CN108360024A - A kind of preparation method of 3D printing copper powder - Google Patents
A kind of preparation method of 3D printing copper powder Download PDFInfo
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- CN108360024A CN108360024A CN201810066480.XA CN201810066480A CN108360024A CN 108360024 A CN108360024 A CN 108360024A CN 201810066480 A CN201810066480 A CN 201810066480A CN 108360024 A CN108360024 A CN 108360024A
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- 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
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- 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
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Abstract
The invention discloses a kind of preparation methods of 3D printing copper powder comprising, dissolving：Copper reagent will be contained to dissolve in aqueous sulfuric acid；Ventilation：It will be passed through non-oxidizing gas by containing in copper reagent described in dissolving；Electrolysis：It is electrolysed by containing addition additive in copper reagent described in dissolving, ventilation, copper powder is made.The present invention efficiently easily by electrochemical method, be passed through the synergistic effect of non-oxidizing gas, additive, to realize to copper powder oxygen content, the regulation and control of pattern and size distribution, whole flow process is simple, and equipment is few needed for production, and required amount of reagent is few, raw material sources are extensive, it is at low cost, it is suitable for large-scale industrial production, it is with good economic efficiency.
Description
Technical field
The invention belongs to 3D printing field of material technology, and in particular to a kind of preparation method of 3D printing copper powder.
Background technology
3D printing technique is extensively using military affairs, space flight, medicine, automobile and electronics etc., and wherein copper system metal is due to tool
There are good plasticity and electric conductivity to be widely used as the metal material of 3D printing.Printing made of metal relatively conventional at present is for skill
Art includes the three categories technology such as physics, chemistry and machinery, but these methods are generally of high cost, efficiency is low, and the copper powder obtained
Oxygen content, size distribution and granule-morphology are all unstable, hinder its development to popular civil nature direction.
Invention content
The purpose of this part is to summarize some aspects of the embodiment of the present invention and briefly introduce some preferably to implement
Example.It may do a little simplified or be omitted to avoid our department is made in this section and the description of the application and the title of the invention
Point, the purpose of abstract of description and denomination of invention it is fuzzy, and this simplification or omit and cannot be used for limiting the scope of the invention.
In view of above-mentioned technological deficiency, it is proposed that the present invention.
Therefore, the present invention overcomes the deficiencies in the prior art, provides a kind of preparation method of 3D printing copper powder.
In order to solve the above technical problems, the present invention provides following technical solutions：A kind of preparation method of 3D printing copper powder,
It includes dissolving：Copper reagent will be contained to dissolve in aqueous sulfuric acid；Ventilation：It will be passed through by containing in copper reagent described in dissolving
Non-oxidizing gas；Electrolysis：It is electrolysed by containing addition additive in copper reagent described in dissolving, ventilation, copper powder is made.
The preferred embodiment of preparation method as 3D printing copper powder of the present invention, the dissolving, wherein the cupric examination
Agent is copper sulphate, and the purity of the copper sulphate is 99.91%~99.99%, the aqueous sulfuric acid, a concentration of 10g/L~
50g/L；The ventilation, wherein the non-oxidizing gas is nitrogen.
The preferred embodiment of preparation method as 3D printing copper powder of the present invention, the electrolysis, wherein the additive
For potassium ferrocyanide or polyethylene glycol 2000, a concentration of 1.0g/L~10g/L of the copper.
The preferred embodiment of preparation method as 3D printing copper powder of the present invention, the electrolysis, wherein the ferrous iron cyanogen
Change potassium, a concentration of 0.4g/L~2.3g/L, the polyethylene glycol 2000, a concentration of 0.01g/L~0.5g/L.
The preferred embodiment of preparation method as 3D printing copper powder of the present invention, the electrolysis is cyclone electrolytic cell, described
Cyclone electrolytic cell, working electrode are stainless steel, are mesh electrode to electrode.
The preferred embodiment of preparation method as 3D printing copper powder of the present invention, the cyclone electrolytic cell, wherein the work
It is 304 stainless steels to make electrode, and the area of the working electrode is 600~700cm2, described to electrode, is the netted of coated titanium tantalum
Electrode.
The preferred embodiment of preparation method as 3D printing copper powder of the present invention, the electrolysis, temperature are 20~30
DEG C, current density is 30~50A/m2, and the time is 0.6~0.8h.
The preferred embodiment of preparation method as 3D printing copper powder of the present invention, the electrolysis, under stirring
Electrolysis, the stirring, speed are 300~400r/min.
The preferred embodiment of preparation method as 3D printing copper powder of the present invention further includes,
Cleaning：Electrolysis copper powder water obtained and washes of absolute alcohol will be passed through；
It is dry：By the copper powder drying through over cleaning.
The preferred embodiment of preparation method as 3D printing copper powder of the present invention, the ethyl alcohol, a concentration of 90~
99.8%, the drying, to be dry in vacuum drying chamber, temperature is 60 DEG C, drying time 3h.
Beneficial effects of the present invention：The present invention efficiently easily by electrochemical method, be passed through non-oxidizing gas, addition
The synergistic effect of agent, to realize that whole flow process is simple to the regulation and control of copper powder oxygen content, pattern and size distribution, needed for production
Equipment is few, and required amount of reagent is few, and raw material sources are extensive, at low cost, is suitable for large-scale industrial production, has good economic effect
Benefit.
Description of the drawings
In order to illustrate the technical solution of the embodiments of the present invention more clearly, required use in being described below to embodiment
Attached drawing be briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for this
For the those of ordinary skill of field, without having to pay creative labor, it can also be obtained according to these attached drawings other
Attached drawing.Wherein：
Fig. 1 is the electron scanning micrograph at the spherical copper powder end that the embodiment of the present invention 1 prepares 3D printing；
Fig. 2 is the electron scanning micrograph that the embodiment of the present invention 5 prepares copper powders；
Fig. 3 is the electron scanning micrograph for the dendriform copper powders that the embodiment of the present invention 8 prepares 3D printing；
Fig. 4 is the electron scanning micrograph for the dendriform copper powders that the embodiment of the present invention 9 prepares 3D printing；
Fig. 5 is the electron scanning micrograph of copper powder prepared by comparative example 1 of the present invention；
Fig. 6 is the electron scanning micrograph of copper powder prepared by comparative example 2 of the present invention；
Fig. 7 is the electron scanning micrograph of copper powder prepared by comparative example 3 of the present invention.
Specific implementation mode
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, with reference to specific embodiment pair
The specific implementation mode of the present invention is described in detail.
Many details are elaborated in the following description to facilitate a thorough understanding of the present invention, still the present invention can be with
Implemented different from other manner described here using other, those skilled in the art can be without prejudice to intension of the present invention
In the case of do similar popularization, therefore the present invention is not limited by following public specific embodiment.
Secondly, " one embodiment " or " embodiment " referred to herein refers to that may be included at least one realization side of the present invention
A particular feature, structure, or characteristic in formula." in one embodiment " that different places occur in the present specification not refers both to
The same embodiment, nor the individual or selective embodiment mutually exclusive with other embodiment.
Embodiment 1：
Anhydrous cupric sulfate (purity 99.99%), potassium ferrocyanide are dried at 80 DEG C of high temperature；
The anhydrous cupric sulfate of drying and potassium ferrocyanide are dissolved in sulfuric acid (20g/L) aqueous solution, a concentration of 8g/ of copper
L, a concentration of 1.5g/L of potassium ferrocyanide, and nitrogen is passed through into copper-containing solution.
Electrolyte obtained above is passed through cuboid cyclone electrolytic cell slot, working electrode is that 304 stainless steel areas are
700cm2, to the mesh electrode that electrode is coated titanium tantalum, electrolysis temperature is 30 DEG C, current density 40A/m2, and electrolysis time is
0.8h, stirring 400r/min are electrolysed, and copper powder is made.
Copper powder obtained above is washed with water, then is washed with 96% absolute ethyl alcohol, is placed on when being dried at 60 DEG C of vacuum drying chamber
Between 3h, obtain be suitable for 3D printing copper powders.
SEM characterizations are carried out to the superfine cupper powder that the present embodiment obtains, as shown in Figure 1, gained superfine cupper powder is spherical in shape, particle
Uniformly, oxygen content 375ppm, a diameter of 3~5 μm.
Embodiment 2：
By anhydrous cupric sulfate (purity 99.94%), potassium ferrocyanide is dried at 70 DEG C of high temperature.
The anhydrous cupric sulfate of drying and potassium ferrocyanide are dissolved in sulfuric acid (30g/L) aqueous solution, copper it is a concentration of
10g/L, a concentration of 2.0g/L of potassium ferrocyanide, and nitrogen is passed through into copper-containing solution.
Electrolyte obtained above is passed through cuboid cyclone electrolytic cell slot, working electrode is that 304 stainless steel areas are
600cm2, to the mesh electrode that electrode is coated titanium tantalum, electrolysis temperature is 30 DEG C, current density 50A/m2, and electrolysis time is
0.8h, stirring 300r/min are electrolysed, and copper powder is made.
Copper powder obtained above is washed with water, then is washed with 97% absolute ethyl alcohol, is placed on when being dried at 60 DEG C of vacuum drying chamber
Between 3h, obtain be suitable for 3D printing copper powders.
SEM characterizations are carried out to the superfine cupper powder that the present embodiment obtains, gained superfine cupper powder is spherical in shape, and particle is uniform, and oxygen contains
It is 203ppm to measure, a diameter of 2~5 μm.
Embodiment 3：
By copper chloride (purity 99.94%), potassium ferrocyanide is dried at 70 DEG C of high temperature.
The anhydrous cupric sulfate of drying and potassium ferrocyanide are dissolved in sulfuric acid (30g/L) aqueous solution, copper it is a concentration of
10g/L, a concentration of 2.0g/L of potassium ferrocyanide, and nitrogen is passed through into copper-containing solution.
Electrolyte obtained above is passed through cuboid cyclone electrolytic cell slot, working electrode is that 304 stainless steel areas are
600cm2, to the mesh electrode that electrode is coated titanium tantalum, electrolysis temperature is 30 DEG C, current density 50A/m2, and electrolysis time is
0.8h, stirring 300r/min are electrolysed, and copper powder is made.
Copper powder obtained above is washed with water, then is washed with 97% absolute ethyl alcohol, is placed on when being dried at 60 DEG C of vacuum drying chamber
Between 3h, obtain be suitable for 3D printing copper powders.
SEM characterizations are carried out to the superfine cupper powder that the present embodiment obtains, gained superfine cupper powder is in cellular irregular particle, oxygen
Content is 1400ppm, a diameter of 3~45 μm.
Embodiment 4：
By anhydrous cupric sulfate (purity 99.94%), potassium ferrocyanide is dried at 70 DEG C of high temperature.
The anhydrous cupric sulfate of drying and potassium ferrocyanide are dissolved in sulfuric acid (30g/L) aqueous solution, copper it is a concentration of
10g/L, a concentration of 2.0g/L of potassium ferrocyanide, and nitrogen is passed through into copper-containing solution.
Electrolyte obtained above is passed through cuboid cyclone electrolytic cell slot, working electrode is that 304 stainless steel areas are
600cm2, to the mesh electrode that electrode is coated titanium tantalum, electrolysis temperature is 30 DEG C, current density 500A/m2, and electrolysis time is
0.8h, stirring 1000r/min are electrolysed, and copper powder is made.
Copper powder obtained above is washed with water, then is washed with 97% absolute ethyl alcohol, is placed on when being dried at 60 DEG C of vacuum drying chamber
Between 3h, obtain be suitable for 3D printing copper powders.
SEM characterizations, the irregular near-spherical particle of gained superfine cupper powder are carried out to the superfine cupper powder that the present embodiment obtains, oxygen contains
It is 2160ppm to measure, a diameter of 5~15 μm.
Embodiment 5：
By anhydrous cupric sulfate (purity 99.94%), potassium ferrocyanide is dried at 70 DEG C of high temperature.
The anhydrous cupric sulfate of drying and potassium ferrocyanide are dissolved in sulfuric acid (30g/L) aqueous solution, copper it is a concentration of
10g/L, a concentration of 2.0g/L of potassium ferrocyanide, and nitrogen is passed through into copper-containing solution.
Electrolyte obtained above is passed through cuboid cyclone electrolytic cell slot, working electrode is that 304 stainless steel areas are
600cm2, to the mesh electrode that electrode is coated titanium tantalum, electrolysis temperature is 30 DEG C, current density 200A/m2, and electrolysis time is
0.8h, stirring 300r/min are electrolysed, and copper powder is made.
Copper powder obtained above is washed with water, then is washed with 97% absolute ethyl alcohol, is placed on when being dried at 60 DEG C of vacuum drying chamber
Between 3h, obtain be suitable for 3D printing copper powders.
SEM characterizations are carried out to the superfine cupper powder that the present embodiment obtains, as shown in Fig. 2, gained superfine cupper powder is near-spherical
Grain, oxygen content 1800ppm, a diameter of 6~10 μm.
Embodiment 6：
By anhydrous cupric sulfate (purity 99.94%), potassium ferrocyanide is dried at 70 DEG C of high temperature
The anhydrous cupric sulfate of drying and potassium ferrocyanide are dissolved in sulfuric acid (30g/L) aqueous solution, copper it is a concentration of
10g/L, a concentration of 2.0g/L of potassium ferrocyanide, and nitrogen is passed through into copper-containing solution.
Electrolyte obtained above is passed through cuboid cyclone electrolytic cell slot, working electrode is that 304 stainless steel areas are
600cm2, to the mesh electrode that electrode is coated titanium tantalum, electrolysis temperature is 30 DEG C, current density 50A/m2, and electrolysis time is
0.8h, stirring 300r/min are electrolysed, and copper powder is made.
Copper powder obtained above is washed with water, then is washed with 97% absolute ethyl alcohol, is placed on when being dried at 60 DEG C of vacuum drying chamber
Between 3h, obtain be suitable for 3D printing copper powders.
SEM characterizations are carried out to the superfine cupper powder that the present embodiment obtains, gained superfine cupper powder is spherical in shape, and particle is uniform, and oxygen contains
It is 205ppm to measure, a diameter of 2~5 μm.
Embodiment 7：
By anhydrous cupric sulfate (purity 99.99%), potassium ferrocyanide is dried at 90 DEG C of high temperature
The anhydrous cupric sulfate of drying and potassium ferrocyanide are dissolved in sulfuric acid (40g/L) aqueous solution, a concentration of 6g/ of copper
L, a concentration of 1.9g/L of potassium ferrocyanide, and nitrogen is passed through into copper-containing solution.
Electrolyte obtained above is passed through cuboid cyclone electrolytic cell slot, working electrode is that 304 stainless steel areas are
650cm2, to the mesh electrode that electrode is coated titanium tantalum, electrolysis temperature is 25 DEG C, current density 45A/m2, and electrolysis time is
0.8h, stirring 400r/min are electrolysed, and copper powder is made.
Copper powder obtained above is washed with water, then is washed with 96% absolute ethyl alcohol, is placed on when being dried at 60 DEG C of vacuum drying chamber
Between 3h, obtain the copper powders suitable for 3D printing.
SEM characterizations are carried out to the superfine cupper powder that the present embodiment obtains, gained superfine cupper powder is spherical in shape, and particle is uniform, and oxygen contains
It is 321ppm to measure, a diameter of 4~7 μm.
Embodiment 8：
By anhydrous cupric sulfate (purity 99.99%), polyethylene glycol 2000 is dried at 80 DEG C of high temperature.
The anhydrous cupric sulfate of drying and polyethylene glycol 2000 are dissolved separately in sulfuric acid (50g/L) aqueous solution, copper it is dense
Degree is 9g/L, a concentration of 0.25g/L of polyethylene glycol 2000, and nitrogen is passed through into copper-containing solution.
Electrolyte obtained above is passed through cuboid cyclone electrolytic cell slot, working electrode is that 304 stainless steel areas are
700cm2, to the mesh electrode that electrode is coated titanium tantalum, electrolysis temperature is 30 DEG C, current density 40A/m2, and electrolysis time is
0.8h, stirring 300r/min are electrolysed, and copper powder is made.
Copper powder obtained above is washed with water, then is washed with 90% absolute ethyl alcohol, is placed on when being dried at 60 DEG C of vacuum drying chamber
Between 3h, obtain the copper powders suitable for 3D printing.
SEM characterizations are carried out to the superfine cupper powder that the present embodiment obtains, as shown in figure 3, gained superfine cupper powder is in dendriform,
Grain uniformly, oxygen content 461ppm, a diameter of 1~5 μm.
Embodiment 9：
By anhydrous cupric sulfate (purity 99.99%), polyethylene glycol 2000 is dried at 80 DEG C of high temperature.
The anhydrous cupric sulfate of drying and polyethylene glycol 2000 are dissolved separately in sulfuric acid (50g/L) aqueous solution, copper it is dense
Degree is 19g/L, a concentration of 0.25g/L of polyethylene glycol 2000, and nitrogen is passed through into copper-containing solution.
Electrolyte obtained above is passed through cuboid cyclone electrolytic cell slot, working electrode is that 304 stainless steel areas are
700cm2, to the mesh electrode that electrode is coated titanium tantalum, electrolysis temperature is 30 DEG C, current density 40A/m2, and electrolysis time is
0.8h, stirring 300r/min are electrolysed, and copper powder is made.
Copper powder obtained above is washed with water, then is washed with 90% absolute ethyl alcohol, is placed on when being dried at 60 DEG C of vacuum drying chamber
Between 3h, obtain the copper powders suitable for 3D printing.
SEM characterizations are carried out to the superfine cupper powder that the present embodiment obtains, as shown in figure 4, gained superfine cupper powder is in irregular long
It is rodlike, oxygen content 500ppm, a diameter of 5~12 μm.
Embodiment 10：
By anhydrous cupric sulfate (purity 99.99%), polyethylene glycol 2000 is dried at 80 DEG C of high temperature.
The anhydrous cupric sulfate of drying and polyethylene glycol 2000 are dissolved separately in sulfuric acid (50g/L) aqueous solution, copper it is dense
Degree is 9g/L, a concentration of 12.5g/L of polyethylene glycol 2000, and nitrogen is passed through into copper-containing solution.
Electrolyte obtained above is passed through cuboid cyclone electrolytic cell slot, working electrode is that 304 stainless steel areas are
700cm2, to the mesh electrode that electrode is coated titanium tantalum, electrolysis temperature is 30 DEG C, current density 40A/m2, and electrolysis time is
0.8h, stirring 300r/min are electrolysed, and copper powder is made.
Copper powder obtained above is washed with water, then is washed with 90% absolute ethyl alcohol, is placed on when being dried at 60 DEG C of vacuum drying chamber
Between 3h, obtain the copper powders suitable for 3D printing.
SEM characterizations are carried out to the superfine cupper powder that the present embodiment obtains, gained superfine cupper powder is in irregularly long rodlike, oxygen content
For 512ppm, a diameter of 3~20 μm.
Embodiment 11：
By anhydrous cupric sulfate (purity 99.99%), polyethylene glycol 2000 is dried at 80 DEG C of high temperature.
The anhydrous cupric sulfate of drying and polyethylene glycol 2000 are dissolved separately in sulfuric acid (50g/L) aqueous solution, copper it is dense
Degree is 9g/L, a concentration of 0.25g/L of polyethylene glycol 2000, and nitrogen is passed through into copper-containing solution.
Electrolyte obtained above is passed through cuboid cyclone electrolytic cell slot, working electrode is that 304 stainless steel areas are
700cm2, to the mesh electrode that electrode is coated titanium tantalum, electrolysis temperature is 30 DEG C, current density 400A/m2, and electrolysis time is
0.8h, stirring 300r/min are electrolysed, and copper powder is made.
Copper powder obtained above is washed with water, then is washed with 90% absolute ethyl alcohol, is placed on when being dried at 60 DEG C of vacuum drying chamber
Between 3h, obtain the copper powders suitable for 3D printing.
SEM characterizations are carried out to the superfine cupper powder that the present embodiment obtains, gained superfine cupper powder is in irregularly long rodlike, oxygen content
For 1864ppm, a diameter of 4~8 μm.
Embodiment 12：
By anhydrous cupric sulfate (purity 99.99%), polyethylene glycol 2000 is dried at 80 DEG C of high temperature.
The anhydrous cupric sulfate of drying and polyethylene glycol 2000 are dissolved separately in sulfuric acid (50g/L) aqueous solution, copper it is dense
Degree is 9g/L, a concentration of 0.25g/L of polyethylene glycol 2000, and nitrogen is passed through into copper-containing solution.
Electrolyte obtained above is passed through cuboid cyclone electrolytic cell slot, working electrode is that 304 stainless steel areas are
700cm2, to the mesh electrode that electrode is coated titanium tantalum, electrolysis temperature is 30 DEG C, current density 40A/m2, and electrolysis time is
0.8h, stirring 800r/min are electrolysed, and copper powder is made.
Copper powder obtained above is washed with water, then is washed with 90% absolute ethyl alcohol, is placed on when being dried at 60 DEG C of vacuum drying chamber
Between 3h, obtain the copper powders suitable for 3D printing.
SEM characterizations are carried out to the superfine cupper powder that the present embodiment obtains, gained superfine cupper powder is in irregularly long rodlike, oxygen content
For 3000ppm, a diameter of 7~18 μm.
Embodiment 13：
By anhydrous cupric sulfate (purity 99.96%), polyethylene glycol 2000 is dried at 90 DEG C of high temperature.
The anhydrous cupric sulfate of drying and polyethylene glycol 2000 are dissolved separately in sulfuric acid (40g/L) aqueous solution, copper it is dense
Degree is 9.4g/L, a concentration of 0.4g/L of polyethylene glycol 2000, and nitrogen is passed through into copper-containing solution.
Electrolyte obtained above is passed through cuboid cyclone electrolytic cell slot, working electrode is that 304 stainless steel areas are
700cm2, to the mesh electrode that electrode is coated titanium tantalum, electrolysis temperature is 30 DEG C, current density 50A/m2, and electrolysis time is
0.7h, stirring 350r/min are electrolysed, and copper powder is made.
Copper powder obtained above is washed with water, then is washed with 92% absolute ethyl alcohol, is placed on when being dried at 60 DEG C of vacuum drying chamber
Between 3h, obtain the copper powders suitable for 3D printing.
SEM characterizations are carried out to the superfine cupper powder that the present embodiment obtains, gained superfine cupper powder is in dendriform, and particle is uniform, oxygen
Content is 194ppm, a diameter of 2~4 μm.
Embodiment 14：
By anhydrous cupric sulfate (purity 99.93%), polyethylene glycol 2000 is dried at 85 DEG C of high temperature.
The anhydrous cupric sulfate of drying and polyethylene glycol 2000 are dissolved separately in sulfuric acid (50g/L) aqueous solution, copper it is dense
Degree is 9.6g/L, a concentration of 0.5g/L of polyethylene glycol 2000, and nitrogen is passed through into copper-containing solution.
Electrolyte obtained above is passed through cuboid cyclone electrolytic cell slot, working electrode is that 304 stainless steel areas are
670cm2, to the mesh electrode that electrode is coated titanium tantalum, electrolysis temperature is 27 DEG C, current density 46A/m2, and electrolysis time is
0.71h, stirring 364r/min are electrolysed, and copper powder is made.
Copper powder obtained above is washed with water, then is washed with 93% absolute ethyl alcohol, is placed on when being dried at 60 DEG C of vacuum drying chamber
Between 3h, obtain the copper powders suitable for 3D printing.
SEM characterizations are carried out to the superfine cupper powder that the present embodiment obtains, gained superfine cupper powder is in dendriform, and particle is uniform, oxygen
Content is 203ppm, a diameter of 1~3 μm.
Comparative example 1：
Compared with Example 1, other than being added without potassium ferrocyanide, other conditions are same as Example 1, that is, dissolve cupric
After reagent, subsequent operation is carried out directly as electrolyte.
The superfine cupper powder obtained to this comparative example carries out SEM characterizations, and the results are shown in Figure 5, gained copper powder in more water chestnuts not
Regular polyhedron, particle is uneven, distribution is big, oxygen content 1030ppm, a diameter of 1-9 μm.
Comparative example 2：
Compared with Example 1, in addition to the potassium ferrocyanide for a concentration of 1.5g/L being added is replaced with the ferrous iron of 1.5g/L
Outside Cymag, other conditions are same as Example 1.
SEM characterizations are carried out to the superfine cupper powder that this comparative example obtains, the results are shown in Figure 6, and gained copper powder is in rodlike or ellipse
Circle, particle is uneven, distribution is big, oxygen content 1258ppm, a diameter of 1-10 μm.
Comparative example 3：
Compared with Example 4, in addition to the polyvinyl alcohol 2000 for a concentration of 0.25g/L being added is replaced with 0.25g/L's
Outside polyvinyl alcohol 12000, other conditions are same as Example 4.
SEM characterizations are carried out to the superfine cupper powder that this comparative example obtains, the results are shown in Figure 7, and gained copper powder is with small irregular
Particle shape flocks together, and distribution is big, oxygen content 850ppm, a diameter of 1~12 μm.
The present invention efficiently easily by electrochemical method, be passed through the synergistic effect of non-oxidizing gas, additive, come real
Now to copper powder oxygen content, the regulation and control of pattern and size distribution, whole flow process is simple, and equipment is few needed for production, required amount of reagent
Few, raw material sources are extensive, at low cost, are suitable for large-scale industrial production, with good economic efficiency.
It should be noted that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although with reference to preferable
Embodiment describes the invention in detail, it will be understood by those of ordinary skill in the art that, it can be to the technology of the present invention
Scheme is modified or replaced equivalently, and without departing from the spirit of the technical scheme of the invention and range, should all be covered in this hair
In bright right.
Claims (10)
1. a kind of preparation method of 3D printing copper powder, it is characterised in that：Including,
Dissolving：Copper reagent will be contained to dissolve in aqueous sulfuric acid；
Ventilation：It will be passed through non-oxidizing gas by containing in copper reagent described in dissolving；
Electrolysis：It is electrolysed by containing addition additive in copper reagent described in dissolving, ventilation, copper powder is made.
2. preparation method as described in claim 1, it is characterised in that：The dissolving, wherein the copper reagent that contains is sulfuric acid
The purity of copper, the copper sulphate is 99.91%~99.99%, the aqueous sulfuric acid, a concentration of 10g/L~50g/L；Institute
State ventilation, wherein the non-oxidizing gas is nitrogen.
3. preparation method as claimed in claim 1 or 2, it is characterised in that：The electrolysis, wherein the additive is ferrous iron
Potassium cyanide or polyethylene glycol 2000, a concentration of 1.0g/L~10g/L of the copper.
4. preparation method as claimed in claim 3, it is characterised in that：The electrolysis, wherein the potassium ferrocyanide, concentration
For 0.4g/L~2.3g/L, the polyethylene glycol 2000, a concentration of 0.01g/L~0.5g/L.
5. the preparation method as described in claim 1,2 or 4, it is characterised in that：The electrolysis is cyclone electrolytic cell, the eddy flow electricity
Solution, working electrode are stainless steel, are mesh electrode to electrode.
6. preparation method as claimed in claim 5, it is characterised in that：The cyclone electrolytic cell, wherein the working electrode is
The area of 304 stainless steels, the working electrode is 600~700cm2, it is described to electrode, it is the mesh electrode of coated titanium tantalum.
7. the preparation method as described in claim 1,2,4 or 6, it is characterised in that：The electrolysis, temperature are 20~30 DEG C,
Current density is 30~50A/m2, the time is 0.6~0.8h.
8. preparation method as claimed in claim 7, it is characterised in that：The electrolysis, it is described to stir to be electrolysed under stirring
It mixes, speed is 300~400r/min.
9. the preparation method as described in claim 1,2,4,6 or 8, it is characterised in that：Further include,
Cleaning：Electrolysis copper powder water obtained and washes of absolute alcohol will be passed through；
It is dry：By the copper powder drying through over cleaning.
10. preparation method as claimed in claim 9, it is characterised in that：The ethyl alcohol, a concentration of 90~99.8%, it is described dry
Dry, to be dry in vacuum drying chamber, temperature is 60 DEG C, drying time 3h.
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 |
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| CN108360024A true CN108360024A (en) | 2018-08-03 |
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| CN113084186A (en) * | 2021-03-30 | 2021-07-09 | 武汉大学 | Flower-shaped copper particle and preparation method thereof |
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| CN103388160A (en) * | 2013-07-19 | 2013-11-13 | 北京科技大学 | Method for preparation of ultrafine copper powder by waste circuit board copper dissolution-electrodeposition combined method |
| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103388160A (en) * | 2013-07-19 | 2013-11-13 | 北京科技大学 | Method for preparation of ultrafine copper powder by waste circuit board copper dissolution-electrodeposition combined method |
| 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 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113084186A (en) * | 2021-03-30 | 2021-07-09 | 武汉大学 | Flower-shaped copper particle and preparation method thereof |
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