CN104028771A - Method for preparing copper-tungsten alloy powder - Google Patents
Method for preparing copper-tungsten alloy powder Download PDFInfo
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- CN104028771A CN104028771A CN201410281248.XA CN201410281248A CN104028771A CN 104028771 A CN104028771 A CN 104028771A CN 201410281248 A CN201410281248 A CN 201410281248A CN 104028771 A CN104028771 A CN 104028771A
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Abstract
The invention relates to a method for preparing copper-tungsten alloy powder. According to the method, a copper sheet is used as an anode, a noble electrode is used as a cathode, sodium tungstate solution is used as anodic solution, solution with pH ranging from 0 to 14 is used as cathodic solution, electrolyzation is performed under the constant current 1-100mA/cm<2> or constant voltage 10-300V, the sodium tungstate solution is electrolyzed with a cation membrane, a product obtained is cleaned and dried so as to obtain copper-tungsten compound precursor, and the copper-tungsten compound precursor is subjected to high temperature reduction in the hydrogen atmosphere so as to obtain copper-tungsten alloy powder. The method has the advantages that the uniformity problem of the copper-tungsten alloy powder is solved, preparation time, especially that of the precursor, is greatly shortened, and the copper-tungsten alloy powder obtained is pure.
Description
Technical field
The invention belongs to materialogy field, relate in particular to a kind of copper-tungsten, is a kind of method of preparing copper-tungsten powder specifically.
Background technology
W-Cu composite is because having good Physical and mechanical properties, and stronger Burning corrosion resistance, thermal shock resistance, and excellent thermal control and microwave absorbing property etc., be widely used in the function and structure devices such as electric contactor, vacuum circuit breaker, heat sink material.Meanwhile, W-Cu functional composite material has the Good All-around Properties such as the height electricity of high-melting-point, low thermal coefficient of expansion, low sputtering raste and the copper of tungsten is led, thermal conductivity concurrently, is considered to the poly-plasma facing material of the most promising core.And particularity can be used for military material (as rocket nozzle, aircraft larynx lining), a transmitting, kinetic energy penetrator field, and the lead frame of computer central processing system, large scale integrated circuit etc.
Traditional W-Cu composite, because of W and the immiscible and larger angle of wetting of Cu, can only form pseudo-alloy, and the density after wetability and sintering when powder sintered is all poor, has a strong impact on performance and the application of W-Cu composite.In W-Cu Alloyapplication, often require W-Cu material have higher densification degree and uniformly structure to improve its performance.
Cationic membrane has certain selection permeability, can make cation selecteed in anode see through ionic membrane in cathode chamber, and perfluorinated sulfonic acid cation-exchange membrane can allow the Na in anode chamber
+ion see through ionic membrane enter cathode chamber, thereby cancellation Na
+the impact of ionic impurity.
Summary of the invention
For the defect existing in above-mentioned prior art, technical problem to be solved by this invention is to provide a kind of method of preparing copper-tungsten powder, it is poor that the preparation method of described this copper-tungsten powder will solve copper-tungsten powder density of the prior art, has a strong impact on the performance of W-Cu composite and the technical problem of application.
A kind of method of preparing copper-tungsten powder of the present invention, taking copper sheet as anode, taking inert electrode as negative electrode, the sodium tungstate solution taking concentration as 0.005 ~ 2.5mol/L is anolyte, taking pH scope at 0 ~ 14 acid solution, aqueous slkali or salting liquid as catholyte, be 1 ~ 100mA/cm at constant current
2or electrolysis 3 ~ 30 minutes under the condition that constant voltage is 10 ~ 300V, cationic membrane electrolysis sodium tungstate solution, then will after the product cleaning obtaining, dry, obtain copper tungsten compound presoma, by described copper tungsten compound presoma high temperature reduction under atmosphere of hydrogen, described hydrogen reduction method is that presoma is put into tube furnace, under atmosphere of hydrogen with the programming rate of 2.5 ~ 10 DEG C/min, first at 350 ~ 450 DEG C of reduction 1 ~ 2h, then at 600 ~ 750 DEG C of reduction 3 ~ 6h, obtain copper-tungsten powder.
Further, adopt a slot electrode to carry out a solution, described electrolytic cell be one taking copper sheet as anode, taking inert electrode as negative electrode, cationic membrane is the two-compartment cell of barrier film.
Further, described cationic membrane is perfluorinated sulfonic acid cation-exchange membrane;
Further, described inert electrode is glass-carbon electrode, graphite electrode, titanium electrode (net), platinum electrode (net) or stainless steel electrode.
Further, the maximum concentration of described anolyte is saturated concentration.
The preferred pH scope of the catholyte further, adopting is 1 ~ 5;
Further, described electrolytic method had been both constant-potential electrolysis or constant-current electrolysis.
Further, the current range that described constant-current electrolysis adopts is 1 ~ 100mA/cm
2.Preferably 50 ~ 100 mA/cm
2, voltage range 10 ~ 300V that constant-potential electrolysis adopts.Preferably 50 ~ 150V;
Further, the cleaning fluid adopting is deionized water;
Further, drying course is that 30 ~ 80 DEG C of constant temperature are placed 1 ~ 2h in air dry oven.
The present invention utilizes the advantage of electrolysis with ion-exchange film, by Na
+be transferred to cathode chamber, without any impurity or foreign ion, anode chamber adds without any other chemical reagent, ensures the purity of anode presoma product, and copper tungsten compound presoma reduces the uniform copper-tungsten powder obtaining.
The present invention compares with prior art, and its technological progress is significant.The present invention has not only solved the homogeneity question of copper-tungsten powder, and the preparation time of preparation time especially presoma is shortened greatly, and the pure copper-tungsten powder obtaining.Technique of the present invention is simple, and easily operation, invests littlely, and synthetic quantity is large, can directly apply to suitability for industrialized production.
Brief description of the drawings
Fig. 1, the present invention prepare the process chart of copper-tungsten powder;
The XRD of copper-tungsten powder figure in Fig. 2, embodiment;
The EDS of copper-tungsten powder energy spectrogram in Fig. 3, embodiment;
The EDS face scintigram of copper-tungsten powder in Fig. 4, embodiment.
Detailed description of the invention
By reference to the accompanying drawings the present invention is further set forth below by specific embodiment, but do not limit the present invention.
Embodiment
Taking the sodium tungstate solution of the 0.01mol/L of 95ml as anolyte, taking the hydrochloric acid solution of the 0.01mol/L of 90ml as catholyte, taking copper sheet as anode, titanium net is negative electrode, and constant current 0.6A electrolysis 306S(electrolysis time is according to Na
+ion all transfers to that theoretical electric weight that cathode chamber consumes calculates,
), obtain electrolysate.
The anodic product that electrolysis is obtained washed with de-ionized water three times, are then put into 60 DEG C of oven dry 2h of constant temperature in air dry oven, obtain pure copper tungsten precursor compound.
Copper tungsten precursor compound is put into tube furnace programming rate with 2.5 DEG C/min under atmosphere of hydrogen first at 400 DEG C of reductase 12 h, then, at 700 DEG C of reduction 5h, can obtain copper-tungsten powder.The copper-tungsten powder test XRD analysis result obtaining is as Fig. 2, and EDS EDAX results is if Fig. 3, EDS face scanning result are as Fig. 4.
By observing XRD figure in Fig. 2, can determine and obtain the copper-tungsten powder that powder has only contained copper and two kinds of metallic elements of tungsten.By observing EDS energy spectrogram in Fig. 3, can determine only cupric, the two kinds of elements of tungsten of powder that obtain, there is no the tungsten-copper alloy powder of other impurity elements.Finally, by observing EDS face scintigram in Fig. 4, the tungsten copper powder that can determine is the pure copper-tungsten powder mixing.
The above is only giving an example of embodiments of the present invention; it should be pointed out that for those skilled in the art, do not departing under the prerequisite of the technology of the present invention principle; can also make some improvement and modification, these improve and modification also should be considered as protection scope of the present invention.
Claims (9)
1. prepare the method for copper-tungsten powder for one kind, it is characterized in that: taking copper sheet as anode, taking inert electrode as negative electrode, sodium tungstate solution taking concentration as 0.005 ~ 2.5mol/L is anolyte, taking pH scope at 0 ~ 14 acid solution, aqueous slkali or salting liquid as catholyte, be 1.0 ~ 100mA/cm at constant current
2or electrolysis 3 ~ 30 minutes under the condition that constant voltage is 10 ~ 300V, adopt cationic membrane electrolysis sodium tungstate solution, then will after the product cleaning obtaining, dry, obtain copper tungsten compound presoma, by described copper tungsten compound presoma high temperature reduction under atmosphere of hydrogen, described high temperature reduction method is that presoma is put into tube furnace, under atmosphere of hydrogen with the programming rate of 2.5 ~ 10 DEG C/min, first at 350 ~ 450 DEG C of reduction 1 ~ 2h, then at 600 ~ 750 DEG C of reduction 3 ~ 6h, can obtain copper-tungsten powder.
2. a kind of method of preparing copper-tungsten powder as claimed in claim 1, is characterized in that: adopt a slot electrode to carry out electrolysis, described electrolytic cell be one taking copper sheet as anode, taking inert electrode as negative electrode, cationic membrane is the two-compartment cell of barrier film.
3. a kind of method of preparing copper-tungsten powder as claimed in claim 1, is characterized in that: described cationic membrane is perfluorinated sulfonic acid cation-exchange membrane.
4. a kind of method of preparing copper-tungsten powder as claimed in claim 1, is characterized in that: described inert electrode is glass-carbon electrode, graphite electrode, titanium electrode (net), platinum electrode (net) or stainless steel electrode.
5. a kind of method of preparing copper-tungsten powder as claimed in claim 1, is characterized in that: the pH scope of the catholyte adopting is 1 ~ 5.
6. a kind of method of preparing copper-tungsten powder as claimed in claim 1, is characterized in that: described electrolytic method is constant-potential electrolysis or constant-current electrolysis.
7. a kind of method of preparing copper-tungsten powder as claimed in claim 1, is characterized in that: the preferred current range of described constant-current electrolysis is 50 ~ 100mA/cm
2.
8. a kind of method of preparing copper-tungsten powder as claimed in claim 1, is characterized in that: the preferred voltage range of described constant-potential electrolysis is 50 ~ 150V.
9. a kind of method of preparing copper-tungsten powder as claimed in claim 1, is characterized in that: drying course is that 30 ~ 80 DEG C of constant temperature are placed 1 ~ 2h in air dry oven.
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Cited By (8)
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| CN104789994A (en) * | 2015-04-09 | 2015-07-22 | 上海应用技术学院 | Preparation method of tungsten-silver alloy powder |
| CN104789993A (en) * | 2015-04-09 | 2015-07-22 | 上海应用技术学院 | Preparation method of silver-molybdenum alloy powder |
| CN104894606A (en) * | 2015-04-09 | 2015-09-09 | 上海应用技术学院 | Preparation method of tungsten-nickel alloy powder |
| CN104894604A (en) * | 2015-04-09 | 2015-09-09 | 上海应用技术学院 | Preparation method of molybdenum-iron alloy powder |
| CN104889414A (en) * | 2015-04-09 | 2015-09-09 | 上海应用技术学院 | A preparation method of ferro-tungsten alloy powder |
| CN104894605A (en) * | 2015-04-09 | 2015-09-09 | 上海应用技术学院 | Preparation method of molybdenum-nickel alloy powder |
| CN105441986A (en) * | 2015-11-16 | 2016-03-30 | 上海应用技术学院 | Preparation method for Mox-(M)-Wy alloy powder |
| CN112708794A (en) * | 2021-03-29 | 2021-04-27 | 陕西斯瑞新材料股份有限公司 | Method for preparing copper-tungsten alloy by adopting superfine tungsten powder |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104789994A (en) * | 2015-04-09 | 2015-07-22 | 上海应用技术学院 | Preparation method of tungsten-silver alloy powder |
| CN104789993A (en) * | 2015-04-09 | 2015-07-22 | 上海应用技术学院 | Preparation method of silver-molybdenum alloy powder |
| CN104894606A (en) * | 2015-04-09 | 2015-09-09 | 上海应用技术学院 | Preparation method of tungsten-nickel alloy powder |
| CN104894604A (en) * | 2015-04-09 | 2015-09-09 | 上海应用技术学院 | Preparation method of molybdenum-iron alloy powder |
| CN104889414A (en) * | 2015-04-09 | 2015-09-09 | 上海应用技术学院 | A preparation method of ferro-tungsten alloy powder |
| CN104894605A (en) * | 2015-04-09 | 2015-09-09 | 上海应用技术学院 | Preparation method of molybdenum-nickel alloy powder |
| CN105441986A (en) * | 2015-11-16 | 2016-03-30 | 上海应用技术学院 | Preparation method for Mox-(M)-Wy alloy powder |
| CN112708794A (en) * | 2021-03-29 | 2021-04-27 | 陕西斯瑞新材料股份有限公司 | Method for preparing copper-tungsten alloy by adopting superfine tungsten powder |
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