CN109763128B - Method for preparing superfine flaky copper powder by alloy corrosion method - Google Patents
Method for preparing superfine flaky copper powder by alloy corrosion method Download PDFInfo
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- CN109763128B CN109763128B CN201910224408.XA CN201910224408A CN109763128B CN 109763128 B CN109763128 B CN 109763128B CN 201910224408 A CN201910224408 A CN 201910224408A CN 109763128 B CN109763128 B CN 109763128B
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Abstract
The invention relates to a method for preparing superfine flaky copper powder by an alloy corrosion method, belonging to the field of metal powder materials, and the preparation method comprises the following steps: cutting a copper-zinc alloy sheet into 2 pieces with the area of 0.8-1.5cm, soaking the copper-zinc alloy sheet in a hydrochloric acid solution with the mass percentage concentration of 5-10%, heating the solution to 35-45 ℃, blowing oxygen, stirring, reacting for 1-3 hours, washing with deionized water, drying, and ball-milling to obtain the superfine flaky copper powder. Compared with the preparation of flake copper powder by pure copper ball milling, the superfine flake copper powder obtained by the method has the advantages of low production cost, easily obtained raw materials, simple preparation process, short ball milling time, regular shape, large diameter-thickness ratio, uniform particle size distribution and higher economic benefit.
Description
Technical Field
The invention relates to the field of metal powder materials, in particular to a method for preparing superfine flaky copper powder by an alloy corrosion method.
Background
Copper powder is used as an important component of a conductive phase in electronic paste and is widely applied to the aspects of conductive paste, conductive adhesive and the like. The morphology and the particle size of the copper powder have great influence on the conductivity of the slurry, and the prepared copper powder generally comprises a spherical copper powder and a flaky copper powder. The spherical copper powder is mainly in point contact, the contact area is small, the flaky copper powder is generally in surface contact, and the specific surface area is large, so that the copper conductor slurry prepared from the flaky copper powder has better conductivity. At present, people prepare flaky copper powder by mechanically ball-milling pure copper, and the obtained flaky copper powder has different shapes, poorer surface smoothness and weaker electrical conductivity. Therefore, the preparation of the flaky copper powder with uniform particle size and regular shape has an important influence on the improvement of the conductivity of the copper conductor paste.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for preparing superfine flaky copper powder by an alloy corrosion method, the prepared flaky copper powder has regular shape, large diameter-thickness ratio and uniform particle size distribution, and the method effectively reduces the production cost of manufacturers and improves the production efficiency.
The copper-zinc alloy is a mixture of copper metal elementary substance Cu and zinc metal elementary substance Zn. Brass alloys composed of copper and zinc have a hardness greater than that of pure copper, since the alloy has a hardness greater than the metals in its components; the copper-zinc alloy is soaked in a hydrochloric acid solution, copper in the alloy does not react with hydrochloric acid, zinc in the alloy reacts with hydrochloric acid to be corroded and dissolved, only copper remains in the whole copper-zinc alloy, at the moment, a metal sheet is corroded to be in a net-shaped structure and is crisp, and the net-shaped copper can be prepared into flake copper powder after ball milling. Compared with the preparation of flake copper powder by pure copper ball milling, the superfine flake copper powder obtained by the method has the advantages of low production cost, easily obtained raw materials, simple preparation process, short ball milling time, regular shape, large diameter-thickness ratio, uniform particle size distribution and higher economic benefit.
The technical scheme of the invention is as follows:
step (1), cutting the copper-zinc alloy into pieces with the area of 0.8-2cm2Left and right alloy pieces;
step (2), preparing a hydrochloric acid solution, and putting the cut alloy sheet into the hydrochloric acid solution;
step (3), heating the hydrochloric acid solution to a certain temperature by using a water bath kettle;
introducing oxygen into the hydrochloric acid solution through a plastic guide pipe, and stirring the hydrochloric acid solution through a stirrer;
step (5), reacting for 1-3 hours to obtain a reticular copper sheet, washing with deionized water and drying;
step (6), adding the dried reticular copper sheets and the medium balls into a ball mill, adding a ball milling medium, setting the ball milling speed and time, and obtaining a mixture after ball milling;
and (7) sieving the mixture in the ball milling tank after grinding, washing the obtained copper powder with deionized water for 3-5 times, and drying in a vacuum drying oven at 100 ℃ for 2 hours to obtain the superfine flaky copper powder.
Preferably, the zinc content in step (1) is between 5 and 55 percent by mass.
Preferably, the mass percentage concentration of the hydrochloric acid solution in the step (2) is 5-10%.
Preferably, the hydrochloric acid in step (3) is heated to a temperature of 35 ℃ to 45 ℃.
Preferably, the oxygen introduced in the step (4) is high-purity oxygen with the oxygen content of more than 99.9%. The stirring speed was 200 rpm.
Preferably, in the step (5), the copper sheet is washed by deionized water for 3 to 4 times, and then is dried in a vacuum drying oven at the temperature of 100 ℃ for 10 to 15 minutes.
Preferably, the mass ratio of the mesh copper to the dielectric spheres in the step (6) is 1: 60-80. The medium ball is a stainless steel ball with the diameter phi of 25 mm, 5-20% of the weight of the copper sheet is added with hexadecanol as a ball milling medium, the rotating speed during ball milling is 1100-1200 r/m, and the ball milling is carried out for 3-5 hours.
Compared with the prior art, the invention has the following beneficial effects:
the method adopts the copper-zinc alloy as the raw material, when the cut sheet-shaped alloy is soaked in the hydrochloric acid solution, copper in the alloy does not react with the hydrochloric acid, zinc in the alloy reacts with the hydrochloric acid to be corroded and dissolved, only copper remains in the whole copper-zinc alloy, at the moment, a metal sheet presents a net-shaped structure after being corroded and is crisp, and the net-shaped copper can be prepared into the sheet-shaped copper powder after ball milling. And (4) cleaning the mesh copper sheet subjected to the corrosion reaction with deionized water, drying and ball-milling to obtain the superfine flaky copper powder. The method has the advantages of easily available raw materials, simple preparation process and low cost; the prepared superfine flaky copper powder has regular shape, large diameter-thickness ratio and uniform particle size distribution. Simple process, short ball milling time, low production cost and higher economic benefit.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a flow chart of a preparation process for preparing superfine flaky copper powder by an alloy corrosion method;
FIG. 2 is an SEM photograph of the ultrafine copper flake powder, and the text below FIG. 2 is not clear to show the contents of the drawing.
Detailed Description
The technical solutions of the present invention are described below clearly and completely by way of specific examples, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
Step (1), cutting the copper-zinc alloy with 50% of block or column zinc content into 1cm by using a cutting tool2Left and right alloy pieces.
And (2) preparing a hydrochloric acid solution with the mass percentage concentration of 10%, and putting the cut alloy sheet into the hydrochloric acid solution.
And (3) heating the hydrochloric acid solution by using a water bath kettle until the temperature is 45 ℃.
And (4) introducing high-purity oxygen with the purity of more than 99.9 percent into the hydrochloric acid solution through a plastic guide pipe, and stirring the hydrochloric acid solution through a stirrer at the rotating speed of 200 revolutions per minute.
And (5) taking out the copper sheet after the reaction time is 3 hours, washing the reticular copper sheet for 3-4 times by using ionized water, and drying for 12 minutes in a vacuum drying oven at 100 ℃ for later use.
Step (6), drying the reticular copper sheet and the medium ball according to the weight ratio of 1: 80, adding the medium ball into a ball mill, wherein the medium ball is a stainless steel ball with the diameter of phi 25 mm, adding hexadecanol which is used as a grinding medium and accounts for 20 percent of the weight of the reticular copper sheet, and carrying out ball milling for 5 hours at the rotating speed of 1200 r/min.
And (7) sieving the copper powder mixture in the ball milling tank after grinding, repeatedly washing the obtained copper powder for 3-5 times by 10% hydrochloric acid, and then washing the copper powder for 3-5 times by using deionized water. Drying in a vacuum drying oven at 100 ℃ for 2 hours to obtain the required superfine flaky copper powder.
The flaky copper powder obtained by the method is uniformly dispersed, has the particle size of about 1-2 mu m and does not have the agglomeration phenomenon. The peaks of zinc and copper oxide were found to be absent by XRD testing, confirming that the powder produced was pure copper powder. The prepared slurry is sintered and then the performance of the slurry is measured, the resistance is 6-8m omega, and the adhesion is 19-23N. Is superior to the slurry prepared by spherical copper powder with the diameter of 2 mu m under the same condition.
Example 2
Step (1), cutting the copper-zinc alloy with 50% of block or column zinc content into 1cm by using a cutting tool2Left and right alloy pieces.
And (2) preparing a hydrochloric acid solution with the mass percentage concentration of 10%, and putting the cut alloy sheet into the hydrochloric acid solution.
And (3) heating the hydrochloric acid solution by using a water bath kettle until the temperature is 45 ℃.
And (4) introducing high-purity oxygen with the purity of more than 99.9 percent into the hydrochloric acid solution through a plastic guide pipe, and stirring the hydrochloric acid solution through a stirrer at the rotating speed of 200 revolutions per minute.
And (5) taking out the reticular copper sheet after the reaction time reaches 1 hour, washing the reticular copper sheet for 3-4 times by using deionized water, and drying the copper sheet for 15 minutes in a vacuum drying oven at 100 ℃ for later use.
Step (6), drying the copper sheet and the medium ball according to the weight ratio of 1: 60 are introduced into a ball mill, the medium balls being stainless steel balls having a diameter of 25 mm. Adding hexadecanol which is 5 percent of the weight of the copper sheet as a grinding medium, performing ball milling at the rotating speed of 1100 r/min for 3 hours to obtain a copper powder mixture.
And (7) sieving the copper powder mixture in the ball milling tank after grinding, repeatedly washing the obtained copper powder for 3-5 times by 10% hydrochloric acid, washing the copper powder for 3-5 times by deionized water, and drying the copper powder for 2 hours at 100 ℃ in a vacuum drying oven to obtain the required superfine flaky copper powder.
The flaky copper powder obtained by the method has uniform dispersion, the particle size is about 1-2 mu m, and a small part of agglomeration phenomenon exists. The peaks of zinc and copper oxide were found to be absent by XRD testing, confirming that the powder produced was pure copper powder.
Example 3
Step (1), cutting the copper-zinc alloy with 50% of block or column zinc content into 2cm area by using a cutting tool2Left and right alloy pieces.
And (2) preparing a hydrochloric acid solution with the mass percentage concentration of 8%, and putting the cut alloy sheet into the hydrochloric acid solution.
And (3) heating the hydrochloric acid solution by using a water bath kettle, wherein the heating temperature is 45 ℃.
And (4) introducing high-purity oxygen with the purity of more than 99.9 percent into the hydrochloric acid solution through a plastic guide pipe, and stirring the hydrochloric acid solution through a stirrer at the rotating speed of 200 revolutions per minute.
And (5) when the reaction time reaches 3 hours. And taking out the copper sheet. The copper sheets were washed 3-4 times with deionized water. Drying the mixture in a vacuum drying oven at 100 ℃ for 11 minutes for later use.
And (6) adding the dried copper sheet and the medium ball into a ball mill according to the weight ratio of 1 to 60, wherein the medium ball is a stainless steel ball with the diameter phi of 25 mm. Adding hexadecanol which is 20 percent of the weight of the copper sheet as a grinding medium, performing ball milling at the rotating speed of 1200 rpm for 5 hours to obtain a copper powder mixture.
And (7) sieving the copper powder mixture in the ball milling tank after grinding, repeatedly washing the obtained copper powder for 3-5 times by 10% hydrochloric acid, and then washing the copper powder for 3-5 times by using deionized water. Drying in a vacuum drying oven at 100 ℃ for 2 hours to obtain the required superfine flaky copper powder.
The flaky copper powder obtained by the method is uniformly dispersed, has the particle size of about 2-4 mu m and does not have the agglomeration phenomenon. The peaks of zinc and copper oxide were found to be absent by XRD testing, confirming that the powder produced was pure copper powder. The prepared slurry is sintered and then the performance of the slurry is measured, the resistance is 10-15m omega, and the adhesion is 14-17N. Is superior to the slurry prepared by 4 mu m spherical copper powder under the same condition.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (1)
1. A method for preparing superfine flaky copper powder by an alloy corrosion method is characterized by comprising the following steps:
step (1), cutting the copper-zinc alloy into pieces with the area of 0.8-2cm2The alloy sheet of (1), wherein the zinc content in the copper-zinc alloy is 5-55% by mass;
step (2), preparing a hydrochloric acid solution, and putting the cut alloy sheet into the hydrochloric acid solution with the mass percentage concentration of 5% -10%;
step (3), heating the hydrochloric acid solution to 35-45 ℃ by using a water bath kettle;
introducing high-purity oxygen with the concentration of more than 99.9% into the hydrochloric acid solution through a plastic guide pipe, and simultaneously stirring the hydrochloric acid solution through a stirrer for reaction, wherein the stirring speed is 200 revolutions per minute;
step (5), stirring and reacting for 1-3 hours to obtain a reticular copper sheet, washing the reticular copper sheet for 3-4 times by using deionized water, and then drying the reticular copper sheet for 10-15 minutes in a vacuum drying oven at the temperature of 100 ℃;
and (6) putting the dried reticular copper sheet and the medium balls into a ball mill, wherein the mass ratio of the reticular copper sheet to the medium balls is 1: 60-80, wherein the medium ball is a stainless steel ball with the diameter phi of 25 mm; adding hexadecanol which is 5-20 percent of the weight of the copper sheet as a ball milling medium, wherein the rotating speed is 1100 and 1200 revolutions per minute during ball milling, and carrying out ball milling for 3-5 hours to obtain a copper powder mixture;
and (7) sieving the copper powder mixture in the ball mill, washing the obtained copper powder with deionized water for 3-5 times, and drying in a vacuum drying oven at 100 ℃ for 2 hours to obtain the superfine flaky copper powder.
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| CN103273056B (en) * | 2013-05-27 | 2016-01-20 | 中国科学院过程工程研究所 | A kind of flake copper and preparation method thereof |
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