CN108360024B - Preparation method of 3D printing copper powder - Google Patents
Preparation method of 3D printing copper powder Download PDFInfo
- Publication number
- CN108360024B CN108360024B CN201810066480.XA CN201810066480A CN108360024B CN 108360024 B CN108360024 B CN 108360024B CN 201810066480 A CN201810066480 A CN 201810066480A CN 108360024 B CN108360024 B CN 108360024B
- Authority
- CN
- China
- Prior art keywords
- copper powder
- copper
- electrolysis
- printing
- concentration
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C5/00—Electrolytic production, recovery or refining of metal powders or porous metal masses
- C25C5/02—Electrolytic production, recovery or refining of metal powders or porous metal masses from solutions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
Abstract
The invention discloses a preparation method of 3D printing copper powder, which comprises the following steps of dissolving: dissolving a copper-containing reagent in an aqueous solution of sulfuric acid; ventilating: introducing a non-oxidizing gas into the dissolved copper-containing reagent; electrolysis: and adding an additive into the dissolved and ventilated copper-containing reagent for electrolysis to obtain the copper powder. The method efficiently and conveniently realizes the regulation and control of the oxygen content, morphology and particle size distribution of the copper powder by the electrochemical method, the introduction of the non-oxidizing gas and the synergistic effect of the additive, and has the advantages of simple whole process, less equipment required for production, less required reagent amount, wide raw material source, low cost, suitability for large-scale industrial production and good economic benefit.
Description
Technical Field
The invention belongs to the technical field of 3D printing materials, and particularly relates to a preparation method of 3D printing copper powder.
Background
The 3D printing technology is widely used in military, aerospace, medicine, automobiles, electronics, and the like, in which copper-based metals are largely used as metal materials for 3D printing due to their good plasticity and conductivity. At present, the common printing metal preparation technologies comprise three major technologies, namely physical, chemical and mechanical technologies, but the methods are generally high in cost and low in efficiency, and the oxygen content, the particle size distribution and the particle morphology of the obtained copper powder are all unstable, so that the development of the copper powder towards popularization and civilization is hindered.
Disclosure of Invention
This section is for the purpose of summarizing some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. In this section, as well as in the abstract and the title of the invention of this application, simplifications or omissions may be made to avoid obscuring the purpose of the section, the abstract and the title, and such simplifications or omissions are not intended to limit the scope of the invention.
The present invention has been made in view of the above-mentioned technical drawbacks.
Therefore, the invention overcomes the defects in the prior art and provides the preparation method of the 3D printing copper powder.
In order to solve the technical problems, the invention provides the following technical scheme: a preparation method of 3D printing copper powder comprises the following steps of dissolving: dissolving a copper-containing reagent in an aqueous solution of sulfuric acid; ventilating: introducing a non-oxidizing gas into the dissolved copper-containing reagent; electrolysis: and adding an additive into the dissolved and ventilated copper-containing reagent for electrolysis to obtain the copper powder.
As a preferable scheme of the preparation method of the 3D printing copper powder, the dissolving step is carried out, wherein the copper-containing reagent is copper sulfate, the purity of the copper sulfate is 99.91-99.99%, and the concentration of the sulfuric acid aqueous solution is 10-50 g/L; the aeration, wherein the non-oxidizing gas is nitrogen.
In the electrolysis, the additive is potassium ferrocyanide or polyethylene glycol 2000, and the concentration of copper is 1.0-10 g/L.
In a preferable embodiment of the method for preparing 3D printing copper powder, the electrolysis is performed, wherein the concentration of the potassium ferrocyanide is 0.4 g/L-2.3 g/L, and the concentration of the polyethylene glycol 2000 is 0.01 g/L-0.5 g/L.
As a preferable scheme of the preparation method of the 3D printing copper powder, the electrolysis is cyclone electrolysis, a working electrode of the cyclone electrolysis is stainless steel, and a counter electrode of the cyclone electrolysis is a mesh electrode.
The preferable scheme of the preparation method of the 3D printing copper powder is that the cyclone electrolysis is carried out, wherein the working electrode is 304 stainless steel, the area of the working electrode is 600-700 cm2, and the counter electrode is a titanium-tantalum-coated mesh electrode.
As a preferable scheme of the preparation method of the 3D printing copper powder, the electrolysis is carried out at the temperature of 20-30 ℃, the current density of 30-50A/m 2 and the time of 0.6-0.8 h.
According to the preferable scheme of the preparation method of the 3D printing copper powder, the electrolysis is carried out in a stirring state, and the stirring speed is 300-400 r/min.
As a preferable scheme of the preparation method of the 3D printing copper powder, the preparation method further comprises the following steps,
cleaning: washing the copper powder obtained by electrolysis with water and absolute ethyl alcohol;
and (3) drying: and drying the cleaned copper powder.
As a preferable scheme of the preparation method of the 3D printing copper powder, the ethanol concentration is 90-99.8%, and the drying is carried out in a vacuum drying oven at the temperature of 60 ℃ for 3 hours.
The invention has the beneficial effects that: the method efficiently and conveniently realizes the regulation and control of the oxygen content, morphology and particle size distribution of the copper powder by the electrochemical method, the introduction of the non-oxidizing gas and the synergistic effect of the additive, and has the advantages of simple whole process, less equipment required for production, less required reagent amount, wide raw material source, low cost, suitability for large-scale industrial production and good economic benefit.
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 description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise. Wherein:
FIG. 1 is a scanning electron micrograph of 3D printed spherical copper powder prepared according to example 1 of the present invention;
FIG. 2 is a scanning electron micrograph of copper powder prepared according to example 5 of the present invention;
FIG. 3 is a scanning electron microscope photomicrograph of a 3D printed dendritic copper powder prepared according to example 8 of the present invention;
FIG. 4 is a scanning electron micrograph of 3D printed dendritic copper powder prepared according to example 9 of the present invention;
FIG. 5 is a scanning electron micrograph of a copper powder prepared according to comparative example 1 of the present invention;
FIG. 6 is a scanning electron micrograph of a copper powder prepared according to comparative example 2 of the present invention;
FIG. 7 is a scanning electron micrograph of a copper powder prepared according to comparative example 3 of the present invention.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with examples are described in detail below.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
Furthermore, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Example 1:
drying anhydrous copper sulfate (purity of 99.99%) and potassium ferrocyanide at high temperature of 80 deg.C;
the dried anhydrous copper sulfate and potassium ferrocyanide are dissolved in sulfuric acid (20g/L) aqueous solution, the concentration of copper is 8g/L, the concentration of potassium ferrocyanide is 1.5g/L, and nitrogen is introduced into the copper-containing solution.
And (3) introducing the obtained electrolyte into a cuboid rotational flow electrolytic cell, wherein the working electrode is 304 stainless steel and the area of the working electrode is 700cm2, the counter electrode is a titanium-tantalum-coated mesh electrode, the electrolysis temperature is 30 ℃, the current density is 40A/m2, the electrolysis time is 0.8h, and stirring at 400r/min for electrolysis to obtain the copper powder.
And washing the prepared copper powder with water, then washing with 96% absolute ethyl alcohol, and drying in a vacuum drying oven at 60 ℃ for 3h to obtain the copper powder suitable for 3D printing.
SEM representation is carried out on the superfine copper powder obtained in the embodiment, and as shown in figure 1, the obtained superfine copper powder is spherical, uniform in particle, 375ppm in oxygen content and 3-5 microns in diameter.
Example 2:
anhydrous copper sulfate (purity 99.94%) and potassium ferrocyanide are dried at high temperature of 70 deg.C.
The dried anhydrous copper sulfate and potassium ferrocyanide are dissolved in sulfuric acid (30g/L) aqueous solution, the concentration of copper is 10g/L, the concentration of potassium ferrocyanide is 2.0g/L, and nitrogen is introduced into the copper-containing solution.
And (3) introducing the obtained electrolyte into a cuboid rotational flow electrolytic cell, wherein the working electrode is 304 stainless steel and the area is 600cm2, the counter electrode is a titanium tantalum coated mesh electrode, the electrolysis temperature is 30 ℃, the current density is 50A/m2, the electrolysis time is 0.8h, and stirring is carried out at 300r/min for electrolysis to obtain the copper powder.
And (3) washing the prepared copper powder with water, then washing with 97% absolute ethyl alcohol, and drying in a vacuum drying oven at 60 ℃ for 3h to obtain the copper powder suitable for 3D printing.
SEM representation is carried out on the superfine copper powder obtained in the embodiment, and the obtained superfine copper powder is spherical and uniform in particle, the oxygen content is 203ppm, and the diameter is 2-5 microns.
Example 3:
drying copper chloride (purity of 99.94%) and potassium ferrocyanide at high temperature of 70 deg.C.
The dried anhydrous copper sulfate and potassium ferrocyanide are dissolved in sulfuric acid (30g/L) aqueous solution, the concentration of copper is 10g/L, the concentration of potassium ferrocyanide is 2.0g/L, and nitrogen is introduced into the copper-containing solution.
And (3) introducing the obtained electrolyte into a cuboid rotational flow electrolytic cell, wherein the working electrode is 304 stainless steel and the area is 600cm2, the counter electrode is a titanium tantalum coated mesh electrode, the electrolysis temperature is 30 ℃, the current density is 50A/m2, the electrolysis time is 0.8h, and stirring is carried out at 300r/min for electrolysis to obtain the copper powder.
And (3) washing the prepared copper powder with water, then washing with 97% absolute ethyl alcohol, and drying in a vacuum drying oven at 60 ℃ for 3h to obtain the copper powder suitable for 3D printing.
SEM representation is carried out on the superfine copper powder obtained in the embodiment, and the obtained superfine copper powder is porous irregular particles, the oxygen content is 1400ppm, and the diameter is 3-45 mu m.
Example 4:
anhydrous copper sulfate (purity 99.94%) and potassium ferrocyanide are dried at high temperature of 70 deg.C.
The dried anhydrous copper sulfate and potassium ferrocyanide are dissolved in sulfuric acid (30g/L) aqueous solution, the concentration of copper is 10g/L, the concentration of potassium ferrocyanide is 2.0g/L, and nitrogen is introduced into the copper-containing solution.
And (3) introducing the obtained electrolyte into a cuboid rotational flow electrolytic cell, wherein the working electrode is 304 stainless steel and the area is 600cm2, the counter electrode is a titanium-tantalum-coated mesh electrode, the electrolysis temperature is 30 ℃, the current density is 500A/m2, the electrolysis time is 0.8h, and stirring is carried out for 1000r/min to carry out electrolysis, so as to obtain the copper powder.
And (3) washing the prepared copper powder with water, then washing with 97% absolute ethyl alcohol, and drying in a vacuum drying oven at 60 ℃ for 3h to obtain the copper powder suitable for 3D printing.
SEM representation is carried out on the superfine copper powder obtained in the embodiment, and the obtained irregular spherical-like particles of the superfine copper powder have the oxygen content of 2160ppm and the diameter of 5-15 microns.
Example 5:
anhydrous copper sulfate (purity 99.94%) and potassium ferrocyanide are dried at high temperature of 70 deg.C.
The dried anhydrous copper sulfate and potassium ferrocyanide are dissolved in sulfuric acid (30g/L) aqueous solution, the concentration of copper is 10g/L, the concentration of potassium ferrocyanide is 2.0g/L, and nitrogen is introduced into the copper-containing solution.
And (3) introducing the obtained electrolyte into a rectangular cyclone electrolytic cell, wherein the working electrode is 304 stainless steel and the area is 600cm2, the counter electrode is a titanium-tantalum-coated mesh electrode, the electrolysis temperature is 30 ℃, the current density is 200A/m2, the electrolysis time is 0.8h, and stirring is carried out at 300r/min for electrolysis to obtain the copper powder.
And (3) washing the prepared copper powder with water, then washing with 97% absolute ethyl alcohol, and drying in a vacuum drying oven at 60 ℃ for 3h to obtain the copper powder suitable for 3D printing.
SEM representation of the superfine copper powder obtained in the example is carried out, and as shown in figure 2, the obtained superfine copper powder is spherical-like particles, the oxygen content is 1800ppm, and the diameter is 6-10 μm.
Example 6:
drying anhydrous copper sulfate (purity of 99.94%), potassium ferrocyanide at high temperature of 70 deg.C
The dried anhydrous copper sulfate and potassium ferrocyanide are dissolved in sulfuric acid (30g/L) aqueous solution, the concentration of copper is 10g/L, the concentration of potassium ferrocyanide is 2.0g/L, and nitrogen is introduced into the copper-containing solution.
And (3) introducing the obtained electrolyte into a cuboid rotational flow electrolytic cell, wherein the working electrode is 304 stainless steel and the area is 600cm2, the counter electrode is a titanium tantalum coated mesh electrode, the electrolysis temperature is 30 ℃, the current density is 50A/m2, the electrolysis time is 0.8h, and stirring is carried out at 300r/min for electrolysis to obtain the copper powder.
And (3) washing the prepared copper powder with water, then washing with 97% absolute ethyl alcohol, and drying in a vacuum drying oven at 60 ℃ for 3h to obtain the copper powder suitable for 3D printing.
SEM representation is carried out on the superfine copper powder obtained in the embodiment, and the obtained superfine copper powder is spherical and uniform in particle, the oxygen content is 205ppm, and the diameter is 2-5 microns.
Example 7:
drying anhydrous copper sulfate (purity of 99.99%), potassium ferrocyanide at high temperature of 90 deg.C
The dried anhydrous copper sulfate and potassium ferrocyanide are dissolved in sulfuric acid (40g/L) aqueous solution, the concentration of copper is 6g/L, the concentration of potassium ferrocyanide is 1.9g/L, and nitrogen is introduced into the copper-containing solution.
And (3) introducing the obtained electrolyte into a cuboid rotational flow electrolytic cell, wherein the working electrode is a 304 stainless steel mesh electrode with the area of 650cm2, the counter electrode is a titanium-tantalum-coated mesh electrode, the electrolysis temperature is 25 ℃, the current density is 45A/m2, the electrolysis time is 0.8h, and stirring at 400r/min for electrolysis to obtain the copper powder.
And washing the prepared copper powder with water, washing with 96% absolute ethyl alcohol, and drying in a vacuum drying oven at 60 ℃ for 3h to obtain the copper powder suitable for 3D printing.
SEM representation is carried out on the superfine copper powder obtained in the embodiment, and the obtained superfine copper powder is spherical and uniform in particle, the oxygen content is 321ppm, and the diameter is 4-7 microns.
Example 8:
anhydrous copper sulfate (purity 99.99%) and polyethylene glycol 2000 are dried at 80 deg.C.
Respectively dissolving the dried anhydrous copper sulfate and polyethylene glycol 2000 in a sulfuric acid (50g/L) aqueous solution, wherein the concentration of copper is 9g/L, the concentration of polyethylene glycol 2000 is 0.25g/L, and introducing nitrogen into the copper-containing solution.
And (3) introducing the obtained electrolyte into a cuboid rotational flow electrolytic cell, wherein the working electrode is 304 stainless steel and the area of the working electrode is 700cm2, the counter electrode is a titanium-tantalum-coated mesh electrode, the electrolysis temperature is 30 ℃, the current density is 40A/m2, the electrolysis time is 0.8h, and stirring is carried out at 300r/min for electrolysis to obtain the copper powder.
And (3) washing the prepared copper powder with water, then washing with 90% absolute ethyl alcohol, and drying in a vacuum drying oven at 60 ℃ for 3h to obtain the copper powder suitable for 3D printing.
SEM representation is carried out on the superfine copper powder obtained in the embodiment, and as shown in figure 3, the obtained superfine copper powder is dendritic and uniform in particle, the oxygen content is 461ppm, and the diameter is 1-5 μm.
Example 9:
anhydrous copper sulfate (purity 99.99%) and polyethylene glycol 2000 are dried at 80 deg.C.
Respectively dissolving the dried anhydrous copper sulfate and polyethylene glycol 2000 in a sulfuric acid (50g/L) aqueous solution, wherein the concentration of copper is 19g/L, the concentration of polyethylene glycol 2000 is 0.25g/L, and introducing nitrogen into the copper-containing solution.
And (3) introducing the obtained electrolyte into a cuboid rotational flow electrolytic cell, wherein the working electrode is 304 stainless steel and the area of the working electrode is 700cm2, the counter electrode is a titanium-tantalum-coated mesh electrode, the electrolysis temperature is 30 ℃, the current density is 40A/m2, the electrolysis time is 0.8h, and stirring is carried out at 300r/min for electrolysis to obtain the copper powder.
And (3) washing the prepared copper powder with water, then washing with 90% absolute ethyl alcohol, and drying in a vacuum drying oven at 60 ℃ for 3h to obtain the copper powder suitable for 3D printing.
SEM representation of the superfine copper powder obtained in the example shows that the obtained superfine copper powder is irregular long rod-shaped, the oxygen content is 500ppm, and the diameter is 5-12 μm as shown in figure 4.
Example 10:
anhydrous copper sulfate (purity 99.99%) and polyethylene glycol 2000 are dried at 80 deg.C.
Respectively dissolving the dried anhydrous copper sulfate and polyethylene glycol 2000 in a sulfuric acid (50g/L) aqueous solution, wherein the concentration of copper is 9g/L, the concentration of polyethylene glycol 2000 is 12.5g/L, and introducing nitrogen into the copper-containing solution.
And (3) introducing the obtained electrolyte into a cuboid rotational flow electrolytic cell, wherein the working electrode is 304 stainless steel and the area of the working electrode is 700cm2, the counter electrode is a titanium-tantalum-coated mesh electrode, the electrolysis temperature is 30 ℃, the current density is 40A/m2, the electrolysis time is 0.8h, and stirring is carried out at 300r/min for electrolysis to obtain the copper powder.
And (3) washing the prepared copper powder with water, then washing with 90% absolute ethyl alcohol, and drying in a vacuum drying oven at 60 ℃ for 3h to obtain the copper powder suitable for 3D printing.
SEM representation is carried out on the superfine copper powder obtained in the embodiment, and the obtained superfine copper powder is in an irregular long rod shape, the oxygen content is 512ppm, and the diameter is 3-20 microns.
Example 11:
anhydrous copper sulfate (purity 99.99%) and polyethylene glycol 2000 are dried at 80 deg.C.
Respectively dissolving the dried anhydrous copper sulfate and polyethylene glycol 2000 in a sulfuric acid (50g/L) aqueous solution, wherein the concentration of copper is 9g/L, the concentration of polyethylene glycol 2000 is 0.25g/L, and introducing nitrogen into the copper-containing solution.
And (3) introducing the obtained electrolyte into a rectangular cyclone electrolytic cell, wherein the working electrode is 304 stainless steel and the area of the working electrode is 700cm2, the counter electrode is a titanium-tantalum-coated mesh electrode, the electrolysis temperature is 30 ℃, the current density is 400A/m2, the electrolysis time is 0.8h, and stirring is carried out at 300r/min for electrolysis to obtain the copper powder.
And (3) washing the prepared copper powder with water, then washing with 90% absolute ethyl alcohol, and drying in a vacuum drying oven at 60 ℃ for 3h to obtain the copper powder suitable for 3D printing.
SEM representation is carried out on the superfine copper powder obtained in the embodiment, and the obtained superfine copper powder is in an irregular long rod shape, the oxygen content is 1864ppm, and the diameter is 4-8 mu m.
Example 12:
anhydrous copper sulfate (purity 99.99%) and polyethylene glycol 2000 are dried at 80 deg.C.
Respectively dissolving the dried anhydrous copper sulfate and polyethylene glycol 2000 in a sulfuric acid (50g/L) aqueous solution, wherein the concentration of copper is 9g/L, the concentration of polyethylene glycol 2000 is 0.25g/L, and introducing nitrogen into the copper-containing solution.
And (3) introducing the obtained electrolyte into a rectangular cyclone electrolytic cell, wherein the working electrode is 304 stainless steel and the area of the working electrode is 700cm2, the counter electrode is a titanium-tantalum-coated mesh electrode, the electrolysis temperature is 30 ℃, the current density is 40A/m2, the electrolysis time is 0.8h, and stirring at 800r/min is carried out for electrolysis to obtain the copper powder.
And (3) washing the prepared copper powder with water, then washing with 90% absolute ethyl alcohol, and drying in a vacuum drying oven at 60 ℃ for 3h to obtain the copper powder suitable for 3D printing.
SEM representation is carried out on the superfine copper powder obtained in the embodiment, and the obtained superfine copper powder is in an irregular long rod shape, the oxygen content is 3000ppm, and the diameter is 7-18 mu m.
Example 13:
anhydrous copper sulfate (purity 99.96%) and polyethylene glycol 2000 are dried at high temperature of 90 deg.C.
Respectively dissolving the dried anhydrous copper sulfate and polyethylene glycol 2000 in a sulfuric acid (40g/L) aqueous solution, wherein the concentration of copper is 9.4g/L, the concentration of polyethylene glycol 2000 is 0.4g/L, and introducing nitrogen into the copper-containing solution.
And (3) introducing the obtained electrolyte into a cuboid rotational flow electrolytic cell, wherein the working electrode is 304 stainless steel and the area of the working electrode is 700cm2, the counter electrode is a titanium-tantalum-coated mesh electrode, the electrolysis temperature is 30 ℃, the current density is 50A/m2, the electrolysis time is 0.7h, and stirring is carried out at 350r/min for electrolysis to obtain the copper powder.
And (3) washing the prepared copper powder with water, then washing with 92% absolute ethyl alcohol, and drying in a vacuum drying oven at 60 ℃ for 3h to obtain the copper powder suitable for 3D printing.
SEM representation is carried out on the superfine copper powder obtained in the embodiment, and the obtained superfine copper powder is dendritic and uniform in particle, the oxygen content is 194ppm, and the diameter is 2-4 microns.
Example 14:
anhydrous copper sulfate (purity 99.93%), polyethylene glycol 2000 were dried at 85 deg.C.
The dried anhydrous copper sulfate and polyethylene glycol 2000 are respectively dissolved in sulfuric acid (50g/L) water solution, the concentration of copper is 9.6g/L, the concentration of polyethylene glycol 2000 is 0.5g/L, and nitrogen is introduced into the copper-containing solution.
And (3) introducing the obtained electrolyte into a rectangular cyclone electrolytic cell, wherein the working electrode is 304 stainless steel and the area is 670cm2, the counter electrode is a titanium-tantalum-coated mesh electrode, the electrolysis temperature is 27 ℃, the current density is 46A/m2, the electrolysis time is 0.71h, and stirring is carried out for 364r/min to carry out electrolysis, so as to obtain the copper powder.
And (3) washing the prepared copper powder with water, then washing with 93% absolute ethyl alcohol, and drying in a vacuum drying oven at 60 ℃ for 3h to obtain the copper powder suitable for 3D printing.
SEM representation is carried out on the superfine copper powder obtained in the embodiment, and the obtained superfine copper powder is dendritic and uniform in particle, the oxygen content is 203ppm, and the diameter is 1-3 microns.
Comparative example 1:
compared with example 1, the subsequent operation was carried out as an electrolytic solution directly after dissolving the copper-containing reagent, under the same conditions as in example 1 except that potassium ferrocyanide was not added.
SEM representation is carried out on the superfine copper powder obtained in the comparative example, and the result is shown in figure 5, the obtained copper powder is a polyhedron with irregular rhombohedral angles, the particles are not uniform, the distribution range is large, the oxygen content is 1030ppm, and the diameter is 1-9 mu m.
Comparative example 2:
the same conditions as in example 1 were used except that potassium ferrocyanide added at a concentration of 1.5g/L was replaced with sodium ferrocyanide at a concentration of 1.5g/L as compared with example 1.
SEM representation is carried out on the superfine copper powder obtained in the comparative example, and the result is shown in figure 6, the obtained copper powder is rod-shaped or oval, the particles are uneven and have a large distribution range, the oxygen content is 1258ppm, and the diameter is 1-10 mu m.
Comparative example 3:
the same conditions as in example 4 were used except that polyvinyl alcohol 2000 added at a concentration of 0.25g/L was replaced with polyvinyl alcohol 12000 at a concentration of 0.25g/L as compared with example 4.
SEM representation is carried out on the superfine copper powder obtained in the comparative example, and the result is shown in figure 7, the obtained copper powder is gathered together in the form of small irregular particles, the distribution range is large, the oxygen content is 850ppm, and the diameter is 1-12 mu m.
The method efficiently and conveniently realizes the regulation and control of the oxygen content, morphology and particle size distribution of the copper powder by the electrochemical method, the introduction of the non-oxidizing gas and the synergistic effect of the additive, and has the advantages of simple whole process, less equipment required for production, less required reagent amount, wide raw material source, low cost, suitability for large-scale industrial production and good economic benefit.
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (1)
1. A preparation method of 3D printing copper powder is characterized by comprising the following steps: drying anhydrous copper sulfate with the purity of 99.96 percent and polyethylene glycol 2000 at the high temperature of 90 ℃;
respectively dissolving the dried anhydrous copper sulfate and polyethylene glycol 2000 in 40g/L sulfuric acid aqueous solution, wherein the concentration of copper is 9.4g/L, the concentration of polyethylene glycol 2000 is 0.4g/L, and introducing nitrogen into the copper-containing solution;
introducing the obtained electrolyte into a cyclone electrolytic cell, wherein the working electrode is 304 stainless steel with the area of 700cm2The counter electrode is a mesh electrode coated with titanium and tantalum, the electrolysis temperature is 30 ℃, and the current density is 50A/m2Stirring for 350r/min for electrolysis for 0.7h to obtain copper powder;
and washing the prepared copper powder with water, then washing with 92% absolute ethyl alcohol, and drying in a vacuum drying oven at 60 ℃ for 3h to obtain the copper powder suitable for 3D printing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810066480.XA CN108360024B (en) | 2018-01-24 | 2018-01-24 | Preparation method of 3D printing copper powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810066480.XA CN108360024B (en) | 2018-01-24 | 2018-01-24 | Preparation method of 3D printing copper powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108360024A CN108360024A (en) | 2018-08-03 |
| CN108360024B true CN108360024B (en) | 2020-04-14 |
Family
ID=63006668
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810066480.XA Active CN108360024B (en) | 2018-01-24 | 2018-01-24 | Preparation method of 3D printing copper powder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108360024B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113084186B (en) * | 2021-03-30 | 2022-03-04 | 武汉大学 | Flower-shaped copper particle and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103388160B (en) * | 2013-07-19 | 2016-05-25 | 北京科技大学 | Method by the molten copper-electro-deposition of waste printed circuit board coupling legal system for superfine cupper powder |
| CN105436518A (en) * | 2015-12-28 | 2016-03-30 | 广东华科新材料研究院有限公司 | Preparation method of oxidation-resistant ultrafine spherical copper powder |
| CN106623898A (en) * | 2016-12-19 | 2017-05-10 | 西安欧中材料科技有限公司 | Metal Cu powder and preparation method thereof |
| CN206692751U (en) * | 2017-03-24 | 2017-12-01 | 金川集团股份有限公司 | The device of copper powder dissolution velocity in a kind of quickening the anode mud of copper electroplating |
-
2018
- 2018-01-24 CN CN201810066480.XA patent/CN108360024B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN108360024A (en) | 2018-08-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108554426B (en) | Difunctional cobalt diselenide material and preparation and application thereof | |
| CN111097402B (en) | Nano beta-lead dioxide catalyst, preparation method and application thereof | |
| CN109402678B (en) | Method for removing lead ions in electrolytic copper foil electrolyte | |
| CN108520965B (en) | Preparation method of platinum-precious metal-copper ternary alloy nano hollow cube | |
| CN106672975A (en) | Preparation method of low-cost nano-porous silica powder | |
| CN108360024B (en) | Preparation method of 3D printing copper powder | |
| JPH029722A (en) | Production of manganese oxide powder | |
| CN113832473B (en) | Molten salt electrochemical method for co-producing metal/carbon composite material and hydrogen | |
| CN109295310A (en) | The method that metal gas-based reduction prepares high pure metal vanadium powder | |
| CN1827266A (en) | Process for preparing nano nickel powder | |
| CN111924938B (en) | Electrochemical method for removing calcium ions in brine and recycling calcium carbonate | |
| CN109234767B (en) | Preparation method of superfine spherical copper powder | |
| CN109701511B (en) | Preparation method of titanium oxide with fractal structure | |
| CN103820834A (en) | Preparation and silver doping methods of titania nanotubes | |
| CN110512229A (en) | A kind of preparation method of water electrolysis analysis oxygen electrode | |
| CN110629253B (en) | Method for electrorefining lead bullion by using ionic liquid and method for recovering metal bismuth and silver | |
| CN110684990A (en) | Molybdenum phosphide nano material and preparation method and application thereof | |
| CN105271208B (en) | A kind of graphene and preparation method thereof | |
| CN114262905B (en) | CO trapping 2 Molten carbonate electrolyte of (2) and use thereof | |
| CN111411368B (en) | Method for treating dichloromethane through electrochemical dechlorination under catalysis of palladium | |
| JP2001137858A (en) | Water treatment method and titanium oxide electrode to be used therein | |
| CN106854768A (en) | electrodeposition preparation method of superfine copper powder | |
| CN112981467A (en) | Method for reducing carbon pollution in molten salt electrolysis process | |
| CN105220182A (en) | A kind of method preparing porous titanium valve | |
| CN1824436A (en) | Production of cuprous oxide powder and bronze powder using sulfur dioxide reduction method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |