CN101956090B - Method for preparing nano porous copper by adopting Cu-Zn alloy - Google Patents
Method for preparing nano porous copper by adopting Cu-Zn alloy Download PDFInfo
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- CN101956090B CN101956090B CN2010101056491A CN201010105649A CN101956090B CN 101956090 B CN101956090 B CN 101956090B CN 2010101056491 A CN2010101056491 A CN 2010101056491A CN 201010105649 A CN201010105649 A CN 201010105649A CN 101956090 B CN101956090 B CN 101956090B
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Abstract
The invention discloses a method for preparing nano porous copper by adopting Cu-Zn alloy. The method comprises the following steps of: preparing copper and zinc in a proportion that the copper is 60 weight percent or 70 weight percent or 80 weight percent of the zinc under the protection of nitrogen to obtain alloys by adopting a smelt technology; carrying out Tafel curve testing by taking a 1M NaCl solution as an electrolyte and utilizing a three-electrode method to obtain easies corrosion voltages of different alloys; carrying out water bath at 50-70 DEG C in the 1M NaCl solution under the condition that the volume ratio of corrosive liquid to the alloy volume is (1,000-1,500):1; carrying out electrochemical corrosion on the alloys under the easies corrosion voltages; dropwise adding 1-2ml of concentrated NH3.H2O solution every other 20 minutes to ensure that the electrolyte contains certain complex compounds to promote the reaction; and stopping the reaction until the cathode does not discharge obvious bubbles any more to obtain the nano porous copper. The nano porous copper prepared through the method has the advantages that the aperture is fine and small, the ligament outline is clear, the aperture is 50-200nm, and the ligament width is 70-100nm.
Description
Technical field
The invention belongs to the nano porous metal technical field of material, being specifically related to the Cu-Zn alloy is matrix, utilizes electrochemical method to prepare the method for nano porous copper.
Background technology
The metal nano porous material not only has the big internal surface area of nano material, high porosity and uniform nanoporous; And excellent properties such as high thermal conductivity, high conductivity with metallic substance are anticorrosive, antifatigue, thereby make it on catalysis and separation science, have important use.The surface effects and the dimensional effect that are shown of metal nano porous material makes it at aspects such as electronics, optics, microfluid and micromechanics great application prospect arranged in addition.
The correlative study of nano porous copper at present mainly is through to Zr-Cu, Mn-Cu, Mg-Cu; Binary alloy systems such as Al-Cu are taken off alloy treatment; All prepared nano porous copper, preparation is complicated but the defective of these methods is matrix alloy, and price is higher; Aperture big or small inhomogeneous, tough belt profile is unintelligible.
Summary of the invention
The object of the invention provides a kind of preparation method of nano porous copper, can prepare that the aperture is tiny evenly, the nano porous copper of ligament clear-cut, reaches aperture 50～200nm, tough bandwidth 70～100nm.
The technical scheme that the present invention adopted is, a kind of Cu-Zn of employing alloy prepares the method for nano porous copper, implement according to following steps,
Step 1 takes by weighing pure copper powder and pure spelter according to weight percent Cu-wt60%Zn or Cu-wt70%Zn or Cu-wt80%Zn;
Step 2, pure copper powder and pure spelter that step 1 is taken by weighing place plumbago crucible, carry out melting under the nitrogen protection; Earlier be heated to 500～520 ℃ from room temperature through 20～30 minutes; And be incubated 30～40 minutes minutes, be heated to 920～950 ℃ through 30～40 minutes again, and be incubated 50～60 minutes; Cooled to 330～350 ℃ through 100～120 minutes; And be incubated 100～120 minutes, and cool to room temperature then with the furnace, obtain alloy Cu-wt60%Zn or alloy Cu-wt70%Zn or alloy Cu-wt80%Zn;
Step 3; The NaCl solution of preparation 1M is as electrolytic solution; In CHI660D type electrochemical workstation, be reference electrode with the mercurous chloride electrode, platinum electrode is a supporting electrode; Utilize three-electrode method to carry out the test of Ta Feier curve, obtain the most perishable voltage of alloy Cu-wt60%Zn or alloy Cu-wt70%Zn or alloy Cu-wt80%Zn respectively;
Step 4, the most perishable voltage that utilizes step 3 to obtain is in MCP-1 type potentiostat; With the mercurous chloride electrode is reference electrode, and platinum electrode is a supporting electrode, and the NaCl solution of 1M is as electrolytic solution; Bath temperature is 50～70 ℃, and corrosive fluid and alloy are 1000～1500: 1 by volume, adopts potentiostatic method; Under the most perishable voltage, alloy is carried out galvanic corrosion, every simultaneously at a distance from 20 minutes, in electrolytic solution, drip dense NH
3H
2O solution 1～2ml when negative electrode no longer includes tangible bubble and emits, promptly obtains nano porous copper.
Characteristics of the present invention also are,
The purity of pure copper powder is 99.9%.
The purity of pure spelter is 99.9%.
It is matrix that the inventive method adopts the Cu-Zn alloy of relatively economical, uses the NaCl and the NH of environmentally safe
3H
2O utilizes the method for galvanic corrosion as corrosive fluid, and the preparation aperture is tiny evenly, the nano porous copper of ligament clear-cut.
Description of drawings
Fig. 1 is a preparing method's of the present invention schema;
Fig. 2 is the surperficial SEM photo that obtains superfine foam copper after the Cu-wt80%Zn corrosion;
Fig. 3 is the section SEM photo that obtains superfine foam copper after the Cu-wt80%Zn corrosion.
Embodiment
Below in conjunction with accompanying drawing and specific embodiment the present invention is elaborated.
Embodiment 1
Cu-wt60%Zn takes by weighing copper powder 60g (purity 99.9%) and pure spelter 90g (purity 99.9%) by weight percentage, places plumbago crucible, under nitrogen protection, carries out melting.The main technique of melting is: from room temperature, be heated to 520 ℃ through 20 minutes, 520 ℃ of insulations 40 minutes; Be heated to 950 ℃ through 40 minutes again; 950 ℃ of insulations 60 minutes, cool to 350 ℃ through 120 minutes, 350 ℃ of insulations 120 minutes; Cool to room temperature then with the furnace, obtain alloy Cu-wt60%Zn.
Preparation 1M NaCl solution is as electrolytic solution; In CHI660D type electrochemical workstation, be reference electrode with the mercurous chloride electrode, platinum electrode is a supporting electrode; Utilize three-electrode method to carry out the test of Ta Feier curve, the most perishable voltage that obtains alloy Cu-wt60%Zn is 0.9V.
The most perishable voltage that the step obtains in the utilization in MCP-1 type potentiostat, is reference electrode with the mercurous chloride electrode; Platinum electrode is a supporting electrode, and the NaCl solution of 1M is as electrolytic solution, and bath temperature is 70 ℃; Corrosive fluid and alloy Cu-wt60%Zn are 1500: 1 by volume, adopt potentiostatic method, under the voltage of the most perishable voltage 0.9V, alloy are carried out galvanic corrosion; Every simultaneously at a distance from 20 minutes, in electrolytic solution, drip dense NH
3H
2O solution 1～2ml when negative electrode no longer includes tangible bubble and emits, promptly obtains nano porous copper.
Embodiment 2
Cu-wt70%Zn takes by weighing copper powder 45g (purity 99.9%) and pure spelter 105g (purity 99.9%) by weight percentage, places plumbago crucible, under nitrogen protection, carries out melting.The main technique of melting is: from room temperature, be heated to 510 ℃ through 25 minutes, 510 ℃ of insulations 35 minutes; Be heated to 940 ℃ through 35 minutes again; 940 ℃ of insulations 50 minutes, cool to 340 ℃ through 110 minutes, 340 ℃ of insulations 110 minutes; Cool to room temperature then with the furnace, obtain alloy Cu-wt70%Zn.
Preparation 1M NaCl solution is as electrolytic solution; In CHI660D type electrochemical workstation, be reference electrode with the mercurous chloride electrode, platinum electrode is a supporting electrode; Utilize three-electrode method to carry out the test of Ta Feier curve, the most perishable voltage that obtains alloy Cu-wt70%Zn is 1.0V.
The most perishable voltage that the step obtains in the utilization in MCP-1 type potentiostat, is reference electrode with the mercurous chloride electrode; Platinum electrode is a supporting electrode, and the NaCl solution of 1M is as electrolytic solution, and bath temperature is 60 ℃; Corrosive fluid and alloy Cu-wt70%Zn are 1200: 1 by volume, adopt potentiostatic method, at the most perishable voltage are under the voltage of 1.0V alloy to be carried out galvanic corrosion; Every simultaneously at a distance from 20 minutes, in electrolytic solution, drip dense NH
3H
2O solution 1～2ml when negative electrode no longer includes tangible bubble and emits, promptly obtains nano porous copper.
Embodiment 3
Cu-wt80%Zn takes by weighing copper powder 30g (purity 99.9%) and pure spelter 120g (purity 99.9%) by weight percentage, places plumbago crucible, under nitrogen protection, carries out melting.The main technique of melting is: from room temperature, be heated to 500 ℃ through 30 minutes, 500 ℃ of insulations 30 minutes; Be heated to 920 ℃ through 30 minutes again; 920 ℃ of insulations 60 minutes, cool to 330 ℃ through 100 minutes, 330 ℃ of insulations 100 minutes; Cool to room temperature then with the furnace, obtain alloy Cu-wt80%Zn.
Preparation 1M NaCl solution is as electrolytic solution; In CHI660D type electrochemical workstation, be reference electrode with the mercurous chloride electrode, platinum electrode is a supporting electrode; Utilize three-electrode method to carry out the test of Ta Feier curve, the most perishable voltage that obtains alloy Cu-wt80%Zn is 1.25V.
The most perishable voltage that utilizes aforesaid method to obtain in MCP-1 type potentiostat, is reference electrode with the mercurous chloride electrode; Platinum electrode is a supporting electrode, and 1M NaCl solution is as electrolytic solution, 50 ℃ of water-baths; Corrosive fluid and alloy Cu-wt80%Zn are 1000: 1 by volume, adopt potentiostatic method, at the most perishable voltage are under the voltage of 1.25V alloy to be carried out galvanic corrosion; Every simultaneously at a distance from 20 minutes, in electrolytic solution, drip dense NH
3H
2O solution 1～2ml makes and contains certain title complex in the electrolytic solution, promotes reaction to carry out.To negative electrode not when having tangible bubble to emit, reaction stops, and promptly obtains nano porous copper.
The surperficial SEM photo of the nano porous copper that obtains and section SEM photo such as Fig. 2, shown in Figure 3, the preparation aperture is tiny evenly, the nano porous copper of ligament clear-cut, aperture 50～200nm, tough bandwidth 70～100nm.
Claims (3)
1. a method that adopts the Cu-Zn alloy to prepare nano porous copper is characterized in that, implement according to following steps,
Step 1 takes by weighing pure copper powder and pure spelter according to weight percent Cu-wt60%Zn or Cu-wt70%Zn or Cu-wt80%Zn;
Step 2, pure copper powder and pure spelter that step 1 is taken by weighing place plumbago crucible, carry out melting under the nitrogen protection; Earlier be heated to 500～520 ℃ from room temperature through 20～30 minutes; And be incubated 30～40 minutes minutes, be heated to 920～950 ℃ through 30～40 minutes again, and be incubated 50～60 minutes; Cooled to 330～350 ℃ through 100～120 minutes; And be incubated 100～120 minutes, and cool to room temperature then with the furnace, obtain alloy Cu-wt60%Zn or alloy Cu-wt70%Zn or alloy Cu-wt80%Zn;
Step 3; The NaCl solution of preparation 1M is as electrolytic solution; In CHI660D type electrochemical workstation, be reference electrode with the mercurous chloride electrode, platinum electrode is a supporting electrode; Utilize three-electrode method to carry out the test of Ta Feier curve, obtain the most perishable voltage of alloy Cu-wt60%Zn or alloy Cu-wt70%Zn or alloy Cu-wt80%Zn;
Step 4, the most perishable voltage that utilizes step 3 to obtain is in MCP-1 type potentiostat; With the mercurous chloride electrode is reference electrode, and platinum electrode is a supporting electrode, and the NaCl solution of 1M is as electrolytic solution; Bath temperature is 50～70 ℃, and corrosive fluid and alloy are 1000～1500: 1 by volume, adopts potentiostatic method; Under the most perishable voltage, alloy is carried out galvanic corrosion, every simultaneously at a distance from 20 minutes, in electrolytic solution, drip dense NH
3H
2O solution 1～2ml when negative electrode no longer includes tangible bubble and emits, promptly obtains nano porous copper.
2. method according to claim 1 is characterized in that, the purity of said pure copper powder is 99.9%.
3. method according to claim 1 is characterized in that, the purity of said pure spelter is 99.9%.
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| CN102766893B (en) * | 2012-07-24 | 2014-12-10 | 上海交通大学 | Preparation method of nano porous copper capable of being patterned |
| CN103695677A (en) * | 2013-12-31 | 2014-04-02 | 内蒙古蒙西高新技术集团有限公司 | Industrial preparation method of copper-zinc alloy powder for preparing diethyl zinc |
| CN103643065A (en) * | 2013-12-31 | 2014-03-19 | 内蒙古蒙西高新技术集团有限公司 | Novel preparation method of copper zinc alloy powder for preparing diethyl zinc |
| CN108199003A (en) * | 2017-12-27 | 2018-06-22 | 长安大学 | A kind of big/mesoporous antimony cathode of three-dimensional, preparation method and applications |
| CN109468512B (en) * | 2018-12-06 | 2020-01-31 | 太原理工大学 | Preparation method of surface porous magnesium alloys |
| CN110656297B (en) * | 2019-10-17 | 2021-01-12 | 北京化工大学 | Method for preparing high-conductivity porous copper foil based on brass strip |
| CN111485277A (en) * | 2020-03-27 | 2020-08-04 | 绍兴市俱和环保科技有限公司 | Method for preparing porous liquid absorption core |
| CN111736378A (en) | 2020-06-17 | 2020-10-02 | Tcl华星光电技术有限公司 | Substrate, preparation method thereof and display panel |
| CN114875264B (en) * | 2021-02-05 | 2023-05-09 | 清华大学 | Three-dimensional grading layering porous copper and preparation method thereof |
| CN114373939A (en) * | 2021-12-10 | 2022-04-19 | 江阴纳力新材料科技有限公司 | Composite current collector, manufacturing method, pole piece and lithium battery |
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| CN101590528A (en) * | 2009-06-19 | 2009-12-02 | 山东大学 | A kind of preparation method of nano porous copper |
| CN101596598A (en) * | 2009-07-01 | 2009-12-09 | 济南大学 | A kind of preparation method of whole continuous nano-porous copper |
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| CN101590528A (en) * | 2009-06-19 | 2009-12-02 | 山东大学 | A kind of preparation method of nano porous copper |
| CN101596598A (en) * | 2009-07-01 | 2009-12-09 | 济南大学 | A kind of preparation method of whole continuous nano-porous copper |
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