyage is the chemical activity difference utilizing different element in alloy, and optionally remove comparatively active one or more components by chemistry or electrochemical method, all the other components form three-dimensional continuous print porous metal material by modes such as atoms permeating.At present by selective corrosion, oneself is through having prepared the materials such as nanoporous titanium, nano porous copper and nano porous palladium.Disclose a kind of method being taken off Cu-Zn reasonable offer nano porous copper by constant potential in correlation technique, again disclose a kind of high temperature that adopts in correlation technique and take off the overall continuous print nano porous copper of Cu-Al reasonable offer.But the method exists preparation technology's complicated operation, and cost is high, and the production cycle is longer, is not suitable for the shortcoming of large-scale industrial production.At present, still there is no that a kind of preparation technology is simple, cost is low and can be applied to large-scale production about the report preparing Kufil nano material.
Summary of the invention
In view of this, the object of the invention is to the shortcoming and defect overcoming prior art existence, a kind of preparation method of multi-pore micron copper ball is provided on the one hand.This preparation method's technique is simple, with low cost, environmental friendliness and can be applied to large-scale production.
Object of the present invention is achieved through the following technical solutions.
A kind of preparation method of multi-pore micron copper ball comprises the steps: copper source and organic acid complexing agent, organic amine complexing agent to add in solvent, add reducing agent hydrazine hydrate after stirring again to react, centrifugal, get precipitation, washing final vacuum is dry, obtains multi-pore micron copper ball.
Wherein, described copper source is a kind of in Kocide SD, copper nitrate, acetylacetone copper, copper sulphate and copper chloride or at least two kinds mixtures.
Wherein, described organic acid complexing agent is the mixture of a kind of in oleic acid, poly-propionic acid, polyacrylic acid, poly and laurate or at least two kinds.
Wherein, in mol/mL, described copper source and described organic acid complexing agent mole/volume ratio is 0.01 ~ 1.0:1 ~ 20.
Wherein, described organic amine complexing agent is one in ethylenediamine, monoethanolamine, triethylamine, trioctylamine, diethylenetriamine and TEPA or at least two kinds of mixtures.
Wherein, in mol/mL, described copper source and described organic amine complexing agent mole/volume ratio is 0.01 ~ 1.0:1 ~ 20.
It should be noted that, in the present invention mole/volume ratio unit be mol/mL, Ji Tong source unit in mol, the unit of organic amine complexing agent in mL, draw mole/volume ratio.If copper source can be 0.01 ~ 1.0mol, organic amine complexing agent is 1 ~ 20mL, hereafter occur mole/volume ratio is identical therewith.
Wherein, described solvent is one in water, ethanol, ethylene glycol, diglycol, Diethylene Glycol, dipropylene glycol and glycerine or at least two kinds of mixtures.
Wherein, in mol/mL, described copper source and described solvent mole/volume ratio is 0.01 ~ 1.0:50 ~ 500;
Described copper source and described reducing agent hydrazine hydrate mole/volume ratio is 0.01 ~ 1.0:1 ~ 20.
Wherein, the described reaction time is 30 ~ 300min, and reaction temperature is 18 ~ 22 DEG C;
Described centrifugal condition is in 3000 ~ 8000r/min centrifuge washing 4 times.
Wherein, the solvent of described washing is one in deionized water, absolute ethyl alcohol and acetone or at least two kinds of mixtures;
Described vacuum drying condition is for be less than 0.01MPa, drying at room temperature 6 ~ 12h in vacuum.
The present invention provides a kind of Porous Cu microballoon on the other hand, and this how empty copper microballoon good dispersion, single dispersing degree is high, can be mass-produced, and is applied to efficient catalytic, antibacterial field.
A kind of multi-pore micron copper ball adopting above-mentioned preparation method to prepare.
Compared with prior art, the present invention has following advantage and beneficial effect: the present invention utilizes wet chemistry to reduce to prepare Porous Cu material, using the raw material of cheapness as reactant, reaction condition is green gentle, technological process is simple to operation, and generates the good dispersion of Porous Cu microballoon, and single dispersing degree is high, can be mass-produced, and be applied to efficient catalytic, the field such as antibacterial.
Accompanying drawing explanation
Fig. 1 is X-ray diffraction (XRD) spectrogram of Porous Cu microballoon prepared by embodiment 1;
Fig. 2 is the field emission scanning electron microscope figure (SEM, × 20000) of Porous Cu microballoon prepared by embodiment 1;
Fig. 3 is the isothermal nitrogen adsorption curve of Porous Cu microballoon prepared by embodiment 1.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.
Embodiment 1
3.2g copper nitrate, 5mL are gathered propionic acid, 8mL triethylamine adds in 80mL alcohol solvent successively, 3mL hydrazine hydrate is added after stirring, after reacting 60min under room temperature, 8000r/min deionized water centrifuge washing 4 times, get and be deposited in vacuum and be less than drying at room temperature 6h under the condition of 0.01MPa, obtain multi-pore micron copper product.
Get Porous Cu material obtained above, x-ray diffractometer (XRD) is adopted to carry out thing phase atlas analysis to it, field emission scanning electron microscope (SEM) is adopted to observe the pattern of particle, adopt the specific area of specific surface area analysis instrument (BET) particle tested, result respectively as shown in Figure 1, Figure 2 and Figure 3.The characteristic peak of metallic copper simple substance as can see from Figure 1, wherein without any the characteristic peak of the second-phase such as cuprous oxide or cupric oxide; As can be seen from Figure 2 the loose structure of copper ball, hole distribution is even, and pore size is 60 ~ 80nm, and the uniform particle diameter of copper microballoon, good dispersion, soilless sticking phenomenon.The specific area that can obtain Porous Cu microballoon from Fig. 3 is 5.4m
2/ g.
Embodiment 2
5.5g Kocide SD, 8mL polyacrylic acid, 5mL trioctylamine are added in 450mL diglycol solvent successively, 5mL hydrazine hydrate is added after stirring, after reacting 100min under room temperature, 6000r/min deionized water centrifuge washing 4 times, get and be deposited in vacuum and be less than drying at room temperature 8h under the condition of 0.01MPa, obtain multi-pore micron copper product.
That prepares in the XRD figure of gained Kufil nanometer sheet, SEM figure and isothermal nitrogen adsorption curve and embodiment 1 is similar, shows that the thing of this Porous Cu microballoon is metallic copper simple substance mutually, does not have other impurity; Size is that the hole distribution of 60 ~ 80nm is even, and microspherulite diameter is homogeneous, good dispersion, without obvious agglomeration.
Embodiment 3
2.1g acetylacetone copper, 3mL laurate, 5mL TEPA are added in 100mL glycerine solvent successively, 10mL hydrazine hydrate is added after stirring, after reacting 180min under room temperature, 5000r/min deionized water centrifuge washing 4 times, get and be deposited in vacuum and be less than drying at room temperature 10h under the condition of 0.01MPa, obtain multi-pore micron copper product.
That prepares in the XRD figure of gained Kufil nanometer sheet, SEM figure and isothermal nitrogen adsorption curve and embodiment 1 is similar, shows that the thing of this Porous Cu microballoon is metallic copper simple substance mutually, does not have other impurity; Size is that the hole distribution of 60 ~ 80nm is even, and microspherulite diameter is homogeneous, good dispersion, without obvious agglomeration.
Embodiment 4
1.2g copper chloride, 6mL poly, 6mL monoethanolamine are added in 60mL aqueous solvent successively, 1mL hydrazine hydrate is added after stirring, after reacting 30min under room temperature, 3000r/min deionized water centrifuge washing 4 times, get and be deposited in vacuum and be less than drying at room temperature 6h under the condition of 0.01MPa, obtain multi-pore micron copper product.
That prepares in the XRD figure of gained Kufil nanometer sheet, SEM figure and isothermal nitrogen adsorption curve and embodiment 1 is similar, shows that the thing of this Porous Cu microballoon is metallic copper simple substance mutually, does not have other impurity; Size is that the hole distribution of 60 ~ 80nm is even, and microspherulite diameter is homogeneous, good dispersion, without obvious agglomeration.
Embodiment 5
6.3g copper sulphate, 3mL laurate, 5mL ethylenediamine are added in 300mL dipropylene glycol solvent successively, 18mL hydrazine hydrate is added after stirring, after reacting 300min under room temperature, 5000r/min deionized water centrifuge washing 4 times, get and be deposited in vacuum and be less than drying at room temperature 12h under the condition of 0.01MPa, obtain multi-pore micron copper product.
That prepares in the XRD figure of gained Kufil nanometer sheet, SEM figure and isothermal nitrogen adsorption curve and embodiment 1 is similar, shows that the thing of this Porous Cu microballoon is metallic copper simple substance mutually, does not have other impurity; Size is that the hole distribution of 60 ~ 80nm is even, and microspherulite diameter is homogeneous, good dispersion, without obvious agglomeration.
The present invention utilizes wet chemistry reduction to prepare Porous Cu material, and using the raw material of cheapness as reactant, reaction condition is green gentle, technological process is simple to operation, and generates the good dispersion of Porous Cu microballoon, and single dispersing degree is high, can be mass-produced, and be applied to efficient catalytic, the field such as antibacterial.
Applicant states, the present invention illustrates detailed construction of the present invention and technique by above-described embodiment, but the present invention is not limited to above-mentioned detailed construction and technique, does not namely mean that the present invention must rely on above-mentioned detailed construction and technique could be implemented.Person of ordinary skill in the field should be understood that any improvement in the present invention, to equivalence replacement and the interpolation of auxiliary element, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (10)
1. the preparation method of a multi-pore micron copper ball, it is characterized in that, copper source and organic acid complexing agent, organic amine complexing agent is comprised the steps: to add in solvent, add reducing agent hydrazine hydrate after stirring again to react, centrifugal, get precipitation, washing final vacuum is dry, obtains multi-pore micron copper ball.
2. preparation method according to claim 1, is characterized in that, described copper source is a kind of in Kocide SD, copper nitrate, acetylacetone copper, copper sulphate and copper chloride or at least two kinds mixtures.
3. preparation method according to claim 1, is characterized in that, described organic acid complexing agent is the mixture of a kind of in oleic acid, poly-propionic acid, polyacrylic acid, poly and laurate or at least two kinds.
Preferably, in mol/mL, described copper source and described organic acid complexing agent mole/volume ratio is 0.01 ~ 1.0:1 ~ 20.
4. preparation method according to claim 1, is characterized in that, described organic amine complexing agent is one in ethylenediamine, monoethanolamine, triethylamine, trioctylamine, diethylenetriamine and TEPA or at least two kinds of mixtures.
5. preparation method according to claim 1, is characterized in that, in mol/mL, described copper source and described organic amine complexing agent mole/volume ratio is 0.01 ~ 1.0:1 ~ 20.
6. preparation method according to claim 1, is characterized in that, described solvent is one in water, ethanol, ethylene glycol, diglycol, Diethylene Glycol, dipropylene glycol and glycerine or at least two kinds of mixtures.
7. preparation method according to claim 1, is characterized in that, in mol/mL, described copper source and described solvent mole/volume ratio is 0.01 ~ 1.0:50 ~ 500;
Preferably, described copper source and described reducing agent hydrazine hydrate mole/volume ratio is 0.01 ~ 1.0:1 ~ 20.
8. preparation method according to claim 1, is characterized in that, the described reaction time is 30 ~ 300min, and reaction temperature is 18 ~ 22 DEG C;
Preferably, described centrifugal condition is in 3000 ~ 8000r/min centrifuge washing 4 times.
9. preparation method according to claim 1, is characterized in that, the solvent of described washing is one in deionized water, absolute ethyl alcohol and acetone or at least two kinds of mixtures;
Preferably, described vacuum drying condition is for be less than 0.01MPa, drying at room temperature 6 ~ 12h in vacuum.
10. the multi-pore micron copper ball adopting claim 1 to prepare.
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| CN105710383A (en) * | 2016-04-30 | 2016-06-29 | 安徽农业大学 | Method for preparing Cu powder by reducing CuO by adopting glycerinum |
| CN109722087A (en) * | 2018-12-29 | 2019-05-07 | 中国有色桂林矿产地质研究院有限公司 | A kind of copper-based composite antibacterial coating material of argentiferous and preparation method thereof |
| CN110153443A (en) * | 2019-07-11 | 2019-08-23 | 中国科学院深圳先进技术研究院 | A kind of copper nanometer sheet and its preparation method and application |
| CN110560702A (en) * | 2019-09-16 | 2019-12-13 | 上海交通大学 | method for preparing micron-sized single crystal copper powder at room temperature |
| CN114082938A (en) * | 2022-01-11 | 2022-02-25 | 苏州思美特表面材料科技有限公司 | Metal particle and preparation method and application thereof |
| CN115011956A (en) * | 2022-06-28 | 2022-09-06 | 南通赛可特电子有限公司 | Organic copper surface protective agent and preparation method thereof |
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