CN113210601B - Preparation method of coated modified copper powder and coated modified copper powder - Google Patents
Preparation method of coated modified copper powder and coated modified copper powder Download PDFInfo
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- CN113210601B CN113210601B CN202110482311.6A CN202110482311A CN113210601B CN 113210601 B CN113210601 B CN 113210601B CN 202110482311 A CN202110482311 A CN 202110482311A CN 113210601 B CN113210601 B CN 113210601B
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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
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/102—Metallic powder coated with organic material
Abstract
The invention aims to provide a preparation method of coated modified copper powder with good oxidation resistance. The preparation method of the coated modified copper powder provided by the invention comprises the following steps: (1) mixing and stirring a coating agent and absolute ethyl alcohol to obtain a mixed solution; (2) placing the mixed solution and copper powder in an ultrasonic stirring reaction kettle for coating; (3) the coated copper powder enters a dryer for heating nitrogen gas to circularly flow and dry; (4) condensing the dried other part, and recovering anhydrous ethanol and nitrogen gas in the condensation process.
Description
Technical Field
The invention belongs to the technical field of metal preparation, and particularly relates to a preparation method of coated modified copper powder and the coated modified copper powder.
Background
The superfine copper powder becomes a basic functional powder material with large application potential and high added value by virtue of excellent physical and chemical properties and some special properties, and is mainly applied to production of powder metallurgy, electronic materials, friction materials, oil-containing bearings, conductive materials, medicines, diamond products, mechanical parts and the like. The nano copper powder is also beginning to be applied to high-tech fields such as petroleum catalysts, lubricants, conductive and decorative coatings, electromagnetic shielding materials and the like.
The solid phase method, the gas phase method and the liquid phase method are generally adopted to prepare the superfine copper powder. The electrolytic method in the liquid phase method for preparing the superfine copper powder is a mature and common method for industrially producing the copper powder; when the superfine copper powder is produced by an electrolytic method, partial copper powder is easily oxidized in the drying process of wet copper powder, the oxidized copper powder needs to be reduced by introducing hydrogen, and in order to prevent reoxidation after reduction by introducing hydrogen, an antioxidant is directly scattered in the copper powder in the traditional method. Due to the fact that the anti-oxidation agent is not uniformly dispersed, the resistivity of part of copper powder is increased, and meanwhile, in the hydrogen introduction reduction process, due to the fact that the superfine copper powder is large in specific surface area and surface free energy and easy to spontaneously sinter, the defects that the particle size is increased, the shape is damaged, the formability is poor, the resistivity is further increased and the like are caused.
CN201310082882.6 an anti-oxidation method for superfine copper powder, washing the superfine copper powder produced by an electrolysis method with pure water until the superfine copper powder meets the requirements; preparing a first antioxidant by using one or two of benzotriazole, methyl benzotriazole or citric acid; preparing a second antioxidant by using ascorbic acid or glucose; pouring the first antioxidant into the washed copper powder according to a certain proportion, soaking, adding the second antioxidant, and soaking; and filtering, drying and sieving to finish the anti-oxidation treatment of the superfine copper powder. However, the method has complicated processing steps and relatively high processing cost.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of coated modified copper powder with better oxidation resistance.
In order to solve the technical problem, the invention provides a preparation method of coated modified copper powder, which comprises the following steps:
(1) mixing and stirring a coating agent and absolute ethyl alcohol to obtain a mixed solution;
(2) placing the mixed solution and copper powder in an ultrasonic stirring reaction kettle for coating;
(3) the coated copper powder enters a dryer for heating nitrogen gas to circularly flow and dry;
(4) condensing the dried other part, and recovering anhydrous ethanol and nitrogen gas in the condensation process.
Preferably, in the step (1), the coating agent and the absolute ethyl alcohol are mixed according to the ratio of (0.0001-0.08): (0.1-0.8) in a mass ratio.
Preferably, the mass ratio of the copper powder to the coating agent to the absolute ethyl alcohol in the step (2) is 1: (0.0001-0.08): 0.5.
preferably, the coating agent is oleic acid or benzotriazole.
Preferably, in the step (2), in the ultrasonic stirring reaction kettle, the mixing time is 5-30 minutes, and the stirring rate is as follows: 200-500R/M, ultrasonic power: 300-.
Preferably, in the step (3), the drying time is 1-2 hours, and the drying temperature is 40-70 ℃.
Preferably, the nitrogen recovered in the step (4) is introduced into the dryer in the step (3) again for heating nitrogen circulation drying.
Preferably, after the nitrogen recovered in the step (4) is purified by filtration, the nitrogen is introduced into the dryer of the step (3) again for heating nitrogen circulation drying.
Preferably, the copper powder is superfine copper powder produced by an electrolytic method, an atomization method or a wet metallurgy method, and the particle size of the copper powder is 10nm-10 um.
The invention also provides the coated modified copper powder prepared by the preparation method, which comprises a copper powder main body and a coating agent coated outside the copper powder main body.
The coated modified copper powder prepared by the preparation method of the coated modified copper powder with good oxidation resistance has good oxidation resistance.
Drawings
The foregoing and other objects, features and advantages of the invention will be apparent from the following more particular description of preferred embodiments of the invention, as illustrated in the accompanying drawings. Like reference numerals refer to like parts throughout the drawings, and the drawings are not intended to be drawn to scale in actual dimensions, emphasis instead being placed upon illustrating the principles of the invention.
FIG. 1 is a schematic flow chart of a process for preparing coated modified copper powder according to an embodiment of the present invention;
Detailed Description
To facilitate an understanding of the invention, reference will now be made to the following more complete description taken in conjunction with the accompanying drawings.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The embodiment of the invention provides a preparation method of coated modified copper powder, which comprises the following steps:
(1) mixing and stirring a coating agent and absolute ethyl alcohol to obtain a mixed solution;
(2) placing the mixed solution and copper powder in an ultrasonic stirring reaction kettle for coating;
(3) the coated copper powder enters a dryer for heating nitrogen gas to circularly flow and dry;
(4) condensing the dried other part, and recovering anhydrous ethanol and nitrogen gas in the condensation process.
The preparation method of the coated modified copper powder provided by the embodiment has the advantages of simple process flow, recycling and low cost, and the obtained coated modified copper powder has good oxidation resistance. The copper powder is exposed in the air, and after 14 days, the mass of the copper powder is increased to 0.0018%, which shows that the copper powder has very good oxidation resistance.
The preparation method of the coated modified copper powder provided by the embodiment can better recover absolute ethyl alcohol and nitrogen, and greatly reduces the cost.
According to the preparation method of the coated modified copper powder, the recovered absolute ethyl alcohol can be used for modification of the next batch of copper powder, so that the waste of the absolute ethyl alcohol in the modification process is reduced to a greater extent.
In a preferred embodiment, in step (1), the coating agent and the absolute ethyl alcohol are mixed according to the ratio of (0.0001-0.08): (0.1-0.8) in a mass ratio. In the embodiment, the coating agent and the absolute ethyl alcohol are matched according to a reasonable mass ratio, so that the prepared coated modified copper powder has good oxidation resistance.
For the superfine powder, the ethanol has better dispersibility to the superfine powder, the coating agent has better solubility in the ethanol, and the coating agent is not easy to harden in the drying process. Meanwhile, the boiling point of the ethanol is low, so that the ethanol is convenient to evaporate and recycle.
In a preferred embodiment, the mass ratio of the copper powder, the coating agent and the absolute ethyl alcohol in the step (2) is 1: (0.0001-0.08): 0.5. in the embodiment, the coated modified copper powder prepared by matching the copper powder, the coating agent and the absolute ethyl alcohol according to a reasonable mass ratio has good oxidation resistance.
In a preferred embodiment, the coating agent is oleic acid or benzotriazole.
In a preferred embodiment, in step (2), the mixture is stirred in the reaction tank with ultrasonic wave for 5-30 minutes at a stirring rate: 200-500R/M, ultrasonic power: 300-. In a further preferred embodiment, the mixing time in the ultrasonic agitation reaction kettle is 10 minutes, 12 minutes, 15 minutes, 18 minutes or 20 minutes; in a further preferred embodiment, the stirring rate in the ultrasonic stirring reaction kettle is 250R/M, 300R/M, 400R/M or 450R/M. In a further preferred embodiment, the ultrasonic power in the ultrasonic agitation reaction kettle is 350W, 400W, 450W, 500W or 550W.
In a preferred embodiment, in step (3), the drying time is 1-2 hours and the drying temperature is 40-70 ℃. In further preferred embodiments, the drying time is 1.2 hours, 1.5 hours or 1.8 hours. In a further preferred embodiment, the drying temperature is 45 ℃, 50 ℃, 55 ℃, 60 ℃ or 65 ℃.
In a preferred embodiment, the nitrogen recovered in the step (4) is introduced into the dryer in the step (3) again to be heated and dried in a nitrogen circulation manner, so that the recovery circulation of the nitrogen is realized, and the cost is reduced to a greater extent.
In a preferred embodiment, the nitrogen recovered in the step (4) is purified by filtration, and then is introduced into the dryer in the step (3) again for heating nitrogen circulation drying.
In a preferred embodiment, the copper powder is ultra-fine copper powder produced by electrolytic, atomization or hydrometallurgical processes, the particle size of the copper powder being between 10nm and 10 um.
The embodiment of the invention also provides coated modified copper powder obtained by the preparation method mentioned in any one of the embodiments, and the coated modified copper powder comprises a zinc powder main body and a coating agent coated outside the zinc powder main body.
In order that the technical solutions of the present invention may be further understood and appreciated, several preferred embodiments are now described in detail.
Example 1
Preparing materials: copper powder to be coated: coating agent: the mass ratio of the absolute ethyl alcohol is 1 (0.001-0.05): 0.5, preparing the mixture ratio. The coating agent is oleic acid.
The preparation is carried out with reference to the process flow of fig. 1.
Mixing a coating agent: mixing absolute ethyl alcohol and a coating agent according to a ratio.
After the cladding agent is mixed, adding the mixed solution and the superfine copper powder into an ultrasonic stirring reaction kettle, mixing for 15 minutes, wherein the stirring speed is 280R/M, and the ultrasonic power is as follows: 450W
And after the copper powder is dispersed and coated, drying the copper powder in a coating atmosphere dryer, continuously introducing nitrogen into the dryer, wherein the drying time is about 2 hours, and the drying temperature is 55 ℃.
And condensing the dried gas, recovering absolute ethyl alcohol in the condensation process, filtering and purifying the recovered nitrogen, and then feeding the nitrogen into a dryer for reuse, wherein the recovered absolute ethyl alcohol is continuously used for preparing the next batch of coated modified copper powder, so that the continuous manufacturing production is facilitated.
Example 2
Preparing materials: copper powder to be coated: coating agent: the mass ratio of the absolute ethyl alcohol is 1 (0.001-0.05): 0.5, preparing the mixture ratio, wherein the coating agent is benzotriazole.
Mixing a coating agent: mixing absolute ethyl alcohol and a coating agent according to a ratio.
After the coating agent is mixed, adding the coating solvent into an ultrasonic stirring reaction kettle, wherein the mixing time is 20 minutes, and the stirring speed is as follows: 400R/M, ultrasonic power: 450W.
After the copper powder is dispersed and coated, the copper powder is dried in a coating atmosphere dryer, nitrogen is continuously introduced into the dryer, the drying time is 1.5 hours, and the drying temperature is 60 ℃.
Condensing the dried gas, recovering absolute ethyl alcohol in the condensing process, filtering and purifying the recovered nitrogen, and then feeding the nitrogen into a dryer for reuse, wherein the recovered absolute ethyl alcohol is continuously used for preparing the next batch of coated modified copper powder, and the continuous manufacturing production is facilitated.
Comparative example 1
Preparing materials: copper powder to be coated: coating agent: the mass ratio of the absolute ethyl alcohol is 1 (0.001-0.05): 2, preparing the mixture ratio. The coating agent is oleic acid.
Mixing a coating agent: mixing absolute ethyl alcohol and a coating agent according to a ratio.
After the cladding agent is mixed, adding the mixed solution and the superfine copper powder into an ultrasonic stirring reaction kettle, mixing for 15 minutes, wherein the stirring speed is 280R/M, and the ultrasonic power is as follows: 450W
And after the copper powder is dispersed and coated, drying the copper powder in a coating atmosphere dryer, continuously introducing nitrogen into the dryer, wherein the drying time is about 2 hours, and the drying temperature is 55 ℃.
Condensing the dried gas, recovering absolute ethyl alcohol in the condensing process, filtering and purifying the recovered nitrogen, and then feeding the nitrogen into a dryer for reuse.
The coated modified copper powders prepared in examples 1-2 and comparative example 1 were exposed to air in an indoor ventilation environment, and the mass growth of the copper powders was measured after 72 hours, 7 days and 14 days, respectively, and the specific data are shown in table 1.
TABLE 1
| 72 hours | 7 days | 14 days | |
| Example 1 | 0.0015％ | 0.0015％ | 0.0018％ |
| Example 2 | 0.0015％ | 0.0016％ | 0.0019％ |
| Comparative example 1 | 0.0015％ | 0.0018％ | 0.0040％ |
As can be seen from the data in table 1, the mass growth of the coated and modified copper powders prepared in examples 1 and 2 after being exposed to air for 14 days is only 0.0018% and 0.0019%. The coated modified copper powder prepared by the embodiment has better oxidation resistance.
In comparative example 1, the amount of absolute ethyl alcohol is increased, but the amount of absolute ethyl alcohol is large, so that the coating of the copper powder is influenced, and the obtained coated modified copper powder is relatively low in oxidation resistance.
The above-mentioned embodiments only express some embodiments of the invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of intellectual property rights of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the scope of intellectual property rights of the present invention shall be subject to the appended claims.
Claims (4)
1. The preparation method of the coated modified copper powder is characterized by comprising the following steps of:
(1) mixing and stirring a coating agent and absolute ethyl alcohol to obtain a mixed solution;
(2) placing the mixed solution and copper powder in an ultrasonic stirring reaction kettle for coating;
(3) the coated copper powder enters a dryer for heating nitrogen gas to circularly flow and dry;
(4) condensing the dried gas, and recovering absolute ethyl alcohol and nitrogen in the condensation process;
in the step (1), the coating agent and the absolute ethyl alcohol are mixed according to the ratio of (0.0001-0.08): (0.1-0.8), wherein the mass ratio of the copper powder to the coating agent to the absolute ethyl alcohol in the step (2) is 1: (0.0001-0.08): 0.5;
the coating agent is oleic acid or benzotriazole;
and (3) filtering and purifying the nitrogen recovered in the step (4), and then introducing the nitrogen into the dryer in the step (3) again for heating nitrogen circulation drying, wherein in the step (3), the drying time is 1-2 hours, and the drying temperature is 40-70 ℃.
2. The method for preparing coated modified copper powder according to claim 1, wherein in the step (2), the ultrasonic stirring is performed in the reaction kettle for 5 to 30 minutes at a stirring rate: 200-500R/M, ultrasonic power: 300-.
3. The method for preparing coated modified copper powder according to claim 1, wherein the copper powder is ultrafine copper powder produced by electrolysis, atomization or hydrometallurgy, and the particle size of the copper powder is 10nm to 10 μm.
4. A coated modified copper powder obtained by the method according to any one of claims 1 to 3, comprising a copper powder body and a coating agent coated on the copper powder body.
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| JP2006117959A (en) * | 2004-10-19 | 2006-05-11 | Fukuda Metal Foil & Powder Co Ltd | Copper powder for electronic material |
| CN105499559A (en) * | 2014-09-24 | 2016-04-20 | 比亚迪股份有限公司 | Modified copper powder as well as preparation method and electronic paste thereof |
| CN106141168A (en) * | 2016-08-23 | 2016-11-23 | 金川集团股份有限公司 | A kind of wet method anti-oxidation method of copper powder |
| CN109954876B (en) * | 2019-05-14 | 2020-06-16 | 广东工业大学 | Preparation method of antioxidant micro-nano copper material |
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