CN113084178A - Preparation method of nano copper-based powder - Google Patents

Preparation method of nano copper-based powder Download PDF

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Publication number
CN113084178A
CN113084178A CN202110368024.2A CN202110368024A CN113084178A CN 113084178 A CN113084178 A CN 113084178A CN 202110368024 A CN202110368024 A CN 202110368024A CN 113084178 A CN113084178 A CN 113084178A
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copper
ball milling
powder
ball
preparation
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CN113084178B (en
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陈�峰
魏至成
闫志巧
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Institute Of Materials And Processing Guangdong Academy Of Sciences
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Institute Of Materials And Processing Guangdong Academy Of Sciences
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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
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • 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
    • 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
    • B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • 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
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling

Abstract

The invention discloses a preparation method of copper-based nanopowder, and belongs to the field of high-ductility metal nanopowder preparation. The invention comprises the following steps: carrying out ball milling on the copper-based material, wherein an oxygen source and a superfine grinding material with the particle size not more than 1mm are used in the ball milling process; after ball milling, the resulting product is reduced. Compared with the conventional ball milling technology, the invention accelerates the refining process of the copper-based material, solves the problem that the high-ductility material is easy to plastically deform and cold weld and cannot be effectively ground in the ball milling process, and widens the application of the ball milling technology in the field of superfine metal powder preparation. Compared with the liquid phase reduction method which is the main method for industrially preparing the superfine copper powder at present, the method greatly reduces the production cost of the nano copper-based powder, improves the production efficiency and is beneficial to promoting the application of the nano copper-based powder.

Description

Preparation method of nano copper-based powder
Technical Field
The invention relates to the field of preparation of high-ductility metal nano powder, in particular to a preparation method of nano copper-based powder.
Background
The nano copper powder is expected to replace gold or silver and other noble metals due to low cost of raw materials: in the field of petrochemical industry, the high activity of the nano powder can make the nano powder be used as a catalyst for organic transformation and photocatalysis; in the field of electronic industry, the high-conductivity nano copper powder can be used as a material of conductive ink for printing flexible circuits; in the field of energy industry, the good thermal conductivity can be used as a heat-carrying fluid to carry out heat dissipation and temperature reduction on equipment; in the field of energy conservation and environmental protection, the catalyst can be used as a fuel additive to catalyze the fuel to be fully combusted and play a role in purifying tail gas; by utilizing the characteristics of adhesion and soft polishing, the nano copper powder can also be used as an additive of lubricating oil for mechanical equipment, can promote the lubricating oil to generate a stable oil film, and achieves the effects of self-sealing, self-repairing and the like.
At present, most of the nano copper powder is prepared by a liquid phase reduction method in a mode of from small to large, and the prepared powder has small particle size, high crystallinity and more shape change. However, in the preparation process, powder with fine particles is easy to agglomerate; a large amount of a solvent such as water or alcohol; the reducing agent used is extremely toxic or has high cost; after preparation, the by-products need to be repeatedly cleaned and removed; the liquid phase preparation technology has no potential for industrial low-cost production in terms of process due to the defects of low yield, complex production process, difficult control of process parameters and the like. The domestic copper powder manufacturers can provide the nano copper powder, the price of the nano copper powder is high (the commercial copper powder with the particle size of 25nm is sold in 1.2 hundred million RMB per ton), and the market cannot accept the nano copper powder, so that the application and popularization of related products in modern industrial production are limited.
The ball milling technology is suitable for large-scale production of products due to the characteristics of simple and convenient operation, low equipment cost and the like, and is often used for refining powder, homogenizing components, mechanically alloying and preparing non-equilibrium phases such as supersaturated solid solutions, metastable crystal phases, quasicrystal phases, amorphous alloys, nanocrystals and the like. During the ball milling process, the milled powder is placed in a ball milling tank, and the processes of deformation, superposition, cold welding and crushing are repeated under the action of the grinding balls and the tank wall, so that the effect of powder refinement is finally achieved, and the method is widely applied to modern industrial production. However, in practice, it is difficult to achieve the nano-size of the copper-based powder by the conventional ball milling technique due to the high ductility of the copper-based material.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a preparation method of copper-based nanopowder, which can realize the nanocrystallization of the copper-based powder through a ball milling technology.
The application can be realized as follows:
the application provides a preparation method of nano copper-based powder, which comprises the steps of carrying out ball milling on a copper-based material, wherein an oxygen source and a superfine grinding material with the particle size not more than 1mm are used in the ball milling process; after ball milling, the resulting product is reduced.
In an alternative embodiment, the copper-based material includes at least one of a copper metal material and a copper oxide material.
In an alternative embodiment, when the copper-based material is a copper oxide-containing material, the source of oxygen is the copper oxide.
In an alternative embodiment, the mass ratio of the fine abrasive to the copper-based material is 1:10 to 10: 1.
In an alternative embodiment, the material of the fine abrasive is a hard abrasive including at least one of stainless steel, wear-resistant steel, tungsten carbide, alumina, and zirconia.
In an alternative embodiment, the reduction temperature does not exceed 250 ℃.
In an alternative embodiment, large balls having a diameter of not less than 5mm are also used in the ball milling process.
In an alternative embodiment, the ball to material ratio of the large grinding balls to the copper-based material is from 10:1 to 100: 1.
The beneficial effect of this application includes:
by adding the fine grinding material and the oxygen source in the ball milling process, the problem that the high-ductility material cannot be effectively ground due to easy plastic deformation and cold welding in the ball milling process is solved. The invention can accelerate the refinement of the powder, the obtained copper-based powder particles can reach the nanometer level, and the application of the ball milling technology in the field of superfine metal powder preparation is widened. Compared with the conventional ball milling, the method realizes the nano-crystallization of the particle size of the high-ductility copper-based material; compared with low-temperature ball milling, the ball milling condition is milder, and the burden on equipment is lower; compared with the main method of industrially preparing the superfine copper powder in the prior art, the method has the advantages of simple operation, high yield, low production cost and suitability for large-scale production.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a morphology of pure copper powder in example 1, example 2, comparative example 1 and comparative example 2;
FIG. 2 is a graph of the morphology of the powder after 30 hours of ball milling in example 1;
FIG. 3 is an enlarged view of a portion of the area in FIG. 2;
FIG. 4 is a morphology of the reduced powder of example 1;
FIG. 5 is a graph showing the morphology of the powder after ball milling for 20 hours in comparative example 1;
FIG. 6 is a graph showing the morphology of the powder after ball milling for 30 hours in comparative example 2;
FIG. 7 is a graph of the morphology of cuprous oxide powder in example 2, example 3, example 4 and comparative example 3;
FIG. 8 is a graph of the morphology of the powder after 30 hours of ball milling in example 2;
FIG. 9 is a graph of the morphology of the reduced powder of example 2;
FIG. 10 is a graph of the morphology of the powder after 30 hours of ball milling in example 3;
FIG. 11 is a graph of the morphology of the powder of comparative example 3 after 30 hours of ball milling;
FIG. 12 is a graph of the morphology of the powder after 30 hours of ball milling in example 4.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The following is a detailed description of the method for preparing the copper-based nanopowder provided by the present application.
Although the ball milling technology has been widely applied to the preparation of nanocrystalline materials, the nanopowder is different from nanocrystalline materials: as long as the grain size is nano-scale, the material can be called as a nanocrystalline material, and the actual material macro-size can be millimeter-scale; only the material with each particle size of nanometer level, good dispersibility and no obvious agglomeration can be called as nanometer powder. The existing conventional ball milling technology has great difficulty in producing the copper-based nano powder under mild ball milling conditions, and the main reasons are as follows: copper and copper-based materials have good ductility, are easy to generate plastic deformation under the impact of grinding balls, are compacted into flat sheets, and are cold-welded into larger aggregates after the ball milling time is continuously prolonged. In order to solve the problems, researchers adopt an ultralow temperature vibration ball milling technology to crush raw material copper powder with the particle size of 10 microns into nano powder with the particle size of 30nm after 3 hours under the conditions of liquid nitrogen cooling and the ball-to-material ratio of 100: 1. However, the low-temperature ball milling technology has the problems of powder loss caused by liquid nitrogen volatilization and fluid control, high requirements on frost resistance, corrosion resistance and tightness of equipment, degassing after ball milling and the like, and is difficult to produce on a large scale.
The invention creatively provides a preparation method of nano copper-based powder suitable for industrial large-scale production, which comprises the following steps: carrying out ball milling on the copper-based material, wherein an oxygen source and a superfine grinding material with the particle size not more than 1mm are used in the ball milling process; further, the method also comprises the step of reducing the ball-milled product.
The method provided by the invention can be used for refining the copper and the copper-based powder to submicron or even nanometer level by adopting conventional ball milling equipment under mild experimental conditions, is simple to operate and is suitable for large-scale production. The reason for this is that: compared with the method which is easily thought by ordinary technicians in the industry and improves the crushing energy in the ball milling process by increasing the quality of the grinding balls (namely the ball-to-material ratio), the method improves the energy utilization efficiency in the ball milling process by adding the fine grinding materials on the basis of the original ball milling technology instead of increasing the total energy in the ball milling process by increasing the size and the quality of the grinding balls, thereby avoiding the resource waste and not increasing the burden on equipment; copper and copper-based powder which cannot be significantly refined by conventional ball milling is refined to submicron or even nanometer level by increasing the interaction between the grinding material and the ground material.
It is to be noted that, in the present application, the particle size of the fine abrasive is too large, and thus the fine abrasive cannot sufficiently collide with the powder or shear the powder, and cannot function as the fine abrasive. Preferably, the particle size of the fine abrasive in this application is 1 to 1000. mu.m. It is to be noted that, in order to facilitate separation of the fine abrasive from the copper-based powder, it is more preferable to use an abrasive having a particle size of 100-.
Further, the oxygen source may be a gaseous oxygen source, such as oxygen gas or an oxygen-containing gas, or a solid oxygen source, such as copper oxide. The oxidation may, by reference, be carried out by opening the tank, introducing an oxygen-containing gas into the tank or adding copper oxide to the tank, the "tank" being the ball mill tank.
When the copper-based material comprises a copper oxide, the source of oxygen is the copper oxide.
Further, the reduction of the copper-based material obtained by the ball milling may be carried out by contacting the oxidized copper-based material with a reducing gas. In alternative embodiments, the mass ratio of the fine abrasive to the copper-based material is 1:10 to 10:1, such as 1:10, 1:5, 1:2, 1:1, 2:1, 5:1, or 10:1, and the like, and may be any other ratio within the range of 1:10 to 10: 1. It is to be noted that if the mass ratio of the fine abrasive to the copper-based material is too low, the fine powder cannot be ground in a short time, and even the effect of refining the powder cannot be obtained.
The material of the fine abrasive is a hard abrasive, and the hard abrasive may include, but is not limited to, at least one of stainless steel, wear-resistant steel, tungsten carbide, alumina, and zirconia, and in addition, other commonly used abrasive materials may also be used.
In alternative embodiments, the copper-based material may include, but is not limited to, at least one of a copper metal material and a copper oxide material. Wherein, the copper metal material may include, but is not limited to, pure copper, copper alloys, mixtures of copper with other alloying elements or non-alloying elements, and the like, and the copper oxide material may include, but is not limited to, copper oxide, mixtures of copper oxide with other alloying elements or non-alloying elements.
The above copper-based material is referred to as powder or granule. Since the finer the particle size of the powder is, the more the ball milling time can be shortened, the particle size of the powder is preferably 3mm or less. In a more preferred embodiment, the powdered copper-based material has a particle size distribution of 1-100 μm, such as 5-20 μm, and the like.
In alternative embodiments, the ball milling may include any one of vibratory ball milling, planetary ball milling, and agitator ball milling, and may also include other conventional ball milling methods. The ball milling process can be normal temperature ball milling or low temperature ball milling, and preferably, normal temperature ball milling is adopted.
In the ball milling process, the rotation speed of the ball mill under rotation conditions (such as planetary ball milling or stirring ball milling) is 200-600rpm, such as 200rpm, 300rpm, 400rpm, 500rpm or 600 rpm. In order to achieve a sufficient refining effect, the ball milling time is usually 20 hours or more under mild ball milling conditions.
In an alternative embodiment, a large grinding ball with a diameter of not less than 5mm is also used in the ball milling process, for example, a large grinding ball with a diameter of 6-20mm can be used, and the ball-to-material ratio of the large grinding ball to the copper-based material is 10:1-100: 1.
it is worth to be noted that the invention does not excessively limit the specific diameter and number of the large grinding balls used in the ball grinding process, and only needs that the diameter of all the large grinding balls is not less than 5mm, the ratio of the total amount of the large grinding balls to the ball material of the copper-based material is 10:1-100:1, and the specific parameters can be obtained by research personnel through limited experiments.
In an alternative embodiment, an auxiliary agent such as a process control agent is used in the ball milling process, and the process control agent is an organic substance, such as paraffin, stearic acid, and other organic substances with a lower decomposition temperature.
It should be noted that the ball milling conditions and operations not mentioned in the present invention can refer to the prior art, and will not be described herein.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
(1) Weighing copper powder and a process control agent: respectively weighing 50g of copper powder (the particle size distribution is 3-20 μm, the appearance is shown in figure 1) and 1.5g of paraffin;
(2) selecting a superfine grinding material: weighing 50g of stainless steel balls with the diameter of 0.5mm as a superfine grinding material;
(3) mixing and discharging: uniformly mixing the three materials, putting the mixture into a ball milling tank with the volume of 2L, and putting 2.0kg of large milling balls with the diameter of 6-20mm, wherein the ball-material ratio is 40: 1;
(4) ball milling: setting the rotation speed of the planetary ball mill to be 300rpm and the revolution speed to be 150 rpm;
(5) oxidation using a gaseous oxygen source: when the ball milling time reaches 1, 3, 5, 10 and 20 hours respectively, opening the tank to oxidize the copper-based material obtained by ball milling;
(6) reduction: the powder after ball milling for 30 hours is subjected to H at 200 DEG C2Keeping the temperature for 1 hour under the atmosphere.
The morphology of the copper powder after 30 hours of ball milling is shown in fig. 2, and fig. 3 is an enlarged view of a portion of the area in fig. 2. The micron-sized copper powder is crushed into nano-sized particles with the particle size of 50-150 nm; the BET specific surface area is 3.8417m2(ii)/g, average particle size 174.31 nm; laser particle size distribution D50And 161 nm. The morphology after reduction is shown in fig. 4, and sintering occurs to a certain extent, with an oxygen content of less than 1%. It is worth pointing out that the separation of the stainless steel ball and the nano copper powder can be realized by simple screening.
Comparative example 1
(1) Weighing copper powder and a process control agent: respectively weighing 50g of copper powder (the particle size distribution is 3-20 μm, the appearance is shown in figure 1) and 1.5g of paraffin;
(2) mixing and discharging: mixing the two materials uniformly, putting the mixture into a ball milling tank with the volume of 2L, and putting 2.0kg of large milling balls with the diameter of 6-20mm, wherein the ball-material ratio is 40: 1;
(3) ball milling: setting the rotation speed of the planetary ball mill to be 300rpm and the revolution speed to be 150 rpm;
(4) sampling: samples were taken after 20 hours of ball milling.
That is, the difference from example 1 is that no fine abrasive is added during the ball milling process, and the pot opening oxidation is not performed, and the scanning electron micrograph of the powder after sampling is shown in fig. 5. It can be seen that the copper powder is plastically deformed into a flat sheet with the size of 0.8-2 μm under the action of the grinding balls due to the good ductility of the metal copper, and the conventional ball milling technology does not have a good thinning effect.
Comparative example 2
(1) Weighing copper powder and a process control agent: respectively weighing 50g of copper powder (the particle size distribution is 3-20 μm, the appearance diagram is shown in figure 1) and 1.5g of paraffin;
(2) selecting a superfine grinding material: weighing 50g of stainless steel balls with the diameter of 0.5mm as a superfine grinding material;
(3) mixing and discharging: uniformly mixing the three materials, putting the mixture into a ball milling tank with the volume of 2L, and putting 2.0kg of large milling balls with the diameter of 6-20mm, wherein the ball-material ratio is 40: 1;
(4) ball milling: setting the rotation speed of the planetary ball mill to be 300rpm and the revolution speed to be 150 rpm;
(5) sampling: samples were taken after 30 hours of ball milling.
That is, the difference from example 1 is that the same fine abrasive having a diameter of 0.5mm was used, but the pot oxidation was not performed in the ball milling process, and the scanning electron micrograph of the powder after sampling is shown in FIG. 6. It can be seen that even with the addition of fine abrasive, the raw copper powder still cannot be ground without the use of an oxygen source.
Example 2
(1) Weighing copper powder and a process control agent: weighing 16g of copper powder (with particle size distribution of 3-20 μm and morphology shown in figure 1) and 1.5g of paraffin respectively;
(2) selecting a superfine grinding material: weighing 50g of spherical hydroxyl iron powder with the diameter of 0.5-2 mu m as a superfine grinding material;
(3) selecting a solid oxygen source: weighing 34g of cuprous oxide powder (with particle size distribution of 0.5-2 μm, and morphology shown in FIG. 7) as solid oxygen source;
(4) mixing and discharging: uniformly mixing the four materials, putting the mixture into a ball milling tank with the volume of 2L, and putting 2.0kg of large milling balls with the diameter of 6-20mm, wherein the ball-material ratio is 40: 1;
(5) ball milling: setting the rotation speed of the planetary ball mill to be 300rpm and the revolution speed to be 150 rpm;
(6) reduction: the powder after ball milling for 30 hours is subjected to H at 200 DEG C2Keeping the temperature for 1 hour under the atmosphere.
I.e. differs from example 1 in that cuprous oxide powder is used as the solid oxygen source. The morphology of the powder after ball milling is shown in fig. 8, and the mixed copper-based powder is finely ground. The morphology after reduction is shown in fig. 9, the powder is sintered to a certain extent, and the oxygen content is less than 1%.
Example 3
(1) Weighing copper oxide and process control agent: weighing 56.3g cuprous oxide powder (particle size distribution 0.5-2 μm, morphology shown in FIG. 7) and 1.5g paraffin respectively;
(2) selecting a superfine grinding material: weighing 50g of spherical hydroxyl iron powder with the diameter of 0.5-2 mu m as a superfine grinding material;
(3) mixing and discharging: uniformly mixing the three materials, putting the mixture into a ball milling tank with the volume of 2L, and putting 2.0kg of large milling balls with the diameter of 6-20mm, wherein the ball-material ratio is 40: 1;
(4) ball milling: setting the rotation speed of the planetary ball mill to be 300rpm and the revolution speed to be 150 rpm;
(5) reduction: the powder after ball milling for 30 hours is subjected to H at 200 DEG C2Keeping the temperature for 1 hour under the atmosphere.
The morphology of the cuprous oxide powder after 30 hours of ball milling is shown in fig. 10. The cuprous oxide powder is crushed into particles with the particle size of 50-150nm, and the large flaky substances in the figure are flattened hydroxyl iron powder in the ball milling process. When the original powder contains copper oxide, the micron-sized powder can be ground to the nanometer level only by adding a fine grinding material in the ball milling process. The oxygen content of the reduced powder is less than 1%. It is worth pointing out that the fine size of the hydroxyl iron powder is not beneficial to separating from the nanometer copper powder.
Comparative example 3
(1) Weighing copper oxide and process control agent: respectively weighing 50g of cuprous oxide powder (particle size distribution of 0.5-2 μm, morphology shown in FIG. 7) and 1.5g of paraffin;
(2) mixing and discharging: mixing the two materials uniformly, putting the mixture into a ball milling tank with the volume of 2L, and putting 2.0kg of large milling balls with the diameter of 6-20mm, wherein the ball-material ratio is 40: 1;
(3) ball milling: setting the rotation speed of the planetary ball mill to be 300rpm, the revolution speed to be 150rpm and the ball milling time to be 30 hours;
(4) sampling: after ball milling for 30 hours, the ball milled cuprous oxide powder was sampled.
The morphology of the ball-milled copper powder is shown in fig. 11. It can be seen that the cuprous oxide powder is plastically deformed by the grinding balls to form flat flakes having a size of 0.5 to 1.5 μm. The original powder contains copper oxide, but no fine grinding material is added in the ball milling process, so that the micron-sized powder cannot be crushed to the nanometer level.
Example 4
(1) Weighing copper oxide and process control agent: weighing 56.3g cuprous oxide powder (particle size distribution 0.5-2 μm, morphology shown in FIG. 7) and 1.5g paraffin respectively;
(2) selecting a superfine grinding material: weighing 50g of stainless steel balls with the diameter of 0.5mm as a superfine grinding material;
(3) mixing and discharging: uniformly mixing the three materials, putting the mixture into a ball milling tank with the volume of 2L, and putting 2.0kg of large milling balls with the diameter of 6-20mm, wherein the ball-material ratio is 40: 1;
(4) ball milling: setting the rotation speed of the planetary ball mill to be 300rpm and the revolution speed to be 150 rpm;
(5) reduction: the powder after ball milling for 30 hours is subjected to H at 200 DEG C2Keeping the temperature for 1 hour under the atmosphere.
Namely, the difference from example 2 is that 50g of a stainless steel ball having a diameter of 0.5mm is used as the fine abrasive. The morphology of the powder after ball milling is shown in fig. 12, and the cuprous oxide powder is crushed into particles with the particle size of 50-150 nm. When the original powder contains copper oxide, the micron-sized powder can be crushed to the nanometer-sized powder only by adding a fine grinding material in the ball milling process. The oxygen content of the reduced powder is less than 1%.
Example 5
This example differs from example 1 in that: the ball-to-feed ratio of the superfine abrasive to the copper-based material is 1: 10.
Example 6
This example differs from example 1 in that: the ball-to-feed ratio of the superfine abrasive to the copper-based material is 10: 1.
Example 7
This example differs from example 1 in that: the ball material ratio of the large grinding ball to the copper-based material is 10: 1.
Example 8
This example differs from example 1 in that: the ball material ratio of the large grinding ball to the copper-based material is 100: 1.
In conclusion, the invention creatively provides a method for reducing a ball-milled product by using an oxygen source and a fine grinding material with the grain diameter not more than 1mm in the process of ball milling a copper-based material. The invention solves the problem that the high-ductility material is easy to plastically deform and cold weld and cannot be effectively ground in the ball milling process. The invention can accelerate the refinement of powder, the obtained copper-based powder particles can reach the nanometer level, and the application of the ball milling technology in the field of superfine metal powder preparation is widened. Compared with the conventional ball milling, the method realizes the nano-crystallization of the particle size of the high-ductility copper-based material; compared with low-temperature ball milling, the ball milling condition is milder, and the burden on equipment is lower; compared with the main method of industrially preparing the superfine copper powder in the prior art, the method has the advantages of simple operation, high yield, low production cost and suitability for large-scale production.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (9)

1. A method for preparing nano copper-based powder is characterized by comprising the following steps: carrying out ball milling on the copper-based material, wherein an oxygen source and a superfine grinding material with the particle size not more than 1mm are used in the ball milling process; after ball milling, the resulting product is reduced.
2. The method of claim 1, wherein the copper-based material comprises at least one of a copper metal material and a copper oxide material.
3. The method of claim 1, wherein the source of oxygen comprises a gaseous or solid source of oxygen.
4. The production method according to claim 2, wherein when the copper-based material is a copper oxide-containing material, the oxygen source is the copper oxide.
5. The production method according to claim 1, wherein the mass ratio of the fine abrasive to the copper-based material is 1:10 to 10: 1.
6. The preparation method according to claim 1, wherein the fine abrasive is made of a hard abrasive, and the hard abrasive comprises at least one of stainless steel, wear-resistant steel, tungsten carbide, alumina and zirconia.
7. The method of claim 1, wherein the reduction temperature is not more than 250 ℃.
8. The method according to claim 1, wherein large balls having a diameter of not less than 5mm are further used in the ball milling process.
9. The preparation method according to claim 8, wherein the ball-to-material ratio of the large grinding ball to the copper-based material is 10:1 to 100: 1.
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